JPH09136973A - Antifungal film material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifungal film material capable of resonance excitation of water molecules in water conducive to formation of fungi such as bacteria and mildews as well as environmental water indispensable for multiplication of fungi to control multiplication thereof, and effectively exhibiting the oxidizing power of titanium oxide and the oligodynanic effect of silver or copper over a long period to effect safe and sure sterilization and mildew killing. SOLUTION: A suitable synthetic resin material is blended with 0.3-3wt.%. fine ceramic powder 1B having a particle size of at most 1μm and obtd. by firing a composition comprising 40-60wt.% silicon carbide or silicon oxide, 20-30wt.% aluminum oxide, 4-8wt.% manganese oxide, 4-8wt.% zinc oxide, 2-5wt.% titanium oxide and 0.1-1wt.% silver or copper, and is then formed into a film. Alternatively, the fine ceramic powder 1B is mixed and dispersed in a suitable impregnating material, and the resulting dispersion is applied or printed on one or both surfaces of a desirable synthetic resin film material 1A, provided that the wt. proportion of the dispersion to the film material is 0.1 to 1wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of safely and reliably sterilizing and sterilizing chemicals such as germicides and fungicides, and is particularly useful as a material for packaging containers and packaging bags for foods. Relates to a very suitable antibacterial film material.

[0002]

2. Description of the Related Art Since foods have abundant water including nutrients essential for the reproduction of bacteria and fungi, when they have a proper temperature and oxygen, they are proliferated remarkably and deteriorated or decomposed in a short time. Be invited. For this reason, foods with a particularly high moisture content are sterilized and killed by pressurization, boiling, ultraviolet rays, ozone, etc., and made into a substantially aseptic state and also provided for distribution in a highly sealed canned or bottled packaging form. However, in such canned and bottled products, the cost of the container itself is high, and it is bulky and multi-plyed. It is replaced by a so-called simple packaging, which is a packaging bag made of a film material having a temper.

On the other hand, in the current simple packaging, even if it is provided with provisional waterproofing property and air-proofing property, the hermeticity is remarkably inferior to that of a canned container or a bottled container. To do this, add fungicides and fungicides to the food itself,
So-called additives such as synthetic preservatives are added to prevent deterioration and decay over a long period of time.

[0004] In recent years, however, as health-consciousness has become richer, the safety of foods has become even stronger, and the avoidance of purchasing foods containing additives has increased, which makes them safe as foods. It has been attempted to extract natural antibacterial components present in the shoots, germs, fruit cores, etc. of plants that are said to be added to foods to prevent deterioration and spoilage. Since the components are extremely unstable with respect to acids, alkalis, and various enzymes, there is an inherent problem that the sterilizing and fungicidal effects are unstable and the usable foods are significantly limited.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and forms bacterial cells such as bacteria and fungi in place of the technical idea of chemical killing by chemical agents such as bactericides and fungicides. Water and water molecules of environmental moisture, which are essential when these bacteria and mold fungi propagate, are excited and excited by electromagnetic waves in the near-infrared and far-infrared regions to suppress the growth of the fungi and to be oxidized by titanium oxide. The present invention is intended to provide an antibacterial film material that safely and surely sterilizes and molds by effectively exerting an oligodynamic action of silver or copper over a long period of time.

[0006]

The technical means adopted by the present invention to solve the above-mentioned problems is that the particle size is 1 μm.
Below, 40 to 60% by weight of silicon carbide or silicon oxide, 20 to 30% by weight of alumina oxide, 4 to 8% by weight of manganese oxide and zinc oxide, respectively, and titanium oxide 2
To 5% weight, and silver or copper 0.1 to 1.0%
A ceramic fine powder fired at a composition ratio by weight is mixed with an appropriate synthetic resin material at a ratio by weight of 0.3 to 3%, and is formed into a film by a T-die method, an inflation method, a calendar method or the like. Is something
Further, the ceramic fine powder formed by firing is dispersed and mixed in an appropriate adhering material, and the ceramic fine powder is attached to one side or both sides of the base film material made of a desired synthetic resin film material. In contrast, the composition is formed by coating or printing such that the ratio is 0.1 to 1% by weight.

