JP3465004B2 - Antibacterial resin film - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin film having an antibacterial effect against various bacteria and fungi.

[0002]

2. Description of the Related Art It has been conventionally known that silver and copper have a bactericidal action. For example, silver is widely used as a disinfectant in the form of an aqueous solution (Ag ⁺ ) of silver nitrate or the like. It is also known that silver or a compound thereof is adsorbed on an adsorbing substance such as activated carbon, alumina, silica gel, or zeolite and used for the purpose of sterilization. As described above, Japanese Patent Laid-Open No.
No. 2-241939 and Japanese Patent Application Laid-Open No. 62-238900, there are polyolefin resin moldings and papers containing zeolite which holds a metal having a bactericidal action in an ionic state. Further, as disclosed in JP-A-62-70221, there is no antibacterial and / or bactericidal action represented by the formula M ₂ O.Al ₂ O ₃ .SiO ₂ (where M is silver, etc.). It is a regular aluminosilicate.

[0003]

Therefore, an object of the present invention is to provide an antibacterial substance having a high antibacterial property and its durability and a high safety, and a resin containing a resin composition containing the same. It provides a film.

What achieves the above-mentioned object is to synthesize a synthetic resin particle by binding a metal having an antibacterial action to an N-long chain acylamino acid directly attached to the surface of the synthetic resin particle.
-Long chain acylamino acid antibacterial properties formed on the surface of
An antibacterial film formed from an antibacterial resin composition containing an antibacterial material to which a water-insoluble metal salt is attached .
The metal is preferably any one selected from the group consisting of silver, copper, lead, zinc, tin and bismuth. In addition, the particles have different antibacterial properties.
It is preferable that at least one kind of metal having antibacterial properties is bound. Furthermore, it is preferable that the metal is silver as an essential metal, and further that any of copper, lead, zinc, tin, and bismuth is used. The acyl group in the N-long chain acylamino acid salt is preferably any of stearoyl group, lauroyl group, myristoyl group and palmitoyl group. The amino acid portion of the N-long chain acylamino acid is any of glycine, alanine, valine, leucine, phenylalanine, tyrosine, threonine, tryptophan, methionine, aspartic acid, glutamic acid, lysine, arginine, and histidine. Also,
The film is preferably a stretched film.

The antibacterial film of the present invention will be described. The antibacterial film of the present invention is formed of an antibacterial resin composition containing an antibacterial material in which a metal having an antibacterial action is bound to N-long chain acylamino acids attached to the surface of synthetic resin particles. The antibacterial material has an N-long-chain acylamino acid attached to the surface of the synthetic resin particles, and the N-long-chain acylamino acid is a water-insoluble salt of an N-long-chain acylamino acid bound to an antibacterial metal. Has become. More specifically, the antibacterial material includes an N-long chain acylamino acid directly attached to the surface of a synthetic resin particle, a metal and an N having an antibacterial action after the N-long chain acylamino acid is attached.
-A long-chain acylamino acid antibacterial metal salt of N-long-chain acylamino acid formed on the surface of the synthetic resin particles is attached to the synthetic resin particles by binding. That is, in this antibacterial substance, the N-long chain acylamino acid water-insoluble salt of the metal having an antibacterial action formed on the surface of the synthetic resin particles is attached to the surface of the synthetic resin particles.

The synthetic resin particles in the antibacterial material make it easy to control the particle size of the formed antibacterial material, and the specific gravity can be selected according to the purpose. Antibacterial material can be created. Furthermore, since the particle size and the specific gravity can be selected by using the synthetic resin particles as described above, the formed antibacterial material can be easily added to the resin or the like.
That is, the dispersibility may not be sufficient only with the N-long chain acylamino acid antibacterial metal salt, and the dispersibility is improved.

The synthetic resin particles may be any particles as long as they can form particles. Also, the properties of the particles differ depending on the purpose for which the antibacterial material is added. Generally, polystyrene particles, polyolefin particles (polyethylene, polypropylene), polyvinyl acetate particles, polyester particles, crosslinked polystyrene particles, polyamide particles, polymeta particles are used because of their stability, dispersibility, particle shape, particle size uniformity, etc. Acrylate particles and fluororesin particles are suitable. In particular, polystyrene particles and crosslinked polystyrene particles are suitable. And as the particle size of the particles,
It is about 0.01 μm to 1 mm. Further, as shown in Reference Examples 1 and 2, the particle size of the particles is preferably 11 μm to 6.1 μm.

