JPH06312477A - Antibacterial thin film and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain an antibacterial thin film in which a molecular film of an Angstrom order can be formed and which is chemically bonded to a base by covalent bond. CONSTITUTION:Since a cationic complex chemical adsorption single molecular film 3 in which a film forming molecule is rigidly fixed directly or indirectly to a base (glass board 1) by covalent bond by using a chlorosilyl group and halogenated sulfinyl group as functional groups for fixing the molecule to the base has a quinolinyl group for forming complex with Cu<2+> as a functional group having antibacterial properties, it becomes a thin and rigid antibacterial thin film which has not been heretofore existed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial thin film and its manufacturing method.

[0002]

2. Description of the Related Art The influence of bacteria on human life is immeasurable. There are many things that cannot be obtained without the beneficial action of bacteria, such as pharmaceuticals and food products. However, it is also true that harmful bacteria exist for humans, and it has been strongly demanded to protect human life from the harmful bacteria themselves and from damage caused by the harmful bacteria. There is a long history of research on antibacterial agents that has been made to meet the demand.
On the other hand, given the rapid increase in demand for high value-added products, a number of products complaining of antibacterial properties and deodorant properties have been born.

First of all, clothing is the most important object requiring antibacterial properties. Among them, what has particularly been conventionally required to have antibacterial properties is that which is generally in direct contact with the skin. Examples include underwear, socks, diapers, sportswear and the like. As a method of making clothing as described above, it is general to knit using fibers having antibacterial properties.

The antibacterial fiber suppresses the growth of bacteria on the fiber,
It is a raw yarn that makes sanitary processed textile products with deodorant effect,
In order to be a raw thread for clothing, in addition to the texture, texture, color and the like, it is necessary to consider the sensory and psychological factors that come from the feeling of the raw material. Furthermore, even if the antibacterial effect is large, it must be safe for the human body, and the effect must be maintained even if washed, and special functions such as shrink-proofing must not be disturbed.

As a method of further imparting antibacterial properties while satisfying the above requirements, there are roughly two methods. The first method is a method in which a substance having an antibacterial property is present in the fiber, and the second method is a method in which sweat is quickly dried in order to keep away bacteria that decompose sweat.

Specifically, as the first method, a method of incorporating copper into the fiber, a method of weaving a copper wire into the fiber,
A method of directly sputtering copper into the fiber, a method of incorporating an organic chlorine-based substance in the fiber, a method of kneading zeolite into which silver ions and copper ions are introduced by ion exchange into the fiber, and a method of kneading organic mercury or organic tin into the fiber There were ways, etc. It has long been known empirically that copper and silver have antibacterial effects, and not only are silver spoons and the like high-end products, but they have also been paid attention to from the viewpoint of disease prevention. There is. Since silver may be difficult in terms of cost, copper is generally used instead of silver. In addition, organic mercury and organic tin are applied to prevent shellfish from adhering to the outer wall of the ship bottom.

The second method includes a method of directly coating fibers with chitin and a method of forming an ultrafine porous structure based on polyurethane resin. It strongly absorbs sweat, quickly diffuses it, and evaporates it to prevent the growth of bacteria and give it a refreshing feel. We have made this possible by developing fibers that can effectively absorb, diffuse, and evaporate.

Although the clothing has been described above, there are also those in which the same technique is applied to other bedding, interior products, building materials, etc. so that molds do not grow.

[0009]

However, the above-mentioned 2
The current situation is that one method does not have a sufficient antibacterial effect. In the first method, it is its toxicity that is always a problem. Irritation to the skin of the human body and penetration of drugs into the body cannot be said to be completely overcome. In fact, organic mercury and organic tin are no longer used because of their strong toxicity, and organic chlorine-based substances are no longer used because they generate toxic substances such as dioxins by heating and UV irradiation. On the other hand, the method using silver or copper is not so serious in toxicity, but is often problematic in terms of durability. In other words, it can be removed by washing, washing, etc.,
That is, the antibacterial effect is not guaranteed in the long term.

