JPH0827404A - Antimicrobial coating composition, method for coating the same and product therefrom - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial coating composition which contains glass particles, ceramic particles, porous silica gel particles including antlmicrobial metallic tons and an organosilane which is hydrolyzable and polymerizable by polycondensation, thus shows antimicroblal effect durable for a prolonged period of time. CONSTITUTION:Glass particles, ceramic particles or porous silica gel particles which include antimicrobial metallic ions and is composed of 25-60wt.% of SiO2, 18-60wt.% of B2O3, 0-20wt.% of Al2O3, 8-30wt.% of R2O (R2 is Li, Na, K), 0-20wt.% of R'O (R' is Ca, Mg, Zn, Ba) and 0.05-2.0wt.% of Ag2O and an organosilane such as tetraalkoxysilane or alkyltrialkoxysllane which can be hydrolyzed and polymerized by polycondensatlon reaction or a partial hydrolyzate thereof are formulated to give this antimicrobial coating composition which can stably sustain the antimicrobial effect for a prolonged period of time, when it is applied to the surfaces of plastics, metals, woods, fibers, papers and so on.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition which can be applied to the surface of plastic, glass, metal, wood, fiber, paper and the like to impart an antibacterial function.

[0002]

2. Description of the Related Art Heretofore, there have been proposed some attempts to exert an antibacterial effect by forming an organic or inorganic coating film on the surface of metal, plastic, wood or the like (JP-A-2-26407).
4, JP-A-2-251585, JP-A-63-221175). Generally, a coating composition for forming such an antibacterial coating film,
It is composed of a coating agent as a binder and a filler having an antibacterial action. However, when an organic antibacterial agent is used as the filler, there is a drawback that the antibacterial action is temporarily large but its sustainability is poor. 3-124810. On the other hand, the antibacterial performance of the inorganic antibacterial agent is generally the metal ion (eg Ag + ion, Cu + ion) contained in the filler.
Ions), and specific examples thereof include crystalline ones such as zeolite and ceramics each containing silver ion, and silver ion-containing glass. However, since the zeolite containing silver ions has a high hygroscopic property of the zeolite itself, it has poor processing and storage properties, and the elution rate of silver ions is not constant, which makes it difficult to maintain a constant antibacterial effect. It is described inside.

Further, in the case of using a resin binder as a coating agent, the filler having antibacterial activity is completely covered with the binder, so that the antibacterial effect is not sufficiently exerted and it cannot be easily put into practical use. It is described in JP-A-2-264074.

[0004]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention is made of plastic, metal, wood,
It is an object of the present invention to provide a coating composition which is applied to the surface of fiber paper or the like and has a stable and long-lasting antibacterial effect.

[0005]

The present invention provides: 1) an antibacterial filler composed of glass particles, ceramic particles, or porous silica gel particles each having a metal ion having an antibacterial action, and 2) hydrolysis and polycondensation. It is an antibacterial coating composition containing as a main component a binder component composed of an organosilane or a partial hydrolyzate thereof.

(A) Antibacterial Filler The antibacterial coating composition of the present invention first contains an antibacterial filler having a metal ion having an antibacterial action.
The antibacterial filler is glass particles, ceramic particles, or porous silica gel particles each having a metal ion having an antibacterial effect.

Metal ions having an antibacterial action include silver (Ag), zinc (Zn), copper (Cu), and tin (S).
Although each ion of n) can be used, silver is preferable because it has the highest antibacterial property. Hereinafter, the antibacterial filler having silver ions as a representative will be described. This includes glass with silver, ceramics carrying silver ions,
There is each particle of silica gel carrying silver ions. The average particle size is 50 μm or less, preferably 10 μm.
μm or less. In this way, the particle size is limited, when the average particle size exceeds 50 μm, not only the surface area of the particles becomes too small, but the antibacterial performance is not sufficiently exhibited, and the coating film also has poor adhesion to the substrate. Moreover, only a film having no surface smoothness can be formed. There is no particular lower limit to the average particle size of each filler, but those having a particle size of 10 μm or more are usually easily available. The respective fillers, that is, particles of glass having silver ions, particles of ceramics having silver ions, and particles of silica gel having silver ions will be described below.

1. Silver-Containing Glass As the silver-containing glass preferable in the present invention, there are two types of borosilicate type and phosphate type. The composition of each glass is described in detail below.

(1) Borosilicate type The composition of borosilicate type silver-containing glass is expressed in weight% and is expressed as SiO2 25-60, B2O3 18-60, Al2O3 0-20, R2.
O (R = Li, Na, K, R2O is the sum of those oxides) 8 to 30, R'O (R '= Ca, Mg, Zn, and Ba), and R'O is one of those oxides. Total) 0-20,
Ag2O is 0.05 to 2.0. The reason for limiting the composition in this way is as follows.

In the present invention, the SiO2 component forms the skeleton of glass, and its content is 25-60% by weight,
It is preferably 30 to 55% by weight. Ag less than 25% by weight
+ The amount of ions and glass components eluted is too large, and the life (or durability) of the antibacterial glass composition is extremely shortened. On the other hand, if it exceeds 60% by weight, the viscosity is increased and it becomes difficult to melt the glass, and the elution amount of Ag + ions is too small, and the antibacterial performance is not sufficient.

