JP5988476B2 - Antibacterial / antifungal metal ion water and cosmetics and fabrics containing the same - Google Patents

Description

This invention has a metal film having antibacterial and antifungal properties on a surface of at least one side of a plastic film as a base material, and is used as a sheet-like antibacterial agent obtained by cutting the film into a size according to the use, or The present invention relates to a technique for immersing the sheet-like antibacterial film in water or a dilute organic acid and obtaining the metal ion water in which vibration is sometimes applied to promote ion elution. In addition, the sheet-like antibacterial agent is used as a packaging material to maintain the freshness and life of foods and flowers, or the metal ion water having antibacterial and antifungal properties is used as a preservative or permanent for cosmetics and ice making raw material water. The present invention relates to a technique that is used as a deodorant after treatment, and sometimes used as a disease treatment material.

Conventionally, containers and bags formed by cutting a laminated film in which two polyester films have a vapor-deposited silver film in a sandwich structure and mixing 1 to 2% by weight in a plastic resin are well known, and have antibacterial metals. Cutting boards, bags, and storage containers, which are resin compositions in which ions pass between molecules of a plastic resin and exhibit antibacterial properties, are commercially available. (Patent Document 1)

In addition, an inorganic antibacterial agent in which silver complex ions are supported on zeolite is mixed in the plastic resin at a ratio of about 2% by weight, and the metal ions that escape from the molecules of the plastic resin with the water content of the food as a solvent. There are also bags and containers that make use of antibacterial properties.

The silver antibacterial agents such as nano silver and zeomic are not the main material that constitutes plastic films or bags and containers made of them, but are mixed with about 2% of antibacterial agents as bags and containers made mainly of plastic resin. Has been launched. (Non-Patent Document 1)

Bags and containers made of plastic films that have been mixed with inorganic antibacterial agents and have antibacterial effects by elution of the antibacterial agents have been developed for a long time. Have been replaced by those containing antimicrobial agents. (Non-Patent Document 1)

In addition, a thin and soft non-stretched plastic film is adhered as the lid of the container, and the flexibility of the film and the air layer formed between the film and the container are used as cushions to prevent food damage from damaging food. Food packaging containers are also used.

Prior art that uses vacuum or ion deposition of copper or copper alloy, and applies adhesive to the back surface, which is a non-deposition surface, for flooring and doorknobs, etc., and uses the antibacterial properties of the metal surface Also seen. According to this document, no protection by a resin coat or another film is described on the metal deposition surface. (Patent Document 2)

According to Patent Document 2, the antibacterial effect of the metal deposition surface is effective at first glance, but due to the weakness of the interface between the base film and the deposition surface not described in the document, that is, the extremely thin metal deposition surface is the interface. However, it is weak against contact and irritation and easily peels off, so that the durability required for a certain degree of use is always low, and copper or its alloy is naturally sulfided and discolored. In some cases, the color may change to greenish blue, but according to the description, those chemical changes are not predicted and no protective measures are described.

Also, the deposited copper or copper alloy has a very weak intermolecular bond even when the metal vapor or the metal ions forming the deposited film is cooled or ion-exchanged to return to the metal copper or alloy. Therefore, unlike solid copper and solid alloys, there is no description that the ions are easily eluted, and that the characteristics are different, and products such as door knobs described in the document have no practicality.

Although it is possible to obtain a sheet-like antibacterial agent by coating an existing inorganic antibacterial agent or organic antibacterial agent on a plastic film, the antibacterial agent is buried in the binder necessary for bonding to the film. However, it is difficult to elute many antibacterial ions, and those near the surface of the film slide down and cannot function sufficiently. Further, there is a problem that a process of bonding an antibacterial agent to the film sheet is necessary, and the original function is reduced at a high cost.

Since the polyester film described in Patent Document 1 has a silver film with a sandwich structure, only the silver ion elution is exposed to the cut surface, so the balance between cost and function is not good. Even if a powder obtained by cutting a laminated film having a silver layer in a sandwich structure with two polyester films cut vertically and horizontally is put into 1 part of purified water 100 and shaken, it may be insignificant depending on the pH and temperature conditions. Even if the concentration goes up and down, it becomes saturated at a concentration of around 100 ppb.

Japanese Patent No. 4175486 JP 2010-247450 A

Title Latest Trends in Freshness Preservation Technology (Pages 22-24) Publisher Toray Research Center, Research Department, National Bibliography Number 21692749

In order to maintain the freshness and longevity of fresh foods and flowers, replenishment of water, prevention of oxidation, suppression of growth of microorganisms such as bacteria and fungi, adsorption of ethylene gas, and low temperature storage are important methods. In particular, low-temperature storage including freezing for the purpose of inhibiting the growth of microorganisms is strongly required, but for foods and florets that cannot be frozen or are not suitable for freezing, the suppression of the growth of microorganisms itself is a very effective means of maintaining freshness and extending lifespan. is there.