On the other hand, in the second method, there is no antibacterial action at all, but since it is only to dry the sweat before the bacteria propagate, it is difficult to reduce the bacteria if they adhere. . Other than the method of structurally promoting the drying of sweat, this also has a problem in durability.

It is an object of the present invention to provide an antibacterial thin film capable of film formation and film thickness control in the angstrom order and firmly bonded to a substrate, and a method for producing the same.

[0012]

In order to achieve the above object, the antibacterial thin film of the present invention has a structure in which molecules constituting the thin film directly or indirectly form Si, Ge, Sn, Ti, Z.
An organic thin film fixed by a covalent bond via at least one atom selected from r, S and C, wherein the organic thin film has a functional group having antibacterial properties in its molecule.

In the above structure, the organic thin film is preferably a monomolecular film or a monomolecular cumulative film. Further, in the above structure, the functional group having antibacterial properties is a chelate skeleton formed by the functional group represented by the general formula (Formula 1) and the functional group represented by the general formula (Formula 1) and a metal ion. , A functional group represented by the general formula (Formula 2), a functional group containing a chelate skeleton formed by the functional group represented by the general formula (Formula 2) and a metal ion, and a quaternary ammonium group. A quaternary phosphonium group and the above general formula (Formula 3)
It is preferably at least one functional group selected from the functional groups represented by.

Further, in the above-mentioned constitution, the molecules constituting the organic thin film are a mercury chrome derivative, a thimerosal derivative, a phenylmercuric acetate derivative, a quinoform derivative,
At least one derivative selected from an acrinol derivative, an oxyquinoline sulfate derivative, a nitrofurazone derivative, a porphyrin derivative, a phthalocyanine derivative, a porphyrin derivative complexed with a metal ion, and a phthalocyanine derivative complexed with a metal ion is preferable.

In the above structure, the metal ions are Cu ⁺ , Cu ²⁺ , Zn ²⁺ , Ni ²⁺ , Co ²⁺ , C.
o ³⁺ , Co ⁴⁺ , Co ⁵⁺ , Co ⁶⁺ , Fe ²⁺ , Fe ³⁺ , Mn
It is preferably at least one selected from ²⁺ and Mg ²⁺ .

Next, the first method for producing an antibacterial thin film of the present invention comprises a mercury chrome derivative, a thimerosal derivative,
At least one selected from phenylmercury acetate derivatives, quinoform derivatives, acrinol derivatives, oxyquinoline sulfate derivatives, nitrofurazone derivatives, porphyrin derivatives, phthalocyanine derivatives, porphyrin derivatives complexed with metal ions, and phthalocyanine derivatives complexed with metal ions. A molecule having a derivative, the functional group represented by the general formula (Formula 4) in the molecule,
A functional group containing a chelate skeleton formed by a functional group represented by the general formula (Formula 4) and a metal ion, a functional group represented by the general formula (Formula 5), and a functional group represented by the general formula (Formula 5) A functional group containing a chelate skeleton formed of a functional group and a metal ion, a quaternary ammonium group, a quaternary phosphonium group, a functional group represented by the general formula (Formula 6) to (Formula 8),
The molecule having at least one functional group selected from the halogenated sulfonyl group represented by the general formula (Formula 9), the halogenated sulfinyl group represented by the general formula (Formula 10) and the cyano group (—CN) is activated. This is to form a chemisorption film by contacting with a substrate having various hydrogen or alkali metal to cause a low molecular desorption reaction.

