JPH0859406A - Coating liquid of ceramic antibacterial agent and coating method thereof - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a coating liquid of a ceramic antibacterial material and a coating method thereof, which can easily and effectively impart an antibacterial function to various substrates without using a paint. The purpose is to [Structure] 0.01 to 20% by weight of a ceramic antibacterial agent having an average particle size of 0.05 to 0.7 μm surface-treated with a coupling agent, and a dispersion liquid 80 to 99.95.
A coating liquid of a ceramic-based antibacterial agent made up by weight, and applying the coating liquid to the surface of the base material and then performing heat treatment to fix the antibacterial agent to the base material to provide an antibacterial function on the base material surface. Method for coating ceramic antibacterial agent coating liquid

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a coating liquid for a ceramic antibacterial agent, which is highly safe and has a long-lasting antibacterial effect.
The present invention also relates to a coating method for coating a ceramic-based antibacterial agent, which imparts a novel antibacterial function using the same to various substrates.

[0002]

2. Description of the Related Art Heretofore, many ceramic antibacterial agents have been proposed in which various ceramics contain an antibacterial substance. An example is shown in Table 1.

[0003]

[Table 1]

These ceramic antibacterial agents shown in Table 1 are problematic in that the antibacterial substance alone has a long-lasting effect, thermal stability, can be handled only by liquid, and has reaction stability with other substances. Therefore, it can be said that ceramics are used as microcapsules in order to solve these problems. Phosphate intercalation compounds such as aluminum phosphate are those in which thiazole or quaternary ammonium ions are included between the layers, while silver ion-based ceramic antibacterial agents are kept in an ionic state by ion exchange or the like. There is. Then, an antibacterial resin (hereinafter referred to as a kneading method) can be obtained by kneading these ceramic antibacterial agents into the resin. For example, Japanese Patent Publication No. 63-540
No. 13 discloses an antibacterial zeolite composition in which zeolite is loaded with silver ions by ion exchange, nylon,
A method for producing an antibacterial fiber by mixing with polyester, an acrylic polymer or the like and spinning it is disclosed in Japanese Patent Publication No. 5-80954, wherein an antibacterial zeolite or the like is contained in a resin such as polyethylene, polypropylene or ABS. No antibacterial resin composition is disclosed. In addition, an antibacterial resin (hereinafter referred to as a spray transfer method) is obtained by spraying a spray liquid containing these ceramic antibacterial agents onto the inner surface of a resin molding die and then molding and transferring the antibacterial agent to the surface of the resin.
Can be obtained. For example, Japanese Patent Application Laid-Open No. 6-80528 discloses a method of obtaining an antibacterial resin by spraying a spray liquid containing an antibacterial phosphate double salt onto the inner surface of a mold using a two-fluid nozzle and then molding. ing. Furthermore, the present inventors have already described in Japanese Patent Application No. 5-54923,
A method for producing a silver-based inorganic antibacterial agent fine particle suspension having an average particle size of 0.3 μm or less is proposed, and in addition, in Japanese Patent Application No. 5-62889, the fine particle suspension is used as a spray liquid to form a resin surface. We have proposed a method for producing an antibacterial resin that does not impair the luster. An antibacterial paint can be obtained by mixing these ceramic antibacterial agents with the paint. For example, Japanese Examined Patent Publication No. 3-48230 discloses a method for producing an antiseptic / antifungal coating composition in which an antibacterial zeolite is mixed with a coating. The antibacterial function can be imparted to the resin by coating the resin with such an antibacterial paint.

[0005]

