JP6764889B2 - Antibacterial and antifungal paint, algae-proof paint, antibacterial and antifungal member manufacturing method, and algae-proof member manufacturing method - Google Patents

Description

The present invention relates to an antibacterial antifungal paint, an algae-proof paint, a method for producing an antibacterial antifungal member, and a method for producing an algae-proof member.

Due to the growing hygiene concept in recent years, fungi such as bacteria and molds in food and pharmaceutical factories, buildings such as hospitals and nursing homes, food kitchen equipment, medical equipment, medical equipment, and even general household items. Antibacterial agents, antifungal agents, disinfectants, etc. are used to prevent the spread and infection of the disease.
Therefore, it is desired to impart antibacterial and antifungal properties to various members not only in public facilities but also in general households.

Organic or inorganic antibacterial agents have been proposed to solve these problems.
In particular, with regard to inorganic antibacterial agents, conventionally, metal ions such as silver ion (Ag ⁺ ), zinc ion (Zn ²⁺ ), and divalent copper ion (Cu ²⁺ ) suppress the growth of microorganisms or microorganisms. It is known to act bactericidal against (for example, Patent Document 1). Based on this finding, many antimicrobial materials in which these metal ions are supported on substances such as zeolite and silica gel, and antimicrobial materials in which the metal is combined with titanium oxide having a photocatalytic action have been developed.

Japanese Unexamined Patent Publication No. 2003-221304

Among them, paints using silver have been used in recent years for antibacterial and antifungal applications, but silver has a problem of high cost.
Therefore, it is desired to develop an antibacterial and antifungal paint and an antibacterial and antifungal member using a metal cheaper than silver as an antibacterial and antifungal component.

In addition, various members for which antibacterial and antifungal properties are desired are often also desired to be provided with algae resistance at the same time.

Therefore, the problem to be solved by the present invention is to use low-cost copper oxide as an antibacterial antifungal component and / or an algae-proof component, and to exhibit excellent dispersion stability and excellent coatability against changes over time. It is an object of the present invention to provide an antibacterial antifungal paint, an algae-proof paint, a method for producing an antibacterial antifungal member, and a method for producing an algae-proof member.

As a result of diligent research and experiments to achieve the above problems, the present inventors have obtained a predetermined composition and component concentration containing copper oxide particles having a predetermined average particle size and a dispersant having a predetermined acid value. We have found that the above problems can be solved by using a paint and applying this paint to the surface of a base material by a coating method such as printing and drying it to form a coating film. Based on this finding, the present invention has been found. Is completed.

That is, the present invention is as follows.
The antibacterial antifungal coating material according to the embodiment of the present invention is an antibacterial antifungal coating material containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, and a solvent. The acid value of is 73 mgKOH / g or more and 130 mgKOH / g or less, the content of the copper oxide particles is 0.5% by mass or more and 60% by mass or less, and the content of the dispersant is 0.05% by mass. It is characterized in that it is 20% by mass or less and the content of the solvent is 20% by mass or more and 99.45% by mass or less.
Further, the antibacterial antifungal coating material of another embodiment of the present invention is an antibacterial antifungal coating material containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, a latex, and a solvent. The acid value of the dispersant is 73 mgKOH / g or more and 130 mgKOH / g or less, the content of the copper oxide particles is 0.5% by mass or more and 50% by mass or less, and the dispersant is contained. The amount is 0.05% by mass or more and 20% by mass or less, the content of the latex is 0.05% by mass or more and 40% by mass or less, and the content of the solvent is 5% by mass or more and 99.4% by mass or less. It is characterized by being. In the antibacterial and antifungal paint, the latex is preferably an acrylic latex.

