TWI523923B - Water-based coating agent, anti-mildew agent and antibacterial agent - Google Patents

Description

Water coating agent, anti-fungal agent and antibacterial agent

The present invention relates to an aqueous coating agent which is resistant to mildew and antibacterial properties even when exposed to conditions such as high humidity conditions which are prone to mildew, or wind and rain.

Further, the present invention relates to an antifungal agent and an antibacterial agent comprising the aqueous coating agent, and further relates to a paper material and a fibrous material treated with the aqueous coating agent.

Originally, in Japan, where high temperature and humidity were present, molds were more harmful, and the health hazards of molds have become a social problem. In addition, under the conditions of high temperature and high humidity, it is difficult to maintain the production of mold for a long time. Therefore, various antifungal agents have been blended with the coating agent since the past. It is known to use organic antifungal agents such as Carbendazim (BCM), Thiabendazole (TBZ), Octyl Isothiazolin (OIT) in the top coat of the coating (Japanese special JP-A-2010-254597: Patent Document 1), or Zinc Pyrithione (Japanese Patent Laid-Open Publication No. 2008-137913: Patent Document 2). In addition, inorganic systems are known to contain silver zeolite (silver). A coating agent for a photocatalyst such as silver or titanium oxide such as loaded zeolite.

Prior art organic mold inhibitors or zinc pyrithione, in addition to defects due to heat or ultraviolet light, such as deterioration, discoloration, etc., due to water-related places in the home or where the rain will fall, the agent will float out of the surface, It has a high anti-mildew effect at the beginning, but its persistence is problematic. On the other hand, an inorganic silver-based substance has a drawback that it is not effective without an ion and has a poor anti-mildew effect. Further, although a photocatalyst such as titanium oxide has high weather resistance, it is not able to exert an effect in a place where light is not irradiated, and the solid is present in a discontinuous layer in the resin, and has a drawback that the anti-mildew effect is weak.

In addition, a boron compound such as DOT has been known to have a slightly weak antifungal property since ancient times, but is particularly excellent in safety, such as antibacterial property, insect resistance, and algae resistance. However, it is water-soluble, and there is a disadvantage that it is easily lost in the place where it is in contact with water even if it is sealed in the resin, and immediately loses its effectiveness.

Further, there is an example in which a calcium borate compound is blended in a polyoxyethylene rubber base polymer (Japanese Patent Laid-Open Publication No. 2007-31651: Patent Document 3), and an example of mixing boron oxide and boron in a styrene resin (Japanese special) Japanese Patent Laid-Open No. Hei 9-25389: Patent Document 4), but none of the mold resistance has reached a level that can be satisfied.

Zinc compounds have also been known as antibacterial agents since ancient times, but they are also highly water-soluble, and have the disadvantage of being immediately lost in the place where they are in contact with water even if they are sealed in the resin.

Prior technical document Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-254597

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-137913

Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-31651

Patent Document 4: Japanese Patent Laid-Open No. 9-25389

The present invention provides not only excellent mold resistance, antibacterial property, safety, and weather resistance, but also does not cause discoloration, even when used in a place of high humidity or in a water-related place at home or rainwater, It is also possible to maintain a high-proof, antibacterial water-based coating agent, an anti-fungal agent, and an antibacterial agent. Further, the present invention provides a paper or a fibrous material treated with the aqueous coating agent for other purposes.

The inventors of the present invention repeated the intensive review to achieve the above objectives and found that the water-based compositions containing the following (A), (B), and (C) have excellent mold and antibacterial properties, and safety. The water-based coating agent which is excellent in deterioration and discoloration does not occur, and the present invention has been completed.

Accordingly, the present invention provides the following water-based mildew-proof, antibacterial coating agents, as well as paper materials and fibrous materials.

[1] An aqueous coating agent comprising (A) a resin latex having a film forming ability by emulsion polymerization using a surfactant, and having a solid content of 100 parts by mass, (B) 0.01 to 5 parts by mass of the boron compound, (C) 0.01 to 5 parts by mass of the zinc compound, and (B) the ratio of use of the boron compound to the (C) zinc compound is 10:1 to 0.1 by mass ratio: 1.