Therefore, various wrapping papers, bags, and packaging containers made of a plastic resin mixed with an antibacterial agent have been developed. In the case where a film or a resin molded product mainly composed of a plastic resin mixed with an antibacterial agent is used as a food packaging container or a sheet or film for wrapping paper, the antibacterial metal ion has a nano-order size. It takes time for the ions to pass through the molecules of the plastic resin and exhibit antibacterial properties on the surface of the film or resin composition. In order to reach an ionic concentration sufficient to maintain the freshness of foods and flowers, it is actually close to the surface of the resin layer forming the packaging container, bag, wrapping paper raw film, packaging container, bag, wrapping paper It is an existing antibacterial agent.

The antibacterial agent present on the non-contact surface between the plastic resin forming the film or plastic container and the food or inside the resin forming them hardly works. For example, silver ions with antibacterial properties need an ion concentration of at least 10 ppb or more to help maintain the freshness of food, but the antibacterial agents located inside the food container and near the non-contact surface do not work. In order to be effective, more extra antibacterial agents must be added, even though it is considered wasteful. In addition, since metal ions do not move through the air, the antibacterial surface of food containers, bags or wrapping papers can be directly touched by food or flowers to make use of the antibacterial and antifungal properties of the metal ions. It is essential.

Naturally, plastic films and plastic resin compositions mixed with antibacterial agents have some thickness. Actually, if antibacterial agents can be concentrated near the surface in contact with food and flowers, antibacterial properties can be realized. Ideally, neither a plastic film nor a resin composition can concentrate the antibacterial agent in one place, and an ultrathin film mixed with an antibacterial agent or a thin resin composition and another film that is not. Alternatively, providing a sufficient thickness by stacking the layers of the resin composition increases the number of processes and may be irrational.

In addition, the plastic film forming the food packaging container according to the present invention does not have a thickness of at least 100 microns or more, so that the shape of the food itself cannot be maintained for stimulation or distribution due to the weight of the food itself or physical distribution. The antibacterial agent present inside the plastic resin forming the contact surface and the container is hardly effective rather than worse.

In addition, since only antibacterial agents that exist near the surface of films and resin molded products work, in the case of packaging containers and wrapping paper made of plastic resins that do not adhere or fuse with other substances such as polyethylene and polypropylene, they are close to the surface. There are cases where the existing antibacterial agents are easy to slide down and cannot be effective.

Among plastic resins used for food packaging containers, flower buds and food wrapping paper, polyolefin resins such as polyethylene and polypropylene are the mainstream raw materials in the industry, and micron-sized antibacterial agents are these. It is only a foreign material that is very easy to slide down.

Food packaging containers that are made by heat-sealing a non-stretched plastic resin film, for example, a thin film of polyethylene or polypropylene, on the lid of the plastic container and taking advantage of the elasticity of the air layer and unstretched film in the container Even if it protects food from being stimulated by time and helps prevent oxidation, it cannot maintain freshness due to aggressive antibacterial and antifungal properties.

One of the methods that can maintain the freshness of fresh foods such as fruits and prolong their lifespan is to prevent oxidation. However, the flexibility of the contact surface with foods and the mitigation of physical irritation caused by the air layer are alleviated. Therefore, it is not enough to prevent damage to food and reduce oxidation even a little, to prevent low temperature storage and food deterioration, or to extend the life span of flowering plants that absorb moisture through the stem and breathe. Giving antibacterial metal ion water to suppress the growth of microorganisms in the trachea is a very effective means.

In addition, silver ion water, copper ion water, zinc ion water and ion water of their alloys are almost all means obtained by melting the nitrates, sulfates and chlorides of the metals listed, such as tap water, ground water, High concentration ionic water in which the metal is dissolved in dilute organic acid water represented by dilute citric acid could not be obtained.
In addition, ionic water in which the metal salt is dissolved is designated as a deleterious substance poison, and it requires administrative approval to handle it. However, tap water, ground water, distilled water, purified water, and metal ionic water using dilute citric acid as a solvent are not available. It is safe except for excessive drinking.

Cosmetics are usually required to have no component changes for more than 3 years, and organic preservatives are used to prevent component changes without causing chemical changes in the main components. Changes to inorganic preservatives are required to meet consumer safety orientation. For example, even if pure silver foil is soaked in water for a long period of time, only an aqueous silver ion solution of about 25 ppb can be obtained, and at this concentration, it is sufficient as a preservative for cosmetics and its cost is high.

The raw water used to make ice is mostly tap water and is required by law to contain at least 1 ppm chloride ion. For this reason, in order to obtain commercial ice, a process of removing chlorine is necessary. However, once the salt is desalted, the local organisms start to breed from that moment. Required. Silver ions are not only safe and cause no change in taste, but pure water freezes as molecules, so silver ions do not mix with ice.