The algae-proof coating material of one embodiment of the present invention is an algae-proofing coating material containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, and a solvent, and the acid of the dispersant. The valence is 73 mgKOH / g or more and 130 mgKOH / g or less, the content of the copper oxide particles is 0.5% by mass or more and 60% by mass or less, and the content of the dispersant is 0.05% by mass or more and 20. It is characterized by having a mass% or less and a content of the solvent of 20% by mass or more and 99.45% by mass or less.
Further, the algae-proof coating material of another embodiment of the present invention is an algae-proofing coating material containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, a latex, and a solvent. The acid value of the dispersant is 73 mgKOH / g or more and 130 mgKOH / g or less, the content of the copper oxide particles is 0.5% by mass or more and 50% by mass or less, and the content of the dispersant is The content of the latex is 0.05% by mass or more and 20% by mass or less, the content of the latex is 0.05% by mass or more and 40% by mass or less, and the content of the solvent is 5% by mass or more and 99.4% by mass or less. It is characterized by that. In the algae-proof paint, the latex is preferably an acrylic latex.
The antibacterial and antifungal paint according to the embodiment of the present invention and the algae-proof paint according to the embodiment of the present invention preferably contain an organic compound having a phosphate group as a dispersant.
The antibacterial antifungal paint according to the embodiment of the present invention and the algae-proof paint according to the embodiment of the present invention preferably contain 0.010% by mass or more and 2.0% by mass or less of the surface energy adjusting agent. In the antibacterial antifungal paint and the algae-proof paint, it is preferable that the surface energy adjusting agent is a fluorine-containing nonionic surfactant.

Further, in the method for producing an antibacterial antifungal member of the present invention, the above antibacterial antifungal coating material is applied to screen printing, spray coating, spin coating, slit coating, die coating, bar coating, knife coating, air doctor coating, and roll coating. , Electrostatic coating, offset printing, reverse printing, flexo printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and the process of applying to the substrate surface using a method selected from the dipping method. It is characterized by including a step of drying the antibacterial antifungal coating material after application to form a coating film.

In the method for producing an algae-proof member of the present invention, the above-mentioned algae-proof coating is applied to screen printing, spray coating, spin coating, slit coating, die coating, bar coating, knife coating, air doctor coating, roll coating, and electrostatic coating. , Offset printing, reverse printing, flexo printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and the step of coating on the substrate surface using at least one coating method selected from the dipping method. It is characterized by including a step of drying the algae-proof coating material after application to form a coating film.

The antibacterial antifungal paint and the algae-proof paint according to the present invention are excellent in dispersion stability of copper oxide particles which are antibacterial antifungal components and / or algae-proof components against changes over time, and are also excellent in coatability. Therefore, it can be applied by printing, and can be suitably used for antibacterial antifungal use and / or algae prevention use.
Since the method for producing an antibacterial antifungal member and the method for producing an algae-proof member according to the present invention use the antibacterial antifungal paint or the algae-proof paint, they are desired only on the entire surface of the base material or a desired portion. It is possible to provide an antibacterial antifungal member and / or an algae-proof member imparted with excellent antibacterial antifungal property and / or algae-proof property in the pattern of.

It is a sample photograph at the start of the algae resistance test for the paint A of Example 1. It is a sample photograph 2 weeks after the start of the algae resistance test for the paint A of Example 1.

Hereinafter, a mode for carrying out the present invention (hereinafter, also referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
First, the antibacterial antifungal paint and the algae-proof paint of the present invention (these are also collectively referred to as “the paint of the present invention” in the present specification) will be described in detail.

[paint]
The coating material of one embodiment of the present invention is characterized by containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, and a solvent at a predetermined content.
Another embodiment of the present invention is characterized in that it contains copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, a solvent, and a latex in a predetermined content.

[[Copper oxide particles]]
The coating material of the present invention contains copper oxide particles having a predetermined average particle size in a predetermined content as an antibacterial antifungal component and / or an algae-proof component. Specific examples of the copper oxide particles include cuprous oxide particles, cupric oxide particles, or other copper oxide particles having an oxidation number, and the core part is copper and the shell part is copper oxide having any oxidation number. Examples include particles having a certain core / shell structure. These particles may contain metal salts and / or metal complexes as small amounts of impurities. Among them, cuprous oxide particles are preferable because they have excellent antibacterial and antifungal properties and anti-algae properties.

