JPH0686571B2 - Antibacterial / conductive composition and antibacterial / conductive resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antibacterial / conductive composition and an antibacterial / conductive resin composition using this composition, and more specifically to a resin, rubber or paint. Addition to ink, adhesive, backing agent, cement, gypsum, paper, fiber or cosmetics and other materials, antibacterial, antifungal, antialgal, conductive,
For imparting deodorizing property, it has small coloring property, good dispersibility, and also has good heat resistance and chemical resistance so that it does not discolor, has no elution and is excellent in abrasion resistance, weather resistance, etc. The present invention relates to an antibacterial / conductive composition that forms very large particles and an antibacterial / conductive resin composition containing the antibacterial / conductive composition.

[Conventional technology]

Conventionally, various antibacterial agents using heavy metals have been developed, but there are problems of heat resistance and residual acid radicals due to the use of antibacterial metal salts, especially discoloration during addition to resin, generation of gas, influence of pH There was such a problem. This is a phenomenon that occurs because a metal salt such as silver nitrate, silver sulfate, or copper (II) nitrate is used. This tendency is particularly strong in silver nitrate, which is said to have excellent antibacterial properties, and improvement of this problem has been desired.

[Problems to be Solved by the Invention]

The present invention has been made against the background of the problems of the prior art, and is safer by using colloidal silver that has a very excellent bactericidal power for imparting antibacterial properties and hardly harms the human body. The property can be secured, and discoloration due to heat, acid, etc. can be prevented, and since the pH becomes neutral, obstacles to it can be eliminated. In addition, since it contains ultrafine particles of silver, it has excellent conductivity, and when it is used as a resin, it is possible to permanently prevent electrification.

INDUSTRIAL APPLICABILITY The present invention has a strong bactericidal activity against a wide range of bacteria such as bacteria, fungi, or algae in a low and high humidity atmosphere, has good heat resistance, does not discolor even at 500 ° C., and is dispersed. Good, good elution, low coloring power, hardness,
Provided are an antibacterial / conductive composition which is excellent in water resistance, chemical resistance, weather resistance, etc., and is a conductive fine particle having a large surface area, and an antibacterial / conductive resin composition containing the antibacterial / conductive composition. The purpose is to

[Means for Solving the Problems]

The present invention provides (a) a tetraalkoxysilane represented by the general formula Si (OR ¹ ) ₄ (wherein R ¹ represents a hydrocarbon residue having 1 to 5 carbon atoms) and a general formula R ² Si (OR ³ ) ₃ from an organoalkoxysilane represented by the formula (R ² represents an organic group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms) 3 to 50% by weight in terms of solid content of at least one selected organosilicon compound, (b) 0.05 to 5% by weight in terms of silver component of colloidal silver, and (c) colloidal silica, colloidal alumina, silica gel, zeolite, An antibacterial / conductive composition containing activated carbon, ultrafine particles, and at least one inorganic compound selected from the group consisting of silica, alumina and titania as the main component in an amount of 10 to 90% by weight in terms of anhydrous form.

Further, the present invention is an antibacterial / conductive resin composition containing 0.02 to 30% by weight of the antibacterial / conductive composition.

The present invention has a strong bactericidal activity, and unlike silver nitrate, it has little harm to the human body, is electrically conductive, and has heat resistance, corrosion resistance, and
The ultrafine particle silver of colloidal silver, which has excellent durability, is attached to an inorganic compound having a large surface area, and it is fixed by an organic silicon compound to maximize antibacterial and electroconductivity. .

The present invention will be described below for each constituent element.

(A) Organosilicon Compound The organosilicon compound used in the present invention is represented by, for example, the general formula Si (OR ¹ ) ₄ (in the formula, R ¹ represents a hydrocarbon residue having 1 to 5 carbon atoms). Tetraalkoxysilane and / or the general formula R ² Si (OR ³ ) ₃ (wherein R ² has 1 carbon atom)
~ 8 organic group, R ³ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. ) Organoalkoxysilanes represented by

These organosilicon compounds are hydrolyzed in the presence of water to form a hydrolyzate, and the hydrolyzate is polycondensed to form a partial condensate, which is further polymerized into a gel. As the organosilicon compound of the present invention, these hydrolyzates and partial condensates can also be used. Further, the organosilicon compound may be hydrolyzed in the presence of a mixed liquid of colloidal silver and an inorganic compound, and in this case, the resulting composition is a gel-like material containing the inorganic compound having a silver component. .
When this gel-like material is further heated, a gel which is a complete condensate is produced.