B2O3 promotes the elution of glass and contributes to the stabilization of Ag + ions, and is 18 to 60% by weight, preferably 20 to 55% by weight. If it is less than 18% by weight, the elution amount of Ag + ions is too small, the antibacterial performance is weak, and metallic silver is likely to precipitate during glass melting. If it exceeds 60% by weight, the glass elution amount becomes too large and the life becomes extremely short, and if it is contained more than that amount, it is not so effective in stabilizing Ag + ions.

Although Al2O3 is not an essential component, it suppresses the elution of glass and contributes to the stabilization of Ag + ions.
It is 20% by weight, preferably 1 to 10% by weight. If it exceeds 20% by weight, the amount of glass eluted is too small, the antibacterial performance is weakened, the viscosity is increased, and the glass is difficult to melt.

R2O (wherein R represents Li, Na and K) promotes melting and elution of glass. Li2O, Na2O,
And the total content of K2O is 8 to 30% by weight, preferably
It is 10 to 20% by weight. If it is less than 8% by weight, the effect of promoting elution is small, and if it is 30% by weight or more, the amount of glass eluted is too large and the durability is poor.

R'O (where R'represents Ca, Mg, Zn and Ba) is not an essential component, but it promotes melting and elution of glass like R2O, and CaO, MgO, ZnO, And the total amount of BaO is 0 to 20% by weight, preferably 0 to 10% by weight
Is. If it exceeds 20% by weight, the amount of glass eluted becomes too large when used in combination with R2O, resulting in poor durability.

Ag2O is an essential component for antibacterial property, which becomes Ag + ion in glass, and is 0.05 to 2.0% by weight, preferably 0.1.
It is 1 to 1.0% by weight. If it is less than 0.05% by weight, the elution of Ag + ions is suppressed and the antibacterial property is poor, and if it exceeds 2.0% by weight, the precipitation of metallic silver having little antibacterial property is considerably increased, and the cost required for glass production becomes expensive.

(2) Phosphate type The composition of the phosphate type glass is expressed in% by weight, and P2O5 3
5-75, SiO2 0-20, B2O3 0-20, Al2O3 0-2
0, R2O (R = Li, Na, K) + R'O (R '= Ca, Mg, Zn, B
a) 10 to 40 and Ag2O 0.05 to 3.0. The reason for limiting the composition in this way is as follows.

In the present invention, P2O5 forms the skeleton of glass and also contributes to the stabilization of Ag + ions. The content of P2O5 is 35 to 75% by weight, preferably 40
~ 60% by weight. If it is less than 35% by weight, the glass will be devitrified, and the properties as amorphous cannot be maintained. On the other hand, if it is 75% by weight or more, the volatilization of P2O5 becomes too much, which makes it difficult to control the composition during melting.

Although SiO2 is not an essential component, it plays a role of suppressing the elution of glass, and its content is 0 to 20% by weight,
It is preferably 0 to 15% by weight. If it exceeds 15% by weight, the amount of glass eluted is too small, the antibacterial performance is weakened, the viscosity is increased, and the glass is difficult to melt.

Although B2O3 is not an essential component, it accelerates the melting of the glass and is contained in an amount of 0 to 20% by weight, preferably 0 to 10% by weight. If it exceeds 20% by weight, the amount of glass eluted is too large and the life becomes extremely short.

Al2O3 is not an essential component, but it suppresses the elution of glass, and it is contained in an amount of 0 to 20% by weight, preferably 1 to 15% by weight. If it exceeds 20% by weight, the amount of glass eluted is too small, the antibacterial performance is weakened, and the viscosity is increased so that the glass is difficult to melt.

R2O (where R represents Li, Na, K) +
The content of R'O (where R'represents Ca, Mg, Zn, Ba) is
It is 10 to 40% by weight, preferably 15 to 30% by weight. R2O
(Where R represents Li, Na, K) + R'O (where R'is C
a, Mg, Zn and Ba) are essential components because they are mainly introduced in the form of phosphate. If it is less than 10% by weight, the water resistance of the glass tends to be poor, and P2O5 must be introduced in the form of an ammonium salt or the like, so that the cost required for glass production becomes expensive. On the other hand, when it is 40% by weight or more, the amount of glass eluted is too large and the durability is poor.

Ag 2 O is an essential component for antibacterial property which becomes Ag ions in glass, and is 0.05 to 5.0% by weight, preferably 0.1.
~ 3.0% by weight. If it is less than 0.05% by weight, the elution of Ag + ions is suppressed and the antibacterial property is poor, and if it exceeds 5.0% by weight, the amount of metallic silver having less antibacterial property is considerably increased, and the cost required for glass production becomes expensive.

2. Ceramic Body Supporting Silver Ions The silver-supporting ceramics are mainly produced by exchanging alkali ions in the ceramic body with silver ions by an ion exchange method. Preferable examples of such silver-supported ceramics include Novalon (ceramic body in which silver ion is supported on zirconium phosphate) manufactured by Toagosei Kagaku Kogyo Co., Ltd., and hydroxyapatite porous spherical particles manufactured by Sekisui Plastics Industry. be able to.