[2] The aqueous coating agent according to [1], wherein (B) the boron compound is 0.1 to 5 parts by mass, and the (C) zinc compound is 0.5 to 5 masses per 100 parts by mass of the solid component of the component (A). Share.

[3] The aqueous coating agent according to [1] or [2], wherein the ratio of use of the (B) boron compound to the (C) zinc compound is 10:1 to 1:1 by mass ratio.

[4] The aqueous coating agent according to [1] or [2], wherein the resin latex of the component (A) is formed into a dry film at 20 to 150 °C.

[5] The aqueous coating agent according to [1] or [2], wherein the resin latex of the component (A) is at least one selected from the group consisting of an acrylic resin latex, a urethane resin latex, a vinyl chloride resin latex, and a polyfluorene. Oxygen resin latex and acrylic acid polyoxyethylene copolymer resin latex.

[6] The aqueous coating agent according to [1] or [2], wherein the surfactant in the resin latex of the component (A) is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant. Group of people.

[7] The aqueous coating agent according to [1] or [2], wherein the boron compound of the component (B) is at least one selected from the group consisting of disodium tetraborate tetrahydrate, sodium tetraborate decahydrate, and boric acid.

[8] The aqueous coating agent according to [1] or [2], wherein the zinc compound of the component (C) is at least one selected from the group consisting of zinc acetate and zinc sulfate.

[9] An antifungal agent comprising the aqueous coating agent of [1] or [2].

[10] An antibacterial agent comprising the aqueous coating agent of [1] or [2].

[11] A paper which is treated with an aqueous coating agent such as [1] or [2].

[12] The paper material of [11], which is used for wallpaper, paper tube, and paper products.

[13] A fibrous material which is treated with an aqueous coating agent such as [1] or [2].

[14] The fibrous material according to [13], wherein the fiber treated with the aqueous coating agent is a natural polyamide fiber, a synthetic polyamide fiber, a polyurethane fiber, a polyester fiber, a polypropylene fiber, a poly Ethylene fiber, polyacrylonitrile fiber or cellulose-containing fiber.

[15] A method for producing an aqueous coating agent characterized by using (A) a resin latex having a film forming ability by emulsion polymerization using a surfactant, and having a solid content of 100 parts by mass, (B) a boron compound 0.01 ~5 parts by mass, (C) 0.01 to 5 parts by mass of the zinc compound, and (B) a boron compound and (C) a zinc compound to produce a water-based coating agent in a ratio of 10:1 to 0.1:1 by mass ratio When the components (A) and (B) are mixed, the component (C) is mixed.

The present invention provides an aqueous coating agent which is excellent in both mildewproof and antibacterial functions, excellent in safety and weather resistance, and which can maintain long-term effects even under conditions of high humidity or wind and rain. Inorganic materials such as plastic materials, paper materials, wood, fiber materials, metal materials, concrete materials, etc. inside and outside the house. Especially suitable for paper and fiber.

The aqueous coating agent of the present invention contains (A) a resin emulsion having a film forming ability by emulsion polymerization using a surfactant, (B) a boron compound, and (C) a zinc compound.

(A) A resin emulsion having a film forming ability by emulsion polymerization using a surfactant, and a known method, for example, an emulsion or an ionic emulsifier may be used for the synthesis by an emulsion polymerization method, or a commercially available product may be used. . The film forming ability means that the particle properties on the surface of the coating film after drying are eliminated at a certain temperature or higher, and the functions of fine cracks and the like are not caused during drying. Although the temperature range is not particularly limited, it is preferably 20 to 150 ° C, more preferably 30 to 150 ° C, which is suitable for forming a dry film.

The component (A) may be formed by forming a film after evaporation of water, and is preferably a resin latex which is formed on a substrate such as wood, paper, or fiber material and which does not affect the appearance of the film after several days of coating. .

Preferred examples of the component (A) include acrylic resin latex, urethane resin latex, vinyl chloride resin latex, polyoxymethylene resin latex, and acrylic acid. The polyoxymethylene copolymer resin emulsion can be suitably used alone or in combination of two or more kinds of latexes.

Commercially available acrylic resin emulsions include VINYBLAN manufactured by Nissin Chemical Industry Co., Ltd., YODOSOL manufactured by Henkel Japan Co., Ltd., and ARON manufactured by East Asia Synthetic Co., Ltd.

