JP2000154340A - Antimicrobial inorganic porous material composition and use thereof - Google Patents

Abstract

(57) [Abstract] [Problem] An inorganic porous material composition as an additive capable of preventing color contamination by a mineral contained in a liquid such as an infusion liquid, a beverage or a food even when the liquid is in contact with the liquid. A medical product such as a medical tube or a medical device, a cutting board, or a food contact product such as a food packaging material or a food tray using the inorganic porous material composition. SOLUTION: Platinum, gold, silver,
An antimicrobial composition obtained by vacuum-depositing at least one or more antimicrobial metals selected from copper or zinc by ion plating or sputtering, mixing the composition into a polymer, or mixing the composition with a polymer -Medical or food contact products applied to the surface of molded articles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antimicrobial inorganic porous material composition having high human safety. Also, the present invention
The present invention relates to a polymer composition containing an antibacterial inorganic porous material composition. The present invention also relates to an antimicrobial medical product or food contact product formed from a polymer composition containing the antimicrobial inorganic porous material composition. Further, the present invention relates to an antibacterial product obtained by adhering the antibacterial inorganic porous material composition to the surface of the polymer composition. The present invention also relates to a medical product or a food contact product obtained by adhering the antimicrobial inorganic porous material composition to the surface of the polymer composition. The present invention also relates to an antimicrobial medical tube or medical device, an antimicrobial cutting board, an antimicrobial cutting board, a food packaging material, or a tray obtained by attaching an antimicrobial inorganic porous material composition to the surface of a polymer composition. .

[0002]

2. Description of the Related Art Conventionally, many organic antibacterial agents have been used as antibacterial agents. However, organic antibacterial agents generally exert a stronger antibacterial effect than silver-based inorganic antibacterial agents, but have low chemical stability such as heat resistance, and their decomposition products and volatile substances from the viewpoint of safety to the human body. Such factors often cause problems with environmental hormones and the like, and now awareness of human safety of silver-based inorganic antibacterial agents is increasing. As a typical silver-based inorganic antibacterial composition, an antibacterial zeolite obtained by ion-exchanging silver, copper or zinc of a metal having antibacterial properties into zeolite is known. For example, Japanese Patent Publication No. 63-54013 and U.S. Pat.No. 4,775,585 propose a bactericidal polymer composition by mixing a polymer with an antibacterial zeolite obtained by ion-exchanging a metal selected from silver, copper and zinc into zeolite. However, it was not always perfect in terms of coloring contamination and human safety.

[0003] Further, as a technique for improving color contamination by an antibacterial zeolite, there is Japanese Patent Publication No. 63-256958 and US Patent No. 4,938,955, in which a zeolite is mixed with a polymer by substituting ammonium ions and an antibacterial metal. The color contamination at the time is reduced. Further, since an excellent antibacterial effect can be obtained by mixing silver-substituted zeolite into a polymer, a technique utilizing this is, for example,
In 14992 and U.S. Pat. No. 4,923,450, there is also reported a catheter in which silver-substituted zeolite is used as an antibacterial agent in a medical tube, but it has problems in moldability, antibacterial properties and economic efficiency. Furthermore, a method for obtaining an antibacterial catheter using silver other than silver-substituted zeolite is disclosed in U.S. Pat.
No. 5,520,664 discloses that an inner surface of a catheter is coated with silver by an ion beam to obtain antibacterial properties. However, surface treatment of a resin with metallic silver does not release ions sufficiently and does not have a sufficient antibacterial effect.