3. Silica gel carrying silver ions Silver ions can be easily liberated and a stable antibacterial effect for a long period cannot be expected by merely physically adsorbing silver ions on silica gel. However, in recent years, a product has been put on the market that exhibits stable antibacterial activity by adsorbing a silver complex salt on silica gel and further coating it with silica. Preferable examples of such silver-supported silica gel include Amenitop manufactured by Matsushita Electric Industrial Co., Ltd., Bactenon beads manufactured by JEOL Ltd., and the like.

The above-mentioned antibacterial filler is mixed in a proportion of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, relative to 100 parts by weight of the binder component (solid content) described below. In this way, the proportion of the filler is limited, if it is less than 1 part by weight, a sufficient antibacterial effect cannot be obtained, and if it exceeds 100 parts by weight, the proportion of the filler in the film becomes too large and a strong coating is obtained. This is because a film cannot be obtained.

(B) Binder 1. Crosslinking type tetraalkoxysilane coating agent The binder used in the present invention is a hydrolyzable and polycondensable organosilane or a partial hydrolyzate thereof, specifically, an alkoxysilane, particularly a tetraalkoxysilane or It is an alkyltrialkoxysilane, or a product obtained by hydrolyzing the alkyltrialkoxysilane and allowing the polycondensation reaction to proceed to some extent. It is required that the film strength after drying is not remarkably lowered even if a porous film is formed after drying and the glass containing silver is filled. Further, in consideration of coating on a substrate (plastic or the like) which is unstable to heat, it is desirable that the film can be formed even at a relatively low temperature.

A tetraalkoxysilane-based coating agent is mentioned as one that satisfies such conditions. Such a coating agent is mainly composed of an alkoxide represented by the general formula Si (OR ¹ ) 4 (wherein R ¹ represents a hydrocarbon residue having 1 to 5 carbon atoms), its hydrolyzate, and its condensate. As an ingredient. Since these coating agents are solidified by the dehydration condensation polymerization reaction of the hydrolyzate, it is possible to form a fine porous coating film by controlling the degree of polymerization. A preferable example of such a tetraalkoxysilane-based coating agent is G93 manufactured by Fine Glass Technology.

Further, the binder used in the present invention is
Having a water-repellent effect is more effective for antibacterial effect. Because this coating film forms a porous film, it is considered that the crosslinking reaction in the coating agent is not completely terminated and hydrophilic hydroxyl groups and the like partially remain in the coating film. Therefore, in the coating film, a hydrophobic hydrocarbon group such as an alkyl group,
If there is no fluoroalkyl group, etc., it may adsorb a large amount of water in the atmosphere, and as a result, even if it is filled with antibacterial glass, there is a risk of creating an environment in which mold, bacteria, etc. can easily propagate. Because there is. Therefore, as a material satisfying such a condition, a cross-linking type organopolysiloxane coating agent can be mentioned. The organopolysiloxane-based coating agent here has a Si-O bond as the main chain after the cross-linking reaction, and a part of the Si is directly alkyl group,
It means that a water-repellent group such as a fluoroalkyl group is bonded.

As such an organopolysiloxane-based coating agent, Atom Chemical Paint Co., Ltd. Atom Cerazeon # 300 and Shinto Paint Co., Ltd. Graceram # 330 are exemplified as preferable commercial products.

2. Cross-linking type organic / inorganic composite coating agent As this type of coating agent, an alkyl silicate type and its hydrolysis or partial polymerization product is used for the inorganic type molecule,
Organic molecules using fluororesin, acrylic resin, epoxy resin, etc. are currently on the market, and specific examples are Gracerum # 320 manufactured by Shinto Paint Co., Ltd., Fluorohard manufactured by Tonen Co., Ltd., and Finehard manufactured by the same company. , CERAPROTEX manufactured by the same company, and COPONYL # 1701 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. are exemplified as preferable commercial products.

However, these fluororesins, acrylic resins,
If too much resin component such as epoxy resin is added, the resin will completely cover the filler particles,
Since the antibacterial metal ions in the particles cannot be eluted, the content thereof is at most 80% by weight of the binder component (solid content), preferably 30 to 65% by weight.

Since the present coating agent is also a crosslinking reaction type, it is possible to form a fine porous coating film by controlling the degree of polymerization thereof. Furthermore, the organic / inorganic composite system was selected because, like the cross-linking reaction type organopolysiloxane coating agent, the siloxane bond gives the coating film hardness and abrasion resistance, and the organic molecules are water-repellent to the coating film.
This is because it gives flexibility and adhesion.

(C) Coating Method As described above, the present antibacterial coating agent (A),
Consisting of a mixture of (B), plastic, metal, wood,
When applied on the surface of fibers, paper, etc., a film having a thickness of 3 to 80 μm (thickness after curing) is obtained, and an antibacterial function can be imparted. As the coating method, a spraying method such as air spraying, a dipping (impregnation) method, a pouring method, or the like can be used. Of these, the air spray method is particularly effective when applied on a large-area substrate. But (A),
When the mixture of (B) is directly sprayed onto the substrate by the air spray method, the filler particles tend to prevent the binder from adhering to the glass substrate, and the film tends to peel off. Therefore, in the present invention, the binder (B) alone is first applied to the substrate by several μ.
A method was devised in which the coating was carried out by the air spray method, and the mixture of (A) and (B) was further coated on the semi-cured film. The optimum film thickness of the second layer changes depending on the particle size of the filler, and at least the average particle size of the filler is necessary.
By thus dividing the coating film into two layers, a relatively strong film having good adhesion to the substrate can be prepared.