[Problems to be solved] Japanese Patent Publication Sho 63-5401
In the method for producing an antibacterial resin by the kneading method disclosed in Japanese Patent Publication No. 3 and Japanese Patent Publication No. 5-80954, only the antibacterial agent exposed on the resin surface can contribute to the antibacterial effect. The antibacterial agent is completely useless, and when the antibacterial agent is kneaded into the resin, the temperature becomes high, so that the antibacterial substance is decomposed or discolored. Therefore, embedding the antibacterial agent only on the resin surface saves the antibacterial agent.
The fact that there is no decomposition or discoloration is disclosed in JP-A-6-8052.
This is a method for producing an antibacterial resin by the spray transfer method disclosed in Japanese Patent Publication No. 8 etc., and since the mold to be spray-applied is cooled, the antibacterial agent is not exposed to a high temperature and decomposes and discolors. However, it is not possible to impart an antibacterial function to the molded article afterwards, as in the above-mentioned kneading method. The antibacterial paint disclosed in Japanese Examined Patent Publication No. 3-48230 is one method that can give an antibacterial function to various base materials such as wood and resin, but the paint is scattered. It is often done by hand at another factory with special equipment due to the problem of polluting the surroundings and air pollution by organic solvents, the coating cost is high including the labor of transportation, and the paint is antibacterial. There is a drawback that the agent is easily hidden and the antibacterial effect is difficult to obtain. The present invention is to provide a method for easily and effectively imparting an antibacterial function to various substrates afterwards without using a paint.

[0006]

In order to solve the above problems, a ceramic antibacterial agent 0.01 to 20 having an average particle size of 0.05 to 0.7 μm, which is surface-treated with a coupling agent, is used. % By weight and dispersion 80-99.9
Ceramic antibacterial agent coating liquid consisting of 5% by weight: and 0.01 to 20% by weight of ceramic antibacterial agent having an average particle size of 0.05 to 0.7 μm surface-treated with a coupling agent , And dispersion liquid 80-99.9
Ceramics characterized by applying a coating liquid of 5% by weight to the surface of a base material and then performing heat treatment to fix the antibacterial agent to the base material to impart an antibacterial function to the surface of the base material. We propose a coating method for coating antibacterial agents. The ceramic antibacterial agent according to the present invention,
It is not limited to the use of the ceramic antibacterial agents as shown in Table 1 in which various ceramics contain antibacterial substances. The average particle size of the ceramic antibacterial agent according to the present invention is preferably in the range of 0.05 to 0.7 μm, more preferably 0.05 to 0.3 μm. It is thought that when the surface is wiped, the force that moves the antibacterial agent outweighs the force that the coupling agent binds to the base material,
In particular, the dropout of large antibacterial particles became noticeable, and
If the number of large particles increases, the gloss of the substrate surface will be impaired, which is not preferable. The coupling agent according to the present invention has a silane coupling agent, a macromolecular coupling agent, and a titanate coupling agent, each of which has a ceramic antibacterial agent-bonding unit and a base material-bonding unit. , Aluminum-based coupling agents, zirconia-based coupling agents, fluorine-based coupling agents and the like can be used. Good results can be obtained by selecting a coupling agent having a unit that is easily compatible with the target substrate depending on the target substrate.

In the surface treatment method for the coupling agent according to the present invention, the average particle diameter of the ceramic antibacterial agent is 0.05.
~ 0. In the μm range, a shear mixer
Known surface treatment methods such as a dry method in which the coupling agent is added while stirring the antibacterial agent and an organic solvent method in which the antibacterial agent and the coupling agent are added to the solvent and stirred are used. on the other hand,
When the average particle size of the ceramic antibacterial agent is larger than 0.7 μm, the antibacterial agent, the dispersion, and the antibacterial agent are added to a wet pulverizer using a pulverizing medium such as a known medium mill, planetary mill, vibration ball mill, or ball mill. Also, a coupling agent is added and wet pulverization is performed. Examples of the dispersion include alcohols such as ethanol, methanol, n-propanol, isopropanol, and secondary butanol, aromatic hydrocarbons such as toluene, ketones such as methyl ethyl ketone, and methylene chloride. The halogenated hydrocarbons, fluorocarbons such as fluorocarbon 225, water, and the like can be used. The amount of the coupling agent added to the ceramic antibacterial agent according to the present invention is 0.1 to 1
0% by weight, more preferably 0.5 to 3% by weight. In the case of the ceramic antibacterial agent surface-treated with the coupling agent for the coating liquid according to the present invention,
It is preferably in the range of 0.01 to 20% by weight, more preferably 0.1 to 2% by weight. If it is less than 0.01% by weight, the antibacterial effect is not sufficiently obtained, and if it exceeds 20% by weight, the fluidity of the coating liquid becomes poor and it becomes difficult to handle.

