JPH0421615A - Antimicrobial composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent adhesion by mixing a tetraalkoxysilane, a zirconium tetraalkoxide and/or a trialkoxyboron, an organic solvent, a specific filler and a specific metallic salt in a specific ratio. CONSTITUTION:At least each one the following components A to E are mixed in a weight ratio of A:B:C:D:E=100:(10-80):(300-4000):(5-400):(0.3-50) to afford the objective antimicrobial composition; (A) a compound expressed by formula I (R<1> is 1-5C hydrocarbon residue), hydrolysate or polycondensate of the compound is mixed with (B) a compound expressed by formula II or formula III (R<2> and R<3> are 1-5C hydrocarbon residue), hydrolysate or partially polycondensed product of the compound, (C) an organic solvent, (D) a filler selected from ultrafine granular metal oxide, silica gel, zeolite or activated charcoal and (E) a metallic salt of silver, copper or zinc. Said composition gives a non- exuding and safe coated film having excellent antimicrobial property, deodorant property, resistance to radiation, resistance to heat (non-fume property), weatherability, resistance to chemicals and moisture-controlling property, etc., and is produced at a low temperature-normal temperature in a low cost, and furthermore, a coated film having a large specific surface are can be formed.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an antibacterial composition, and more particularly, to cement, ceramic products, plastics, paper, fibers, wood, minerals, metals, and other products. Coating or printing on the surface of organic or inorganic coatings, and by simply heating at low temperature for a short time or drying at room temperature, it has antibacterial properties, deodorizing properties, humidity control properties, heat radiation properties, as well as heat resistance and weather resistance. , relates to an antibacterial composition for forming a transparent or colored thin film with excellent water resistance, chemical resistance, etc.

[Conventional technology] Conventionally, antibacterial resin paints and antibacterial resins that use antibacterial zeolite using antibacterial metals and antibacterial activated carbon as fillers have been used as antibacterial compositions that make the base material antibacterial. In addition, many organic antibacterial agents and bio-based antibacterial agents for filling have been disclosed, but in all cases, antibacterial properties are inhibited by the covering power of the binder resin, and ■ it is difficult to uniformly disperse the antibacterial agent. , ■ The antibacterial agent has poor chemical resistance, hot water resistance, and weather resistance (especially UV resistance), ■ There is a problem with the long-term sustainability of antibacterial properties, ■ Obtaining a large specific surface area to effectively express antibacterial properties. (The antibacterial property is caused by the catalytic action of the antibacterial metal salt, which converts some of the oxygen it comes into contact with into active oxygen, and the contact area is important because it is due to this active oxygen.) have.

[Problem to be solved by the invention]

The present invention was made against the background of the problems of the prior art, and can provide a coating film with excellent antibacterial and deodorizing properties.
It is also possible to form coatings with a large specific surface area on cement, ceramic products, plastics, paper, fibers (especially yarn), wood, minerals, metals, and other products, and the coatings are non-leaching and safe. The purpose is to provide an antibacterial composition that has excellent thermal radiation properties, heat resistance (smokeless), weather resistance, chemical resistance, humidity control properties, etc., can be processed at low to room temperature, and has low manufacturing costs. do.

[Means to solve the problem]

The present invention relates to 3(a) a tetraalkoxysilane represented by the general formula Si (OR' )4 (in the formula, R1 represents a hydrocarbon residue having 1 to 5 carbon atoms), and a hydrolyzate of the tetraalkoxysilane. and at least one silane compound selected from the group consisting of a partial polycondensate of the hydrolyzate 10
0 parts by weight, (b) zirconium tetraalkoxide represented by the general formula Zr (OR2)- (wherein R2 represents a hydrocarbon residue having 1 to 5 carbon atoms), and hydrolysis of the zirconium tetraalkoxide. and/or at least one zirconium compound selected from the group consisting of a partial polycondensate of the hydrolyzate and/or general formula B (OR3)
3 (wherein R3 represents a hydrocarbon residue having 1 to 5 carbon atoms) from the group consisting of trialkoxyboron, a hydrolyzate of the trialkoxyboron, and a partial polycondensate of the hydrolyzate. 10 to 80 parts by weight of at least one selected boron compound, (c) 300 to 4,000 parts by weight of an organic solvent, (d) selected from the group consisting of ultrafine metal oxide, silica gel, zeolite, and activated carbon. At least one filler5~
(e) 0.3 to 50 parts by weight of an antibacterial metal salt consisting of at least one metal salt selected from metal salts of silver, copper, and zinc. The present invention provides a sexual composition.