Even if the silver yarn described in Patent Document 1 is put into the raw material water for ice, the practical scale of the tank of 10 tons to 50 tons is insufficient for the speed of elution of silver ions and the dispersion of silver ions in the tank. Not suitable for.

The film having a metal film described in the present invention is characterized in that silver, copper, zinc, or an alloy thereof is formed on at least one side of a base material using a plastic film as a base material. The metal film that can be in direct contact with the food as a surface at least in part and is in contact with the food is like a lump of metal ions having antibacterial or antifungal properties, and is a tank. To do.

In addition, among the metal vapor deposition films described in the present invention, when the metal forming the metal vapor deposition film is silver, the metal vapor is dissolved by water present on the surface of food or flowers, or tap water in a container such as a vase. The feature is that metal ions can be eluted quickly. Even if silver is hydroxylated, it is unstable, but if it is not heated to 50 ° C or higher, it will become silver oxide and the elution of ions will not be reduced. However, it should be stored with the air and moisture blocked or suppressed as much as possible. For example, it can be used as a packaging material, a freshness-keeping material, or a raw material film of silver ion water because the rate of change to silver hydroxide or sulfidation can be delayed.

The metal vapor deposition film according to the present invention is well known in the vapor deposition film industry when the metal to be deposited is silver, copper, zinc or an alloy thereof, and is naturally necessary for preventing discoloration and scratches due to chemical changes. It is characterized by not having a resin coating layer for protecting the metal film or another protective transparent film on the metal film.

The thickness of the base plastic film which is a constituent material of the packaging material described in the present invention is characterized by having a thickness of 100 microns or more in order to maintain the shape of the packaging container. However, when used as a film or sheet immersed in water to obtain packaging material or antibacterial / antifungal metal ion water, the thickness may be about 25 to 50 microns. Furthermore, when it is used as a sheet immersed in water to obtain antibacterial and antifungal metal ion water, it is more economical to make the thickness of the film around 12 microns.

In addition, the food packaging material according to the present invention is characterized in that it conforms to the size of the food to be stored and packaged, is provided with a hole from which the food does not fall out, and the hole is not cut through.

A circle from each point that divides the circumference of a circle with a certain radius suitable for food size into 6-24 parts on a laminated film with silver, copper or zinc or their alloys as a film on one side of the plastic film A notch is made toward the center of the hole, but it is not a hollow hole.

Alternatively, the container as the food packaging material described in the present invention has a size suitable for food, but has a dent suitable for food size by a known molding method such as vacuum molding or press molding without providing a hole. It is characterized by making it.

When it is used as a packaging sheet, an antibacterial / antifungal metal layer is provided on at least one side of the transparent plastic film, but the metal layer is also transparent, so it is difficult to understand the front and back. In order to prevent erroneous operation, it is important to implement the present invention characterized in that coloring and distinguishing between the metal surface and the other surface is in direct contact with the food and flowers to be packaged by the metal surface. is there. Further, even in the case of food packaging containers, since a film having a metal film is cut and formed, the distinction between the front and the back is important in terms of preventing erroneous work and is characterized by it.

Moreover, when using as a packaging sheet, it is desirable to wrap a flat wrapping paper made from the raw material so as to follow the three-dimensional shape of the food as much as possible, and to keep the state. For example, when packaging apples, a polystyrene foam net is attached to prevent scratches, but the net is flat when the apple is placed between the apple and the net so that the metal surface of the packaging sheet is in contact with the apple. The wrapping paper sheet is three-dimensional along the apple, and the contact state can be maintained in a larger area, which is effective.

In addition, the packaging container and the packaging sheet according to the present invention are generally covered with the metal surface even if there is peeling due to the weakness of the interface between the base film and the metal surface, or even if the ultrathin metal layer has some scratches. It is characterized by being able to exert the expected function as long as it can come into contact with the surface of the package in a three-dimensional manner, thus strengthening the interface of applying an anchor coat or corona treatment to the base film It is characterized in that no process is necessary.

Alternatively, when the metal constituting the film is silver, as long as the silver does not lose its function as silver sulfide, copper or zinc or their alloys will react with the base and change color, but antibacterial metal ions Since it can be eluted, it can be used as a raw material sheet for producing food packaging containers, wrapping paper and antibacterial metal ion water according to the present invention.

The raw material film and raw material sheet which can manufacture the food packaging container and packaging sheet or antibacterial metal ion water according to the present invention, when using silver as the vapor deposition metal forming the same, it is a film-like or sheet-like antibacterial agent made of pure silver. Yes, the deposited silver can be eluted into tap water, ground water, distilled water, purified water, and ion-exchanged water. When the deposited metal is silver or an alloy thereof, nitrogen gas can be sealed during storage, and the reaction with sulfurous acid gas slightly contained in the air can be suppressed by sealing out the air. Can prevent or delay hydroxylation.