On the other hand, as a silver-based inorganic antibacterial agent other than silver zeolite, as shown in US Pat. No. 5,180,585, a first coating comprising titanium oxide or the like as a core is to deposit silver from silver nitrate in an aqueous dispersion system and oxidize it. In the case of silver or silver halide, or in the case of copper, copper is deposited with a soluble copper salt in an aqueous system to form copper oxide and copper sulfide, and then the second coating is performed. Alternatively, a coating coated with alumina is known, but there has been a problem that the release of silver ions is rather suppressed by such a protective coating and the antibacterial effect is low. In the above-mentioned U.S. Pat. No. 5,180,585, titanium oxide is used as a core material, silver is deposited on the core material from silver nitrate in an aqueous dispersion system and coated, and then silver oxide is formed.The silver oxide coating is protected with silica to protect the silver oxide coating. Although coating is performed, it takes a long time for the antibacterial effect to be exhibited by the protective coating of silica, and this is not suitable because it is ineffective unless the effect is exhibited in a short time, such as for food and medical use, and is not suitable. Also, in a tube for infusing an infusion solution, it is necessary to avoid that silver ions cause a change in the mineral balance of the infusion solution component due to substitution.

[0005]

A zeolite obtained by ion-exchange of silver, copper or zinc as an antibacterial metal is capable of releasing a constant amount of silver ions in a normal state.
It is safe to keep silver ion concentration at pb level. However, when it comes into contact with infusions, drinking water and foods to be antibacterial, the minerals contained therein will replace silver ions, and the mineral balance of the infusion components will change, or silver ions will replace the minerals. And a large amount of silver ions are released, resulting in significant color contamination in the system. It is known that this is because silver-substituted zeolite easily replaces another ion, which is a weak point of the ion exchanger, and releases silver ions. If the amount of ion exchange is reduced, there is a problem that the life of the antibacterial agent is shortened and the antibacterial agent cannot be put to practical use.

According to US EPA standards, the allowable concentration of silver in drinking water is 100 ppb, and if it is less than 100 ppb, it is unsuitable for food use. -The most important thing is that chemical-treated metal coating is inefficient, and various drug components remain as impurities. . Since the antibacterial effect of a metal having antibacterial properties can be obtained in the state of metal ions, it is important that the metal ions for antibacterial be easily eluted. It is necessary to efficiently obtain a constant metal ion by supporting it on a porous carrier.

[0007]

According to the present invention, an inorganic porous material particle is provided with one or more kinds of antibacterial metals selected from platinum, gold, silver, copper or zinc by ion plating or sputtering. By means of vacuum deposition, an antibacterial inorganic porous body composition comprising a metal-deposited inorganic porous body obtained by vacuum-depositing 0.5 to 10% by weight of the inorganic porous body by weight is used as the antibacterial component. The problem has been solved. The inorganic porous material in the present invention means a porous material of a silicate mineral or a phosphate mineral, and the former silicate mineral includes zeolite, diatomaceous earth, kaolinite, montmorillonite, silica gel, and meta. Magnesium silicate and porous glass, and the latter phosphate minerals include zirconium phosphate and calcium phosphate (apatite). The inorganic porous body of the present invention,
Since it is porous in itself, it can carry a large amount of fine metal clusters and can maintain a high surface free energy level. That is, although metal particles do not have antibacterial activity, metal atoms having a high free energy level can react with bacterial protein enzymes to cause enzyme inhibition and kill bacteria (microscopic effect of metal).
Therefore, the metal cluster according to the present invention has an ideal antibacterial activity.

In the present invention, the inorganic porous material has a particle size of
10 μm or less, preferably 5 μm or less is used, but the ion exchange capacity is suppressed by performing metal deposition on such an inorganic porous material. It was also found that the mineral balance did not disturb the mineral balance even when it came into contact with the minerals contained therein. In the case of metal deposition of an inorganic porous material as in the present invention, unlike a liquid treatment coating by a chemical reaction, since it does not contain impurities, for example, a medical product such as a medical tube or a medical tool, or a cutting board or a food package It has been confirmed that even when used in food contact products such as materials and food trays, it exhibits sufficient antibacterial properties to maintain human safety.