The present invention is directed to tetraalkoxysilane; Si (OR' ), which gradually undergoes hydrolysis; and zirconium tetraalkoxide, Zr (OR2), which undergoes rapid hydrolysis.
)n or trialkoxyboron; 1 of B(OR3)i
A seed or two or more are added to this, an organic solvent is added to adjust the hydrolysis rate and concentration, ultrafine metal oxide is used as a transparent filler with a large specific surface area, silica gel with excellent adsorption ability, and ion exchange. Based on the knowledge that an effective antibacterial inorganic coating with excellent adhesion can be easily formed by adding and blending zeolite, activated carbon, and antibacterial metal salts of silver, copper, or zinc. This was done based on the following.

Therefore, this coating film is hardened to the touch by drying at room temperature for a short time, and further hardened by heating at 60 to 300°C for 1 to 60 minutes. Further, this coating film is cured over a period of 2 to 10 days at room temperature.

Hereinafter, the present invention will be explained in detail in terms of constituent elements.

(a) Silane compound Tetraalkoxysilane used in the present invention; Si(O
R1) 4 is hydrolyzed in the presence of water to become a hydrolyzate (tetrasilanol), and the hydrolyzate is polycondensed to produce a partial polycondensate or a complete condensate, and the partial condensate further increases in molecular weight. When a coating film is formed, it is cured by heating, and in the composition of the present invention, it acts as a binder together with b) the zirconium compound and/or the boron compound.

R' in such tetraalkoxysilane has 1 to 1 carbon atoms.
5 hydrocarbon residues, such as alkyl groups having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-7"O pyl group, 1-propyl group, n-butyl group, 5ec-butyl group, t
-butyl group, etc.

Specific examples of these tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-1-propoxysilane, tetra-n-butoxysilane, and tetra-5ec.
-butoxysilane, tetra-t-butoxysilane, and the like.

Among these tetraalkoxysilanes, tetramethoxysilane is particularly preferred.

These tetraalkoxysilanes can be used alone or in combination of two or more.

In addition, such tetraalkoxysilane partially liberates alcohol by hydrolysis, producing a corresponding hydrolyzate (tetrasilanol), and polycondensation of the hydroxyl substituent by producing silanol occurs in an aqueous medium. , a partial polycondensate of silanol is produced, which is further polycondensed to produce a silica component which is a complete polycondensate.

Therefore, the silane compound (a) in the present invention includes not only the above-mentioned tetraalkoxysilane but also its hydrolyzate and partial polycondensate of the hydrolyzate.

Such hydrolysates and partial polycondensates may be those produced from tetraalkoxysilane in the composition, or may be prepared by preparing the composition, such as ethyl silica 1-40 (Colcoat). (manufactured by ■) may be blended.

0)) Zirconium tetraalkoxide used in the present invention; oxide), and the hydrolyzate is polycondensed to produce a partial polycondensate, and when the partial condensate has a higher molecular weight and becomes a coating film, it is cured by heating, and the composition of the present invention Among them, it functions as a binder together with (a) a silane compound and (a) a boron compound.

R2 in the zirconium tetraalkoxide is a hydrocarbon residue having 1 to 5 carbon atoms, such as an alkyl group having 1 to 5 carbon atoms, specifically a methyl group, ethyl group, n-propyl group, i-propyl group, etc. group, n-butyl group, 5ec-butyl group, t-butyl group, etc.