Regarding the ratio of the particles to the N-long chain acylamino acid salt, the higher the required level of antibacterial property, the higher the content of the N-long chain acylamino acid salt. Generally, the mixing ratio of the particles and the N-long chain acylamino acid salt is 100 by weight.
It is preferably about 0: 1 to 1: 1. N-long chain acylamino acids are water-soluble and have a surface-active action before binding to a metal having antibacterial properties. Therefore, it directly adheres to the surface of the synthetic resin.

The metal having an antibacterial action used for forming the N-long chain acylamino acid salt used in the present invention is preferably selected from silver, copper, lead, zinc, tin, bismuth and the like. . And among the above metals, antibacterial activity,
From the viewpoint of safety, silver or copper is particularly suitable. The N-long chain acylamino acid used for forming the N-long chain acylamino acid salt used in the present invention is an amino acid having a long chain acyl group (fatty acid residue) at the N position. As the long-chain acyl group, higher fatty acid residues are preferable, and for example, decanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oleoyl group and the like are preferable. Further, the acyl group is not limited to a single one, and plural kinds of the above acyl groups may be used.

The amino acid moiety may be any of monoaminomonocarboxylic acid, monoaminodicarboxylic acid and diaminomonocarboxylic acid. When the antibacterial material has a high antibacterial property, it is preferable to use monoaminodicarboxylic acid. Since this monoaminodicarboxylic acid has two carboxyl groups, a metal having an antibacterial effect is easily bonded. , Can have a strong antibacterial effect as a whole. As a general application, a salt in which an amino acid has one metal having an antibacterial action bound thereto has sufficient antibacterial activity. Specific examples of amino acids include glycine, alanine, valine, leucine, phenylalanine, tyrosine, threonine, tryptophan, and methionine as the monoaminomonocarboxylic acid, and aspartic acid and glutamic acid as the monoaminodicarboxylic acid. As diaminomonocarboxylic acid, lysine,
Arginine and histidine. The N-long chain acylamino acid is not limited to one kind, and many kinds may be used.

Therefore, preferred specific examples of the N-long chain acylamino acid salt contained in the antibacterial material include silver N-stearoyl glutamate, silver N-lauroyl glutamate,
N-myristoyl glutamate, N-stearoyl silver aspartate, N-lauroyl silver aspartate, N
-Silver myristoyl aspartate, copper N-stearoyl glutamate, copper N-lauroyl glutamate, copper N-myristoyl glutamate, copper N-stearoyl aspartate, copper N-lauroyl aspartate, copper N-myristoyl aspartate, silver N-stearoyl valine , N-lauroylvaline silver, N-myristoylvaline silver, N-stearoylvaline copper, N-lauroylvaline copper, N-myristoylvaline copper, N-stearoylphenylalanine silver, N-lauroylphenylalanine silver,
N-myristoyl phenylalanine silver, N-stearoyl phenylalanine copper, N-lauroyl phenylalanine copper, N-myristoyl phenylalanine copper, N-stearoyl arginine silver, N-lauroyl arginine silver,
N-myristoylarginine silver, N-stearoylarginine copper, N-lauroylarginine copper, N-myristoylarginine copper, N-stearoylglutamate zinc, N-lauroylglutamate zinc, N-myristoylglutamate zinc, N-stearoylaspartate zinc, N -Zinc lauroyl aspartate, zinc N-myristoyl aspartate, bismuth N-stearoyl glutamate, bismuth N-lauroyl glutamate,
N-myristoyl glutamate bismuth, N-stearoyl aspartate bismuth, N-lauroyl aspartate bismuth, N-myristoyl aspartate bismuth, N-stearoyl valine zinc, N-lauroyl valine zinc, N-myristoyl valine zinc, N-stearoyl valine zinc , N-lauroyl valine zinc, N-myristoyl valine bismuth, N-stearoyl phenylalanine zinc, N-lauroyl phenylalanine zinc, N
-Myristoyl phenylalanine zinc, N-stearoyl phenylalanine bismuth, N-lauroyl phenylalanine bismuth, N-myristoyl phenylalanine bismuth, N-stearoyl arginine zinc, N-lauroyl arginine zinc, N-myristoyl arginine zinc, N-stearoyl arginine bismuth, N-lauroyl Arginine bismuth, N-myristoyl arginine bismuth, lead N-stearoyl glutamate, lead N-lauroyl glutamate, lead N-myristoyl glutamate, lead N-stearoyl aspartate, lead N-lauroyl aspartate, lead N-myristoyl aspartate, N- Stearoylglutamate tin, N-lauroylglutamate tin, N-myristoylglutamate tin, N
-Stearoyl tin aspartate, N-lauroyl tin aspartate, N-myristoyl tin aspartate, N
-Stearoyl valine tin, N-lauroyl valine tin, N
-Myristoyl valine tin, N-stearoyl phenylalanine tin, N-lauroyl phenylalanine tin, N-myristoyl phenylalanine tin, N-stearoyl arginine tin, N-lauroyl arginine tin, N-myristoyl arginine tin and the like. The N-long chain acylamino acid salt is sparingly soluble in water and various organic solvents.