The copper oxide particles contained in the coating material of the present invention have an average particle diameter of 1 nm or more and 500 nm or less.
Here, the "mean particle size" means the hydrodynamic average diameter of the copper oxide particles under a wet condition, and may be slightly different from the value of the "mean secondary particle size" described later. In the "mean particle size" in the present invention, that is, the hydrodynamic average diameter, it is an agglomerate formed by a plurality of primary particles and a primary particle which does not form a secondary particle and exists independently. It is the average particle size obtained as a measurement target without distinguishing it from the next particle.
On the other hand, the "average secondary particle size" described later is an average particle size obtained on the assumption that all the particles to be measured are secondary particles, and there are primary particles that do not constitute secondary particles. This is because it is also excluded from the measurement target.

In the present invention, the average particle size of the copper oxide particles can be measured by using a dynamic light scattering method. More specifically, the measurement target is copper oxide particles dispersed in the solvent used for the coating material, and the signal measured by the dynamic light scattering method is analyzed by the photon correlation method to obtain an autocorrelation function. The average particle size can be obtained by analyzing the obtained autocorrelation function by the cumulant method.
Since the copper oxide particles of the present invention have an average particle size of 1 nm or more and 500 nm or less, the dispersion stability in the paint can be improved, and thus the antibacterial and antifungal performance and the algae-proof performance of the paint can be improved. it can. In addition, the coatability of the paint can be improved, and thus the printing method can be used as a method of applying the paint to the surface of the base material.

The average secondary particle size of the copper oxide particles contained in the coating material of the present invention is not particularly limited, but is preferably 5 nm or more, 500 nm or less, more preferably 200 nm or less, and further preferably 80 nm or less. The average secondary particle size is the average particle size of aggregates (secondary particles) formed by aggregating a plurality of primary particles of cuprate oxide particles. When the average secondary particle size is 500 nm or less, a fine pattern is likely to be formed on the surface of the base material, which is preferable. The secondary particle size refers to the particle size of the secondary particles obtained from the image data acquired when the copper oxide particles dispersed in diethylene glycol are observed using a transmission electron microscope (TEM). Usually, an arbitrary part of the image is cut out, and the average value of the secondary particle size of 100 or more particles contained in this part is obtained to calculate the average secondary particle size.

The preferred range of the average primary particle size of the primary particles constituting the secondary particles is 1 nm or more, 100 nm or less, more preferably 50 nm or less, and further preferably 20 nm or less. When the average primary particle size is 100 nm or less, the surface area becomes large, so that the antibacterial and antifungal performance is improved. When the average primary particle size is 1 nm or more, the average particle size can be in the range of 1 nm or more and 500 nm or less.
The average primary particle size means the average value of the primary particle size obtained for a plurality of primary particles by image analysis. Here, the primary particle size is the particles of the primary particles obtained from the image data acquired when the cuprous oxide nanoparticles dispersed in the dispersion medium are observed using a transmission electron microscope (TEM). It refers to a diameter, and usually, an arbitrary part of an image is cut out, and the average value of the primary particle size of 100 or more particles contained in this part is obtained to calculate the average primary particle size.

By changing the particle size (average particle size, average secondary particle size, secondary particle size, average primary particle size, or primary particle size) of the copper oxide particles contained in the paint, the paint is made by localized surface plasmon resonance. And the color tone of the coating film can be changed, and further, the wavelength of light absorbed by the coating material or the coating film can be changed.

When the coating material of the present invention is a latex-free embodiment, the content of copper oxide particles is 0.5% by mass or more and 60% by mass or less, preferably 1.0 to 60% by mass, based on 100% by mass of the coating material. It is by mass, more preferably 5.0 to 50% by mass. When the content is 0.5% by mass or more, the function as an antibacterial and antifungal component can be sufficiently exhibited, and when it is 60% by mass or less, the aggregation of copper oxide particles can be easily suppressed. is there.

When the coating material of the present invention is an embodiment containing latex, the content of the copper oxide particles is preferably 0.5% by mass or more and 50% by mass or less in 100% by mass of the coating material from the viewpoint of dispersion stability. Is 1.0 to 40% by mass, more preferably 2.0 to 35% by mass.