Commercially available urethane-based resin emulsions include WLS series manufactured by DIC Co., Ltd., Ucoat manufactured by Sanyo Chemical Co., Ltd., and CHEMITYLEN.

Commercially available vinyl chloride resin emulsions include VINYBLAN manufactured by Nissin Chemical Industry Co., Ltd.

Commercially available polyoxynated resin latexes include X-51-1318 and X-52-8148 manufactured by Shin-Etsu Chemical Co., Ltd., and polyacrylic acid-based acrylic latexes are available from Nissin Chemical Industry Co., Ltd. (limited shares) Chaline R-170EM.

For the above emulsion polymerization, any of the well-known emulsion polymerization methods can be employed. Monomers and other polymerization aids may be added at a time (for example, an emulsifier such as an alkyl sulfate ester, a polymerization initiator such as ammonium persulfate, a chain transfer agent such as a mercaptan, or a pH adjuster such as sodium carbonate; A foaming agent or the like may be continuously added, and a part thereof may be continuously or dividedly added during the polymerization.

However, in the present invention, it is necessary to use a surfactant in the emulsion polymerization.

The surfactant used in the emulsion polymerization may, for example, be the following surfactants (1) to (4), and one of the surfactants may be used. Or two or more.

(1) anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzenesulfonates, alkyl diphenyl ether disulfonates, alkylnaphthalenesulfonates A surfactant such as a fatty acid salt, a dialkyl sulfosuccinate, an alkyl phosphate, or a polyoxyethylene alkyl phenyl phosphate; or a reactive surfactant which can be polymerized with an acrylic monomer.

(2) Nonionic surfactants, such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly An alkylene alkyl ether, a polyoxyethylene derivative, a glycerin fatty acid ester, a polyoxyethylene hydrogenated castor oil, a polyoxyethylene alkylamine, an alkylalkanolamine, or an acetylene alcohol, An acetylene glycol and a surfactant of the ethylene oxide adduct, or a reactive surfactant polymerizable with an acrylic monomer.

(3) A cationic surfactant such as an alkyltrimethylammonium chloride, an alkyldimethylammonium chloride, an alkylbenzylammonium chloride or an alkylamine salt.

(4) A polymeric surfactant having a double bond in a molecule having a free radical polymerization ability, such as an alkylarylsulfosuccinate, a methacryl oxime polyoxyalkylene sulfate, a polyoxyethylene decyl propylene A polymerizable surfactant such as a phenyl ether sulfate salt.

Preferred surfactants are (1) anionic surfactants or (2) nonionic surfactants.

The amount of the surfactant used is generally from 0.5 to 10% by mass, more preferably from 2 to 10% by mass, based on the solid content of the resin.

However, protective colloids such as polyvinyl alcohol or polyacrylic acid are not good.

(B) Boron-based compounds include water-soluble boric acid, sodium tetraborate decahydrate (hereinafter sometimes referred to as borax), disodium octaborate tetrahydrate (hereinafter sometimes abbreviated as DOT), and borax, DOT. The alkali metal salt of boric acid is preferred, and DOT is particularly preferred.

(C) The zinc compound is not particularly limited as long as it is water-soluble, and zinc acetate, zinc lactate, zinc sulfate, and zinc chloride are preferred, and zinc acetate is particularly preferred.

(B) The boron-based compound and the (C) zinc compound are used together, and the two substances are simultaneously used to exhibit excellent anti-mildew and antibacterial properties.

That is, it is known that (B) a boron-based compound and (C) a zinc compound coexist with (A) a resin latex having a film forming ability by emulsion polymerization using a surfactant, and are insoluble in evaporation of water. The salt of boric acid and zinc in water is formed into a continuous layer in the resin, and the antifungal activity is excellent, and the mold and the antibacterial property excellent in durability are exhibited even when exposed to moisture. Further, it is excellent in weather resistance and heat resistance, and ultraviolet rays or heat do not deteriorate the activity, and discoloration does not occur.

Here, (B) the boron-based compound is 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and most preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the solid content of the resin emulsion of the component (A). (C) The zinc compound is used in an amount of 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the solid content of the resin emulsion of the component (A). When the amount is too small, sufficient mold resistance cannot be obtained. When the amount of the antibacterial property is too large, the stability of the resin latex becomes poor, and a good coating film cannot be obtained.