Silver reacts with moisture in the air and with the moisture of the packaged object to form silver hydroxide, but silver ions can be eluted while silver hydroxide itself exists in a very unstable state. When the temperature environment is around 50 degrees, it is transformed into silver oxide and silver ion elution is considerably reduced. In short, silver should be excluded from the metal selection for use in environments where priority should be given to preventing sulfurization.

In this connection, it is important that the metal deposited film according to the present invention is stored in a dry state using a moisture-proofing agent, or the chemical change under normal temperature and normal pressure is prevented or delayed by removing air or injecting nitrogen gas. .

Even when a film having an antibacterial / antifungal metal film as a film is cut and immersed in water to elute the antibacterial / antifungal metal ions to obtain the metal ion water, the metal film layer can be formed by using a vacuum deposition method. The bond between the metal molecules that form is very weak, so it can be quickly and easily dissolved in tap water in the neutral range at room temperature, and antibacterial water with sufficient ion concentration can be obtained even if only a thin metal film is formed. It is characterized by. If ion elution is attempted while applying ultrasonic vibration, elution can be further promoted and a metal ion concentration can be increased.

A plastic film having an antibacterial and antifungal metal as a vapor-deposited film according to the present invention can be cut to a required size and is an antibacterial agent in sheet form or film form.

After forming a metal layer having antibacterial and antifungal functions according to the present invention, a metal layer in contact with water, such as tap water that flows or vibrates in a cut state or in a film state, is simply Dissolves in water. If water is reduced and concentrated afterwards, it is possible to cope with changes in the concentration required for growth inhibition due to bacteria and mold species, and to obtain metal ion water at the required concentration.
In addition to using a film having a metal film as a packaging container or wrapping paper, it is also characterized in that antibacterial and antifungal functions can be exerted by spraying the metal ion water onto foods and flowers.
Based on the above technical matters, the means for solving the problems related to the claimed invention are summarized as follows.
At least one side of the base material of the plastic film, the antimicrobial silver is antibacterial metal or antifungal metal, any one metal selected from copper or zinc, or by vacuum evaporation coating of an alloy containing these A method for producing antibacterial / antifungal metal ion water , comprising a step of producing an antifungal sheet and a step of immersing the antibacterial / antifungal sheet in a diluted citric acid solution.

The food packaging container or wrapping paper using the sheet-shaped antibacterial agent according to the present invention has a metal film having antibacterial and antifungal properties and, for example, many contact surfaces with fruits, and the metal ions are directed toward the moisture of the fruits. Bacteria and mold that elute and adhere to the surface of fruits are inhibited by antibacterial and antifungal functions, helping to maintain freshness. Degradation of freshness of food due to microbial contamination such as bacteria and mold occurs from or near the food surface.

Microorganisms that promote spoilage that naturally adhere to fresh foods such as clogs, fruits, vegetables, meat and fish are initially present only on the surface of the food. If microorganisms are present inside them, they are foods that are originally sick or have deteriorated for some reason. Is very useful in extending life.

In addition, since florets absorb moisture through the trachea and continue to breathe, microorganisms propagate in the trachea, impairing hydration and causing freshness degradation, so antibacterial ions are very useful in prolonging the life of florets and are used in vegetables. However, the same effect can be expressed.

When the antibacterial metal forming the deposited film is copper or an alloy thereof, the minimum growth inhibitory concentration is lower than silver, so it not only suppresses the growth of bacteria but also helps to suppress the growth of mold related to decaying deterioration. Actively help to maintain freshness. Of course, the anti-fungal function can be expressed depending on the concentration of silver ions.

In addition, the metal vapor deposited film left in the fan shape without being hollowed out can serve as an impact cushion for food, and can also exert an effect of reducing the irritation at the distribution stage. In particular, silver or its alloy copper or its alloy is a metal with low hardness, which is useful for mitigating impacts and stimuli on foods during distribution.

Furthermore, the sheet having a metal film as a food packaging container, wrapping paper or other packaging material according to the present invention has an exposed metal surface and is in contact with an object to be packaged. In addition to contributing to faster cooling, the sheet for wrapping paper can be effective by simply putting the sheet, which is a film cut not only for fresh food, but also for maintaining the freshness of the florets and extending the life of the flower into a vase.

The antibacterial metal ion water according to the present invention, particularly silver ion water, can be provided at a low cost so that it can be used as a preservative for cosmetics. The role as a water purifier can also be greatly expected. Sometimes it is useful for acne treatment caused by acne bacteria as a facial pack material soaked in non-woven fabric, etc., utilizing its safe sterilizing power.

A thioglycolate solution is used as a permanent solution for permanent treatment at a beauty salon to break the cystine chain structure of keratin that makes up the hair. Since it can be converted to silver sulfide by reacting with sulfur component, it is useful for deodorization. If permanent treatment is to break the sulfur bond of cystine, the silver ion contained in a certain concentration of silver ion water breaks the sulfur bond of cystine. it can.