Examples of the base material according to the present invention include thermoplastic resins, thermosetting resins, rubber, natural fibers, paints, woods, papers, etc., which can be combined with a coupling agent unit. You can use it without any restrictions. or,
The shape of the base material can be applied to molded products (sheets, pipes, films, molds, etc.), foams, paints, fibers, non-woven fabrics, composite materials, etc., but the size and shape are not particularly limited. is not. As the coating method for the coating liquid according to the present invention, known methods such as brush coating, cotton flannel coating, tampo coating, roller coating, spray coating, aerosol coating and dip coating can be used without limitation. The heat treatment according to the present invention is carried out directly using an infrared heater, an infrared lamp, a dryer, a hand dryer, a heat roller, an iron, or the like, or via a stainless plate, a resin heat-resistant sheet, or the like. It is performed by heating or pressurizing. The heating temperature varies depending on the base material, but in the case of a thermoplastic resin, it is preferable to set the heating temperature to the approximate heat distortion temperature or higher. In the case of vacuum forming, the formed resin plate is further formed. However, according to the present invention, it is easy to apply the coating liquid to the thermoplastic plate in advance, and then heat and mold it. Thus, an antibacterial resin molded product can be obtained. The present invention can also be applied to the textured surface of the resin, and in this case, the durability when wiped with a cloth tends to be better than that of the glossy surface.

[0009]

[Advantages] By adopting the above-mentioned constitution, the present invention can provide various substrates with an antibacterial function later, and since the antibacterial agent is fine particles, it is bonded to the substrate by the coupling agent. Since the strength is superior, the antibacterial agent is directly exposed on the surface of the base material without dropping off and without impairing the gloss of the base material, and an antibacterial base material excellent in antibacterial effect can be obtained with a small amount of antibacterial agent. can get.

[0010]

【Example】

1. Preparation of antibacterial agent [Reference Example 1] Preparation of antibacterial phosphoric acid double salt 348.8 g of 75% phosphoric acid aqueous solution was heated to 50 ° C. and stirred while stirring aluminum hydroxide (Al (OH) ₃ ) 2
0.8 g, calcium hydroxide (Ca (OH) ₂ ) 64.1
g and zinc oxide (ZnO) 253.4 g are added and reacted. After the reaction slurry was cooled in a greenhouse, it was transferred to a 2 l ball mill and kneaded for 6 hours, and then silver nitrate (AgNO ₃ ) 2
3.7 g was added and kneading continued for a further 24 hours. The obtained reaction slurry was washed with water, filtered, dried at 300 ° C., and crushed into powder (hereinafter referred to as “antibacterial agent powder 1”). The content of silver ions carried by the antibacterial powder 1 is
The amount was 3.0% by weight and the average particle size was 2.7 μm.

[Reference Example 2] Preparation of antibacterial zeolite Ammonium nitrate (NH ₄ N) was added to 720 ml of deionized water.
O ₃₎ 80 g silver nitrate (AgNO ₃₎ 9.5 g, sodium type A zeolite (Tosoh - manufactured Toyobiruda -) dried product 200g was added, then filtered and stirred for 3 hours in a greenhouse, and washed with water Excess silver ions were removed. 110 this
It was dried at ℃ and crushed into powder (hereinafter referred to as "antibacterial agent powder 2"). The content of silver ions carried by the antibacterial agent powder 2 was 3.1% by weight, and the average particle size was 2.9 μm.

Reference Example 3 Preparation of Antibacterial Zirconium Phosphate A dried product 250 of zirconium phosphate (IXL-100; manufactured by Toagosei Kagaku) was added to 1500 ml of 1/20 M silver nitrate aqueous solution.
g was added, and the mixture was stirred in a greenhouse for 3 hours, filtered, and washed with water to remove excess silver ions. This was dried at 110 ° C. and crushed to give a powder (hereinafter referred to as “antibacterial agent powder 3”). The content of silver ions carried by the antibacterial agent powder 3 is 3.
0% by weight, and the average particle diameter was 0.72 μm.