[0007]

The present invention having the above structure has the following functions. That is, the ceramic fine powder to be kneaded with the synthetic resin material is excellent in thermal stability because it has an extremely fine particle size of 1 μm or less and is formed of an inorganic substance, and contains 4 to 8 manganese oxide and zinc oxide, respectively. Since they are mixed in a composition ratio of 100% by weight, they have high dispersibility, are homogeneously dispersed and kneaded in a wide range of synthetic resin materials, and are stable even at high temperatures during molding. In addition, the T-die method, inflation method or When the film material is formed by the calender method or the like, it can be formed without any trouble in the stretching for adjusting the thickness thereof.

Since the ceramic fine powder is fine particles and has excellent dispersibility, when it is formed as a film material, a part of it is exposed on the outer surface of the film material. Far-infrared radiated electromagnetic waves and the generated oxidizing power or oligodynamic action directly act on bacteria and fungi.

Further, since the ceramic fine powder used has a particle size of 1 μm or less and is fired in a state of being simply bonded at a low temperature, the radiative surface area ratio or the contact surface area ratio is extremely large, and the composition is carbonized. Since silicon or silicon oxide is 40 to 60% by weight and alumina oxide is 20 to 30% by weight, radiation efficiency of near infrared rays and far infrared rays is high, and water forming bacteria and environmental water related to its propagation are resonated. And excite. In addition, a large radiant surface area means a large external energy absorption surface area, and since manganese oxide is 4 to 8% by weight and titanium oxide is 2 to 5% by weight as a composition component, the external ultraviolet region Electromagnetic waves are efficiently absorbed, and manganese oxide is resonantly excited with the absorption to act catalytically, and strong oxidizing power is created with the resonant excitation of titanium oxide.

Further, since the ceramic fine powder has a composition component of 4 to 8% by weight of zinc oxide and 0.1 to 1% by weight of silver or copper, zinc oxide is radiated by near infrared rays or far infrared rays. Electron emission that is resonantly excited and exhibits a so-called reducing action based on a difference in ionization tendency with silver or copper is exerted, so that passivation of silver or copper is prevented and an oligodynamic action is maintained for a long time.

[0011]

EXAMPLE An example of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional explanatory view of the antibacterial film material 1 of the present invention. It is appropriately selected according to the use, and polyethylene resin, polypropylene resin, polyester resin, etc. are used as a simple packaging bag for processed foods, and packaging packs for vegetables, fruits, raw eggs, etc. Examples of such materials that are once formed from a thick film material by vacuum molding or compression molding include polyvinyl chloride resin and polystyrene resin, and are used for heavy packaging bags, interior building materials, household goods, etc. A soft polyethylene resin, a soft polyvinyl chloride resin, or the like is used for this.

When these materials are formed into a film, stabilizers, lubricants, etc. are usually added in appropriate proportions in order to facilitate their forming processability, and further, the performance suitable for the purpose of use is added. In order to add film forming processability to each material, plasticizers and colorants, or reinforcing agents and fillers are added in appropriate proportions in order to add so-called compounding. Stabilizers and lubricants are blended in advance, and pelletized pelletized with a material to which a plasticizer is added or plasticized to suit the purpose of use is commercially available over a wide range. It is convenient to select and use.