After the above-mentioned application, the organosilane is hydrolyzed and polycondensed by drying at room temperature or at a temperature of 120 ° C. or lower to make the film sufficiently hard and porous. The fine pores formed in this film also extend in the thickness direction of the film, and silver ions eluted from the antibacterial particles located deep inside the film can reach the surface of the film through these holes and exert an antibacterial action. . If the hydrolyzed product is decomposed, for example, at a temperature exceeding 120 ° C., especially at 200 ° C.
When heated at a temperature above ℃, hydrolysis and polycondensation reactions proceed excessively, and although the hardness of the film is obtained, the porosity of the film is reduced and the antibacterial particles located deep inside the inner layer of the film are removed. Silver ions tend to be hard to reach the surface of the membrane, resulting in poor antibacterial performance.

The coating layer of the antibacterial coated article of the present invention is formed by the difference between the refractive index of the porous substance containing silicon oxide as a main component and the refractive index of the dispersed glass particles (or ceramic particles or porous silica gel particles). Often, the coated article is opaque and thus not transparent, even though the substrate of the coated article is transparent.
When the present invention is applied to an article requiring transparency such as a window and coated on a substrate having transparency (eg glass plate, polyethylene terephthalate plate), a specific uncoated portion should be left on the substrate. Allows coating without significantly impairing the transparency of the substrate.

That is, even if the antibacterial coating film does not cover the entire surface of the substrate, the size of each uncoated portion (minimum width)
Is within 3 cm, the antibacterial effect from the coating film around it also extends to the uncoated portion. Further, even if the total area of the uncoated portion of the antibacterial coating film is too large, a sufficient antibacterial effect is not exhibited.
Therefore, the area of the uncoated portion should not exceed 60% with respect to the total area of the substrate requiring the antibacterial effect (twice the surface area on one side when the antibacterial effect is required on both sides of the substrate), and more preferably It should not exceed 50%, in other words it is preferred that the antimicrobial coating is at least 40%, more preferably at least 50% of the total substrate area.

If the ratio of the area of the antibacterial coating film to the total area of the substrate is too large, the transparency is impaired, so the ratio should be at most 90%. Moreover, the minimum distance between the sides of the adjacent coated portions and the sides of the coated portions, in other words, the minimum width of the uncoated portion, must not exceed 3 cm, and more preferably 1.5 cm. To provide an antibacterial coating while leaving the uncoated part, coat the coated part so that it has a stripe pattern or a grid pattern, or if the uncoated part has an island pattern, or vice versa. If necessary, masking is applied before applying. An antibacterial coated transparent plate having such transparency is a window,
In particular, it can be suitably used for hospital windows, partition windows and the like.

[0038]

EXAMPLES The silver ion elution test method for glass powder, the film performance test method for coating films, and
The antibacterial test methods and the results of those tests are described.

(Silver ion elution test) 50 ml of distilled water and 1 g of a test sample were put in a sample tube with a lid, which was placed in a constant temperature bath at 25 ° C.
The concentration of Ag + ions eluted in water after holding for a certain period of time was measured by atomic absorption spectrometry. (Membrane performance test) For the coating substrate for the membrane performance test,
A 30 mm × 20 mm × 2 mm soda lime silica glass plate was used. Adhesion JIS K 5400 to check the adhesion of coating film
A cross-cut cellophane tape peeling test specified in 8.5.2 was conducted. Boiling water resistance To check the boiling water resistance of the coating film, JIS K 54
The test specified in 00 8.20 was performed. Alkali resistance To check the alkali resistance of the coating film, JIS K
5400 The test specified in 8.21 was conducted. Acid resistance To check the acid resistance of the coating film, JIS K 5400
The test specified in 8.22 was conducted.

(Antibacterial Test) Examples 1 and 2 and Comparative Example 1
The following antibacterial test 1 was performed for ~ 2. (Antibacterial test 1) (a) Cultivation of bacteria A standard agar medium (for bacteria) and Sabouraud agar medium (for fungi) are exposed to the atmosphere for 5 hours, and the bacteria and mold in the atmosphere are kept on each agar for 1 week at room temperature. The cultured product was used as a bacterium for an antibacterial test. (B) Test A sample (10 mm × 10 mm × 1 mm glass substrate coated with an antibacterial coating film) was placed flat on a standard agar medium (for bacteria) and Sabouraud agar medium (for fungus), and The aqueous solutions of bacteria and fungi prepared in the above (a) were added dropwise to the above to cover the sample and the agar medium. This was incubated at room temperature for 7 days, and then the presence or absence of halo (growth arrest zone) formed around the sample was observed to evaluate the antibacterial performance of the present coating agent.

For Examples 3 to 12 and Comparative Examples 3 and 4, the following antibacterial test 2 was conducted. (Antibacterial Test 2) As a base material for coating for antibacterial test in Examples 3 to 11 and Comparative Example 3, a filter paper for air filter was used. The reason why the air filter was selected for the antibacterial test is that the air filter contains water and creates an environment in which mold can grow relatively easily, so if the coating film has antibacterial properties, the effect is expected to be more pronounced. Is. As the filter paper for the air filter, a glass fiber non-woven fabric having a thickness of about 0.5 mm, which was made by wet papermaking of glass fibers having a diameter of about 0.8 μm, was used. The coated air filter paper was cut into a size of about 50 mm × 50 mm to obtain a test piece.