Specific examples of these zirconium tetraalkoxides include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetramylpropoxide, zirconium tetra-n-butoxide, and zirconium tetra-5e.
Examples include c-butoxide and zirconium tetra-t-butoxide.

Furthermore, among these zirconium tetraalcokits, zirconium tetra-n-butoxide is particularly preferred.

These zirconium tetraalkoxides can be used alone or in combination of two or more.

In addition, such zirconium tetraalkoxide liberates alcohol by rapid hydrolysis, producing the corresponding zirconium tetrahydroxide, and polycondensation of the hydroxyl substituents occurs due to the production of the hydroxide. A partial polycondensate is produced, which is further polycondensed to produce a zirconia component which is a complete polycondensate.

Therefore, the zirconium compound (Φ) in the present invention is
In addition to the above-mentioned zirconium tetraalkoxide, the term also includes hydrolysates thereof and partial polycondensates of the hydrolysates. Such hydrolyzate and partial polycondensate may be produced from zirconium tetraalkoxide in the composition, or may be blended in advance at the time of preparing the composition.

(b) boron compound used in the present invention c) trialkoxyboron; B(O
R3) is easily hydrolyzed into a hydrolyzate due to the presence of moisture in the atmosphere or water in the composition, and the hydrolyzate is polycondensed to produce a partial polycondensate, and the partial condensate is It further increases its molecular weight to form a coating film, and functions as a binder together with 3(a) silane compound and 3(b) zirconium compound, but in the composition of the present invention, it is used together with (b) zirconium tetraalkoxide. (a)
It promotes the hydrolysis of tetraalkoxysilane, and also has the function of curing the coating film at room temperature.
At 00°C, it becomes glassy with pyroboric acid (R2B40?) and has the function of further advancing the hardening of the coating film.

R3 in such trialkoxyborane is, for example, an alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 5
Examples include ec-butyl group and t-butyl group.

Specific examples of these trialkoxyborons include trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-n-propoxyboron, tri-n-propoxyboron, and tri-n-propoxyboron.
Examples include tri-butoxyboron, tri-5ec-butoxyboron, and tri-butoxyboron.

Among these trialkoxyborons, trimethoxyboron is particularly preferred.

These trialkoxyborons can be used alone or in combination of two or more.

In addition, such trialkoxyboron is rapidly hydrolyzed to liberate alcohol and produce the corresponding boron trihydroxide, and the production of the hydroxide causes polycondensation of the hydroxyl substituent,
A partial polycondensate of the hydroxide is produced, which is further polycondensed to produce a complete polycondensate of boric anhydride; B20ff.

Therefore, the boron compound (b) in the present invention includes not only the above-mentioned trialkoxyboron but also its hydrolyzate and partial polycondensate of the hydrolyzate. Such hydrolysates and partial condensates may be produced from trialkoxyboron in the composition, or may be pre-blended during preparation of the composition.

Component (b) in the composition of the present invention is at least one of the zirconium compound and boron compound, and the proportion of component (b) in the composition is 10 to 10 parts by weight per 100 parts by weight of component (a). The amount is 80 parts by weight, preferably 15 to 50 parts by weight.

If component (b) is less than 10 parts by weight, hydrolysis will not proceed in a short time, resulting in poor workability, low coating film hardness, and poor adhesion; on the other hand, if it exceeds 80 parts by weight, hydrolysis will be rapid. If it is too much, the workability will be poor and the film forming property will also be poor, which is not preferable.

(c) Organic solvent The organic solvent is a concentration adjusting agent for the above-mentioned (a) silane compound, (b) zirconium compound and/or (b) boron compound, and also controls the hydrolysis of these (a) and 3 (b) components. It is for adjustment.

Suitable examples of such organic solvents include alcohols, glycol derivatives, or low-boiling organic solvents having a boiling point of 120°C or less.