2. Preparation of coating liquid [Example 1] 15 kg of a titanate-based coupling agent (manufactured by Ajinomoto Co., Inc., product number KRTTS) and 3 kg of ethanol and 1 kg of "antibacterial agent powder 1" obtained in Reference Example 1 In addition, the mixture was dispersed and mixed with a homogenizer for 10 minutes, and then wet-milled using a medium mill (1 l pal mill PMIRL-V type, manufactured by Ashizawa). Using 1150 g of 2 mm ¢ alumina grinding beads (V Cerax; manufactured by Shinto Kogyo), 500 ml per pass
Fifty passes at a processing speed of 1 / min to obtain an antibacterial agent fine particle suspension. The average particle size of the antibacterial agent particle suspension is 0.
It was 15 μm. Next, 960 g of ethanol was added to 40 g of the obtained fine particle suspension of antibacterial agent, and the mixture was mixed with a homogenizer 1
The dispersion liquid was mixed for 0 minutes to obtain a coating liquid having an antibacterial agent concentration of 1% (hereinafter referred to as coating liquid 1). In addition, this
The Ting solution 1 was placed in a container and left for 1 week, but no cohesive sedimentation was observed.

Example 2 A titanate coupling agent (manufactured by Ajinomoto Co., product number KRTTS) was added to 3 kg of ethanol.
15 g and 1 kg of "antibacterial agent powder 2" obtained in Reference Example 2 were added, dispersed and mixed for 10 minutes with a homogenizer, and then a medium mill (1 l pal mill PMIRL-V type, manufactured by Ashizawa).
Was used for wet pulverization. 1 mm ¢ alumina crushing beer
Using 1150 g of V-Serax (manufactured by Shinto Kogyo), 1
70 passes were performed with a processing speed of 500 ml / min to obtain a suspension of fine particles of antibacterial agent. The average particle size of the antibacterial agent particle suspension was 0.28 μm. Next, 960 g of ethanol was added to 40 g of the obtained fine particle suspension of the antibacterial agent, and the mixture was dispersed and mixed by a homogenizer for 10 minutes to prepare a coagulum having an antibacterial agent concentration of 1%.
A coating solution (hereinafter referred to as coating solution 2) was obtained.
Further, this coating liquid 2 was placed in a container and left for 1 week, but no aggregation and sedimentation was observed.

Example 3 A titanate-based coupling agent (manufactured by Ajinomoto Co., product number KRTTS) was added to 3 kg of ethanol.
15 g and 1 kg of "antibacterial agent powder 3" obtained in Reference Example 2 were added, dispersed and mixed for 10 minutes with a homogenizer, and then a medium mill (1 l pal mill PMIRL-V type, manufactured by Ashizawa).
Was used for wet pulverization. 2 mm ¢ alumina crushing beer
Using 1150 g of V-Serax (manufactured by Shinto Kogyo), 1
An antibacterial agent fine particle suspension was obtained by performing 60 passes with a processing speed of 500 ml / min. The average particle size of the antibacterial agent particle suspension was 0.21 μm. Next, 960 g of ethanol was added to 40 g of the obtained fine particle suspension of the antibacterial agent, and the mixture was dispersed and mixed by a homogenizer for 10 minutes to prepare a coagulum having an antibacterial agent concentration of 1%.
A coating solution (hereinafter referred to as coating solution 3) was obtained.
Further, the coating liquid 3 was put into a container and left for 1 week, but no aggregation and sedimentation was observed.

[Comparative Example 1] 2 kg of "antibacterial agent powder 1" obtained in Reference Example 1 was added to a Henschel mixer (IM10B).
A mold; manufactured by Mitsui Miike Koki Co., Ltd., and stirred at 3000 rpm for 10 minutes, and then 15 g of a titanate coupling agent (manufactured by Ajinomoto Co., Inc., product number KR TTS) was gradually added dropwise to the surface treatment. 10g of this surface-treated antibacterial powder
Was added to 990 g of ethanol and dispersed and mixed for 10 minutes with a homogenizer to obtain a coating solution having an antibacterial agent concentration of 1% (hereinafter referred to as coating solution 4). When this coating liquid 4 was placed in a container and allowed to stand for 1 week, all were aggregated and settled and the supernatant was transparent.

[Comparative Example 2] 2 kg of "antibacterial agent powder 2" obtained in Reference Example 2 was added to a Henschel mixer (IM10B).
A mold; manufactured by Mitsui Miike Koki Co., Ltd., and stirred at 3000 rpm for 10 minutes, and then 15 g of a titanate coupling agent (manufactured by Ajinomoto Co., Inc., product number KR TTS) was gradually added dropwise to the surface treatment. 10g of this surface-treated antibacterial powder
Was added to 990 g of ethanol and dispersed and mixed for 10 minutes with a homogenizer to obtain a coating solution having an antibacterial agent concentration of 1% (hereinafter referred to as coating solution 5). When this coating liquid 5 was placed in a container and left for 1 week, all were aggregated and settled and the supernatant was transparent.