A soda lime silica glass plate was used as the antibacterial test coating substrate in Example 12 and Comparative Example 4. The soda lime silica glass plate was used in this test because the glass plate had good transparency.

(A) Strains used (a) Aspergillus niger (b) Cladosporium cladosporioides (c) Penicillium funiculosum bacteria (d) Escherichi coli (E. coli) (e) Staphylococcus aureus (Staphylococcus aureus)

(B) Test mold The test piece was allowed to stand on glucose / peptone / agar medium,
About 1 ml of the spore suspension prepared so as to have a concentration of 1 × 10 ⁶ cells / ml was sprayed with a glass sprayer. This was cultivated at 28 ° C. for 7 days in a constant temperature bath, and then the growth state of the bacteria was observed. Bacteria Place the test piece on a standard agar medium, and from the top, 1 x 10
About 1 ml of the bacterial solution prepared to be ⁶ cells / ml was sprayed with a glass sprayer. This was cultivated in a constant temperature bath at 37 ° C. for 2 days, and the growth condition of the bacteria was observed thereafter.

After that, the test piece was taken out, the test piece was allowed to stand on another standard agar medium, and this culture was repeated 6 times, and then the growth state of the bacteria was observed in the same manner.

The display criteria for the evaluation of this antibacterial test are as follows. A: No growth of bacteria was observed on the test piece. B: The area of the growing portion of the bacteria observed on the test piece does not exceed 1/10 of the total area. C: The area of the growing portion of the bacteria observed on the test piece is 1/10 or more and 1/3 or less of the total area D: The area of the growing portion of the bacteria found on the test piece is 1/3 of the total area Cross over.

Example 1 35.0% by weight of SiO2, 15.0% by weight of Na2O, B2
A raw material prepared by adding 1.0 part by weight of Ag2O to 100 parts by weight of a mixture consisting of 50.0% by weight of O3 (borosilicate type) was melted in an electric furnace at 1100 to 1300 ° C for 2 hours, and then poured into water. After rapidly cooling to vitrify, it was pulverized with a ball mill to have a particle size of 5 to 50 μm (average particle size 10 μm). The above-mentioned silver ion elution test was performed on this glass powder. Table 1 shows the results. Further, this glass powder was applied to a commercially available room-temperature-drying type tetraalkoxysilane coating agent (G93 manufactured by Fine Glass Technology Co., Ltd., solid content: 6.5% by weight) as a binder, and the weight ratio of the coating agent to the glass powder was 1: 0.1. And mixed so that an antibacterial coating agent was prepared. The soda lime silica glass substrate (30 mm × 20 mm × 2 mm glass plate and 10 mm × 10 mm × 1 mm glass plate) surface was previously coated with the above-mentioned commercially available normal-temperature-drying tetraalkoxysilane-based coating agent air spray method, and at room temperature,
It is dried for 30 minutes to form a semi-cured film with a thickness of about 5 μm, the antibacterial coating agent is sprayed onto the substrate on the semi-cured film, and then dried at room temperature to mainly coat organopolysiloxane with a total film thickness of about 15 μm. A cured film as a component was obtained. The cured film contained about 50% by weight of silver-containing glass and about 0.5% by weight of silver component, respectively.

Next, the above-mentioned membrane performance test and antibacterial test were conducted. The results are shown in Table 2. A glass substrate of 30 mm × 20 mm × 2 mm was used for the membrane performance test, and a glass substrate of 10 mm × 10 mm × 1 mm was used for the antibacterial test.

As a result of the film performance test, it was found that, as shown in Table 2, a film having good adhesion to the substrate and stable thermally and chemically was formed. Furthermore, as a result of the antibacterial test, halo (width 1m
m-5 mm) appeared, and it was found that this coating agent has very strong antibacterial performance. The halo that appeared here did not disappear even after culturing for another 4 weeks. From this, it was found that the antibacterial performance of the present coating agent is stable and long-lasting.

[0050]

[Table 1] Table 1 -------------------------------------------- ---- Silver Ion Concentration (μg / 50ml) Example 1 Example 2 Comparative Example 2 ----------------------------- ------------------- 10 days later 2500 2320 4 20 days later 2835 3410 4 30 days later 2780 3720 4 ---------------- --------------------------------

[0051]

[Table 2] Table 2 ============================================= ========================== Example 1 Example 2 Comparative Example 1 Comparative Example 2 ------------ -------------------------------------------------- -------- [Film performance test] Adhesion 100/100 100/100 100/100 100/100 Boiling water resistance No abnormality No abnormality No abnormality Abnormality Alkali resistance No abnormality Abnormality Abnormality Abnormality Acid resistance No abnormalities No abnormalities No abnormalities No abnormalities ------------------------------------------ ---------------------------- [Antibacterial test] Standard agar with halo-with halo without halo with saburo-agar halo-with With halo Without halo Without halo ============================================ ===========================

Example 2 Instead of the borosilicate mixture used in Example 1, P2
Preparation, coating and testing were carried out in the same manner as in Example 1 except that 100 parts by weight of a mixture consisting of 57.5% by weight of O5, 5.1% by weight of Na2O, 7.1% by weight of B2O3 and 10.3% by weight of Al2O3 (phosphate type) was used. . The test results are shown in Tables 1 and 2.