Further, (B) the boron compound and the (C) zinc compound must be used together, and (B) the boron compound and the (C) zinc compound are used, preferably the (C) zinc compound is used in an amount (B). The same amount of the boron-based compound or used in a smaller amount, in terms of mass ratio (B): (C) = 10:1 to 1:1, (B): (C) = 5:1~ 1:1 is better.

In the blending method, the components (A), (B), and (C) may be simultaneously mixed. However, after the component (A) and the component (B) are mixed, the component (C) is preferably mixed.

The solid content of the aqueous coating agent of the present invention is preferably 20 to 50% by mass, more preferably 20 to 25% by mass.

Further, the coating agent obtained in the present invention preferably has an average particle diameter of from 100 to 1,000 nm, and does not change over one month, and maintains stability characteristics.

The article having the coating film of the present invention can be obtained by immersing the material (substrate) to be coated in the aqueous coating agent of the present invention or coating, drying, and coating the coating agent.

The immersion and coating time are not particularly limited, and may be adjusted in accordance with the thickness of an appropriate substrate, for about 5 seconds to 10 hours. At the time of coating, a coating method such as a known coating bar or a spin coater can be used, and the coating thickness is 0.1 to 1,000 μm, and preferably the coating is 1 to 500 μm. Although it is related to the surface state of the substrate, the water-based coating agent impregnating the present invention is deep to the inside of the substrate. good.

Next, the drying temperature is set to 20 to 150 ° C, preferably 30 to 150 ° C, to dry the film to form a film.

The substrate is not particularly limited, and examples thereof include a paper material and a fiber material.

Paper stocks, paper tubes, and paper products can be cited. Specifically, those who have only a paper support alone, those which are coated with a vinyl resin film on a paper support, and those obtained by laminating a vinyl resin film on a paper or a leather support may be mentioned.

The fiber material is natural or synthetic polyamine (wool, silk, nylon, etc.), polyurethane, polyester, polypropylene, polyethylene, polyacrylonitrile, and all kinds of cellulose-containing fiber materials, specifically Natural cellulose fibers (such as cotton, linen, jute, and hemp), enamel raw materials, and regenerated cellulose; and mixtures of the above fibrous materials (for example, comprising polyacrylonitrile/polyester, polyamide/polyester, Polyester/cotton, polyester/tank and polyester/wool materials). The coated treated fibrous material of the present invention may correspond to any type of fiber thread, cloth, fabric, mat, and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited to the examples described below. In the following examples, the parts and % are respectively expressed by mass parts and mass%.

[Manufacturing Example 1] (acrylic resin latex)

In a reaction vessel equipped with a stirrer, a reflux condenser and an isocratic separatory funnel, 550 g of deionized water was added for initial treatment, oxygen was removed, nitrogen gas was introduced, and the temperature was raised to 76 °C. 484 g of butyl acrylate, 516 g of methyl methacrylate, 11 g of N-methyl alcohol acrylamide, 26 g of acrylic acid, and 26 g of 80% methacrylic acid were uniformly mixed, and then 285 g in the beaker. 23 g of HITENOL NF-17 (trade name, manufactured by Dai-ichi Kogyo Co., Ltd., polyoxyethylene styrene phenyl ether sulfate ammonium sulfate) diluted with ionic water was mixed. After standing a little, it was uniformly emulsified by using a homomixer to obtain a monomer emulsion. 4% of the emulsion was put into the reaction vessel, and 0.004 g of iron sulfate was added. The heptahydrate was dissolved in 10 g of deionized water, and was initially charged with 2.4 g of ammonium persulfate dissolved in 20 g of deionized water. After the reaction was terminated for about 10 minutes, the monomer emulsion was added at a constant rate over a period of 4 hours. In addition, 2.4 g of ammonium persulfate was dissolved in 70 g of deionized water, and the addition of the emulsion was started one hour after the isokinetic addition, and the addition was carried out at a constant rate over a period of 4 hours. After aging at 80 ° C for 1 hour, the mixture was cooled to room temperature, and the pH was adjusted to 5 to 7 with aqueous ammonia to obtain an acrylic resin latex having a resin content of about 50%. Moreover, the acrylic resin latex has a film forming ability at 30 °C.