Among these, examples of the alcohols or glycol derivatives include ethylene glycol, which is a monohydric alcohol or dihydric alcohol, or derivatives thereof. Among these, the monohydric alcohol is preferably an aliphatic alcohol having 1 to 8 carbon atoms. , specifically methanol,
Ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, 5eC-butyl alcohol, t-butyl alcohol, n-bentyl alcohol, n-hexyl alcohol, 4-methyl 2-pentanol, 4-methyl- For example, n-pentanol can be mentioned, and examples of ethylene glycol or its derivatives include ethylene glycol, ethylene glycol monobutyl ether, and acetic acid ethylene glycol monoethyl ether. These alcohols and glycol derivatives are preferably i-propyl alcohol, 5ec-butyl alcohol, n-propyl alcohol, n-butyl alcohol, acetic acid ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

Further, examples of low-boiling organic solvents having a boiling point of 120°C or less include toluene, benzene, acetone, methyl ethyl ketone, cyclohexane, and tetrahydrofuran.

These organic solvents can be used alone or in combination of two or more.

The proportion of organic solvent 3(C) in the composition of the present invention is 300 to 4,000 parts by weight, preferably 450 to 3,000 parts by weight, but less than 300 parts by weight, based on 100 parts by weight of component 3(a). If the amount exceeds 4,000 parts by weight, the storage stability of the composition itself will improve, but the solid content in the composition may decrease. It is not possible to achieve a thicker coating film,
Furthermore, the hydrolysis rate decreases, making curing insufficient in a short period of time.

(d) Filler The filler (d) of the present invention adsorbs or ion-exchanges the antibacterial metal in the form of ions in the composition.
Selected from the group consisting of ultrafine metal oxides, silica gel, zeolites and activated carbon.

Hereinafter, the filler (d) of the present invention will be explained in terms of its components.

(Ultrafine metal oxide) The ultrafine metal oxide of the present invention includes colloidal silica in which ultrafine particles of silicic anhydride are dispersed using water or alcohol as a dispersion medium, and alumina sol using water as a dispersion medium. These include colloidal alumina, ultrafine silica created by high-temperature hydrolysis of purified metal salts, ultrafine alumina, and ultrafine titania. These particles preferably have an average particle size of 5 to 100 mμ from the viewpoint of creating a coating film with a large specific surface area.

In addition, from the viewpoint that the composition of the present invention is hydrolyzed by a small amount of water in an acidic region to form a gel film, the ultrafine particulate metal oxide may be an alcoholic colloidal metal oxide or an aqueous colloid with an acidic pH. Preferably, it includes a colloidal metal oxide.

However, in the case of aqueous colloids, the amount used is limited because it affects the pot life of the composition.

(Silica gel) Silica gel is a compound represented by the general formula SiO It has a large specific surface area.

The silica gel of the present invention preferably has an average particle size of 5 μm or less in order to form a thin film with excellent wear resistance.

(Zeolite) The zeolite in the present invention is a natural or synthetic zeolite, and has the general formula % (%) (where M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and n is In this valence, X is the coefficient of the metal oxide, y is the coefficient of warping force, and 2 is the number of crystallized water), and its composition ratio and pore diameter,
There are many types with different specific surface areas.

For example, natural zeolites include anarsin, chabasite, clinoptilolite, erionite, phonoyasite, and mordenite, while synthetic zeolides include A-type zeolide, X-type zeolide, Y-type zeolide, and T-type zeolide. - Examples include zeolite.

Zeolite has a good particle shape, and its particle size is 5μ.
Passes m or less. A preferred zeolite has a particle size of 2μ
m or less, with a specific surface area of 150rrr/g or more, SiO2/
The molar ratio of Afz○ is 14 or less.

The filler of the present invention is preferably a zeolite having a large specific surface area and excellent adsorption ability, such as natural mordenite or the above-mentioned synthetic zeolite.

(Activated carbon) Activated carbon is a black particle of carbon material obtained by carbonizing organic compounds, has a special porous structure, and has excellent adsorption properties.

The particle size of activated carbon is usually about 0.3 to 5 μm, preferably about 0.5 to 2 μm, and the specific surface area is usually about 6
00 to 1,000 i/g or more. Specific examples of this activated carbon include charcoal, coconut shell, coal char type, bone charcoal, and animal charcoal.