Thus, in the present invention, the organosilicon compound functions as a binder while forming a gel-like material.

Here, R ¹ in the tetraalkoxysilane is an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Specific examples of these tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

R ² in the organoalkoxysilane is an organic group having 1 to 8 carbon atoms, such as a methyl group,
Alkyl groups such as ethyl group and propyl group, and γ-
Chloropropyl group, vinyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group , Γ-aminopropyl group and the like.

In addition, R ² in the organoalkoxysilane has 1 to 1 carbon atoms.
An alkyl group having 5 or an acyl group having 1 to 4 carbon atoms,
For example, a methyl group, an ethyl group, a propyl group, a butyl group, an acetyl group and the like.

Specific examples of these organoalkoxysilanes include:
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ- Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyl Examples thereof include triethoxysilane, γ-aminopropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, and 3,4-epoxycyclohexylethyltriethoxysilane.

These organoalkoxysilanes may be used either individually or in combination of two or more.

Of these organosilicon compounds, tetraethoxysilane and methyltrimethoxysilane are preferable.

The proportion of the organosilicon compound in the antibacterial / conductive composition is 3 to 50% by weight, especially 5 to 25% by weight, in terms of solid content.
If it is less than 3% by weight, the binding force is insufficient to elute, and it is not easily hydrolyzed and the productivity is lowered.
If it exceeds 5% by weight, antibacterial properties and electrical conductivity are difficult to be expressed, and the amount of inorganic compounds is relatively small, which is not preferable.

(B) Colloidal silver Colloidal silver is yellow or reddish brown aqueous colloidal silver, and is used as an antibacterial agent and a conductive agent in the present invention.

Since this colloidal silver has a very large bactericidal power and has almost no harm to the human body, it has been widely used for treatment and prevention since ancient times.

It is well known that the silver component of colloidal silver is the most excellent conductor among metals.

Further, silver has excellent heat resistance, good corrosion resistance in the atmosphere, and excellent durability.

Such colloidal silver can be easily prepared by a known method of reducing a metal salt of silver. For example, dilute ammonia water is added to an aqueous solution of silver nitrate to make silver oxide, and then ammonia water is added to form a complex salt, which is diluted with water and then added with an aqueous solution of oxalic acid or tannic acid as a reducing agent and heated. There is a way to do it. Further, as a reduction method, there are a hydrogen, carbon, or carbon monoxide reduction method, a method using an alkali metal, and other known methods.

This colloidal silver usually has a silver content of 0.02 to 1% by weight,
The particle size is 50 mμ or less, the pH is 7.0 ± 1.0, preferably the silver component is 0.05 to 0.2% by weight, and the particle size is 10 mμ or less.

The sterilizing power of silver tends to increase as the particles become finer.

The ratio of colloidal silver to the antibacterial / conductive composition of the present invention is preferably 0.05 to 5% by weight, and particularly preferably 0.1 to 1% by weight in terms of silver component. If it is less than 0.05% by weight, it is difficult to develop antibacterial properties and electroconductivity, while if it exceeds 5% by weight, the color is deep and the coloring property is increased, and the processing is too time-consuming, which is not preferable.

(C) Inorganic compound As the inorganic compound of the present invention, at least one compound selected from the group consisting of colloidal silica, colloidal alumina, silica gel, zeolite, activated carbon, ultrafine particles of silica, alumina and titania is preferably used. .

These inorganic compounds are used to maximize the antibacterial and electroconductivity of silver by adhering the silver component (b) having an average particle size of colloidal silver of about 5 mμ to the surface of an inorganic compound having a large surface area. It is intended.

Next, the inorganic compound used in the present invention will be described for each component.

(Colloidal Silica and Colloidal Alumina) Colloidal silica is a colloidal solution in which ultrafine particles of silicic acid anhydride are dispersed in water or alcohol using water or alcohol as a dispersion medium, and the particle size thereof is 5 to 50 mμ.
Moreover, its appearance is a transparent milky white colloidal liquid.

Colloidal alumina is an alumina sol having a pH of 2.5 to 6 with water as a dispersion medium, containing 5 to 25% by weight of alumina,
An acid such as nitric acid, hydrochloric acid or acetic acid is used as a stabilizer and has an average particle size of 10 to 200 mμ.