Next, in the second method for producing an antibacterial thin film of the present invention, the functional groups represented by the general formulas (Formula 11) to (Formula 12) and the halogenated group represented by the general formula (Formula 13) are used. At least one functional group selected from a sulfonyl group, a halogenated sulfinyl group represented by the general formula (Formula 14) and a cyano group (-CN) is brought into contact with a substrate having active hydrogen or an alkali metal to form a low molecular weight compound. A desorption reaction is performed to form a chemisorption film, and then the chemisorption film is formed with the functional group represented by the general formula (Formula 15), the functional group represented by the general formula (Formula 15), and a metal ion. A functional group containing a chelate skeleton, a functional group represented by the general formula (Formula 16), a functional group containing a chelate skeleton formed by a functional group represented by the general formula (Formula 16) and a metal ion, and a quaternary group. Ammonium group, first -Class phosphonium groups and functional groups represented by the general formula (Formula 17), mercury chrome derivatives, thimerosal derivatives, phenylmercuric acetate derivatives, quinoform derivatives, acrinol derivatives, oxyquinoline sulfate derivatives, nitrofurazone derivatives, porphyrin derivatives, phthalocyanine derivatives, metal ions It forms or introduces at least one functional group selected from a porphyrin derivative complexed with and a phthalocyanine derivative complexed with a metal ion.

Method for producing the first and second antibacterial thin films
In the method, the metal ion is Cu ⁺, Cu²⁺, Z
n²⁺, Ni²⁺, Co²⁺, Co³⁺, Co⁴⁺, Co⁵⁺, Co
⁶⁺, Fe ²⁺, Fe³⁺, Mn²⁺And Mg²⁺Chosen from
It is preferably at least one ion.

[0019]

According to the above-mentioned constitution of the present invention, the molecules constituting the thin film directly or indirectly with the substrate, Si, Ge, S
An organic thin film which is fixed by a covalent bond through at least one atom selected from n, Ti, Zr, S and C. Since the organic thin film has a functional group having antibacterial properties, it is strongly supported as a substrate. It can be a bound antimicrobial film. Further, not only transparency and durability are maintained, but also excellent antibacterial property can be expressed without damaging the surface of the substrate.

Further, according to the preferable constitution of the present invention in which the organic thin film is a monomolecular film or a monomolecular cumulative film, the molecular orientation is good, and film formation and film thickness control on the angstrom order or nanometer level are possible. Or, since the density of the film-constituting molecules can be improved, it is possible to obtain a strong antibacterial thin film having a thinness that has not existed so far.

The functional group having antibacterial properties includes a functional group represented by the general formula (Formula 1) and a chelate skeleton formed by the functional group represented by the general formula (Formula 1) and a metal ion. A functional group, a functional group represented by the general formula (Formula 2),
A functional group having a chelate skeleton formed by a functional group represented by the general formula (Formula 2) and a metal ion, a quaternary ammonium group, a quaternary phosphonium group, and a function represented by the general formula (Formula 3). According to the preferable constitution of the present invention, which is at least one functional group selected from the group, excellent antibacterial properties can be expressed.

Further, the molecules constituting the organic thin film include a mercury chrome derivative, a thimerosal derivative, a phenylmercuric acetate derivative, a quinoform derivative, an acrinol derivative,
According to a preferred constitution of the present invention, it is at least one derivative selected from an oxyquinoline sulfate derivative, a nitrofurazone derivative, a porphyrin derivative, a phthalocyanine derivative, a porphyrin derivative complexed with a metal ion and a phthalocyanine derivative complexed with a metal ion. If so, excellent antibacterial properties can be expressed.

Further, the metal ions are Cu ⁺ , Cu ²⁺ , Z
n ²⁺ , Ni ²⁺ , Co ²⁺ , Co ³⁺ , Co ⁴⁺ , Co ⁵⁺ , Co
According to the preferred constitution of the present invention, which is at least one selected from ⁶⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ and Mg ²⁺ , excellent antibacterial properties can be exhibited.

Next, according to the production method of the present invention, the above-mentioned antibacterial film can be produced efficiently and rationally.

[0025]

EXAMPLES The present invention will be described in more detail below with reference to examples. Mercurochrome is the compound shown in FIG. 1 (a), thimerosal is the compound shown in FIG. 1 (b), phenylmercuric acetate is the compound shown in FIG. 1 (c), and quinoform is the compound shown in FIG. d), and acrinol is the compound shown in FIG. 1 (e),
Oxyquinoline sulfate is the compound shown in FIG. 1 (f), and nitrofurazone is the compound shown in FIG. 1 (g).