[Examples and Comparative Examples]

100 parts by mass of the pre-diluted (A) resin emulsion having a film forming ability by emulsion polymerization using a surfactant, and (A') a resin latex having a film forming ability without using a surfactant, using a stir bar Stirring while massing according to Tables 1 and 2 A coating agent of the examples and the comparative examples was obtained by sequentially adding a dilution water, a 10% aqueous solution of a boron compound, and a 10% aqueous zinc compound solution.

(A) As a resin emulsion having a film forming ability by emulsion polymerization using a surfactant, in Comparative Example 1, in Comparative Example 1, X-51-1318 (polyoxyxene resin latex) manufactured by Shin-Etsu Chemical Co., Ltd. The solid content is about 40%, and a nonionic surfactant is added. In Example 5, CHIMITYLEN GA-500 (a urethane type, solid content of about 50%, with a nonionic surfactant added) manufactured by Sanyo Chemical Co., Ltd. was used.

(A') As a resin emulsion having a film forming ability without using a surfactant, VINYBLAN 2682 (acrylic resin latex, solid content of about 30%, protective colloid) manufactured by Nissin Chemical Industry Co., Ltd. was used in Comparative Example 1. . In Comparative Example 2, ADEKA BONTIGHTER HUX-380 (a urethane resin latex, a solid component of about 38%, self-emulsified latex) was used.

Further, the following (B) boron compound is used as follows.

(B-1) 10% DOT aqueous solution

(B-2) 10% borax aqueous solution

In Comparative Example 4, Rebanakkusu BS-50 (manufactured by Changrong Chemical Co., Ltd.) was used for the isothiazoline-based antiseptic and antifungal agent.

The mixed (C) zinc compound was a 10% aqueous solution of zinc acetate.

In the case of mixing, the (A) resin latex and the (B) boron compound aqueous solution are mixed, and then the (C) zinc acetate aqueous solution is mixed and stirred to obtain an aqueous coating solution.

[Analytical method, evaluation method] [mixed]

When the coating agents of the examples and the comparative examples were produced, a 10% boron compound aqueous solution was added, and the mixture was filtered at 80 mesh, and it was judged by visual observation that no foreign matter was observed as ○. Thereafter, after adding a 10% zinc compound aqueous solution, the filtration was carried out in the same manner with an 80 mesh mesh, and when no foreign matter was present, it was recorded as ○.

Comparative Example 1 is a protective colloid, and Comparative Example 2 is a self-emulsifying latex, and abnormalities such as foreign matter may be observed after mixing.

In Comparative Example 3, the ratio of the boron compound to the zinc compound was higher than the mixing ratio of the present invention, and foreign matter occurred during mixing, which caused an obstacle.

The resin latex having the film forming ability for emulsion polymerization using the surfactant (A) used in the examples contains an anionic or nonionic surfactant, and the surfactant in the resin latex used in the present invention is indispensable. lack.

[Measurement of solid content]

Approximately 1 g of the sample was taken in a small foil made of aluminum foil, placed in a desiccator maintained at 105-110 ° C for 1 hour, taken out from the desiccator, placed in a desiccator, and allowed to cool. The weight was calculated by the following formula to calculate the evaporation residue.

R: evaporation residue (%)

W: mass of aluminum foil small dish containing the sample before drying (g)

L: mass of aluminum foil small dish (g)

T: mass of the aluminum foil small dish containing the dried sample (g)

Size of aluminum foil small dish: 70 ×12h(mm)

[Average particle diameter measurement]

The measurement of 0.01 g of the sample was carried out using a laser particle size analyzer (manufactured by Horiba, Ltd., trade name: LA-950V2), and the average particle diameter (equivalent particle size accumulation) under the condition of the flow rate 2 and the stirring speed 2 was measured. The value of the particle diameter of 50% of the distribution).

[Measurement conditions]

Measuring temperature: 25±1°C

Solvent: ion exchange water

[pH measurement]

The liquid temperature of the sample was maintained at 23 ± 0.5 ° C, and the measurement was carried out by a pH meter (HM-25R manufactured by East Asia DKK Co., Ltd.).