From the table, it was found that in Example 2 as well, as in Example 1, a coating film having good adhesion to the substrate, being stable thermally and chemically, and having extremely strong antibacterial performance was formed.

Comparative Example 1 Preparation, coating and testing were carried out in the same manner as in Example 1 except that a commercially available acrylic resin-based water-based paint was used instead of the room temperature dry type tetraalkoxysilane-based coating agent used in Example 1. (However, excluding silver ion dissolution test of glass powder).
Table 2 shows the test results.

Results of Antibacterial Test In Comparative Example 1, no halo was observed in both standard agar and Sabouraud agar. Although the halo was not observed in the sample of Comparative Example 1 even though the filler contained silver ions, the reason why the coating film completely covered the glass powder was that the silver ions in the glass were not observed. Is probably not eluted.

Comparative Example 2 A silver ion-containing zeolite manufactured by Shinagawa Fuel Co., Ltd. (trade name: Zeomic, containing 2.3% by weight of silver ion in terms of Ag2O) was subjected to the above-described silver ion elution test. Table 1 shows the results. From Table 1, the present zeolite is obtained in Examples 1 and 2
Despite containing a larger amount of silver ions than the glass containing silver, the amount of silver ions eluted is smaller than those,
It was also found that the elution of silver ions was limited to the initial stage of contact with water. Therefore, it can be said that the silver-containing glass stably elutes silver ions over a long period of time as compared with the silver ion-containing zeolite. Therefore, it is considered that silver-containing glass can exhibit the antibacterial activity more stably than silver ion-containing zeolite.

Example 3 The same borosilicate mixture as used in Example 1 was used, and 1.0 part of Ag 2 O was added to 100 parts by weight of this mixture.
The raw material added by weight is 1100 to 130 in an electric furnace.
The mixture was melted at 0 ° C. for 2 hours, rapidly cooled to vitrify, and then pulverized with a ball mill to have a particle size of 5 to 50 μm (average particle size 10 μm) to obtain a filler. A commercially available cross-linking reaction type organopolysiloxane coating agent (Atom Chemical Paint Co., Ltd. Atom Cerazione # 300,
Solid content 29% by weight) in a weight ratio of 1: 0.1,
An antibacterial coating agent was prepared.

30 mm × 20 mm × 2 mm which is a test piece
Soda lime silica glass plate, and about 50mm x 5
The cross-linking reaction-type organopolysiloxane-based coating agent was sprayed in advance on each of the filter papers (glass fiber non-woven fabric) for air filters having a size of 0 mm, and the temperature was about 30 at room temperature.
It is dried for a minute to form a semi-cured film with a thickness of about 5 μm, sprayed with an antibacterial coating agent and dried at room temperature for about 1 week to cure the total film thickness of organopolysiloxane as the main component to about 15 μm. A film is obtained. About this membrane
A membrane performance test (glass plate) and an antibacterial test (filter paper for air filter) according to the above antibacterial test 2 were performed. Table 3 shows the results. As a result of the film performance test, it was found that a film having good adhesion to the substrate and being stable thermally and chemically was formed.

As a result of the antibacterial test shown in the above antibacterial test 2, Cladosporium clados among all bacteria and fungi.
As for porioides and Penicillium funiculosum, no bacterial growth was observed on the test piece, and Aspergillus niger
Although the fungus grows on the test piece, its area is 1 / th of that of the test piece.
It turns out that it doesn't exceed 10. This result shows that the test piece has good antibacterial performance.

Example 4 Instead of the borosilicate type mixture which is the glass raw material used in Example 3, P2O5 65% by weight and Na2O 10% by weight were used.
%, B2O3 10% by weight, Al2O3 5% by weight, CaO 1
A glass filler was obtained in the same manner as in Example 3 except that 100 parts by weight of a mixture containing 0% by weight (phosphate type) was used. This is mixed with a commercially available crosslinking reaction type organopolysiloxane coating agent (Atom Cerazion # 300 manufactured by Atom Chemical Co., Ltd.) used in Example 3 at a weight ratio of 1: 0.1 to prepare an antibacterial coating agent. Then, coating was performed in the same manner as in Example 3 and a membrane performance test was performed. An antibacterial test was conducted in the same manner as in Example 3. Table 3 shows the test results.

From Table 3, it was found that, similarly to Example 3, a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the result of the antibacterial test, it was found that a coating film having good antibacterial performance was formed as in Example 3.

Example 5 Instead of the glass filler prepared in Example 3, commercially available silver ion-supporting ceramics (Novalon manufactured by Toagosei Kagaku Kogyo Co., Ltd., a ceramic body having zirconium phosphate supporting silver ions) was filled. Preparation, coating, and testing were performed in the same manner as in Example 3 except that the agent was used. Table 3 shows the test results.
From Table 3, it was found that a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed.

Example 6 Preparation was carried out in the same manner as in Example 3 except that the commercially available silver ion-supporting silica gel (Amenitop manufactured by Matsushita Electric Industrial Co., Ltd.) was used as the filler instead of the glass filler prepared in Example 3. , Coating and testing were performed. Table 3 shows the test results. From Table 3, it was found that a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed.