(Silica gel) Silica gel is a compound represented by the general formula SiO ₂ · nH ₂ O,
The glass-like transparent or translucent particles have a fine structure with a rough show, for example, 1 g has a large surface area of 450 m ² or more.

(Zeolite) The zeolite in the present invention is a natural or synthetic zeolite and has a general formula xM _{2 / n} O · Al ₂ O ₃ · ySiO ₂ · zH ₂ O (wherein M represents an ion-exchangeable metal ion, Is a monovalent to divalent metal, n is this valence, x is the coefficient of the metal oxide, y is the coefficient of silica, and z is the number of crystal water, respectively) And pore size,
There are many different types such as specific surface area.

For example, natural zeolites include anarsine, chabazite, clinoptilolite, erionite, faujasite, mordenite and the like, while synthetic zeolites include A-type zeolite, X-type zeolite, Y-type zeolite.
Type zeolite and the like.

Zeolite having a large surface area and excellent adsorption ability is preferable, and natural mordenite or the above synthetic zeolite is preferable.

(Activated carbon) Activated carbon is a carbon substance obtained by carbonizing an organic substance, is black particles, has a special porous structure, and is excellent in adsorptivity.

(Ultrafine particle silica, alumina, titania) The present inorganic compound is an ultrafine particle silica produced by a high temperature hydrolysis method of a refined metal salt, an ultrafine particle alumina, or an ultrafine particle titania (both in West Germany. , Manufactured by Degussa) are preferably used.

This has a specific surface area (BET method) of 40 to 400 m ² / g, and an average particle size of primary particles of 7 to 40 mμ.

These inorganic compounds are preferably contained in the antibacterial / conductive composition of the present invention in an amount of 10 to 90% by weight, particularly 40 to 80% by weight, in terms of anhydrous content.

If it is less than 10% by weight, the amount of the substance supporting the colloidal silver component is reduced and the productivity is deteriorated. On the other hand, if it exceeds 90% by weight, the silicon compound is relatively reduced and the bonding strength is weakened. Further, the antibacterial effect is weakened, which is not preferable.

The antibacterial / conductive composition of the present invention is obtained by using an organic silicon compound, colloidal silver and an inorganic compound as main components,
It is preferable to hydrolyze the organosilicon compound in the presence of colloidal silver and an inorganic compound. At this time, the organosilicon compound is uniformly mixed with water, and a hydrophilic organic solvent is used as a regulator for uniformly promoting the hydrolysis. It is more preferred to use.

The hydrophilic organic solvent is a dispersion medium for colloidal silver and an inorganic compound, and in order to prevent the organosilicon compound from being extremely gelated when hydrolyzed by water, a condensation reaction of other hydrolysates is performed. It is for azeotropically distilling off water while controlling.

As the hydrophilic organic solvent, monohydric alcohol or 2
Mention may be made of ethylene glycol which is a polyhydric alcohol or a derivative thereof. Among them, a monohydric alcohol is preferably a lower aliphatic alcohol having 1 to 5 carbon atoms,
Specific examples thereof include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, sec-butyl alcohol and t-butyl alcohol,
Examples of ethylene glycol or a derivative thereof include ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate.

These hydrophilic organic solvents are preferably i-propyl alcohol, sec-butyl alcohol and ethylene glycol monoethyl ether acetate. These hydrophilic organic solvents may be used alone or in combination of two or more.

The proportion of the hydrophilic organic solvent in the composition is 20 to 500 parts by weight, particularly 50 to 150 parts by weight based on 100 parts by weight of the organosilicon compound.
If the amount is less than 20 parts by weight, it is difficult to uniformly mix the organosilicon compound with water.On the other hand, if it exceeds 500 parts by weight, other components are relatively less, resulting in poor performance or poor productivity. It is not preferable.

When preparing the antibacterial / conductive composition of the present invention,
The presence of water is necessary to hydrolyze the organosilicon compound.

As the water, water present in the (b) colloidal silver is usually used, and when water-based colloidal silica or colloidal alumina is used as the inorganic compound, this water can be used. Distilled water or ion-exchanged water can be used.