[preservation stability test]

100 g of the sample was added to a 100 ml glass bottle, made of polyethylene The lid is closed to the mouth of the bottle. Thereafter, the lid portion was completely sealed with an aluminum foil tape and stored in a thermostat bath at 40 ° C for one month.

The presence or absence of foreign matter was confirmed by filtration at 80 mesh, and the change in average particle diameter and pH was measured by the above method.

The aqueous coating agent of the present invention achieves almost no appearance, changes in properties, and good stability over time.

[degree of discoloration]

A commercially available wave plate was coated with a coating bar to a sample of 10 μm, and left at 30 ° C for 24 hours to prepare a coating film.

The coating film obtained by the above method was subjected to a weathering resistance test for 500 hours under the following conditions using a xenon lamp light source.

Radiation: 180W/m ² (300~400nm)

Black panel temperature sensor temperature: 63 ° C

Wet cycle: repeat water spray for 12 minutes, dry for 48 minutes

The individual discoloration (color difference) before and after the weathering test was promoted, and the ΔE value was measured using a color difference meter.

The color difference is a value obtained by measuring the coating film in accordance with JIS K5600-4-4 to K5600-4-6, and the color difference measurement is a simple spectrophotometer: SE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the color difference, the less the discoloration is displayed.

The color difference ΔE ^* _ab between the two colors a and b is the geometric distance between two colors in the (CIE1976) L ^* a ^* b ^* color space (JIS K5600-4-4), using the sub-calculation . Refer to JIS K5600-4-6.

△E ^* _ab =[(ΔL ^* ) ² +(△a ^* ) ² +(△b ^* ) ² 〕 ^1/2

Here, ΔL ^* = L ^* _{T -} L ^* _R

△a ^* =a ^* _T -a ^* _R

△b ^* =b ^* _T -b ^* _R

When L ^* , a ^* , and b ^* are two-degree tristimulus values, they indicate L ^* , a ^* , and b ^* values for a 2 degree observer.

In Comparative Example 4, it was found that the discoloration was caused by the decomposition of the organic OIT in the coating agent by ultraviolet rays, and the film was colored.

[Adhesiveness to wallpaper]

The wallpapers were tested for the initial stage and the examples 1 to 6 after the above-described accelerated weather resistance test by the cross cut test in JIS K5600-5-6. It was found that there was no problem in the adhesion of Examples 1 to 5.

[Mold resistance test]

The sample was applied to a commercially available wallpaper (vinyl chloride cloth) to a thickness of 5 μm and dried at 30 ° C for several hours.

A wood piece of 2 cm × 2 cm × 1 cm which was dried at 60 ° C was used for the wood, and the white cotton cloth used for the cotton cloth according to JIS L0803 was cut into 2 cm × 2 cm, immersed in the sample for 20 seconds, and dried at 30 ° C for several hours.

Further, in Comparative Example 7, a salt was produced at the time of mixing, and the mixing stability was ×, but for comparison, it was filtered at 80 mesh, and subjected to a mold proof function test. Test.

Further, the above-mentioned wallpaper, wood, and cotton cloth were subjected to a weathering resistance test for 500 hours under the following conditions using a xenon lamp light source.

Radiation: 180W/m ² (300~400nm)

Blackboard temperature sensor temperature: 63 ° C

Wet cycle: repeat water spray for 12 minutes, dry for 48 minutes

After the weathering resistance test was carried out, the following five kinds of molds were inoculated at the same time, and the mold resistance test (B method) was carried out in accordance with JIS Z2911.

The evaluation method is as follows. (electron microscope)

Further, for Comparative Example 4, a wallpaper, wood, and cotton cloth which were not subjected to the weather resistance test were used, and an antifungal test was performed. Relative to promotion Before the test, wallpaper: 0, wood: 0, cotton: 1, can be said to be able to observe the development of hyphae after the weather resistance test, it can be called poor durability.

On the other hand, in the water-based coating agent of the present invention, no elution was observed in the accelerated weather resistance test, and it was considered to have a very good effect on mold resistance, and it has durability and extremely high durability.