The antibacterial thin film of the present invention is firmly fixed to a substrate directly or indirectly through an inner layer film by covalent bonding. Further, in principle, film formation and film thickness control on the angstrom order or nanometer level are possible, resulting in a thin and strong antibacterial thin film that has never existed before.

The term "antibacterial property" as used herein includes, in a broad sense, so-called bactericidal property and bactericidal property. The basic technique of the chemisorption method is described in Journal of American Chemical Society Vol. 102 (1980), page 92 (J.
Sagiv et al. J. Am. Chem. So
c. , 102 (1980), 92. ) And Langmuir Volume 6 (1990) page 851 (K. Ogaw).
a et al. , Langmuir, 6 (199
0), 851. ) Etc. This chemical adsorption method is a method in which a molecule called a chemical adsorbent having a chlorosilyl group is immobilized on a substrate having a hydroxyl group or the like on its surface through a dehydrochlorination reaction.

As the chemical adsorbent, a mercury chrome derivative, a thimerosal derivative, a phenylmercuric acetate derivative,
A molecule having at least one derivative selected from quinoform derivatives, acrinol derivatives, oxyquinoline sulfate derivatives, nitrofurazone derivatives, porphyrin derivatives, phthalocyanine derivatives, porphyrin derivatives complexed with metal ions and phthalocyanine derivatives complexed with metal ions. The functional group represented by the general formula (Formula 1), a functional group containing a chelate skeleton formed by a metal ion with the functional group represented by the general formula (Formula 1), and the general formula ( A functional group represented by the chemical formula 2), a functional group containing a chelate skeleton formed by the functional group represented by the general formula (chemical formula 2) and a metal ion, a quaternary ammonium group, a quaternary phosphonium group, the general formula At least one functional group selected from the functional groups represented by the formula (Formula 3), or A functional group capable of becoming a functional group and represented by the general formulas (Formula 7) to (Formula 8); a halogenated sulfonyl group represented by the general formula (Formula 9); Any molecule having at least one functional group selected from the halogenated sulfinyl group and the cyano group (-CN) represented by 10) may be used. However,
Halogen includes Cl, Br and I. Among them, Cl is preferable from the viewpoint of reactivity, but the same chemisorption monomolecular film and chemisorption monomolecular cumulative film can be obtained even with Br or I.

The above metal ions are Cu ⁺ ,
Cu ²⁺ , Zn ²⁺ , Ni ²⁺ , Co ²⁺ , Co ³⁺ , Co ⁴⁺ , C
Examples include, but are not limited to, o ⁵⁺ , Co ⁶⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ and Mg ²⁺ .

In the general formulas (Chemical Formula 3), (Chemical Formula 6) and (Chemical Formula 17), two of the six carbon atoms of the benzene ring are selected, and each of them is covalently bonded to an S or N atom. However, the para position is particularly effective.

As the substrate for fixing the chemical adsorbent, a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group, a quaternary aluminum group and a quaternary phosphonium are formed on the surface of the substrate. Group, thiol group,
It may be any one having at least one functional group selected from an amino group and a sulfate group. In this case, H in the functional group may be a functional group substituted with an alkali metal or an alkaline earth metal. Further, the substrate may be a chemical adsorption film which is already fixed on the substrate having the functional group and has the functional group on the film.

When the surface of the substrate does not have the above-mentioned functional groups or the number of the functional groups is small, UV / ozone treatment, enzyme plasma treatment, treatment with a compound oxidizer such as potassium permanganate solution is carried out to modify the surface. , Create the functional group,
Or it is effective to increase it.