The proportion of the filler (d) in the composition of the present invention is 5 to 400 parts by weight based on 100 parts by weight of component 3(a) on a solid basis.
Parts by weight, preferably 2 to 300 parts by weight. (d
) If the amount of the filler used is less than 5 parts by weight, it is undesirable because it is too small to adsorb the antibacterial metal salt (e) described later, or the ion exchange capacity is insufficient and elution may occur. on the other hand,
If it exceeds 400 parts by weight, the viscosity of the composition increases and the hardness of the coating film decreases, which is not preferable.

(e) Antibacterial metal salts (e) Antibacterial metal salts provide antibacterial properties against microorganisms such as bacteria, molds, and algae, and act as an oxidizing agent for all odors.

In addition, since the antibacterial metal salt 3(e) is a metal salt, the tetraalkoxysilane constituting the component (a), (b)
Tetraalkoxyzirconium and/or
Alternatively, it also functions as an acidic catalyst during hydrolysis of trialkoxyboron.

(e) The antibacterial metal salt is supported in the form of ions on the coating film containing the filler (d) above, and its antibacterial and oxidizing properties are achieved by the catalytic function of these metal ions, which is caused by the oxygen in the air that comes into contact with it. Alternatively, it is thought that part of the dissolved oxygen in the water is converted into active oxygen and is caused by this active oxygen.

This catalytic function theory is inferred from the fact that no silver or copper was detected in the immersion water. From this, it can be said that the antibacterial and deodorizing material of the present invention is effective for a very long period of time.

In addition, the antibacterial metal salt 3(e) is not carried only by the filler (d), but also by the tetraalkoxysilane, which is the component (a), as the binder. The antibacterial coating film of the present invention has strong antibacterial and oxidizing properties because it is also supported on ultrafine gel of zirconium and/or trialkoxyboron.

Such (e) antibacterial metal salts are metal salts of silver, copper, or zinc, specifically silver nitrate, silver sulfate, silver chloride, nitric acid! Examples include copper sulfate, copper bromide, copper acetate, zinc nitrate (■), and zinc perchlorate. However, the present invention is not limited to these. These metal salts are used as a mixed solution by dissolving one or more of them in alcohol or water.

The above mixed solution can be adsorbed or ion-exchanged by (d) the filler in the composition.

The proportion of antibacterial metal salt (e) in the composition of the present invention is 0.3 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of component 3(a).

(e) If the antibacterial metal salt is less than 0.3 parts by weight, the antibacterial activity, which is the objective of the present invention, will be too small, while if it exceeds 50 parts by weight, there is a risk of elution, which is not preferable.

The composition of the present invention may contain other conventionally known additives such as various pigments, dyes, surfactants, various chelating agents, alkali metal salts, carboxylic acid metal salts, various acids, and curing catalysts such as amines. (Hereinafter, these components may be referred to as (f) components).

When preparing the composition of the present invention, for example, component (c) is added to component (e) and dissolved, component (d) is added and stirred, and then component (a) and (b) are added. It can be prepared by adding, stirring, and then filtering.

As described above, the coating composition obtained according to the present invention can be applied to the surfaces of objects such as cement, ceramic products, glass, plastics, paper, fibers (fabric or thread), wood, and inorganic or organic coatings. A dry film thickness of 0.0 cm can be achieved in one coat using brush, spray, dipping, roll, spin code, gravure printing, or other coating methods. A coating film with a thickness of about 1 to 5 μm can be formed, and it can be coated about 2 to 5 times.

When the composition of the present invention is coated on a substrate, the composition is hydrolyzed in a short time at a temperature of room temperature to 60°C, becomes a sol by a polycondensation reaction that occurs simultaneously, and the reaction proceeds further. It becomes a gel. 60~300°
It is cured by heating at C for about 1 to 60 minutes. Further, this coating film cures for 2 to 10 days at room temperature.

When applied to cement-based materials, the alkali in the cement acts as a curing catalyst and hardens at room temperature.