In this antibacterial substance, the adhering N-acyl amino acid salt is a salt in which at least one metal having antibacterial properties is bound in each molecule, and therefore has an extremely high antibacterial activity. ing. Furthermore, since the amino acids form the basic skeleton, toxicity is extremely low,
It can be safely used for various purposes. Furthermore, in antibacterial materials,
Since the attached N-long chain acylamino acid salt is in a water-insoluble stable state, only the metal forming the salt is difficult to flow out, and it is safe, and it can be mixed in a wide range of films such as food grade. it can. In other words, the antibacterial film containing such an antibacterial agent is safe because only the metal forming the salt is unlikely to flow out, and can be used in a wide range such as food.

Further, it is preferable that two or more kinds of N-long chain acylamino acid salts to which different metals having an antibacterial action are bound are attached to the surface of the synthetic resin particles. That is,
It is preferable that two or more kinds of N-long chain acylamino acid salts are attached to the particles, and these N-long chain acylamino acid salts are bound to different metals having antibacterial properties.
As an antibacterial metal and a combination thereof, silver or copper is an essential metal, and other metals (silver, copper, lead, zinc,
One or more selected from tin, bismuth, etc.). Specific examples of preferred combinations include silver and copper,
Silver and zinc, silver and lead, copper and zinc, silver and copper and zinc, silver and copper and lead, silver and copper and bismuth, and copper and zinc and lead.

Further, as described above, two or more kinds of N-long-chain acylamino acid antibacterial metal salts are not attached to one particle, but the antibacterial material is N-adhered to the surface of synthetic resin particles. First long-chain acylamino acid with antibacterial action
Second antibacterial particles having a metal bound thereto and second metal having an antibacterial action different from that of the first antibacterial particles bound to the N-long chain acylamino acid attached to the surface of the synthetic resin particles. It may be composed of a mixture with the antibacterial particles of. That is, different N-long-chain acylamino acid antibacterial metal salts (for example, N-long-chain acylamino acid silver and N-long-chain acylamino acid silver salt) are used.
A mixture of two types of particles to which long-chain acylamino acid copper) is attached may be used. In this antibacterial material, depending on the purpose of use,
The N-long chain acylamino acid antibacterial metal salt to be used as appropriate, the selection of the combination thereof, and the change of the compounding ratio can be appropriately made.

Then, a method of manufacturing the antibacterial material will be described. This method for producing an antibacterial substance comprises a step of contacting synthetic resin particles with an aqueous solution containing N-long chain acylamino acid ions, and a step of contacting the particles with an aqueous solution containing metal ions having antibacterial activity after the step. have.

As the synthetic resin particles, those mentioned above are preferably used. First, the surface of the synthetic resin particle is brought into contact with an aqueous solution containing an N-long chain acylamino acid ion. As a result, the N-long chain acylamino acid is attached to the surface of the synthetic resin. Then, it may be dried if necessary. In this step, the N-long chain acylamino acid ion-containing aqueous solution is prepared by dissolving an N-long chain acylamino acid or a water-soluble N-long chain acylamino acid salt in water.