The material selected in this manner is a fine ceramic powder in order to maintain the film material 1A formed by the molding process to have bactericidal and fungicidal properties against bacteria and fungi, or so-called antibacterial properties that suppress the reproduction thereof. 1B is blended in a proportion of 0.3 to 3% by weight with respect to the weight of the film material 1A. This ceramic fine powder 1B imparts antibacterial properties to the film material 1A to be formed, and the present invention expects an antibacterial effect by using a novel and safe antibacterial means instead of the antibacterial effect by the conventional chemical agents. As the first antibacterial means, the water that forms bacterial cells of fungi and fungi, and the resonance excitement of water molecules of environmental water necessary for the growth of these fungi resonate the physiology of the bacterial cells. In order to inhibit the function and suppress the reproduction, the composition of the composition is designed so that electromagnetic waves in the near-infrared region of 1 to 3 μm and far infrared region of 5 to 6 μm, which have a strong resonance excitation action on water molecules, are emitted. 40 to 60% by weight of silicon carbide or silicon oxide and 20 to 30 of alumina oxide
% By weight.

However, there are a great variety of bacteria and fungi, and depending on the bacterial species, there is a possibility that sufficient antibacterial properties cannot be expected by the resonance excitation of water molecules. Therefore, as a second antibacterial means, a strong oxidizing power is created as titanium oxide absorbs external energy, particularly electromagnetic waves in the ultraviolet region and is excited by resonance to be reduced, and the presence of manganese oxide Manganese oxide acts as a catalyst to further enhance the generation of oxidizing power, and as a result, a wide variety of fungi can be sterilized and killed by fungi. Therefore, 4 to 8% by weight of manganese oxide and titanium oxide are contained in the composition. 2-5% weight is also used.

Furthermore, as a third antibacterial means, a bactericidal action by a trace metal ion held by silver or copper, so-called oligodynamic action is used, particularly in the presence of environmental water necessary for the propagation of bacteria and mold fungi. However, it has an excellent antibacterial property, but with the progress of use, an oxide film or the like is formed on its outer surface to be passivated, resulting in a decrease in oligodynamic action. Therefore, by interposing zinc oxide, which has a higher ionization tendency than silver or copper,
In order to reduce silver or copper by electron emission from the zinc oxide and thus exert an oligodynamic action for a long period of time, 4 to 8% by weight of zinc oxide and 0.1 to 1. The composition is composed of 0% by weight.

Further, the ceramic fine powder 1B has a sufficient dispersibility so that it is exposed not only on the entire film material 1A but also on the outer surface of the film material 1A when it is formed into a film material 1A after being appropriately mixed with the material. In order to maintain kneadability, it is desirable to form the particles as finely as possible. In addition, in order to effectively exhibit antibacterial properties, the radiative surface area ratio related to near-infrared and far-infrared radiation and the receiving surface area ratio related to ultraviolet absorption Alternatively, since it is an indispensable requirement to increase the contact surface area ratio related to the exertion of oligodynamic action, the particle size is formed to be 1 μm or less at the maximum, and the particles of each component related to the composition are sintered together. Instead, a structure is used in which firing is performed at a relatively low temperature so that the binding state, that is, the so-called bulky state due to the reduction of the surface energy is maintained.

The mixing ratio of the ceramic fine powder 1B to the appropriately selected raw material is at least 0.3% by weight so that the film material 1A to be formed exhibits effective antibacterial properties. However, even if the blending ratio exceeds 3% by weight, no particular difference in antibacterial property is recognized, and particularly, there is a problem in stretching during the molding process of the thin film material 1A. It should be noted. Of course, in such a case, it is natural that the raw material is appropriately mixed with a colorant, a filler and the like according to the purpose of use. Thus, the ceramic fine powder 1B in a required ratio is blended with the material selected appropriately, and is molded into a film having a required thickness and width by the T-die method, the inflation method or the calender molding method according to the extrusion molding method. By processing, the antibacterial film material 1 of the present invention is formed.

The object of the present invention can be achieved not only by such technical means but also by the following technical means. As shown in FIG. 2, a film which is adapted to the intended purpose in advance is used as the base film material 2A. , A synthetic resin material having adhesiveness to the base film material 2A on one side or both side surfaces of the base film material 2A is used as a vehicle, and the vehicle is appropriately applied to the base film material 2A or has a viscosity to such an extent that printing is possible. The ceramic fine powder 1B is dispersed and mixed in an appropriate ratio with the adhesive 2B dissolved and diluted with the solvent of 1), and the ceramic fine powder 1B is substantially 0.1 to 1% by weight with respect to the weight of the base film material 2A. The composition of the antibacterial synthetic film material 2 is applied or printed so as to be in a ratio.