The amount of vacuum deposition on the inorganic porous material particles is as follows:
The range of 0.5-10% by weight is appropriate, Staphylococcus aureus,
The minimum inhibitory concentration (MIC) of E. coli is in the range of 100 to 150 ppm, and the antibacterial effect is remarkable. However, when the content is 0.5% by weight or less, the minimum inhibitory concentration becomes 2000ppm or more, and the antibacterial effect is insufficient. At 10% by weight or more, since the deposited metal layer is thick, metal ions are unlikely to appear, and the minimum suppression concentration is 2000 ppm.
It is not preferable because the antibacterial effect decreases,
When the content is more than the weight percentage, coloring contamination due to oxidation of the metal becomes remarkable. In the present invention, the inorganic porous material particles, platinum, gold, silver,
The basic constitution is that at least one kind of antibacterial metal selected from copper or zinc is vacuum-deposited to obtain an antibacterial inorganic porous material composition.

Further, in the present invention, the metal-deposited antimicrobial inorganic porous material composition obtained by the above-mentioned vacuum deposition is made of polypropylene, polyethylene, polyvinyl chloride, polyester, nylon, polystyrene, ABS, polycarbonate, acrylic resin, An antibacterial polymer composition is prepared by mixing 0.5 to 10% by weight of a polymer material such as an epoxy resin, a polyurethane, or an ultraviolet curable resin, and various molded articles, sheets, and films are obtained from the obtained antibacterial polymer composition. If formed, an antimicrobial product that easily achieves the objective standard can be obtained. Furthermore, in the present invention, when molding using a general-purpose poima-compound that does not contain the above antibacterial inorganic porous material composition, in-mold molding, surface processing or surface treatment using the antibacterial inorganic porous material composition A similar antimicrobial effect can be exhibited by the coating.

In the vacuum deposition according to the present invention, argon, helium, or the like is injected at a degree of vacuum of about 7 × 10 ⁻⁵ (Torr) using a vacuum deposition apparatus, and then selected from oxygen, ethylene, and nitrogen. One type is injected, an electric field is applied by a current of 140 amps to generate plasma, and a metal selected from platinum, gold, silver, copper or zinc put in a hearth is evaporated and ionized. A magnetic force of 300-3000 gauss is induced in the zeolite from the back of the equipment that stores the zeolite, and ions are efficiently deposited.

The configuration of the present invention will be described in more detail with reference to the following embodiments. The configuration of the present invention is not limited by the following embodiments.

Example 1 A zeolite of fine particles having an average diameter of 1 to 2 μm was put into a vacuum vapor deposition device having a diameter of 80 cm and a depth of 120 cm, and a 7 ×
The degree of vacuum was set to 10 ^-5 (Torr). Then, argon gas was added to 60
cc and 120 cc of oxygen were injected. Next, an electric field is applied by a current of 140 amps to cause ptezma, put gold into the hearth and evaporate, and induce gold ions in the direction of the zeolite with a magnetic force of 400 gauss by 4% by weight based on the zeolite weight. Gold deposition. The obtained gold-deposited zeolite composition had an MIC against Staphylococcus aureus of 250 ppm, and an excellent antibacterial effect was obtained. Further, the above-mentioned gold-deposited zeolite composition was mixed with polyurethane at 1% by weight to form a catheter tube. 1 g (15 pieces in total) of the finely cut sample pieces were added to 70 ml of a phosphate buffer solution, and ⁵ ml of a bacterial solution of S. aureus (2.2 × 10 ⁵ cells / ml) was further added, followed by shaking at 150 rpm. After inoculation and shaking for 3 hours, the number of bacteria was measured by a pour plate method using a standard agar medium. As a result, an excellent antibacterial effect was observed as shown in Table 1.