In this case, since the surface layer of cement is made denser, it is highly effective in preventing carbonation of the cement material.

When applied to a substrate with a large specific surface area, the composition can be cured at room temperature by adding a small amount of an alkali metal salt as a curing catalyst to the composition.

Further, the curing condition "heating at 60 to 300°C for 1 to 60 minutes" is merely an example and is not limited thereto.

That is, the curing conditions for the coating film can be changed as appropriate depending on the content and use of the composition of the present invention. For example, when spray applied to a surface preheated to 150°C, it cures instantly. Moreover, when applied by spray on a surface preheated to 400°C, an oxide film is instantly formed.

The performance of the coating film of the composition of the present invention, such as hardness, water resistance, chemical resistance, adhesion, density, etc., varies depending on the curing conditions, so it is necessary to adapt the composition depending on the application.

The composition of the present invention can be formed into a thick film by overcoating, and thereby a heat-resistant, transparent antibacterial and weather-resistant anticorrosive film can also be created.

Alternatively, an inorganic pigment can be added to form a cosmetic film.

In this case, the coating film is coated two or three times by repeating application and curing, and no cracks or peeling occur in the resulting coating film even if the coating is coated about five times.

The coating film obtained from the composition of the present invention has antibacterial and deodorizing properties, excellent adhesion, high density, heat resistance, impact resistance, and weather resistance, and is not attacked by water, seawater, or organic chemicals. corrosion protection of metals,
Can be used in a wide range of applications, including high-temperature oxidation prevention, strengthening and neutralization prevention of cement materials, heat resistance and hardening of plastics, flame retardancy of paper, heat retention by heat radiation of fibers, and drying (humidity control) properties. It is. In particular, it can be processed into thread and made into woven fabric, making it an ideal fiber (for example, for underwear).

[Effect]

The antibacterial composition of the present invention forms a coating film with a large specific surface area that supports antibacterial metal ions by applying it to a substrate and curing it by drying at room temperature or heating at a low temperature.

That is, in this coating film, fine particles, which are fillers with a large specific surface area, adsorb or ion-exchange antibacterial metal ions in the composition, and these are combined with tetraalkoxysilane, tetraalkoxyzirconium, and/or trialcoquinboron, which serve as binders. The ultrafine particles formed by hydrolysis and condensation polymerization are incorporated into a film that is strongly adhered to create an antibacterial film with a large specific surface area.

In this way, the antibacterial material coated with the antibacterial composition of the present invention has a structure in which a portion of the oxygen in the air or water that comes into contact with the membrane with a large specific surface area carrying antibacterial metal ions is converted into antibacterial metal ions. It is converted into active oxygen by its catalytic function, and this active oxygen exhibits bactericidal and antibacterial properties.

Furthermore, the membrane obtained from this antibacterial composition has excellent deodorizing properties. That is, the membrane with a large specific surface area adsorbs odors and at the same time oxidizes and decomposes them with the active oxygen, and unlike activated carbon, it is a deodorizing membrane that does not easily become saturated and remains effective for a long period of time. This film also has excellent heat resistance, water resistance, weather resistance, chemical resistance, etc.
Furthermore, it is possible to impart properties such as humidity control properties due to a large specific surface area, heat retention properties due to heat radiation, and antistatic properties.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples.

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

Examples 1 to 7 and Comparative Example 1 First, in the following examples, seven types of compositions A to G and composition H were created as a comparative example using the formulations shown in Table 1 in order to examine various properties. .

As for the preparation method, composition A was prepared by adding component (e) to component 3(C) and dissolving the mixture by heating to 50°C. Next, component (d) was added to this solution and stirred lightly. Add component (a) and [
) ingredients were added, stirred for 5 minutes, and left to stand indoors for 48 hours.

Composition B was obtained by adding component (e) to component 3(C) and dissolving it, then adding component 3(d), stirring lightly, and filtering through a 325 sieve mesh. 3. Add components (a) and 0)) to this solution. The mixture was stirred at OOOrpm for 10 minutes and left in the room for 48 hours.