[Comparative Example 3] 2 kg of "antibacterial agent powder 3" obtained in Reference Example 3 was added to Henschel mixer (IM10B).
A mold; manufactured by Mitsui Miike Koki Co., Ltd., and stirred at 3000 rpm for 10 minutes, and then 15 g of a titanate coupling agent (manufactured by Ajinomoto Co., Inc., product number KR TTS) was gradually added dropwise to the surface treatment. 10g of this surface-treated antibacterial powder
Was added to 990 g of ethanol and dispersed and mixed for 10 minutes with a homogenizer to obtain a coating solution having an antibacterial agent concentration of 1% (hereinafter referred to as coating solution 6). When this coating liquid 6 was placed in a container and left for 1 week, all were aggregated and settled, and the supernatant was transparent.

3. Coating of polystyrene resin test piece with coating liquid, heat treatment (coating) [Example 4] Polystyrene resin test piece (27 x 55 x 2)
mm, Asahi Kasei Styron 666), the coating liquids 1, 2, and 3 obtained in Examples 1, 2, and 3 were applied with a brush, dried at room temperature, and then dried in a dryer heated to 100 ° C. 5
After heating for 1 minute, it was cooled at room temperature (hereinafter PS
Test tubes 1, 2, and 3). The blank resin test piece before applying the coating liquid is referred to as PS test piece 0.

Example 5 Polystyrene resin test piece (2
7 × 55 × 2 mm, Asahi Kasei Styron 666), the coating solutions 1, 2, and 3 obtained in Examples 1, 2, and 3 were applied with a brush, dried at room temperature, and then dried with a hand dryer. After heat treatment for minutes, it was cooled at room temperature (hereinafter referred to as PS test pieces 1H, 2H, and 3H).

Comparative Example 4 Polystyrene resin test pieces (27 × 55 × 2 mm, Asahi Kasei Styron 666) were applied to the coating solutions 1, 2, and 3 obtained in Comparative Examples 1, 2, and 3.
And 3 were applied with a brush, dried at room temperature, put in a dryer heated to 100 ° C. for 5 minutes to be heat-treated, and then cooled at room temperature (hereinafter referred to as PS test pieces 4, 5, and 6). .

Comparative Example 5 Polystyrene resin test pieces (27 × 55 × 2 mm, Asahi Kasei Styron 666) were coated with the coating liquids 1, 2, and 3 obtained in Examples 1, 2, and 3 by brush. After coating and drying at room temperature, it was heat-treated with a hand dryer for 10 minutes and then cooled at room temperature (hereinafter referred to as P
S test pieces 4H, 5H, and 6H).

4. Acrylic modified PVC resin test piece
Coating liquid, heat treatment (coating) [Example 6] Acrylic modified PVC resin test piece (27 x 55)
× 2mm, Cylinder Plastic Industry; Kydak KGD14
00), the coating liquids 1, 2, and 3 obtained in Examples 1, 2, and 3 were applied with a brush and dried at room temperature.
The mixture was placed in a dryer heated to 0 ° C. for 5 minutes for heat treatment, and then cooled at room temperature (hereinafter referred to as KD test pieces 1, 2 and 3).
The blank resin test piece before applying the coating liquid is referred to as KD test piece 0.

[Comparative Example 6] Comparative examples 1, 2, and 3 were applied to acrylic modified vinyl chloride resin test pieces (27 x 55 x 2 mm, Chunchu Plastic Industry Co., Ltd .; Kydak KGD1400).
Apply the coating liquids 4, 5, and 6 obtained in step 1 above with a brush,
After drying at room temperature, it was placed in a dryer heated to 80 ° C. for 5 minutes for heat treatment, and then cooled at room temperature (hereinafter referred to as KD test pieces 4, 5, and 6).