[0013]

[Table 1] 数 Number of initial bacteria After shaking for 3 hours (pcs / ml) (pcs / Ml) 使用 Use of 1% gold-deposited zeolite 1.5 × 10 ⁴ 10 or less Catheter ─── ──────────────────────────── Conventional catheter 1.5 × 10 ⁴ 2.6 × 10 ⁴ (Planck) ──────── ───────────────────────

[0014]

Example 2 Diatomaceous earth of fine particles having an average diameter of 5 μm was
Put it in a vacuum evaporation device of 80cm and depth of 120cm, 7 × 10
^The degree of vacuum was ^-5 (Torr). Then argon gas 60c
c, 130 cc of ethylene was injected. Next, an electric field is applied by a current of 140 amps to generate plasma, silver is put into the hearth and evaporated, and silver ions are induced in the direction of zeolite with a magnetic force of 1000 gauss, and the weight is 5 wt. % Silver was deposited. The obtained silver-deposited inorganic porous material composition has an MIC against Staphylococcus aureus of 125 pp.
m, indicating that it has an excellent antibacterial effect.
Further, the silver-deposited inorganic porous material composition was mixed with polyvinyl chloride at 1% by weight to form a catheter tube. 1 ml of Staphylococcus aureus solution (5.6 × 10 ⁵ cells / ml) suspended in Muller, Hinton, or Bouillon liquid medium was inoculated into the above tube (inner diameter 3 mm), and cultured at 36 ° C. for 6 hours. As a result of measuring the number, an excellent antibacterial effect was recognized as shown in Table 2.

[0015]

[Table 2] 初 Initial number of bacteria After cultivation for 6 hours (pcs / ml) (pcs / ml) ) 使用 Use of silver evaporated diatomaceous earth 1% 5.6 × 10 ⁵ 10 or less Catheter ──── ────────────────────────── Conventional catheter 5.6 × 10 ⁵ 7.5 × 10 ⁸ (Planck) ────────── ────────────────────

[0016]

Example 3 Fine particle zirconia having an average diameter of 5 μm was placed in a vacuum vapor deposition having a diameter of 80 cm and a depth of 120 cm to obtain a 7 × 10
^The degree of vacuum was ^-5 (Torr). Then argon gas 60c
c, 130 cc of ethylene was injected. Then, an electric field is applied by a current of 140 amps to generate plasma, zinc is put in a hearth and evaporated, and zinc ions are induced in the direction of zirconium phosphate with a magnetic force of 1000 gauss to 8 wt. % Zinc was deposited. The obtained zinc-deposited zirconia phosphate had an MIC of 250 ppm against Staphylococcus aureus. 0.3% by weight of the silver-deposited zeolite of Example 2 and 0.5% by weight of the zinc-deposited zeolite of Example 2 were mixed with polyethylene to form a film having a thickness of 30 μm. 1 ml of a suspension of Staphylococcus aureus (6.3 × 10 ⁵ cells / ml) was applied to the surface of the above film (5 cm square),
After culturing for 4 hours, the surface of the sample was washed out with a phosphate buffer, and the number of bacteria was measured. As a result, as shown in Table 3, excellent antibacterial effects were observed, and the sample was effective as a food packaging material.

[0017]

[Table 3] 数 Number of initial bacteria After culture for 24 hours (pcs / ml) (個 / ml) 蒸 着 Silver-deposited zirconia phosphate 0.3% Zinc-deposited zirconia phosphate 0.5% 6.3 × 10 ⁵ 10 or less PE film ───────────────────────────────── Conventional PE film 6.3 × 10 ⁵ 5.0 × 10 ⁷ (blank) ─────────────────────────────────

Example 4 The gold-deposited zeolite having an average particle diameter of 1 to 2 μm obtained in Example 1 was applied to a urethane-based ultraviolet-curing paint UV.
-1050 (product of Nagashima Special Paint Co., Ltd.)
A V-cured coating liquid was used. A polypropylene tube was immersed in the above coating solution, picked up, and applied to a film thickness of about 50 μm by dip coating. Next, after drying at 70 ° C. for 5 minutes, the lamp output is 80 mW / and the irradiation energy is 1440 mJ /
Was cured by UV irradiation. E. coli 5.3 × 10 ⁵ cells / ml were inoculated into the UV-cured tube in the same manner as in Example 1 and cultured for 3 hours, and the number of bacteria was measured. As a result, an excellent antibacterial effect was confirmed as shown in Table 4. .