The proportion of water in the composition is 25 to 2,000 parts by weight, particularly preferably 50 to 800 parts by weight, relative to 100 parts by weight of the organosilicon compound, and if less than 25 parts by weight, hydrolysis of the organosilicon compound does not sufficiently occur. On the other hand, if it exceeds 2,000 parts by weight, the adhesiveness is lowered and the productivity is deteriorated, which is not preferable.

The antibacterial / conductive composition of the present invention may contain a filler or an acid, if necessary, in addition to the above-mentioned components.

Here, the filler is used to impart cosmetic properties, heat radiation properties, and the like, and is, for example, an organic pigment or an inorganic pigment.

The acid is used as a hydrolysis catalyst, and examples thereof include nitric acid, hydrochloric acid, acetic acid, maleic acid, other inorganic acids and organic acids.

Further, the antibacterial / conductive composition of the present invention may be added with other conventionally known additives such as various surfactants, coupling agents, chelating agents, alkali metal salts (curing catalysts) and dyes. .

The antibacterial / conductive composition of the present invention is prepared by first preparing colloidal silver, mixing it with an inorganic compound, a hydrophilic organic solvent and an organic silicon compound and aging to prepare a gel-like material, and heating it. It can be prepared by drying.

As a specific example of preparation of the antibacterial / conductive composition of the present invention, for example, colloidal silver is prepared by adding a 3% by weight aqueous solution of ammonia to a 1% by weight aqueous solution of silver nitrate and gradually dissolving the precipitated silver oxide. Add. This aqueous solution is diluted with water 19
After doubling the dilution, add a few drops of a 3 wt% aqueous solution of tannic acid and warm it to room temperature or 40 to 60 ° C to prepare. To this colloidal silver, colloidal silica, colloidal alumina or alcohol, water, etc. are added, and further silica gel, zeolite, activated carbon, ultrafine particle silica, alumina, titania, etc. are added and mixed, and the mixed solution thus prepared is added. Mix an organosilicon compound such as an organoalkoxysilane and stir at 1,000 rpm for about 30 minutes.

This is aged at room temperature or low temperature for about 6 hours to prepare a hydrogel, and the hydrogel obtained is dried by heating and finally pulverized with a ball mill or the like to give the antibacterial / conductive gel (composition) of the present invention. Obtainable.

The average particle size of the antibacterial / conductive gel of the present invention thus obtained is not particularly limited, but may be, for example, 0.01
Is about 2 μm, preferably 0.02 to 0.1 μm. When colloidal silica, colloidal alumina, fine particles of silica, alumina or titania is used as the inorganic compound (c) of the present invention, the average particle diameter is 0.01 to 0.
When the silica gel, zeolite or activated carbon is used as the inorganic compound (c), it becomes about 1 μm and is 0.05 to 2
It will be about μm.

INDUSTRIAL APPLICABILITY The antibacterial / conductive composition of the present invention can be used over a wide range, for example, it is mixed as an additive in all organic and inorganic coatings to add various functions such as antibacterial / antifungal, antialgal, and antistatic. It is possible.

Further, antibacterial properties, deodorizing properties, and other functions described above can be added by mixing with ink, adhesive, backing agent, cement, gypsum, or the like, or by squeezing into the paper in the papermaking field.

Furthermore, by using the composition of the present invention for medicines and cosmetics, antibacterial properties, ultraviolet absorption properties and the like can be added. Moreover, the antibacterial / conductive composition of the present invention can be formed into ultrafine particles, has a small oil absorption (water) ratio, and has excellent dispersibility, so that it can be uniformly dispersed in various materials described above and even in a small amount. Antibacterial and various other functions are uniformly expressed.

Furthermore, it can be made transparent because it has a very small coloring power.

Further, the antibacterial / conductive composition of the present invention can be used as a coating composition. For example, a film, a fiber, a plate, a container, or other surface of a resin molded article of any shape is coated with a conductive material (antistatic).・ It is possible to obtain antibacterial resin products. In addition, antibacterialization of natural fiber, paper or metal; production of conductive glass, anti-fog glass or conductive ceramics; use for production of antibacterial cement material, antibacterial / antistatic leather or antibacterial sand You can

Next, the antibacterial / conductive resin composition of the present invention is
The conductive composition is contained in a resin.

The antibacterial / conductive resin composition has permanent antibacterial / antifungal properties, and can impart antistatic property to impart permanent antistatic properties. In addition to this, it is possible to contribute to the prevention of dew condensation by improving the moisture absorption and drying properties.