5. Coating of polypropylene resin test piece with coating liquid, heat treatment (coating) [Example 7] Polypropylene resin test piece (27 x 55 x
2 mm, Mitsui Noblen JHH-G), Examples 1, 2,
The coating liquids 1, 2 and 3 obtained in 3 and 3 were applied with a brush, dried at room temperature, placed in a dryer heated to 180 ° C. for 5 minutes for heat treatment, and then cooled at room temperature ( Below P
P test pieces 1, 2, and 3). The blank resin test piece before applying the coating liquid was a PP test piece 0.
And

Comparative Example 7 Polypropylene resin test piece (27 × 55 × 2 mm, Mitsui Noblen JHH-G)
Coating liquids 4, 5, and 6 obtained in Comparative Examples 1, 2, and 3 were applied to the surface with a brush and dried at room temperature.
After heating for 5 minutes in a dryer heated to 0 ° C,
It was cooled at room temperature (hereinafter referred to as PP test pieces 4, 5, and 6).

6. Application of coating liquid and heat treatment (coating) on a special acrylic-modified decorative board resin test piece [Example 8] Special acrylic-modified decorative board resin test piece (27)
× 55 × 1 mm, Aika Kogyo High Board), Example 1,
The coating solutions 1, 2 and 3 obtained in Nos. 2 and 3 were applied by spraying, dried at room temperature, and then heat-treated by passing through a heat roller heated to 180 ° C., then at room temperature. It was cooled (hereinafter referred to as A test pieces 1, 2, and 3). In addition, the blank resin test piece before applying the coating liquid is the A test piece 0
And

[Comparative Example 8] Special acrylic-modified decorative board resin test piece (27 x 55 x 1 mm, Aika Kogyo Hibo-
Coating solution obtained in Comparative Examples 1, 2 and 3 on 4, 5 and 6 sprays, dried at room temperature and then heated to 180 ° C. After heat-treating through the same, it was cooled at room temperature (hereinafter referred to as A test pieces 4, 5, and 6).

7. Application of coating liquid to filter paper test piece, heat treatment (coating) [Example 9] Filter paper test piece (27 x 55 mm, Toyo Filter Paper No.
5C) was coated with the coating liquids 1, 2, and 3 obtained in Examples 1, 2, and 3 by a spray, dried at room temperature, heat-treated by ironing, and then cooled at room temperature. (Hereinafter referred to as R test pieces 1, 2, and 3). A blank resin test piece before applying the coating liquid is referred to as R test piece 0.

[Comparative Example 9] Filter paper test pieces (27 x 55)
mm, Toyo Filter Paper No. 5C), Comparative Examples 1, 2, and 3
The coating solutions 4, 5, and 6 obtained in 1. were applied by spraying, dried at room temperature, heat-treated by ironing, and then cooled at room temperature (hereinafter, R test pieces 4, 5, and 6). And).

8. Application of coating liquid to a cotton cloth test piece, heat treatment (coating) [Example 10] Coating liquid 1 obtained in Examples 1, 2, and 3 on a cotton cloth (weight per unit area: 150 g / m ² ). , 2, and 3
Was sprayed on, dried at room temperature, heat-treated by ironing, and then cooled at room temperature (hereinafter referred to as C test pieces 1, 2, and 3). The blank resin test piece before applying the coating liquid is referred to as C test piece 0.

Comparative Example 10 Cotton cloth (weight per unit area 150
g / m ² ), the coating liquids 4, 5, and 6 obtained in Examples 1, 2, and 3 were spray-coated, dried at room temperature, and then heat-treated by ironing, It was cooled at room temperature (hereinafter referred to as C test pieces 4, 5, and 6).

9. Wiping test of resin test piece [Example 11] The resin test piece (PS test piece 1,
2,3,1H, 2H, 3H, 4,5,6,4H, 5H,
And 6H, KD test pieces 1, 2, 3, 4, 5, and 6, P
P test piece 1, 2, 3, 4, 5, and 6, A test piece 1,
Cleaner for gase for 2, 3, 4, 5, and 6)
Immerse (made by Lion; glass cleaner) for each 1
A wiping test was performed 00 times (hereinafter, PS test pieces 1T, 2T, 3T, 1HT, 2HT, 3HT, 4
T, 5T, 6T, 4HT, 5HT, and 6HT, KD test pieces 1T, 2T, 3T, 4T, 5T, and 6T, PP test pieces 1T, 2T, 3T, 4T, 5T, and 6T, A test piece 1T, 2T, 3T, 4T, 5T, and 6T).