[0018]

[Table 4] 初 Initial number of bacteria After culturing for 3 hours (pcs / ml) (pcs / ml) ml) ＵＶ Gold coated zeolite 1% 5.3 × 10 ⁵ 10 or less UV coating 含有──────────────────────────── Blank 5.3 × 10 ⁵ 8.2 × 10 ⁵ ───────────── ──────────────────

[0019]

Example 5 An acrylic binder and the silver-deposited diatomaceous earth obtained in Example 2 were mixed with thin paper, and the amount of silver-deposited diatomaceous earth was adjusted to 1.5% based on the weight of the paper to perform coating. And dried to obtain antibacterial paper for in-mold. In the extrusion molding of a cutting board having a thickness of 2 cm and 17 cm × 30 cm with a polyethylene resin, the antibacterial paper for the in-mold is inserted into a mold, and the antibacterial paper for the in-mold is inserted in a mold in the injection molding of the cutting board. Was inserted, and in-mold molding was performed so that the antibacterial paper was placed on the surface of the cutting board. As a result of inoculating 4.7 × 10 ⁵ Escherichia coli on the surface of the cutting board in-molded in the same manner as in Example 3 and culturing for 6 hours, the number of bacteria was measured.
As shown in the figure, an excellent antibacterial effect was observed.

[0020]

[Table 5] 数 Initial number of bacteria After culturing for 6 hours (pcs / ml) (pcs / ml) ml) 蒸 着 Silver-deposited diatomaceous earth 4.7 × 10 ⁵ 10 or less In-mold cutting board ───ブ ラ ン ク Blank 4.7 × 10 ⁵ 3.5 × 10 ⁷ ───────────── ──────────────────

[0021]

Example 6 The gold-deposited zeolite obtained in Example 1 was mixed with a urethane-based ultraviolet rope curable paint UV-1050 (a product of Nagashima Special Paint Co., Ltd.) at 1% to obtain a coating liquid for UV curing.
The above-mentioned coating solution was spray-coated on a chest piece (made of alumite) and a diaphragm (made of epoxy resin) in contact with a stethoscope patient, and applied to a thickness of about 35 μm. Then
After a dry explosion at 70 ° C. for 5 minutes, the coating film was UV-cured by irradiating an ultraviolet ray with a lamp output of 80 mW / and an irradiation energy of 1440 mJ /. The MRSA bacterium 5.3 × was placed on the diaphragm set on the UV-cured stethoscope testpiece in the same manner as in Example 3.
10 ⁵ cells / ml was inoculated and the results of measuring the number of bacteria after 6 hours of incubation, excellent antibacterial effect as shown in Table 6 was observed.

[0022]

[Table 6] 数 Initial number of bacteria After culturing for 6 hours (pcs / ml) (pcs / ml) ml) ─────────────────────────────── Gold-deposited zeolite 2.3 × 10 ⁵ 10 or less 1% UV coating 含有──────────────────────────── Blank 2.3 × 10 ⁵ 7.4 × 10 ⁸ ───────────── ──────────────────