N-long-chain acylamino acid or water-soluble N-
As the long-chain acyl amino acid salt, N-stearoyl glutamic acid, N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-stearoyl aspartic acid,
N-lauroyl aspartic acid, N-myristoyl aspartic acid, N-stearoyl valine, N-lauroyl valine, N-myristoyl valine, N-stearoyl phenylalanine, N-lauroyl phenylalanine, N
-Myristoyl phenylalanine, N-stearoyl arginine, N-lauroyl arginine, N-myristoyl arginine and their alkali metal salts (for example,
Sodium, potassium) and the like are preferably used. N-long chain acylamino acid in aqueous solution or aqueous solution N-
The long-chain acylamino acid salt concentration is preferably about 0.01 to 5% by weight. And, if necessary, it may be dried.

The particles having N-long-chain acylamino acid ion or water-soluble N-long-chain acylamino acid salt attached thereto are combined with the N-long-chain acylamino acid to form a water-insoluble salt. Contact with an aqueous solution containing metal ions. Specifically, this step is a water-soluble salt of a metal having antibacterial properties, for example, an aqueous solution of a water-soluble salt such as silver nitrate, copper nitrate, silver sulfate, copper chloride, copper sulfate, zinc nitrate, zinc chloride or bismuth nitrate. And spray this aqueous solution on the particles, or
It is performed by immersing the particles in an aqueous solution. The concentration of the metal salt in the aqueous solution is 0.01 to 5% by weight.
The degree is suitable. By this step, the N-long chain acylamino acid ion adhering to the surface of the particle and the antibacterial metal ion are bound to each other to form an unnecessary N-long chain acylamino acid antibacterial metal salt on the surface of the particle. To be done. Then, it is preferable to spray the above aqueous solution or soak the particles in the aqueous solution, and then dry the particles. The drying temperature is 40 to 2
It is preferably carried out at about 00 ° C. for about 30 minutes to 24 hours. In this way, antibacterial particles having N-long chain acylamino acid antibacterial metal salt formed on the surface are formed.

Since the N-long-chain acylamino acid antibacterial metal salt is formed on the surface of the particles, the attachment work is easy. Furthermore, it is presumed that the N-long-chain acylamino acid antibacterial metal salt is attached to the surface of the particle and the antibacterial metal is exposed in the state of a single molecule or a molecule close thereto. Therefore, the high antibacterial action of the N-long-chain acylamino acid antibacterial metal salt is sufficiently exhibited. Further, the N-long chain acylamino acid is a so-called surfactant and adheres to the surface of the particles almost uniformly. Therefore, the surface of the particles is almost uniform and N
-A long-chain acylamino acid coating is formed, and then a metal is bound, so that the formed N-long-chain acylamino acid antibacterial metal salt coating is also substantially uniform over the entire surface of the particle. . Further, in this step, the synthetic resin particles are brought into contact with an aqueous solution containing two or more different metal ions having an antibacterial action, or after being brought into contact with an aqueous solution containing a metal ion having an antibacterial action, It is preferably carried out by contacting with an aqueous solution containing a metal ion having an antibacterial action different from that of the metal ion.
The former is particularly preferable. In the former case, a water-soluble salt of a metal having antibacterial properties, for example, two or more kinds of water-soluble salts having different metals than silver nitrate, copper nitrate, silver sulfate, copper chloride, copper sulfate, zinc nitrate, zinc chloride, bismuth nitrate, etc. Is selected, and an aqueous solution containing a composite metal ion is added thereto, and the aqueous solution is sprayed on the particles or the particles are dipped in the aqueous solution. In the latter case, the particles are sequentially contacted with different aqueous metal salt solutions (application of the aqueous solution or immersion in the aqueous solution). By doing so, an antibacterial agent having two or more kinds of antibacterial metal salts attached to the surface of the particles can be formed. It has a broader antibacterial spectrum than the one to which only one kind of antibacterial metal is attached, has a higher antibacterial action, and exhibits an antibacterial action against more kinds of fungi. Further, the two or more kinds of N-long chain acylamino acid salts are salts of a metal and an N-long chain acylamino acid each having an antibacterial action, and at least the metals are different from each other.
The long chain acyl amino acids may be the same or different.