10. Durability test of filter paper test piece [Example 12] Filter paper test piece (R test piece 1, 2, 3, 4,
Regarding 5 and 6), a wiping test was conducted 10 times with a gauze placed on a glass plate and moistened with water. (R test pieces 1T, 2T, 3T, 4T, 5T and 6T respectively
And).

11. Washing resistance test of cotton cloth test piece [Example 13] Cotton cloth test piece (C test piece 1, 2, 3, 4,
5 and 6) were washed 5 times together with general household laundry in a household washing machine (hereinafter referred to as C test pieces 1T, 2T, 3T, 4T, 5T, and 6T, respectively).

12. Antibacterial Test [Example 14] An antibacterial test was conducted on the various test pieces obtained above. Meat extract broth medium was diluted 1000 times with phosphate buffered saline, and plated on ordinary agar medium prepared separately for 24 hours. The number of bacteria was 1 to 5 x 1
The mixture was added and dispersed so that the concentration became 0 ⁶ / ml. 0.1 ml of this bacterial solution was dropped at two locations on a test piece (27 × 55 mm), and a membrane filter (diameter 25 mm, pore diameter 0.
2 μm) and cultivated at 35 ° C. 0 and 24
After 10 hours, 10 ml of phosphate buffered saline was added to wash out the bacteria, and 1 ml was taken out, and the number of germ cells was measured by the pour plate culture method using SCDLP agar medium. Converted. The test is for Escherichia coli (Escheri
chia coli: IFO 3301) and Staphylococcus aureu
s: IFO 12732). The results are shown below.