Composition C was prepared by adding component (e) to component 3(C) and dissolving it, followed by component 3(d) and then gently stirring the components (a) and (b). This solution was used immediately after adding water and stirring for 5 minutes.

Compositions R and H were made in the same manner as Composition A.

For compositions E and F, component (e) was added to component 3(C) and dissolved, and then component 3 (→) was added and gently stirred.

After this solution was aged for about 6 hours, component 3 (a) and then component (b) were added and stirred lightly, filtered through a 325 mesh strainer, and left standing in a room for 48 hours.

Composition G was made in the same manner as Composition B.

(Leaving space below) Test Example 1 To examine antibacterial activity, 41 each of polyethylene and polypropylene films (300 x 300 x 1 m (7)) were prepared and coated with compositions A, G and H to create test pieces. The contents of this test piece are shown in Table 2. The method for creating is first).

Corona discharge treatment was performed as a pretreatment for the lumen, and each composition was subjected to IJT treatment using a burneater. A sample was prepared by applying an amount equivalent to 1 gram per gram and heat-treating at 60''C for 5 minutes.

Next, using this test piece, 20
A container measuring 0 x 150 x 20 mm was prepared and an antibacterial activity test was conducted.

■Test outline Cut a test piece container into 5c'Il squares, drop a normal bouillon medium supplemented with E. coli and Staphylococcus aureus, store at 5°C or 25°C, and count viable bacteria after 6 or 24 hours. was measured.

(2) Preparation of Bacterial Solution A culture solution of a test solution cultured in an ordinary bouillon medium at 35°C with night shaking was prepared by diluting it with the same medium so that the number of bacteria per IId was about 105.

■Measurement of bacteria count The bacteria solution on the test piece was washed out with 5CDLP liquid medium, and the number of viable bacteria was measured using the pour plate culture method (cultured at 35°C for 12 days) using a standard agar medium. The number of viable bacteria per sheet was converted. Table 3-1 shows the number of viable bacteria in the E. coli solution and Table 3-2 shows the number of viable Staphylococcus aureus bacteria in the above test results.

Table 3-1 (Escherichia coli solution) Table 3-2 (Staphylococcus aureus solution) However, in the table, the J notation below rlo is based on the detection limit of the bacteria count measurement method used in this test, and the number of bacteria detected is It means that it was not done.

Test Example 2 To examine the antibacterial and deodorizing properties of fibers, cotton threads and nylon threads were prepared, coated with compositions C and D by the dipping method, heated at 60°C for 30 minutes, and left at room temperature for 2 days. I created a processing system.

Next, a woven fabric was created using 40% of this processed yarn and 60% of unprocessed yarn. Further, this woven fabric was washed 30 times in a washing machine using a commercially available detergent, and this was used as a test piece. For comparison, a woven fabric made of only unprocessed yarn was also prepared and used as a control.

The contents of this test piece are shown in Table 4.

Table 4 Table 4 test results First, antibacterial activity test using was carried out.

(Test summary) Tested according to the shake flask method. That is, a test piece was placed in a test solution for Escherichia coli and Pseudomonas aeruginosa in an Erlenmeyer flask and shaken, and the number of viable bacteria in the test solution was measured 6 and 24 hours later.

Table 5-1 shows the number of viable bacteria in the E. coli solution (number of viable bacteria per 1-1 bacterial solution) of the above test results, and the number of viable bacteria in the Pseudomonas aeruginosa solution (number of viable bacteria per 1-1 bacterial solution). are shown in Table 5-2.

Table 5 ■ (Number of Pseudomonas aeruginosa viable bacteria) Next, a deodorizing power test was conducted using the test pieces shown in Table 4.

(Test summary) A test piece (approximately 204 cm) is placed in a glass bottle with an internal volume of 32
After introducing d), a fixed concentration of foul-smelling gas was allowed to live in the container, and the gas inside was sampled over time to measure the odor intensity. Three types of malodorous gases were used: ammonia, acetic acid, and trimethylamine. The odor intensity was measured using the 6-level odor intensity display announced by the Environment Agency, and the number of subjects tested was 6 (4 boys, 2 girls). The above test results are shown in Table 6.