Example 7 A commercially available organic / inorganic composite coating agent (Gracelam # 320 manufactured by Shinto Paint Co., Ltd.) was used in place of the commercially available crosslinking reaction type organopolysiloxane coating agent which was the binder used in Example 3. An antibacterial coating agent was prepared in the same manner as in Example 3 except that Then, in the same manner as in Example 3, the commercially available organic / inorganic composite coating agent was pre-coated, and then the antibacterial coating agent was coated.
After baking and drying at 30 ° C. for 30 minutes, a film performance test and an antibacterial test were performed. Table 3 shows the results.

From Table 3, it was found that also in this example, a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed.

Example 8 Prepared in the same manner as in Example 7, except that the phosphate-containing glass filler prepared in Example 4 was used in place of the silver-containing borosilicate-based glass powder used in Example 7. Coated and tested. Table 3 shows the test results. From Table 3, it was found that also in this example, a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed.

Example 9 Instead of the silver-containing borosilicate glass powder used in Example 7, the commercially available silver ion-supporting ceramics used in Example 5 (Novaron manufactured by Toagosei Kagaku Kogyo Co., Ltd., silver on zirconium phosphate) was used. Preparation, coating, and testing were performed in the same manner as in Example 7 except that a ceramic body carrying ions) was used. Table 3 shows the test results. From Table 3, it was found that also in this example, a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed.

Example 10 In place of the silver-containing borosilicate glass powder used in Example 7, the commercially available silver ion-supporting silica gel (Amenitop manufactured by Matsushita Electric Industrial Co., Ltd.) used in Example 6 was used. Was prepared, coated, and tested in the same manner as in Example 7. Table 3
The test results are shown in. From Table 3, it was found that also in this example, a film having good adhesion to the substrate and being stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed.

Example 11 The same glass powder containing silver as that used in Example 3 was used as the filler. This was mixed with a commercially available crosslinking reaction type tetraalkoxysilane coating agent (G93 manufactured by Fine Glass Technology Co., Ltd.) as a binder at a weight ratio of 1: 0.1 to prepare an antibacterial coating agent. However, since the present coating agent has no hydrophobic group, the present coating film easily adsorbs water due to residual hydroxyl groups generated as a result of hydrolysis of tetraalkoxysilane.

As a result of the antibacterial test, Cladosporium cladosporioides and Penicillium fu among all bacteria and fungi were found.
niculosum has an antibacterial effect, but Aspergillus niger
Has no antibacterial effect. Aspe when using a water-repellent cross-linking organopolysiloxane coating agent and cross-linking organic / inorganic composite coating agent
Since rgillus niger also showed antibacterial effect, it was found that the antibacterial effect of glass containing silver was improved by using a water-repellent binder.

Example 12 A coating agent comprising the same antibacterial glass powder and binder as in Example 3 was applied to one surface of a transparent glass substrate (50 cm × 50 cm × 5 mm) having a soda lime silica composition by an air spray method. It was applied in a striped pattern. That is, spray a slit having a width of about 5 mm with a pattern of about 50 slits at an interval of 5 mm as a mask,
After that, the mask was rotated by 90 degrees and further sprayed to obtain a grid-shaped coating film having a grid width (coating agent application portion) of 5 mm and an interval between adjacent grids and a grid side of 5 mm. As described above, in this test piece, the total area of the coating-uncoated portion (square having a side of 5 mm) remains 25% with respect to the total area on one side of the substrate, and thus the transparency of the substrate is sufficiently ensured. Also for this test piece,
The same membrane performance test and antibacterial test were conducted. Table 3 shows the results.

From Table 3, it was found that also in Example 12, a film having good adhesion to the substrate and stable thermally and chemically was formed. From the results of the antibacterial test, it was found that a coating film having good antibacterial performance was formed over the entire surface of the substrate, although the uncoated portion of the antibacterial agent was left on the substrate. It is considered that the reason why the antibacterial performance spreads over the entire surface of the substrate is that silver ions were eluted in the uncoated portion of the antibacterial agent because the glass powder in the coating film was water-soluble.

Comparative Example 4 The same coating agent containing the same antibacterial glass powder and binder as in Example 3 was applied to one surface of a transparent glass substrate (50 cm × 50 cm × 5 mm) having a soda lime silica composition in the same manner as in Example 12. It was applied in a grid pattern by the air spray method. However, the width of the grid (coating agent application part) is 5
mm, and the distance between the adjacent grids and the sides of the grid was 30 mm. As a result, the ratio of the area of the uncoated portion of the coating agent to the total area of the substrate was 64%. For this test piece, the same membrane performance test and antibacterial test were performed. Table 3 shows the results. From Table 3, it was found that a good antibacterial effect could not be obtained with this test piece. It is considered that this is because the ratio of the portion to which the antibacterial agent was not applied was too large, and thus the elution effect of silver ions as seen in Example 12 was not sufficiently exerted.