Test piece symbol Escherichia coli Staphylococcus aureus (initially added number of bacteria) 1.5 × 10 ⁵ 1.2 × 10 ⁵ PS test piece 0 1.3 × 10 ⁷ 1.0 × 10 ⁵ PS test piece 1 <10 <10 PS test piece 2 <10 <10 PS test piece 3 <10 <10 PS test piece 1H <10 <10 PS test piece 2H <10 <10 PS test piece 3H <10 <10 PS test Piece 4 <10 <10 PS test piece 5 <10 <10 PS test piece 6 <10 <10 PS test piece 4H <10 <10 PS test piece 5H <10 <10 PS test piece 6H <10 <10 PS test piece 1T (Durability test) <10 <10 PS test piece 2T (durability test) <10 <10 PS test piece 3T (durability test) <10 <10 PS test piece 1HT (durability test) <10 <10 PS test piece 2HT (durability test) Test) <10 <10 PS test piece 3HT (durability test) <10 <10 PS test piece 4T (durability test) 1.1 × 10 ⁷ 5.2 × 10 ⁴ PS test piece 5T (durability test) 8.6 × 10 ⁶ 5.1 × 10 ⁴ PS test piece 6T (durability test) 1.0 × 10 ⁷ 3.9 × 10 ⁴ PS test piece 4HT (durability test) 2.1 × 10 ⁷ 3.5 × 10 ⁴ PS test piece 5HT (endurance test) 9.1 × 10 ⁶ 5.1 × 10 ⁴ PS test piece 6HT (endurance test) 2.6 × 10 ⁷ 4.9 × 10 ⁴ KD test piece 0 2.2 × 10 ⁴ 6.5 × 10 ⁴ KD test piece 1 <10 <10 KD test piece 2 <10 <10 KD test piece 3 <10 <10 KD test piece 4 <10 <10 KD test piece 5 <10 <10 KD test piece 6 <10 <10 KD test Piece 1T (endurance test) <10 <10 KD test piece 2T (endurance test) <10 <10 KD test piece 3T (endurance test) <10 <10 KD test piece 4T (endurance test) 3.2 × 10 ⁴ 4. 5 x 10 ⁴ KD test piece 5T (durability test) 1.8 × 10 ⁴ 7.9 × 10 ⁴ KD test piece 6T (durability test) 1.1 × 10 ⁴ 3.2 × 10 ⁴ PP test piece 0 2.7 × 10 ⁷ 4.2 × 10 ⁵ PP test piece 1 <10 <10 PP test piece 2 <10 <10 PP test piece 3 <10 <10 PP test piece 4 <10 <10 PP test piece 5 <10 <10 PP test piece 6 <10 <10 PP test Piece 1T (endurance test) <10 <10 PP test piece 2T (endurance test) <10 <10 PP test piece 3T (endurance test) <10 <10 PP test piece 4T (endurance test) 3.1 × 10 ⁷ 5. 6 x 10 ⁴ PP test piece 5T (durability test) 8.9 × 10 ⁶ 4.9 × 10 ⁴ PP test piece 6T (endurance test) 1.3 × 10 ⁷ 2.0 × 10 ⁴ A test piece 0 3.1 × 10 ⁷ 3.2 × 10 ⁵ A test piece 1 <10 <10 A test piece 2 <10 <10 A test piece 3 <10 <10 A test piece 4 <10 <10 A test piece 5 <10 <10 A test piece 6 <10 <10 A test Piece 1T (endurance test) <10 <10 A test piece 2T (endurance test) <10 <10 A test piece 3T (endurance test) <10 <10 A test piece 4T (endurance test) 2.6 × 10 ⁷ 2. 8 x 10 ⁴ A test piece 5T (durability test) 1.0 × 10 ⁷ 8.5 × 10 ⁴ A test piece 6T (durability test) 3.6 × 10 ⁷ 2.0 × 10 ⁴ R test piece 0 8.3 × 10 ⁷ 5.9 × 10 ⁵ R test piece 1 <10 <10 R test piece 2 <10 <10 R test piece 3 <10 <10 R test piece 4 <10 <10 R test piece 5 <10 <10 R test piece 6 <10 <10 R test Piece 1T (endurance test) <10 <10 R test piece 2T (endurance test) <10 <10 R test piece 3T (endurance test) <10 <10 R test piece 4T (endurance test) 1.7 × 10 ⁶ 2. 8 x 10 ⁴ R test piece 5T (endurance test) 2.6 × 10 ⁵ 7.3 × 10 ³ R test piece 6T (durability test) 3.8 × 10 ⁵ 9.1 × 10 ⁴ C test piece 0 6.0 × 10 ⁷ 9.3 × 10 ⁵ C test piece 1 <10 <10 C test piece 2 <10 <10 C test piece 3 <10 <10 C test piece 4 <10 <10 C test piece 5 <10 <10 C test piece 6 <10 <10 C test Piece 1T (endurance test) <10 <10 C test piece 2T (endurance test) <10 <10 C test piece 3T (endurance test) <10 <10 C test piece 4T (endurance test) 6.5 × 10 ⁵ 4. 3 x 10 ⁴ C test piece 5T (durability test) 4.9 × 10 ⁶ 7.1 × 10 ⁴ C test piece 6T (durability test) 4.1 × 10 ⁵ 2.6 × 10 ⁴

From the above results, the test piece coated with the coating liquid according to the present invention and heat-treated showed a remarkable antibacterial effect even after a durability test such as wiping, and the antibacterial agent did not fall off. I understand. Further, the test pieces coated with the coating liquid of Comparative Examples 1, 2, and 3 having large antibacterial material particles and subjected to heat treatment have a markedly lowered antibacterial effect when subjected to a durability test such as wiping. It is considered that if the material particles are large, they fall off.

[0039]

As is apparent from the above description, the ceramic-based coating liquid according to the present invention can fix the antibacterial material on the substrate by a simple method of applying and then heat-treating. A variety of substrates can be provided with outstanding antibacterial function.

Claims (2)

[Claims] 1. A ceramic antibacterial agent having a mean particle size of 0.05 to 0.7 μm, which is surface-treated with a coupling agent, in an amount of 0.01 to 20% by weight, and a dispersion liquid 80 to 9
Ceramic antibacterial coating liquid consisting of 9.95% by weight 2. 0.01 to 20% by weight of a ceramic-based antibacterial agent having an average particle size of 0.05 to 0.7 μm surface-treated with a coupling agent, and a dispersion liquid 80 to 9
A ceramics system characterized in that the antibacterial agent is fixed by applying a coating liquid of 9.95% by weight to the surface of the base material and then heat treatment to impart an antibacterial function to the surface of the base material. Method for coating antibacterial coating liquid