This resin includes acrylic resin, vinyl chloride resin, polyvinylidene chloride, ABS resin, epoxy resin, urethane resin, polyamide, polyester, polyethylene, polypropylene, polystyrene, polyacetal, polyvinyl alcohol, polycarbonate, fluororesin, polyester elastomer, polyamide elastomer. , Phenol resin, unsaturated polyester resin, melamine resin, urea resin, diacetate, triacetate, cupra,
Thermoplastic or thermosetting resins such as rayon, natural rubber, styrene-butadiene rubber, butadiene rubber, polyisoprene and synthetic rubber such as chloroprene rubber can be mentioned.

The mixing of the antibacterial / conductive composition into the resin is carried out by mixing the raw material monomers or reaction intermediates and then polymerizing,
Examples of the method include, but are not limited to, a method of kneading with a polymer after completion of polymerization, a method of mixing with polymer pellets, a method of mixing with a molding dope, and the like.

The proportion of the antibacterial / conductive composition in the antibacterial / conductive resin composition is usually 0.02 to 30% by weight, particularly preferably 0.5 to 10% by weight, and if less than 0.02% by weight, antibacterial properties and conductivity are expressed. On the other hand, if it exceeds 30% by weight, the characteristics of the resin are lost and the cost rises too much, which is not preferable.

The antibacterial / conductive resin composition thus obtained can be formed into various forms, for example, films, fibers, plates, containers, granules, and the like. For example, household products (apparatus for cooking, baths, etc.) ), Building materials, wraps, pipes, agricultural bags and films, all textile products (clothes, socks, underwear,
Handkerchiefs, towels, bedding, etc.) and all other industrial fields.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the scope of the claims.

In the examples, parts and% are based on weight unless otherwise specified.

Reference Example In order to investigate antibacterial properties, antifungal properties, electrical conductivity, heat resistance, non-elution property, etc., 6 kinds of compounds A to F shown in Table 1 and a compound G were prepared as comparative examples.

Here, the compound A is 300 parts of colloidal silver-1, 300 parts of water and 130 parts of isopropanol in a stainless steel container.
Part and 70 parts of aqueous colloidal silica (pH; 2.5), and after light stirring, 20 parts of ultrafine particulate alumina and 80 parts of silica gel
The mixture was put in and stirred for about 10 minutes. The mixture is heated for 1 hour to form a concentrated solution, and then methyltrimethoxysilane is added to 100%.
Then, the mixture was stirred for about 10 minutes and aged for 5 hours at room temperature.

Then, this was heated at 300 ° C. for 2 hours to prepare a dry gel. The dried gel was crushed with a ball mill for 2 hours to prepare an antibacterial / conductive gel.

Formulations B-F and Formulation G were made similarly.

Table 2 shows the average diameter, specific surface area, apparent specific gravity, and silver content of the primary particles of the antibacterial / conductive gel thus obtained. The average diameter of the primary particles was measured by an electron microscope photograph of 50,000 times, the specific surface area was measured by the BET method, the apparent specific gravity was measured by the weight per unit, and the silver content was measured by the quantitative analysis.

Example 1 In order to examine the antibacterial activity of the antibacterial / conductive composition, the antibacterial / conductive gel shown in Table 2 was used as a test piece, and the minimum inhibitory concentration against these bacteria was measured.

As a test method, the minimum growth inhibitory concentration was defined as the lowest concentration at which growth was inhibited after inoculating and culturing a liquid medium containing a test piece at an arbitrary concentration.

The medium for enrichment was Mueller Hinton Broth (manufactured by Difco), and the medium for measurement was Muel with 0.05% Triton X-100.
ler Hinton Broth (manufactured by Difco), measuring medium 10 ml
After adding an arbitrary amount of the test piece, it was sterilized to obtain a sensitivity measurement medium.

For the inoculum bacterial solution, subculture the test solution in contact with the enrichment medium, incubate at 37 ° C for 18 to 20 hours, and in the enrichment medium so that the number of bacteria is about 10 ⁶ / ml. Diluted and prepared, the culture is made by adding 0.1 ml of bacterial solution for inoculation to the medium for sensitivity measurement, and
Shake culture was performed for 2 days.

The test results are shown in Table 3-1.