As a method of fixing the chemical adsorption film to the substrate, a method of bringing the substrate into contact with the liquid and / or gaseous chemical adsorbent, or a method of dissolving the chemical adsorbent on the substrate is used. Examples of the contacting method include, but are not limited to. When the chemical adsorbent is provided as a solution, the solvent used is preferably composed of molecules containing no active hydrogen. For example, when the chemical adsorbent has a long-chain alkyl group, a mixed solvent of hydrocarbons and halogenated carbons is used, and when it has a carbonyl group, halogenated hydrocarbons and aromatics are used. Are suitable, but are not limited to these.

After fixing the chemisorption film on the substrate,
It is preferable to add a step of removing unreacted molecules because a monomolecular film and a monomolecular cumulative film can be easily formed. The solvent used for the washing and removal is preferably an aprotic solvent.
For example, halogenated hydrocarbons, ethers, lactones, esters, nitriles, amides and the like can be mentioned, but not limited to these.

The antibacterial thin film of the present invention will be described in more detail below, including the manufacturing method. However, the present invention is not limited to the following specific examples. (Example 1) First, an adsorption solution A was prepared. Hexadecane, carbon tetrachloride and chloroform in a weight ratio of 80: 1
In a mixed solvent mixed in a ratio of 2: 8, p which is a chemical adsorbent
-Toluenesulfonic acid 8- {4- (5-trichlorosilylpentyl)} quinolinyl was dissolved at a concentration of 1 wt% to prepare an adsorption solution A.

As shown in FIG. 2, the glass substrate 1 was used as a hydrophilic substrate, washed with an organic solvent, and then immersed in the adsorption solution A for 1 hour. After that, the non-aqueous solvent was washed with chloroform for 15 minutes, and then washed with water for 15 minutes, whereby the chemisorption monomolecular film 2 as shown in FIG. 3 was formed over the entire surface of the substrate. This monomolecular film was firmly fixed to the substrate and was rich in hydrophilicity.

The chemisorption monolayer obtained was 292 by Fourier transform infrared absorption (FTIR) spectrum measurement.
5,2840 (Ownership: -CH ₂ -), 1680 (attribution:
C = N), 1620,1500,1450 (attribution: three or more benzene skeleton), 1470 (attributable: -CH ₂ -),
1380 (attribute: O = S = O), 1080 (attribute: Si
The formation of a film was confirmed by obtaining a signal characteristic of this structure at -O) cm ^-1 .

Next, the glass substrate having the chemisorption monomolecular film 2 was lightly rinsed with dilute sulfuric acid, immersed in a 5% copper sulfate aqueous solution for 1 hour, and then washed with water for 15 minutes. After this treatment, it is dried sufficiently and Cu is measured by X-ray spectroscopy (XPS).
Since the signal derived from was obtained, the uptake of Cu ²⁺ could be confirmed. This incorporation is due to the formation of the cation complex chemisorption monomolecular film 3 as shown in FIG.

Next, the antibacterial effect is determined according to a standard method according to Staphylococus aureus.
Was used as a test bacterium by the bacterial count measurement method (bacterial growth inhibition test method specified by the Japan Antimicrobial Society). Staphylococcus aureus cultivated in a liquid medium for enrichment containing 0.25% agar to about 10 ⁵ co / ml, 1 ml of a live bacterial solution was placed in a petri dish, and the chemisorbed monolayer 2 was prepared. The solution was dropped onto a glass substrate, sufficiently spread so as not to fall from the glass substrate, covered with a petri dish, and cultured in a thermostat at 30 ° C. for 1 week. The culturing was stopped by adding 20 ml of sterile saline to the droplets on the glass substrate for dilution. 1 ml of this diluted solution was placed in another Petri dish, and 20 ml of an agar medium for measuring the number of bacteria, which was kept in a liquid state at 45 ° C., was added thereto and uniformly dispersed. After cooling, the cells were cultured at 30 ° C. for 40 days, and the viable cell count was measured. As a result, the viable cell count was 130 cells / g.

Example 2 First, the same chemical adsorption monolayer 2 as in Example 1 was formed on a glass substrate. Next, the glass substrate having this chemisorption monomolecular film 2 was immersed in a 5% iron sulfate aqueous solution for 1 hour, and then washed with water for 15 minutes. After this treatment, it was sufficiently dried and XPS measurement was performed to confirm the uptake of Fe ²⁺ . This incorporation is due to the formation of the cation complex chemisorption monomolecular film 4 as shown in FIG.