Next, a film formed of a resin composition containing an antibacterial material will be described. The resin composition forming this film contains the above-mentioned antibacterial material.
The amount of the antibacterial material added to the antibacterial resin composition is preferably about 0.05% to 5% by weight, based on the total weight of the resin.
More preferably, it is 0.1% to 3%. Then, as the resin material used in the antibacterial resin composition for forming the film of the present invention, any resin can be used, for example, a polyolefin resin (for example, polypropylene, polyethylene, polybutylene, ethylene-propylene copolymer), Vinyl chloride resin, styrene resin, urethane resin, silicone resin, polyamide, polyvinylidene chloride (eg, polyvinylidene chloride, polyvinylidene fluoride), polyester, polyurethane, polyethylene, polystyrene, polypropylene, etc. can be used, and antibacterial property The resin composition is prepared by adding the above-mentioned antibacterial material to the above resin material.

As a concrete resin composition, for example, a known vinyl chloride resin can be used, and as the vinyl chloride resin component, a homopolymer of vinyl chloride resin, polyvinylidene chloride and vinyl chloride are contained in an amount of 90 mol%. As described above, preferably, a copolymer containing 95 mol% or more and with another copolymerizable monomer (for example, vinylidene chloride, ethylene, propylene, vinyl acetate, etc.) is used, and a plasticizer is added to the copolymer. As, phthalates such as dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, aliphatic polybasic esters such as dioctyl adipate, dioctyl azelate, dioctyl sebacate, epoxidized soybean oil, epoxidized linseed oil, etc. Epoxidized animal and vegetable oils are added, and if necessary, stabilizers, lubricants, and Such as those other additives is blended is used. And, as a stabilizer, conventionally, metals such as barium, zinc, calcium and stearic acid,
Although metal soaps composed of higher fatty acid salts such as lauric acid are used, the N-long chain acylamino acid salt of a metal having antibacterial properties used in the present invention has the function as a stabilizer. The conventional stabilizers of can also be omitted. The antibacterial resin composition of the present invention is prepared by mixing the above vinyl chloride resin base with the above antibacterial material together with a plasticizer and other additives. Further, the antibacterial material may be prepared, for example, by previously adding it to a plasticizer, and adding this to a vinyl chloride resin base together with other additives and mixing them. , Etc.) to which a high concentration of antibacterial material is added, and this high concentration of vinyl chloride resin containing an antibacterial material is added to vinyl chloride resin containing no antibacterial material and kneaded. May be.

Known polyolefins can be used as the resin material, and examples of the polyolefin include:
Monomers such as ethylene homopolymer and propylene homopolymer, or random or block copolymers thereof can be used. Furthermore, a light stabilizer for these polyolefins,
Further, a phenolic antioxidant, a neutralizing agent, a lubricant, a nucleating agent and the like are optionally added. Then, the antibacterial substance is added to the polyolefin together with necessary additives and mixed, and formed into pellets, for example. Further, a pellet containing a high concentration of an antibacterial substance added to a polyolefin is prepared as an antibacterial resin composition, and a master pellet containing the high concentration of the antibacterial substance is used as another polyolefin containing no antibacterial substance. When the resin molded product is appropriately prepared with the pellets, it may be mixed in a mixer to prepare a resin molded product according to the purpose. And the antibacterial film of this invention is formed using the above-mentioned antibacterial resin composition. The film is used as a packaging material.

[0023]