[Confirmation of the adhesion of cotton cloth]

For the cotton cloth, the material was cut into 22 cm × 3 cm and immersed in the sample for 20 seconds, and dried at 30 ° C for several hours. The cotton cloth of the same specification as the JIS L0849 was fixed on the friction piece, and was dry. After 20 times of abrasion with a weight of 200 g, a mold proof function test was carried out. The adhesion and strength of the film were sufficiently maintained, and no reduction in the mold resistance was confirmed.

[Antibacterial test method]

The method is based on JIS Z2801. The Escherichia coli is used for the coliform group. On the surface of the commercially available wallpaper, the bacterial solution adjusted with 1/500 ordinary nutrient liquid (Nutrient broth) was dropped, adhered to a film, and stored at 35 °C. The test was performed on the test liquid on the test piece, and the number of bacteria after 24 hours was measured. The average value of n=2 is shown below.

The aqueous coating agent of the present invention can be said to have excellent antibacterial properties.

For the wallpaper, the person who has been cut into 22 cm × 3 cm is immersed for 20 seconds, and dried at 30 ° C for several hours to be tested according to JIS L0849. The cotton cloth of the same specification was fixed to the friction member, and after 20 times of abrasion in a dry type and a weight of 200 g, the film was adhered to the above-mentioned antibacterial property test, and the adhesion and strength of the film were sufficiently maintained in the examples, and the antibacterial function was not confirmed to be lowered.

On the other hand, in Comparative Examples 4, 6, and 7, it was confirmed that the antibacterial function was lowered.

Claims (12)

An aqueous coating agent comprising (A) a polysiloxane having a film forming ability by emulsion polymerization using at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant; The resin latex other than the resin latex has a solid content of 100 parts by mass, and (B) is selected from 0.01 to 5 parts by mass of at least one boron compound selected from the group consisting of disodium tetraborate tetrahydrate, sodium tetraborate decahydrate, and boric acid. At least one zinc compound from zinc acetate and zinc sulfate is 0.01 to 5 parts by mass, and (B) the ratio of use of the boron compound to the (C) zinc compound is 10:1 to 0.1:1 by mass ratio. The aqueous coating agent according to the first aspect of the invention, wherein the (B) boron compound is 0.1 to 5 parts by mass, and the (C) zinc compound is 0.5 to 5 masses, based on 100 parts by mass of the solid component of the component (A). Share. The aqueous coating agent according to claim 1 or 2, wherein the ratio of the (B) boron compound to the (C) zinc compound is 10:1 to 1:1 by mass ratio. The aqueous coating agent according to claim 1 or 2, wherein the resin latex of the component (A) is formed into a dry film at 20 to 150 °C. The aqueous coating agent according to claim 1 or 2, wherein the resin latex of the component (A) is at least one selected from the group consisting of an acrylic resin latex, a urethane resin latex, a vinyl chloride resin latex, and an acrylic polymer. Oxygen copolymer resin latex. An anti-fungal agent, as claimed in claim 1 or 2 The water-based coating agent is composed. An antibacterial agent comprising the aqueous coating agent of claim 1 or 2. A paper material which is treated with an aqueous coating agent as claimed in claim 1 or 2. For example, the paper of claim 8 is used for wallpaper, paper tube, and paper products. A fibrous material characterized by being a fiber obtained by treating a fiber with an aqueous coating agent according to claim 1 or 2. The fiber material of claim 10, wherein the fiber treated with the aqueous coating agent is natural polyamide fiber, synthetic polyamide fiber, polyurethane fiber, polyester fiber, polypropylene fiber, poly Ethylene fiber, polyacrylonitrile fiber or cellulose-containing fiber. A method for producing an aqueous coating agent characterized by using (A) a film forming ability for emulsion polymerization using at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant. The resin latex other than the polyoxyethylene resin latex has a solid content of 100 parts by mass, and (B) is selected from 0.01 to 5 parts by mass of at least one boron compound selected from the group consisting of disodium tetraborate tetrahydrate, sodium tetraborate decahydrate, and boric acid. (C) 0.01 to 5 parts by mass of at least one zinc compound selected from the group consisting of zinc acetate and zinc sulfate, and used in a ratio of 10:1 to 0.1:1 by mass ratio (B) boron compound and (C) zinc When the compound is used to make a water-based coating agent, (A) After mixing the components (B), the component (C) is mixed.