Next, the number of viable bacteria was measured using the same assay method as in Example 1. As a result, the viable cell count was 80 cells / g. (Example 3) First, a cation complex chemisorption monomolecular film 3 similar to that of Example 1 was prepared as a 6,6-nylon piece (20 mm x 20 mm).
Formed on. Next, the number of viable bacteria was measured using the same assay method as in Example 1. As a result, the viable cell count was 95 cells / g.

Then, the 6,6-nylon piece having the cation complex chemisorption monolayer 3 was immersed in warm water at 80 ° C. for 10 times.
It was soaked for 1 minute and then soaked in ethanol for 5 minutes.
Then, it stirred in 30 degreeC water for 1 hour. Then, the viable cell count was measured again using the same assay method as in Example 1. As a result, it was confirmed that the viable cell count was 97 cells / g, which was not much different from that of Example 1, and that the effect was not changed before and after washing.

After the same washing, the same test was conducted twice a day for 10 days, and the results shown in Table 1 were obtained.

[0044]

[Table 1]

Example 4 First, an adsorption solution B was prepared. Hexadecane, carbon tetrachloride and chloroform were mixed at a weight ratio of 80: 12: 8 to prepare a chemical adsorbent shown in FIG. 6 dissolved at a concentration of 1 wt%, which was designated as adsorption solution B. did.

A glass substrate 1 was used as a hydrophilic substrate similar to that in Example 1, washed with an organic solvent, and then adsorbed on solution B.
Let it soak for an hour. Then, the non-aqueous solvent was washed with chloroform for 15 minutes, and then washed with water for 15 minutes to form a chemisorption monomolecular film 5 as shown in FIG. 7 over the entire surface of the substrate. This monomolecular film was firmly fixed to the substrate and was rich in hydrophilicity.

The chemisorption monolayer obtained was 292 by Fourier transform infrared absorption (FTIR) spectrum measurement.
5,2840 (Ownership: -CH ₂ -), 1680 (attribution:
C = N), 1620,1500,1450 (attribution: three or more benzene skeleton), 1470 (attributable: -CH ₂ -),
The formation of a film was confirmed by obtaining a signal characteristic of this structure at 1380 (attribute: O = S = O) cm ⁻¹ .

Next, the glass substrate having the chemisorption monomolecular film 4 was dipped in a 5% copper sulfate aqueous solution for 1 hour and then washed with water for 15 minutes. After this treatment, dry thoroughly and X
By obtaining the signal derived from Cu by PS measurement, Cu
²⁺ uptake was confirmed. This incorporation is due to the cation complex chemisorption monomolecular film 6 as shown in FIG. Next, the number of viable bacteria was measured using the same assay method as in Example 1. As a result, the viable cell count was 92 cells / g.

(Embodiment 5) First, a cation complex chemisorption monolayer 5 similar to that of Embodiment 4 was prepared with 6,6-nylon pieces (20).
mm × 20 mm). Next, the number of viable bacteria was measured using the same assay method as in Example 1. As a result, the viable cell count is 9
It was 8 co / g. Then, the 6,6-nylon piece having this cation complex chemisorption monomolecular film 5 was immersed in warm water at 80 ° C. for 10 minutes, and then immersed in ethanol for 5 minutes. Then, it stirred in 30 degreeC water for 1 hour. And
The number of viable bacteria was measured again using the same assay method as in Example 1. As a result, the viable cell count was 100 cells / g.
It was confirmed that the effect was not significantly different from that before and after washing. Further, when the same test as in Example 3 was performed, the results shown in Table 2 were obtained.