【Example】

Reference Example 1 As synthetic resin particles, polystyrene particles (manufactured by Sumitomo Chemical Co., Ltd., product number PB-3011W, average particle size 11.1 μm, specific gravity 1.06) were used. As the alkali metal salt of N-long chain acylamino acid, N-stearoyl-L-glutamate disodium (manufactured by Ajinomoto Co., Inc., trade name Amisoft HS-21) was used.
-Stearoyl-L-glutamate disodium 6.5
g was dissolved in 9 l of water to prepare an N-long chain acylamino acid aqueous solution. Using silver nitrate as a water-soluble salt of a metal having antibacterial properties, an aqueous silver nitrate solution was prepared by dissolving about 4 g of silver nitrate in 900 ml of water. First, 100 g of synthetic resin particles were added to an N-long chain acylamino acid aqueous solution, and after soaking and stirring, they were left for about 60 minutes and then pulled up, 6
It was dried at 0 ° C. for about 24 hours to prepare synthetic resin particles having N-long chain acylamino acid attached to the surface. Then, the total amount of the synthetic resin particles described above was added to 900 ml of the above-mentioned silver nitrate aqueous solution, and after soaking and stirring, left for about 60 minutes, then pulled up and dried at 60 ° C. for about 24 hours, and , About 100 g of an antibacterial material (Reference Example 1) to which N-stearoyl-L-glutamate silver was attached was obtained.

Reference Example 2 As synthetic resin particles, polystyrene particles (manufactured by Sumitomo Chemical Co., Ltd., product number PB-30
061 W, average particle size 6.1 μm, specific gravity 1.06) was used. As an alkali metal salt of N-long-chain acylamino acid,
Using disodium N-stearoyl-L-glutamate (manufactured by Ajinomoto Co., Inc., trade name: Amisoft HS-21), about 4 g of this disodium N-stearoyl-L-glutamate was dissolved in 9 l of water to obtain an N-long chain acylamino acid. An aqueous solution was created. Using silver nitrate and copper nitrate as water-soluble salts of metals having antibacterial properties, about 1.2 g of silver nitrate and about 2 g of copper nitrate were dissolved in 900 ml of water to prepare a mixed aqueous solution of silver nitrate and copper nitrate. First, 100 g of synthetic resin particles were added to an N-long chain acylamino acid aqueous solution, and after soaking and stirring, they were left for about 60 minutes, then pulled up and dried at 60 ° C. for about 24 hours, and N-long on the surface. Synthetic resin particles having a chain acylamino acid attached were prepared. Then, the total amount of the above synthetic resin particles was added to 900 ml of the above mixed aqueous solution of silver nitrate and copper nitrate, immersed, stirred, and left for about 60 minutes, then pulled up and dried at 60 ° C. for about 24 hours to obtain a synthetic resin. On the surface of the particles, N-stearoyl-silver L-glutamate and N-stearoyl-
About 1 antibacterial material with L-Glutamate attached (Reference Example 2)
00g was obtained.

Example 1 Polypropylene [melt index (230 ° C.) 2 g / 10 minutes, density = 0.905]
g / cm ³ ] 100 parts by weight, glycerin monostearate 0.5 parts by weight 3 parts by weight of the antibacterial material prepared in Reference Example 1 was added, and the mixture was mixed at 80 ° C. with a Hensyl mixer at 2 ° C.
The mixture was mixed for a minute, a strand was formed at 230 ° C. by an extruder having a screw with a diameter of 40 mm, and the strand was rapidly cooled to obtain a strand cut pellet (master pellet). Similarly, polypropylene [melt index (230 ° C.) 2 g / 10 min, density = 0.905 g /
cm ³ ] 100 parts by weight, 0.5 parts by weight of glycerin monostearate was added, and a Hensyl mixer was used.
The mixture was mixed for 2 minutes at 0 ° C., a strand was formed at 230 ° C. by an extruder having a screw with a diameter of 40 mm, and the strand was rapidly cooled to obtain cut pellets. Then, to 100 parts by weight of the above cut pellets, 10 parts by weight of the above master pellets were added, mixed for 2 minutes at 80 ° C. using a Hensyl mixer, and at 230 ° C. by an extruder having a screw of 40 mm diameter. Strands were formed and quenched to obtain strand cut pellets. This strand cut pellet was loaded into an inflation molding machine having a screw with a diameter of 30 mm, and 2
Melt film formation was performed at 50 ° C. to obtain an unoriented blown film having a thickness of 120 μm.

(Embodiment 2) The film of Embodiment 1 is used for one side.
Cut into a square of 0 cm, and using a biaxial stretching measuring device,
At a temperature of 150 ° C, the vertical and horizontal directions are 2.5 each at the same time.
Double stretching was performed to obtain a biaxially stretched polypropylene film having an average thickness of 20 μm.