In such a case, the adhering material 2B is required to be a vehicle capable of adhering to the base film material 2A. When the base film material 2A is made of polyethylene resin or polypropylene resin, it is a material having particularly poor adhesiveness. ,
It is desirable to subject the surface of the base film material 2A to oxidation treatment such as corona discharge treatment in advance, and a vinyl acetate-ethylene copolymer resin is desirable as a vehicle for the adhesive material 2B. When it is made of polyvinyl chloride or polystyrene resin, vinyl chloride or vinyl acetate resin is preferable, and when it is made of polyester resin, acrylic resin or ester resin is preferable.

In order to apply or print the vehicle, it is necessary to use the adhesive material 2B having a viscosity of about 50 to 5000 pis (centipoise). For this purpose, the vehicle solution is diluted with an organic solvent. Or as an emulsion solution. When vinyl chloride or vinyl acetate resin is used as the vehicle, ethyl acetate, methyl ethyl ketone, etc. are suitable as the organic solvent.

The ratio of the vehicle to the organic solvent in the solvent solution or the ratio of water to the vehicle in the emulsion solution may vary depending on the desired viscosity, but the ratio of the vehicle to the organic solvent or water is about 30 to 5.
It is about 5%. Thus, the coating or printing of the coating material 2B on the surface of the base film material 2A is for exhibiting antibacterial properties, and can effectively exhibit antibacterial properties against bacteria and fungi. Therefore, it is possible to form the thinnest possible film, so that the thickness is usually 10 μm or less, and therefore, the ceramic fine powder 1B is substantially 0.1 to 1% of the weight of the base film material 2A. Since it can be reduced to use by weight, ceramic fine powder 1B
Adhesive 2B to be applied or printed at such a ratio
Should be composed.

Thus, the base film material 2 appropriately selected
Adhesive material 2B with required thickness on one side or two sides of A
The antibacterial film 2 is formed by applying or printing.

The antibacterial property test results of the antibacterial film 1 in which the ceramic fine powder 1B is blended and molded, and the antibacterial film material 2 in which the ceramic fine powder 1B is coated or printed with the adhesive 2B will be described below. The antibacterial film material 1 used in the test is a pellet of a polyvinyl chloride resin hard film, and a ceramic fine powder 1
B was blended in 0.1% weight, 0.3% weight, 3% weight and 5% weight ratio, respectively, and the thickness was 50μ by T-die method.
m, processed into sample 1, sample 2, sample 3 and sample 4, respectively, and further, formed into a film having a thickness of 50 μm only with the polyvinyl chloride hard film forming pellets as a base film material 2A. An adhesive material 2B having a composition of 35% by weight of vinyl chloride resin as a vehicle, 60% by weight of methyl ethyl ketone as an organic solvent, and 5% by weight of ceramic fine powder on one side of the base film material 2A.
The ceramic fine powder 1B is 0.05% weight, 0.1% weight, 1% weight and 3% with respect to the weight of the base film material 2A.
The antibacterial film material 2 applied so as to be attached at a% weight ratio is referred to as Sample A, Sample B, Sample C, and Sample D, respectively.
Further, as a control sample, the base film material 2A with no attachment was used.

Three types of bacteria, Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, were used for the antibacterial test, and the test method was 35 on a standard agar medium.
Using the test bacteria pre-incubated at 48 ° C for 10 hours,
^After adjusting to ^{6 to 7} / ml, 2 ml of the test bacterial solution was dropped on a sterile petri dish, and each sample piece was allowed to stand on this test bacterial solution. Table 1 shows the results of reading the viable cell count after re-culturing after spraying.