[0050]

[Table 2]

From the above five examples, these chemical absorptions are
It has been clarified that the deposited monolayer has a bacterial growth inhibitory effect.
It was. In addition, in this example, the membrane-constituting molecule is immobilized on the substrate.
The functional groups for
Although it is shown that it is a finyl group, in the other claims,
Even when using the halogenated sulfonyl group etc. described
An antibacterial thin film with the same effect can be formed. Furthermore
In this example, the functional group having antibacterial property is Cu. ²⁺And
And Fe²⁺When it is a quinolinyl group that forms a complex with
However, the Ni described in the other claims is²⁺Etc.
Even if it is, it is possible to form an antibacterial thin film with the same effect.
Wear.

As described above, the practicality of the antibacterial thin film of this embodiment is extremely high. The thin film of this example can be formed as long as hydrogen, an alkali metal or an alkaline earth metal which is active in principle is present on the surface of the substrate. In addition, the antibacterial thin film of this embodiment can be used for applications where it could not be done due to various circumstances. For example, the antibacterial thin film of the present embodiment is more suitable for medical devices and the like in terms of stability and film thickness than using any other material.

Further, the odor is generated from the clothes which come into direct contact with the skin, because the socks and the underwear directly absorb the sweat from the skin surface, and the bacteria and air which constitute the flora (normal fungus) on the skin are absorbed there. This is caused by the gas that is emitted when bacteria that float inside adhere to it and propagate as sweat and waste products as nutrients.
Since recent garments are rich in stretchability, odor is particularly noticeable. Although it depends on the type of bacteria, most of the generated gas is aversive. If the antibacterial property is realized, it may be possible to exhibit the deodorant property at the same time. Furthermore, glycolic acid, lactic acid, citric acid, silicic acid, acetic acid, oxalic acid and the like produced by the metabolism of bacteria also cause discoloration of the fiber, and at the same time, they may also exhibit discoloration resistance. From the above, the range of use is extremely wide.

[0054]

As described above, according to the present invention, a thin and strong antibacterial thin film can be efficiently and rationally manufactured. Furthermore, it is possible to provide an antibacterial thin film which exhibits a great effect in terms of antibacterial property and durability, as compared with the antibacterial effect obtained by the conventional method.

[Brief description of drawings]

FIG. 1 is a skeleton on which the chemical adsorbent of the present invention is based. (A) Mercurochrome skeleton (b) Thimerosal skeleton (c) Phenylmercury acetate skeleton (d) Quinoform skeleton (e) Acrinol skeleton (f) Oxyquinoline sulfate skeleton (g) Nitrofurazone skeleton

FIG. 2 is an enlarged view of a main part of a glass substrate according to an embodiment of the present invention.

FIG. 3 is an enlarged view of a main part of a chemisorption monolayer according to an embodiment of the present invention.

FIG. 4 is an enlarged view of a main part of the chemisorption monolayer according to the embodiment of the present invention.

FIG. 5 is an enlarged view of a main part of a chemisorption monolayer according to another embodiment of the present invention.

FIG. 6 is a chemical adsorbent according to another embodiment of the present invention.

FIG. 7 is an enlarged view of a main part of a chemisorption monolayer according to another embodiment of the present invention.

FIG. 8 is an enlarged view of an essential part of a chemisorption monolayer according to another embodiment of the present invention.

[Explanation of symbols]

 1 glass substrate 2,3,4,5,6 chemisorption monolayer

Claims (8)