Table 6 Test Example 3 In order to investigate the antialgae effect of the composition of the present invention on cement materials in the ocean, four pieces of mortar measuring 40 x 40 x 80 mm were prepared. This mortar uses commercially available ordinary Portland cement and commercially available river sand (5an or less) as a fine aggregate, with a weight mixing ratio of cement/water/sand of 110.
The score was 65/2.5. Store this mortar at 20°C for 28 days.
It was created by curing it in water.

In this mortar, compositions B, E, Apply F on the entire surface, It was left indoors for 7 days and used as a test piece.

In addition, as a comparison control, Laertal was prepared without applying the composition. Its specifications are shown in Table 7.

Table 7 In order to investigate the anti-algae ability of the test piece shown in Table 7 at the Chiba beach in Tokyo Bay, the test piece was hung at a depth of about 30 mm below the sea level and the growth of algae was observed for 6 periods. The visually observed test results are shown in Table 8.

(Leaving space below) Moni C Shogetsu Test Example 4 In order to investigate the non-leaching properties of the coating film, test pieces 1 and 6 were used to conduct a standard test for equipment, containers and packaging in accordance with Ministry of Health and Welfare Notification No. 20 of 1981. The test and inspection results were as follows.

General Standard Material Test; Cadmium Passage
Appropriate elution test - Heavy metals (as PB) passed Potassium manganate bone removal amount Appropriate individual specifications Elution test: Evaporation residue n-hebutane Appropriate 20% ethanol Water passage 4% acetic acid Appropriate (Effects of the invention) Antibacterial properties of the present invention The composition can provide a coating film with excellent antibacterial and deodorizing properties, and can also be used as a coating film with a large specific surface area on cement, ceramic products, plastics, paper, fibers, wood, minerals, metals, and other products. Furthermore, the coating film is non-leaching and safe, has excellent heat radiation properties, heat resistance (smokeless), weather resistance, chemical resistance, moisture control properties, etc., and can be processed at low or room temperature. possible, low manufacturing cost,
Furthermore, a wide range of products including bedding, clothing, shoe insoles, medical supplies, water and air conditioning filters, wallpaper, and other fabrics, food containers, various household items, building materials, medical, agricultural, fisheries, and industrial products. It has many advantages such as being able to provide a wide variety of products, and its industrial significance is extremely large.

Claims (2)

[Claims] (1) (a) General formula Si(OR^1)_4 (in the formula, R^
1 represents a hydrocarbon residue having 1 to 5 carbon atoms), a hydrolyzate of the tetraalkoxysilane, and a partial polycondensate of the hydrolyzate. (b) Zirconium tetraalkoxide represented by the general formula Zr(OR^2)_4 (in the formula, R^2 represents a hydrocarbon residue having 1 to 5 carbon atoms) to 100 parts by weight of the seed silane compound. , at least one zirconium compound selected from the group consisting of the hydrolyzate of the zirconium tetraalkoxide and the partial polycondensate of the hydrolyzate and/or the general formula B(OR^3)_3 (wherein R^ 3 represents a hydrocarbon residue having 1 to 5 carbon atoms), a hydrolyzate of the trialkoxyboron, and a partial polycondensate of the hydrolyzate. Seed boron compounds 10-8
(c) 300 to 4,000 parts by weight of an organic solvent; (d) at least one filler selected from the group consisting of ultrafine metal oxides, silica gel, zeolite, and activated carbon;
(e) 0.3 to 50 parts by weight of an antibacterial metal salt consisting of at least one metal salt selected from metal salts of silver, copper, and zinc. sexual composition. (2) The antibacterial composition according to claim 1, wherein the ultrafine particulate metal oxide is an alcoholic colloidal metal oxide and/or an acidic aqueous colloidal metal oxide.