In addition, in order to examine the antibacterial activity of the antibacterial / conductive composition, A ', B', among the antibacterial / conductive gels in Table 2 were used.
The three C's were immersed in tap water for 30 days, then boiled for 2 hours and dried at room temperature.

Using this, the minimum inhibitory concentration against bacteria was measured by the above-mentioned test method.

The test results are shown in Table 3-2.

Example 2 In order to investigate the antibacterial activity of the antibacterial / conductive resin composition, antibacterial / conductive gel was added to and mixed with the resin to prepare test pieces of various antibacterial / conductive resin compositions. The creation method is as follows.

(1) Film: Created by an inflation molding method.

(2) Square plate: Created by the compression molding method.

(3) Woven fabric: Melt-spun and drawn according to a conventional method, and the drawn yarn was scoured and woven.

(4) Coating film: An antibacterial / conductive gel was added to a vinyl acetate paint, mixed, and applied to an aluminum plate.

Coating film: An antibacterial / conductive gel was added to a urethane resin-based paint, mixed, and applied to the shoe skin.

Table 4 shows the contents of the test piece.

In Table 4, the unit of the addition amount of the antibacterial / conductive gel is%.

Next, an antibacterial activity test was conducted using the test pieces 1 to 16 shown in Table 4.

The test method is as follows.

Escherichia coli IFO 3301 (Escherichia coli), Staphylococcus aureus IFO 12732 (Staphylococcus aureus), Aspergillus niger IFO 4407 (Koji mold) were added dropwise to the test piece, and the bacteria were stored at 37 ℃ and the fungus was stored at 30 ℃. After 6 and 24 hours, bacteria were washed out from the test piece with SCDLP liquid medium and bacteria with GPLP liquid medium, and the washings were used as test solutions.

The number of surviving cells of this test solution was measured by the pour plate culture method (bacteria: 37 ° C for 2 days, fungus: 25 ° C for 7 days) using a culture medium for measuring the number of viable cells per test piece. did.

The test results are shown in Table 5-1 (use bacteria name: E. coli), No. 5
Table-2 (use bacteria name: Staphylococcus aureus) and Table 5
3 (name of bacterium used: black koji mold).

Example 3 In order to investigate the conductivity of the antibacterial / conductive composition of the present invention, a 30 × 10 × 5 mm test piece was prepared by pressing at 100 kg / cm ² using various antibacterial / conductive gels shown in Table ^2. Then, the volume specific resistance value (Ω · cm) of this test piece was measured.

The surface resistance value (Ω · cm) was measured by selecting from the test pieces in Table 4.

The results are shown in Table 6.

Example 4 In order to examine the insolubility of the antibacterial / conductive composition of the present invention and the antibacterial property in water, an antibacterial / conductive gel B ′ shown in Table 2 was used to perform a test by the following method.

(No elution) Chloride ions, organic substances (potassium permanganate consumption), general bacteria, coliforms, copper, iron using the test method of the water quality standard of the Water Supply Act (Ministry of Health and Welfare Ordinance No. 56 of 1978) , Silver, lead, cadmium, pH value and turbidity were measured.

Test water is prepared by adding 200 g of antibacterial / conductive gel to tap water 4
The sample was immersed in the solution, allowed to stand at room temperature, and a supernatant was collected after 24 hours. As a control, the same tap water was stored under the same conditions, and the whole amount was collected after 24 hours.

The test results are shown in Table 7-1.

(Antibacterial property in water) Antibacterial / conductive gel B'in Table 2 and G'as a comparative example
To 2% (weight / volume) of deionized water,
erichia coli IFO 3301 or Pseudomonas
aeruginosa IFO 13275 (Pseudomonas aeruginosa)
It was stored at 0 ° C., and the viable cell count was measured after 6 and 24 hours.

The bacterial count was measured by the pour plate culture method using a standard agar medium.

The culture was carried out at 35 ° C for 48 hours.

The test results are shown in Table 7-2.

However, in the table, "1 or less" means that no bacterium was detected because it was due to the measurement limit of the microbial count method used in this test.

Example 5 In order to examine the heat resistance, boiling water resistance, and chemical resistance of the antibacterial / conductive composition of the present invention, two kinds of antibacterial / conductive gels B'and D'in Table 2 were used. The test was carried out by the method of.