[0025]

[Table 1]

[0026]

As described above, according to the present invention, the ceramic fine powder which is blended in the film material or coated or printed with the adhesive is 40 to 60% by weight of silicon carbide or silicon oxide and 20 to 30% by weight of alumina oxide. In the near-infrared region in the wavelength range of 1 to 3 μm and 5 to 7 μm, which resonates the water molecules of bacteria forming fungi and fungi and the environmental water molecules essential for reproduction of the fungi. Electromagnetic waves in the far-infrared region are radiated and these water molecules are resonantly excited, so that the physiological function of bacterial cells is inhibited and its reproduction is significantly suppressed. Further, since the ceramic fine powder is composed of 4 to 8% by weight of manganese oxide and 2 to 5% by weight of titanium oxide, the oxidation accompanying the reduction of titanium oxide due to the absorption of electromagnetic waves in the external ultraviolet region. The generation of force and the resonance excitation of manganese oxide by the infrared electromagnetic wave in the infrared region further enhance the generation of oxidizing power by the catalytic action, so that not only bactericidal and fungicidal against a wide range of fungi but also the growth of fungi is produced. Offensive odor is also decomposed and removed.

In addition, since the ceramic fine powder has a composition of 4 to 8% by weight of zinc oxide and 0.1 to 1% by weight of silver or copper, especially in the presence of environmental moisture related to the growth of fungi. Zinc oxide, which is resonantly excited by electromagnetic waves in the infrared region, is ionized and the difference in ionization tendency with silver or copper causes reduction of silver or copper due to electron emission, so that oligodynamic action is exerted for a long time. Sterile sterilization is achieved.

The ceramic fine powder has an extremely fine particle diameter of 1 μm or less, and the fine particles of the respective composition components are fired at a low temperature in a bonded state due to the reduction of the surface energy. Therefore, since the radiation surface area ratio, the absorption surface area ratio, or the contact surface area ratio is extremely large, the efficient emission of electromagnetic waves in the infrared region and the efficient creation of oxidizing power associated with the absorption of ultraviolet rays, and the efficient oligodynamic action are efficiently exhibited. The effective antibacterial effect can be expected, and the compounding dispersibility with the film material or the adhesive material is extremely good, so that the ceramic fine powder is exposed on the outer surface even when coating or printing with the film material or the adhesive material. Since it is formed, it is an antibacterial film material having many features such as a significantly enhanced antibacterial property.

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view of an antibacterial film material containing a ceramic fine powder.

FIG. 2 is a cross-sectional clarification view of an antibacterial film material coated with ceramic fine powder.

[Explanation of symbols]

 1 product of the present invention containing ceramic fine powder 1A film material 1B ceramic fine powder 2 product of the present invention coated with ceramic fine powder 2A base film material 2B coating or printing

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08J 7/06 C08J 7/06 Z C08K 3/08 KAB C08K 3/08 KAB 3/22 KAE 3 / 22 KAE 3/34 KAH 3/34 KAH C08L 101/00 C08L 101/00

Claims (2)

[Claims] 1. A film material formed by a T-die method, an inflation method or a calendering method using an appropriate synthetic resin material, the particle size of which is 1 μm or less, and 40 to 60% by weight of silicon carbide or silicon oxide cord, Ceramic fine powder obtained by firing 20 to 30% by weight of alumina oxide, 4 to 8% by weight of manganese oxide and zinc oxide, 2 to 5% by weight of titanium oxide, and 0.1 to 1.0% by weight of silver or copper. An antibacterial film material containing the body in a proportion of 0.3 to 3% by weight based on the weight of the film material. 2. A ceramic fine powder is dispersed and mixed in an admixture at an appropriate ratio, and the ceramic fine powder is mixed with one side surface or both side surfaces of the base film material, which is previously formed, with respect to the weight of the base film material. The antibacterial film material according to claim 1, which is formed by applying or printing an adhering material such that the adhering material is applied at a ratio of substantially 0.1 to 1% by weight.