If the method described in this patent is used, iron, nickel, chromium and gold that do not have antibacterial and antifungal functions. Safe ion water in which the metal ions are dissolved in metal such as platinum used for plating and tap water and groundwater can be obtained, which is very useful for environmental conservation when used in a plating factory.

Using a plastic film having a thickness of 100 to 300 microns as a base material, a film having a metal film with a thickness of 10 to 50 nanometers on one side of the base material is obtained by vacuum deposition. The thickness of the base material depends on the type, number, size and softness of the food to be stored and packaged, and the thickness of the metal film forming the film also indicates the type, number, size and softness of the food, the shelf life of the planned food, It can be appropriately changed in consideration of the hardness of the metal itself.

As a method for forming a metal film on a plastic film, a well-known technique such as a vacuum deposition method or an ion deposition method such as sputtering is used. However, the vacuum deposition method is preferable because the bonding of metal molecules constituting the metal film is weak.

In addition, a method of laminating a similar plastic film on the opposite side of the surface having the vapor deposition film on a plastic base film having a thickness of about 12 to 25 microns and laminating the vapor deposition film leads to a reduction in vacuum vapor deposition cost, etc. Useful in some cases.

The plastic film may be a well-known film such as biaxially stretched polyethylene or polypropylene, such as polyolefin, polystyrene, polyester, polyamide, or vinyl chloride film or sheet, but for packaging containers, polyolefin, polystyrene, polyester, etc. A system is preferred. When it becomes a raw material for wrapping paper or metal ion water, a polyester type is preferable. In order to obtain an antibacterial and antifungal metal ion water according to the present invention, a corona treatment or a well-known resin coating may be applied in advance to strengthen the interface between the metal vapor deposition layer and the plastic film. Since it is convenient for the sheet or film to have a weak deposition interface, the above treatment and coating are not necessary.

In the metal vapor deposition plastic film manufacturing industry, polyolefin-based and polyamide-based films can be used as the base material for vapor deposition. However, these resins have a low softening point and melting point. The polyolefin film may be difficult to use because the temperature may be high, and the polyolefin film is difficult to use because the resin is wrinkled due to a short chain molecular structure. In addition to the plastic film, the metal-deposited substrate may be a vinyl chloride sheet or paper with reduced air permeability.

The metal deposited on the polyamide film is mostly tin or aluminum having a low melting point that does not require raising the temperature of the vapor deposition vessel.

Also, ion deposition methods such as sputtering are less productive and costly than vacuum deposition.

The base film constituting the packaging container according to the present invention is characterized by having a thickness exceeding 100 microns, more preferably exceeding 200 microns, and the thickness of the metal film is so thin that the metal layer is transparent. The time is short, and it is not easily affected by the high temperature of the vapor deposition pot of silver, zinc, copper or their alloys having a higher melting point than tin or aluminum.

The metal forming the deposited film is suitably silver, copper, zinc, or an alloy thereof. However, if silver or an alloy thereof is exposed without protecting the metal film that is a feature of the present invention, it may react with sulfurous acid gas even at room temperature and normal pressure to form silver sulfide and lose antibacterial properties. It may not be suitable if it is not used as wrapping paper or is stored for a long period of time, but in that case, nitrogen gas is injected or it is stored in a sealed state and dehumidified such as silica gel. It is important to use an agent to make it dry.

The thickness of the vapor-deposited film of the metal vapor-deposited film according to the present invention is 10 nm to 50 nm, and the object can be achieved to such an extent that it can be seen through even if a metal film is provided on a transparent plastic film. This is a specification that is impossible in the metal vapor deposition film industry from the viewpoint of glitter and aesthetics. When the deposited film thickness exceeds 50 nm, the intermolecular bonds of the metal forming the deposited layer as metal molecules are strengthened, and the metal film is hardly dissolved in tap water, ground water, distilled water, purified water, and ion exchange water.

The metal film surface described in the present invention is not protected by a resin coating or by laminating another film. In the metal vapor deposition film industry, protecting the metal film is regarded as most important for maintaining the glitter and decorating properties of the metal or for preventing scratches on the metal layer. Although not within the industry's common sense, this measure is characteristic to smooth out metal ions that are effective in antibacterial and antifungal processes in a large amount. In addition, antibacterial metal ions eluted from the films and sheets used in wrapping paper and packaging containers do not end up indefinitely, but depending on the temperature and pH conditions, they reach saturation and reach ion saturation to some extent. Stops. In the environment where the present invention is planned, the concentration that almost immediately affects the human body is hardly reached.

Producing a metal vapor-deposited film by forming a metal film with as thin a film thickness as possible meets the economic rationality of the industry. However, even if a single layer of a metal film is provided on a transparent plastic film, it does not show a metallic color due to reflection, but it is important to decorate, or to prevent chemical changes in the deposited metal and prevent scratches. From the technical point of view, it is out of the common sense of the industry.