[0074]

[Table 3] Table 3 ============================================= ========================== Example ---------------------- ------------------------------------------------ 3 4 5 6 ------------------------------------------------ ---------------------- Membrane performance test Adhesion (Number of remaining / 100) 100/100 100/100 100/100 100/100 Boiling water resistance No abnormality No abnormalities No abnormalities No abnormalities Alkali resistance No abnormalities No abnormalities No abnormalities No abnormalities Acid resistance No abnormalities No abnormalities No abnormalities No abnormalities ------------------------ --------------------------------------------- Antibacterial test Aspergillus niger B B B B Cladosporium cladosporioides A A A A Penicillium funiculosum A A A A E. coli A A A A A Staphylococcus aureus A A A A ======================= ===============================================

Table 3 (Continued 1) ========================================== ============================= Example ------------------- -------------------------------------------------- -7 8 9 10 --------------------------------------------- ------------------------- Membrane performance test Adhesion (Number of remaining / 100) 100/100 100/100 100/100 100/100 Boiling resistance Water-based No abnormalities No abnormalities No abnormalities Alkaline resistance No abnormalities No abnormalities No abnormalities No abnormalities Acid resistance No abnormalities No abnormalities No abnormalities No abnormalities --------------------- ------------------------------------------------ Antibacterial test Aspergillus niger B B B B Cladosporium cladosporioides A A A A Penicillium funiculosum A A A A A E. coli A A A A A Staphylococcus aureus A A A A A ==================== ===================================================

Table 3 (continuation 2) ========================================== ============================= Examples Examples Examples Comparative Examples --------------- -------------------------------------------------- ----- 11 12 4 ------------------------------------------ ---------------------------- Membrane performance test Adhesion (Number of remaining / 100) 100/100 100/100 100/100 Boiling resistance Water-based No abnormality No abnormality No abnormality Alkaline resistance No abnormality No abnormality No abnormality No acid resistance No abnormality No abnormality No abnormality --------------------------- ------------------------------------------- Antibacterial test Aspergillus niger C AC Cladosporium cladosporioides A A C Penicillium funiculosum A A C E. coli A A C Staphylococcus aureus A A C =============================== ========================================

[0077]

The coating composition of the present invention has an effect that the antibacterial performance of the filler-containing glass and the silver-containing ceramics is hardly impaired because the produced film is porous. Further, the filler having antibacterial properties used in the present invention can stably obtain the antibacterial action by Ag + ions for a long period of time. Further, by using a water-repellent binder, the antibacterial performance of the coating film can be enhanced. Also, by coating the coating film in two layers (
The first layer is binder only. The second layer is a binder + silver-containing glass) A relatively strong coating film with good adhesion to the substrate can be created. Furthermore, when the present coating agent is applied to a substrate having transparency, an antibacterial coating material that does not significantly impair the transparency of the substrate can be obtained by leaving an uncoated portion of the coating agent on the substrate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Renhito Nagashima 3-5-11 Doshomachi, Chuo-ku, Osaka City Nippon Sheet Glass Co., Ltd.

Claims (12)

[Claims] 1. A main component comprising 1) glass particles, ceramic particles, or porous silica gel particles each having a metal ion having an antibacterial action, and 2) an organosilane capable of hydrolysis and polycondensation or a partial hydrolyzate thereof. And an antibacterial coating composition. 2. The antibacterial coating composition according to claim 1, wherein the organosilane is tetraalkoxysilane or alkyltrialkoxysilane. 3. The antibacterial coating composition according to claim 1, wherein the metal ions are silver ions. 4. The glass particles, expressed in% by weight, are: SiO2 25-60, B2O3 18-60, Al2O3 0-20, R2O 8-30, (R is Li, Na, and K, and R2O. Is the total of those oxides) R'O 0-20 (R 'is Ca, Mg, Zn, and Ba, R'O
Is a total of these oxides) and Ag2O 0.05 to 2.0. The antibacterial coating composition according to claim 1. 5. The glass particles, expressed in% by weight, are: P2O5 35-75 B2O3 0-20, SiO2 0-20, Al2O3 0-20, R2O + R'O 10-40, (R is Li, Na, And K, R2O is the sum of those oxides, and R'is Ca, Mg, Zn, and B.
The composition for an antibacterial coating according to claim 1, wherein the composition is a and R'O is the total of those oxides) and Ag2O 0.05 to 5.0. 6. The antibacterial coating composition according to claim 1, further comprising, in addition to the particles and the organosilane, an oligomer of a resin or an intermediate product of a polymerization reaction. 7. An antibacterial coating composition comprising glass particles, ceramic particles or porous silica gel particles each having an antibacterial metal ion, and an organosilane capable of being hydrolyzed and polycondensed as a main component. A method for producing an antibacterial article, which comprises coating the material surface and then drying. 8. The method for producing an antibacterial article according to claim 7, wherein, as the antibacterial coating composition, in addition to the particles and the organosilane, a composition further containing a resin oligomer or an intermediate product of a polymerization reaction is used. . 9. A porous coating layer containing silicon oxide as a main component, wherein glass particles, ceramic particles, or porous silica gel particles each having a metal ion having an antibacterial action are dispersed in the layer. Antibacterial coated article. 10. The antibacterial coated article according to claim 9, wherein the coating layer further contains a hydrophobic group. 11. The antibacterial coated article according to claim 9, wherein the coating layer further contains a resin. 12. The coating layer is provided on a transparent substrate so as to cover an area of 40 to 90% of the total area of the substrate, and the minimum width of the uncoated surface portion is at most 3c.
The antibacterial coated article according to claim 9, wherein the transparency is m.