Further, in order to examine the antibacterial activity using the gel, the minimum inhibitory concentration against bacteria was measured by the same method as in Example 1.

(Heat resistance) Put the test piece in an electric furnace and store it at 500 ℃ for 3 hours.
The appearance was observed.

(Boiling resistance) A test piece of 2% (weight / volume) was placed in tap water and boiled for 3 hours, and the appearance was observed.

In addition, boiling water of tap water was injected as needed as the same amount of water as the evaporated water.

(Chemical resistance) (1) A test piece of 2% (weight / volume) was mixed in a mixed solution of toluene, xylene, methyl ethyl ketone, acetone, and ethyl acetate, and immersed for 24 hours.

(2) A test piece of 2% (weight / volume) was mixed in a 2% nitric acid solution and immersed for 24 hours.

(3) A test piece of 2% (weight / volume) was mixed in a 2% caustic soda solution and immersed for 24 hours.

The appearance of the test pieces of (1), (2), and (3) above was observed.

The test results are shown in Table 8 and the measurement results of the minimum inhibitory concentration of the test piece against bacteria are shown in Table 8-2.
Shown in.

[Effects of the Invention] As described above, the main features of the antibacterial / conductive composition and the antibacterial / conductive resin composition of the present invention are as follows.

(1) An excellent antibacterial performance is maintained for a long period of time against general bacteria and mold.

(2) The performance of silver, which is a good conductor, is maintained for a long time.

(3) Antibacterial properties and electroconductivity (antistatic properties) can be obtained by adding a small amount to resins and rubbers, resin-based paints and inks, adhesives, joints and backing materials.

(4) Antibacterial and conductive properties can be obtained by adding a small amount to cement, an inorganic coating agent, gypsum, paper, cosmetics and other materials.

(5) It has excellent heat resistance, no gas generation or discoloration at a high temperature of 500 ° C, and no performance deterioration.

(6) It is in the form of fine particles, has good dispersibility, and is uniformly dispersed in various materials. Further, the coloring property is small (it becomes almost transparent depending on the added amount), and the appearance of the material is not damaged.

(7) Excellent boiling water resistance, chemical resistance, weather resistance, and good abrasion resistance.

(8) It has no elution, and its toxicity is almost negligible, so its versatility is wide.

(9) It is porous, has a large surface area, is excellent in deodorizing property, and its effect lasts for a long time.

(10) When mixed in water in a small amount, the entire water becomes antibacterial and its effect lasts for a long time.

The antibacterial / conductive composition of the present invention has the following characteristics as a coating composition.

(1) A transparent or semitransparent conductive and antibacterial thin film is formed.

(2) A film having excellent heat resistance, water resistance, weather resistance, chemical resistance, and hardness can be obtained.

(3) Plastic, metal, glass, cement, fiber,
It can be coated on leather, paper, sand and any other substrate.

(4) It is cured by heating at low temperature (60 to 300 ° C.) for a short time (1 to 60 minutes).

As a result, the present invention has a number of advantages such as being able to provide a wide variety of products such as medical, agricultural, and fishery products in addition to clothing, food and housing related products, as well as industrial products, and has an extremely great industrial significance. is there.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08L 101/00 LSY 7242-4J C09D 5/14 PQM 6904-4J 5/24 PQW 7211-4J C09J 9/02 JAR 7415-4J 11/02 JAU 7415-4J C09K 3/16 102 B

Claims (2)

[Claims] 1. A tetraalkoxysilane represented by the general formula Si (OR ¹ ) ₄ (wherein R ¹ represents a hydrocarbon residue having 1 to 5 carbon atoms) and a general formula R ² Si ( OR ³ ) ₃ (In the formula, R ²
Is an organic group having 1 to 8 carbon atoms, R ³ is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms), and at least one organic silicon compound selected from organoalkoxysilanes 3 to 50% by weight in terms of solid content, (b) 0.05 to 5% by weight in terms of silver component of colloidal silver, and (c) colloidal silica, colloidal alumina, silica gel, zeolite, activated carbon, ultrafine particles of silica, An antibacterial / conductive composition containing, as a main component, at least one inorganic compound selected from the group consisting of alumina and titania in an amount of 10 to 90% by weight on an anhydrous basis. 2. The antibacterial / conductive composition according to claim 1, which is 0.02.
An antibacterial / conductive resin composition containing up to 30% by weight.