When the metal film is about 10 to 50 nanometers, the metal deposited on the transparent plastic film substrate is seen through. In order to eliminate this transparency, the metal layer deposited on the base film is coated with a resin coating or another film, and the difference in refractive index is used to express the metallic color, or two substrates are used. The metal color does not appear unless the metal is deposited on the material with an adhesive having an effect of blocking light. As the coating agent in this case, a two-component crosslinking type resin or a solvent type resin is selected, and so-called dry lamination is mainly used.

The transparent plastic film on which copper or zinc or an alloy thereof according to the present invention is deposited is laminated with another film, whether or not it has a coating for protecting the metallic color and the deposited surface and the same deposited metal film. Is characterized by no need at all.

Metals that can be vacuum-deposited or ion-deposited, such as silver, copper, tin, and aluminum, form a thin metal layer, and the metal layer exposed to the air can easily react with moisture and sulfurous acid gas contained in the air for a short time. It is indispensable to secure glossiness on both sides of the metal film as seen from the front and back, because a transparent protective coating layer made of synthetic resin or a transparent protective film different from the base material is laminated. It is said that.

However, when aluminum or tin is vapor-deposited on a base plastic film, there are cases where the metal film is not protected. When aluminum and tin come into contact with oxygen in the air, they become oxides in a short time, and the deposited metal with a sufficient thickness is covered with the oxide film, and the remaining metal itself without oxidation is the oxide film. It is because it is protected by the base film.

In this case, the metal color which is an important purpose of the vapor-deposited film is exhibited, and it is the one side on the side protected by the film that exhibits glitter and decorating properties. The surface of the tin oxide or aluminum oxide film becomes white turbid, and after the formation of the white turbid film, it does not change at all at room temperature and normal pressure, either photochemically or chemically. This metal vapor-deposited film is mainly used for a sticker substrate or the like that requires a metallic luster on one side.

The food packaging container or wrapping paper of the present invention is one of the purposes to make use of its antibacterial and antifungal properties to help maintain flower florets and food freshness and prolong life. The premise is that the temperature, humidity, and air pressure at which clogging, flower buds and foods can exist are normal, that is, flower buds and foods can continue to be themselves.

In such an environment, copper and silver are Group 11 transition metals referred to in the Mendeleev Periodic Table, and hardly oxidize or halogenate by air. However, both metals react with sulfurous acid gas slightly contained in the air even under normal temperature and pressure. Since the intensity against ultraviolet rays is not strong, it is important to store the light as much as possible, and the same applies to the metal ion water.

When silver becomes silver sulfide, its antibacterial ion elution, conductivity and thermal conductivity are lost, but copper sulfide does not lose its antibacterial and antifungal ion elution and conductivity / thermal conductivity. Also, if the deposited film is thin, sulfidation is likely to proceed. However, the major difference between silver sulfide and copper sulfide is to lose or maintain antibacterial properties. Copper sulfide does not lose its antibacterial and antifungal properties. When used with wrapping paper, the amount of deposited metal is negligible and almost non-toxic even if it changes to copper sulfide.

Furthermore, antibacterial and antifungal properties can be maintained even when copper sulfide reacts slowly with moisture in the air and changes to copper sulfate.

Zinc or its alloy is a metal that is sufficient to form a vapor-deposited coating on one surface of the plastic film described in the present invention because of its low toxicity and antibacterial properties. Absent.

When an antibacterial metal-deposited film according to the present invention is deposited on an alloy such as silver or sterling silver, if the silver reacts with sulfurous acid gas in the air to form silver sulfide, the antibacterial In the case where the metal vapor deposition film described in the present invention is stored as it is as a raw material of a packaging container, a sheet for wrapping paper, or a sheet for producing antibacterial water, or as a product, it is represented by PVA resin such as poval. The water-soluble resin may be coated with a thickness of 1 to 2 microns using a gravure coater or a known coating apparatus. However, it is not necessary if it can be protected by sealed packaging in which the silver deposited film is not in contact with air or ultraviolet rays and kept in a dry state, or by injecting nitrogen gas.

When selecting silver or its alloy as the deposited metal, the safety suitability of the metal alloyed with silver must be confirmed separately, but silver is also a food additive recognized by the Food Sanitation Act and is included in drinking water There is no problem in safety because the metal has no restrictions on the concentration of silver ions.

As for copper, there is no one who asks about the toxicity of copper cooking pots and copper plates for cooking, and it is one of the best choices without being pointed out toxicity because it is a substance recognized by the Food Sanitation Law. Incidentally, copper sulfide is also mixed in a small amount in infant formula. Commercially available brass which is an alloy of copper and zinc (copper 60 to 65 parts; zinc 40 to 35 parts) can also be selected.

Zinc is also an essential metal for human health and may cause poisoning when taken in large quantities, but it causes such problems due to the thickness and amount of the deposited metal described in the present invention. Is not possible, so it can be an option.