[Claims] 1. The molecules constituting the thin film directly or indirectly with the substrate are Si, Ge, Sn, Ti, Zr, S and C.
An organic thin film fixed by a covalent bond through at least one atom selected from the above, wherein the organic thin film has a functional group having antibacterial properties in the molecule. 2. The antibacterial thin film according to claim 1, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film. 3. A functional group having antibacterial properties, a functional group represented by the general formula (Formula 1), and a chelate skeleton formed by the functional group represented by the general formula (Formula 1) and a metal ion. Group, a functional group represented by the general formula (Formula 2), a functional group containing a chelate skeleton formed by the functional group represented by the general formula (Formula 2) and a metal ion, a quaternary ammonium group, a quaternary group The antibacterial thin film according to claim 1 or 2, which is at least one functional group selected from a phosphonium group and a functional group represented by the general formula (Formula 3). [Chemical 1] [Chemical 2] [Chemical 3] 4. A molecule forming an organic thin film forms a complex with a merculochrome derivative, a thimerosal derivative, a phenylmercury acetate derivative, a quinoform derivative, an acrinol derivative, an oxyquinoline sulfate derivative, a nitrofurazone derivative, a porphyrin derivative, a phthalocyanine derivative, and a metal ion. The antibacterial thin film according to claim 1 or 2, which is at least one derivative selected from the porphyrin derivative and the phthalocyanine derivative complexed with a metal ion. 5. The metal ion is Cu ⁺ , Cu ²⁺ , Z
n ²⁺ , Ni ²⁺ , Co ²⁺ , Co ³⁺ , Co ⁴⁺ , Co ⁵⁺ , Co
The antibacterial thin film according to claim 3 or 4, which is at least one selected from ⁶⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ and Mg ²⁺ . 6. Mercurochrome derivatives, thimerosal derivatives, phenylmercuric acetate derivatives, quinoform derivatives,
A molecule having at least one derivative selected from an acrinol derivative, an oxyquinoline sulfate derivative, a nitrofurazone derivative, a porphyrin derivative, a phthalocyanine derivative, a porphyrin derivative complexed with a metal ion and a phthalocyanine derivative complexed with a metal ion, A functional group represented by the general formula (Formula 4) in the molecule, a functional group containing a chelate skeleton formed by the functional group represented by the general formula (Formula 4) and a metal ion, represented by the general formula (Formula 5) A functional group containing a chelate skeleton formed by the functional group represented by the general formula (Formula 5) and a metal ion, a quaternary ammonium group, a quaternary phosphonium group, or a general formula (Formula 6). Functional group shown, general formula (Chemical Formula 7)
A functional group represented by, a functional group represented by the general formula (Formula 8),
A halogenated sulfonyl group represented by the general formula (Formula 9),
A molecule having at least one functional group selected from a halogenated sulfinyl group and a cyano group (-CN) represented by the general formula (Formula 10) is brought into contact with a substrate having active hydrogen or an alkali metal to remove a low molecular weight compound. A method for producing an antibacterial thin film which forms a chemisorption film by a separation reaction. [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] 7. A functional group represented by the general formula (Formula 11), a functional group represented by the general formula (Formula 12), a halogenated sulfonyl group represented by the general formula (Formula 13), and a general formula (Formula 14).
By contacting at least one functional group selected from a halogenated sulfinyl group and a cyano group (-CN) with a substrate having active hydrogen or an alkali metal,
A low molecular weight desorption reaction is performed to form a chemisorption film, and then the chemisorption film is formed of a functional group represented by the general formula (Formula 15), a functional group represented by the general formula (Formula 15) and a metal ion. A functional group containing a chelate skeleton, a functional group represented by the general formula (Formula 16), a functional group containing a chelate skeleton formed by the functional group represented by the general formula (Formula 16) and a metal ion, quaternary Ammonium group, quaternary phosphonium group and functional group represented by the general formula (Formula 17), Mercurochrome derivative, thimerosal derivative, phenylmercuric acetate derivative, quinoform derivative, acrinol derivative, oxyquinoline sulfate derivative, nitrofurazone derivative, porphyrin derivative, phthalocyanine Derivatives, porphyrin derivatives complexed with metal ions and phthalocyanines complexed with metal ions At least one method of producing an antimicrobial film forming or introducing a functional group selected from Nin derivatives. [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] [Chemical 17] 8. The metal ion is Cu ⁺ , Cu ²⁺ , Z
n ²⁺ , Ni ²⁺ , Co ²⁺ , Co ³⁺ , Co ⁴⁺ , Co ⁵⁺ , Co
^The method for producing an antibacterial thin film according to claim 6 or 7, which is at least one selected from ⁶⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ and Mg ²⁺ .