Example 3 The same procedure as in Example 1 and Example 2 was repeated except that 1 part by weight of the antibacterial material of Example 1 was added instead of the antibacterial material of Example 1 as the added antibacterial material.
A biaxially oriented polypropylene film having an average thickness of 20 μm was obtained.

[Experiment] The following experiment was conducted on the antibacterial action of the antibacterial resin film of the present invention. As a test strain, Staphylococcus aureus ATCC 6538P Klebsiella (Klebsiella pneumoniae IFO 13277) was used, and the bacterial solution was cultured in a normal broth medium at 35 ° C. for 18 to 20 hours. Number
It was adjusted to be 5.0 × 10 ^{5 to} 3.0 × 10 ⁶ .
Then, the resin molded products of Examples 1 and 2 were treated to 20 mm × 2.
A test piece cut into a size of 0 mm was prepared and sterilized in an autoclave at 121 ° C. for 15 minutes.
The films of Examples 1 and 2 were fixed so as not to shrink and sterilized. Then, 0.2 ml of the above-mentioned bacterial solution was applied to the surface of the test piece of each Example and stored at 35 ° C. After 18 hours from the start of storage, the surviving bacteria on the test piece were washed out with sterile buffered saline, and the washed-out solution was used as a pour plate using a medium for measuring the number of bacteria (Eiken Chemical Co., Ltd., standard agar medium). The viable cell count was measured by the culture method (35 ° C., 2 days). The results are shown in Table 1 and Table 2.
It was as shown in.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

INDUSTRIAL APPLICABILITY In the antibacterial film of the present invention, the N-long chain acylamino acid salt attached to the contained antibacterial material is in a stable state insoluble in water, and therefore only the metal forming the salt flows out. Because it is difficult and safe, this film can be used as a wide range of packaging materials such as food products.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08K 5/205 C08K 5/205 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 5/18 A01N 25/10 A01N 37/44 A01N 59/16

Claims (12)

(57) [Claims] 1. N- directly attached to the surface of synthetic resin particles
The long-chain acyl amino acid, to bond a metal having antimicrobial activity
As a result, N formed on the surface of the synthetic resin particles
− Long-chain acyl amino acid Antibacterial water-insoluble metal salt is attached
An antibacterial film, which is formed from an antibacterial resin composition containing an antibacterial material. 2. The antibacterial film according to claim 1, wherein the metal is any one selected from the group consisting of silver, copper, lead, zinc, tin and bismuth. 3. The particles are bound with two or more different antibacterial metals having antibacterial activity.
Alternatively, the antibacterial film described in 2. 4. The two or more different metals having an antibacterial action include silver as an essential metal, and further copper, lead, zinc,
The antibacterial film according to claim 3, which is either tin or bismuth. 5. The N-long-chain acylamino acid salt, wherein the acyl group is any of a stearoyl group, a lauroyl group, a myristoyl group, and a palmitoyl group.
The antibacterial film according to any one of 1. 6. The amino acid portion of the N-long chain acylamino acid is any one of glycine, alanine, valine, leucine, phenylalanine, tyrosine, threonine, tryptophan, methionine, aspartic acid, glutamic acid, lysine, arginine, and histidine. Claim 1
6. The antibacterial film according to any one of 1 to 5. 7. The antibacterial film according to claim 1, wherein the film is a stretched film. 8. The antibacterial film according to claim 1, wherein the film is a packaging film. 9. A resin used in the antibacterial resin composition
The material according to claim 1, which is a polyolefin resin.
The antibacterial film according to any one. 10. The synthetic resin fine particles are polystyrene.
Particles or polyolefin particles.
The antibacterial film according to any one of 1. 11. A method of directly attaching to the surface of polystyrene particles
In addition to N-long-chain acylamino acids, metals with antibacterial action
By bonding, the shape on the surface of polystyrene particles
N-long chain acylamino acid antibacterial water-insoluble metal salt formed
Polypropylene resin set containing antibacterial material with adhered
An antibacterial fill characterized by being formed from a product
Mu. 12. The particles have different antibacterial properties.
Two or more kinds of metals having antibacterial properties bound to each other.
11. The antibacterial film according to item 11.