If the plastic film base material and the deposited metal are overlapped, if a blocking phenomenon occurs where they adhere to each other and peeling is not smooth, and the deposited metal is copper, zinc or their alloys, an anti-blocking agent on the metal deposited surface May be coated with a very rough mesh in a dot shape with a thickness of 1 to 2 microns. This is also very different from the prior art in that most of the metal deposition surface is exposed.

Note that the film or sheet described in the present invention has an antibacterial / antifungal metal film, cut the sheet to a size suitable for a package such as food, and antibacterial by covering the food with a metal film surface, Wrapping paper that takes advantage of antifungal properties can be obtained. Further, since the wrapping paper has a specific gravity of about 1.4 and sinks in water, it can be used by cutting to a required size as a sheet for producing antibacterial water that can obtain antibacterial metal ions.
Incidentally, when copper is vapor-deposited on a polyester film with a thickness of 50 nm and cut into 10 cm × 10 cm, the amount of the deposited copper can be calculated as follows.
50 nm is 0.000005 cm, and the specific gravity of copper is 8.94.
0.000005x10x10x8.94 = 0.00447g = 4.47mg

In addition, as a food packaging container, a plastic film having a metal film obtained by the method described in the present invention on one side and having no protective layer on the metal film should not be formed as a hollow hole as described above from the metal film side. The food storage part should just be cut and fan-shaped.

Alternatively, the metal film surface and the food can be touched directly at least in some places by creating a recess suitable for the size and shape of the food by a known molding method such as vacuum molding or press molding. A food packaging container is made. In the first place, metal ions with antibacterial properties cannot exhibit antibacterial and antifungal properties as long as they are not in direct contact with food.

If the food packaging container or sheet according to the present invention deviates from the time of food harvesting and is unused and has a long shelf life, store it in a light-shielding bag or box to prevent reaction with ultraviolet light and store it in a cool and dark place. It is desirable to store it in a sealed state and in a dry state with nitrogen gas sealing or degassing.

The plastic film on which the antibacterial metal described in the present invention is vapor-deposited is applied to a cutting machine to obtain strips having a width of 120 to 200 microns and a length of 25 mm to 60 mm in a weight ratio of 0.5% to 3%. By using a non-woven fabric or paper as a wrapping paper, it is possible to maintain the freshness of fresh foods and florets and extend their life.

Alternatively, a plastic film having an antibacterial metal film according to the present invention is slit, and a so-called bellows-like twisted yarn is wound as it is on a synthetic fiber such as nylon, polypropylene, polyethylene or the like with a vapor deposition surface facing up, or 20 mm. If it is cut to about 65 mm and mixed with non-woven fabric or paper in a weight ratio of 0.5 to 3.0%, it will serve as a wrapping paper or an underlaying antibacterial sheet for packaging, and will help to maintain the freshness of foods and prolong life.

In that case, it is more preferable that the nonwoven fabric or paper contains cellulosic fibers having good water absorption in at least a part of the main raw material.

A face pack material if a fiber having water absorption and water retention properties is immersed in a non-woven fabric that is a part of the constituent raw material in silver ion water having a concentration of 200 to 1000 ppb, cut into an appropriate shape and kept in a water retention state. It is useful for acne treatment caused by acne bacteria, anaerobic bacteria.

The present invention will now be given by way of example to illustrate further details of the invention.
A silver deposited film with a thickness of 50 nanometers is provided on a polyester film with a thickness of 25 microns to obtain a film cut into 10 cm × 10 cm, and this is immersed in a plastic bottle containing 0.5 liters of tap water. It was shaken about twice and stored at room temperature, and the silver ion concentration was 110 ppb when measured for 7 days.

  During execution of this example, fine bubbles appeared on the silver deposition surface. When silver ionizes, one electron is removed from the silver atom, and the water receives hydrogen ion and hydroxide to receive the electron. This is because hydrogen gas was generated as an ion, which is evidence that metallic silver was dissolved in tap water. However, the amount of hydrogen gas is very small and does not induce an explosion.

A pet with 0.5 liters of tap water poured into a silver-deposited film cut to A5 size without any coating or corona treatment on one side of a 25-micron thick polyester film, with a silver layer with a deposited film thickness of 50 nm. It was 610 ppb when immersed in a bottle, replaced with 50 ml of fresh tap water 3 times daily, shaken about 50 times each time, and measured the silver ion concentration after 2 months.

Copper was vacuum-deposited on one side of a polyester film having a thickness of 200 microns, and a film cut to 40 cm × 50 cm was obtained. The deposited film pressure of copper is preferably 10 to 50 nanometers, but in the examples, it was set to 30 nanometers. Although the film after vapor deposition had a copper-specific color, it was transparent. Further, since the deposited metal layer was thin, it did not react indiscriminately to the foreign substance inspection by the metal detector.