In the present invention, platinum, gold, silver, copper or zinc is vacuum-deposited as an antibacterial metal on the particles of the inorganic porous material. Color contamination by the contained mineral can be prevented. The metal-deposited inorganic porous material composition obtained in the present invention sufficiently satisfies the food standard of 100 ppb or less, which is the allowable concentration of silver in drinking water based on EPA, for example, even in the case of silver deposition.
Further, the metal-deposited inorganic porous material composition of the present invention may be a polymer.
The same antibacterial effect can be exerted by mixing the metal-deposited inorganic porous material composition on the surface of the polymer molded article by surface treatment. The metal-deposited inorganic porous material composition of the present invention can be used for medical products such as medical tubes and medical instruments, or cutting boards, food packaging materials and food trays.
And the like, which is extremely useful for use in food contact products, and has high social needs.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 59/20 A01N 59/20 Z A23L 3/00 101 A23L 3/00 101A A61L 29/00 A61L 29/00 Z B65D 1/09 B65D 1/34 1/34 C08J 7/04 CERU C08J 7/04 CER CEZU CEZ C08K 9/02 C08K 9/02 C23C 14/18 C08L 101/16 B65D 1/00 A C23C 14/18 C08L 101/00 (72) Inventor Koji Nakamura Inside Awaji Plant of Nakamura Bussan Co., Ltd. 6-41, Nishiawaji, Higashiyodogawa-ku, Osaka-shi, Osaka

Claims (21)

[Claims] 1. An antimicrobial inorganic porous material composition comprising: vacuum-depositing at least one antimicrobial metal selected from platinum, gold, silver, copper or zinc on an inorganic porous material. object. 2. The inorganic porous material is selected from silicate minerals selected from zeolite, diatomaceous earth, kaolinite, montmorillonite, silica gel, magnesium metasilicate aluminate and porous glass, or zirconium phosphate and calcium phosphate. The antibacterial inorganic porous composition according to claim 1, wherein the composition is a porous substance of a phosphate mineral. 3. The antibacterial inorganic porous material composition according to claim 1, wherein the inorganic porous material is a particle having a particle size of 10 μm or less. 4. The antibacterial inorganic porous material according to claim 1, wherein the amount of the antibacterial metal deposited by vacuum is 0.5% by weight to 50% by weight based on the weight of the inorganic porous body. Body composition. 5. The antibacterial inorganic porous material composition according to claim 1, wherein the vacuum deposition of the antibacterial metal is ion plating or sputtering. 6. Platinum, gold, silver,
An antimicrobial inorganic porous material composition obtained by vacuum-depositing at least one or more antimicrobial metals selected from copper or zinc, wherein the polymer material contains 0.5 to 10% by weight. Antimicrobial polymer composition. 7. The antibacterial polymer composition according to claim 6, wherein the inorganic porous material has a particle size of 10 μm or less. 8. The method according to claim 6, wherein the amount of the antimicrobial metal deposited in a vacuum is 0.5 to 10% by weight of the inorganic porous material.
Or the antibacterial polymer composition according to 7. 9. The antimicrobial polymer composition according to claim 6, wherein the vacuum deposition of the antimicrobial metal is ion plating or sputtering. 10. The antimicrobial polymer composition according to claim 6, which is formed into a medical product. 11. The antibacterial polymer composition according to claim 6, which is a medical tube or a medical device. 12. The antibacterial polymer composition according to claim 6, which is formed into a food contact molded product. 13. The polymer-antibacterial composition according to claim 6, which is a cutting board, a food packaging material, or a food tray. 14. Platinum, gold, silver,
An inorganic porous material composition obtained by vacuum-depositing at least one or more antibacterial metals selected from copper or zinc is a polymer.
An antibacterial product characterized by being in-mold fixed or coated on the surface of a molded product. 15. The antibacterial product according to claim 14, wherein the particle diameter of the inorganic porous material particles is 10 μm or less. 16. The method according to claim 1, wherein the amount of the antimicrobial metal deposited in a vacuum is 0.5 to 50% by weight of the weight of the inorganic porous material.
14 or 15 antibacterial products. 17. The antibacterial product according to any one of claims 14 to 16, wherein the vacuum deposition of the antibacterial metal is ion plating or sputtering. 18. The medical product according to claim 18, wherein the medical product is a medical product.
18. The antibacterial product according to any one of 14 to 17. 19. The antibacterial product according to claim 13, which is a medical tube or a medical device. 20. The antibacterial product according to claim 14, which is a food contact molded product. 21. The antibacterial product according to claim 14, which is a cutting board, a food packaging material, or a food tray.