Press molding was performed from the copper vapor-deposited surface of the film cut to 40 cm × 50 cm, and a total of 30 indentations having a diameter of 6 cm, a depth of 4 cm, and 5 × 6 rows were formed.

Store 30 apples with a diameter of about 8cm in each recess, and store the apples in a state where the lower half of the whole apple enters the recess, and the surface of the apple and the copper coating can be in direct contact here and there. saved.

A comparative experiment was conducted by storing 30 apples in the same state and in the same shape and size as described in the Examples with a similar 200-micron polyester film having no copper vapor-deposited film, and storing them under the same conditions. .

On the 10th day from the start of the experiment, discoloration began on the surface of some apples in the blank, confirming the superiority of the storage container using the copper-deposited film.

Copper was vacuum-deposited with a deposited film thickness of 50 nm on a polyester film having a thickness of 25 microns and an effective width of 600 mm, and the copper-deposited film was cut to obtain a square sheet having a side of 10 cm.

One sheet is inserted into a plastic bottle filled with 500 ml of tap water, and three PET bottles obtained in the same manner are used as three specimens, and a PET bottle filled with tap water without inserting the wrapping paper is used as a blank. I prepared a book.
We purchased six carnations, trimmed them to the same length, and inserted each one randomly selected carnation into a plastic bottle simulating a vase, and conducted an experiment to extend the freshness in the room avoiding direct sunlight.

The evening after the start of the experiment, two carnations of the blank began to wither, and the next day there was a clear difference in flower momentum between the three blanks and the three specimens, at least one of them. When the experiment was continued for 6 days until the carnation stalks broke, all the specimens inserted with a sheet made of a copper-deposited polyester film showed a significant advantage.
After the experiment was completed, when one piece of wrapping paper was taken out, the color peculiar to copper disappeared and partly changed to yellowish green, which seems to be slightly patina. It was.

The same wrapping paper 10cm x 10cm used in this experiment was immersed in a dilute nitric acid solution of 500 parts of concentrated nitric acid 1 part: 100 parts of ion exchanged water at room temperature for a whole day and night. When confirmed and the copper ion concentration of the diluted nitric acid solution was measured, it was 7.1 ppm. It was clogged, and the tap water in the PET bottle used as a sample in the experiment was changed to water containing copper ions. It is calculated that over 82% of the deposited copper is ionized.

In general, solid copper dissolves and does not ionize copper unless it is exposed to a strong acid of ph = 1.0 level at room temperature. Further, even under the test conditions in which the copper ion concentration is measured, solid copper is very hardly soluble in dilute nitric acid solution. However, the vacuum-deposited copper has very weak intermolecular bonds, and it was found that it melted and ionized even at room temperature in tap water, which is almost neutral, and the antibacterial properties were demonstrated from the concentration of dissolved copper ions. It was elucidated.

Maintaining the freshness and longevity of foods by using plastic films with metal coatings with antibacterial and antifungal properties as packaging containers for the distribution of fresh foods such as fruits and logistics or as packaging paper Life can be extended, and the date and time of sale can be extended, and it can greatly contribute to the transportation and sales of foods far away from food production areas and the sales of Japanese fresh foods to overseas markets.
The reverse is also true.

In addition, flower exports and imports have been actively carried out recently, but harmful chemical substances are used to maintain their freshness and prolong life, and environmental pollution is a problem. If antibacterial metal ions are effective in maintaining freshness and prolonging lifespan, they can contribute to environmental protection and conservation.As a result, it is possible to reduce the spoilage of fresh foods and prolong the lifespan of flowering plants, thereby conserving the environment. It brings about an effect and a big economic effect.

Tap water, ground water, distilled water, ion-exchanged water, purified water, or copper ion water using dilute organic acid as a solvent is excellent in safety and is not restricted in handling unless designated as agricultural chemicals and used for drinking.

It turns out that the ion concentration of silver ion water using tap water as a solvent exceeds 600 ppb, and obtains safe silver ion water that can fully demonstrate the sterilization effect even if it is diluted. It was found that sufficient freshness can be maintained just by spraying. It has become possible to prevent the loss of food and flowers and bring about economic effects.

In addition, metal plating uses a metal salt to be plated and has a metal ion solution. However, the metal ion solution must be treated almost as a deleterious substance, focusing on safety management and environmental protection. Although it has been necessary to use so-called non-permeable water such as tap water and ground water, it can be obtained as dilute citric acid water, and safety management and environmental conservation efforts are greatly reduced.

Claims (1)

At least one side of the base material of the plastic film, the antimicrobial silver is antibacterial metal or antifungal metal, any one metal selected from copper or zinc, or by vacuum evaporation coating of an alloy containing these A method for producing antibacterial / antifungal metal ion water , comprising a step of producing an antifungal sheet and a step of immersing the antibacterial / antifungal sheet in a diluted citric acid solution.