The copper oxide particles may be commercially available products or may be synthesized and used. Commercially available products include, for example, cupric oxide particles manufactured by CIK Nanotech having an average primary particle size of 50 nm. When synthesized and used, examples of the synthetic method include the following methods (1) to (3).
(1) Water and a copper acetylacetonato complex are added to a polyol solvent to dissolve the organic copper compound by heating, then water necessary for the reaction is added afterwards, and the temperature is further raised to reduce the organic copper. Method of heating and reducing with.
(2) A method of heating an organic copper compound (copper-N-nitrosophenylhydroxylamine complex) at a high temperature of about 300 ° C. in an inert atmosphere in the presence of a protective agent such as hexadecylamine.
(3) A method of reducing a copper salt dissolved in an aqueous solution with hydrazine.
Among these, the method (3) is preferable because it is easy to operate and copper oxide particles and cuprous oxide particles having a small particle size can be obtained.

[[Dispersant]]
Next, the dispersant will be described.
The coating material of the present invention contains a dispersant having a predetermined acid value in a predetermined content.

Known dispersants can be used, for example, long-chain polyaminoamides and salts of polar acid esters, unsaturated polycarboxylic acid polyaminoamides, polyaminoamide polycarboxylic acid salts, long-chain polyaminoamides and acid polymers. Examples thereof include polymers having a basic group such as a salt. Examples thereof include alkylammonium salts, amine salts and amidamine salts of polymers such as acrylic polymers, acrylic copolymers, modified polyester acids, polyether ester acids, polyether carboxylic acids and polycarboxylic acids. Further, a phosphorus-containing organic compound described later is a suitable dispersant.
As such a dispersant, commercially available ones can also be used.

The acid value (mgKOH / g) of the dispersant used in the coating material of the present invention is 20 mgKOH / g or more and 130 mgKOH / g or less, preferably 30 mgKOH / g or more and 110 mgKOH / g or less, and more preferably 35 mgKOH / g or more and 105 mgKOH / g. It is less than or equal to g. Within this range, dispersion stability is excellent, which is preferable. This is particularly effective for copper oxide particles having a small average particle size.
The acid value indicates the total amount of free fatty acids and fatty acids, and is measured in accordance with JIS K 0070: 1992, 3.1 “Neutralization Titration Method”.

The commercially available dispersant having an acid value in the above range is not particularly limited, but for example, "DISPERBYK (registered trademark) -101" (acid value 30 mgKOH / g) and "DISPERBYK-102" (acid value 101 mgKOH / g). ), "DISPERBYK-110" (acid value 52 mgKOH / g), "DISPERBYK-111" (acid value 129 mgKOH / g), "DISPERBYK-140" (acid value 73 mgKOH / g), "DISPERBYK-142" (acid value 46 mgKOH) / G), "DISPERBYK-145" (acid value 76 mgKOH / g), "DISPERBYK-118" (acid value 36 mgKOH / g), "DISPERBYK-180 (acid value 94 mgKOH / g)", "DISPERBYK-2025" (acid value 38 mgKOH / g), "BYK-9076" (acid value 38 mgKOH / g), "ANTI-TERRA®-204" (acid value 41 mgKOH / g), ANTI-TERRA-U (acid value 24 mgKOH / g) ( (Manufactured by Big Chemie); Hyprad (registered trademark) ED-212 (acid value 20 mgKOH / g), Hyprad ED-213 (acid value 25 mgKOH / g), Hyprad ED-360 (acid value 52 mgKOH / g) (Kusumoto) (Manufactured by Kaseisha); etc. One of these may be used alone, or a plurality of them may be mixed and used.

The number average molecular weight of the dispersant is not particularly limited, but is preferably 300 to 300,000, for example. When it is 300 or more, the film strength is excellent and the dispersion stability of the obtained paint tends to increase, and when it is 30,000 or less, it is easy to bake.

Among the above-mentioned dispersants, for example, phosphorus-containing organic compounds can be mentioned. The phosphorus-containing organic compound may be adsorbed on copper oxide, and in this case, aggregation is suppressed by the steric hindrance effect. The phosphorus-containing organic compound is a material that exhibits electrical insulation in the insulating region. The phosphorus-containing organic compound may be a single molecule or a mixture of a plurality of types of molecules.

As the phosphorus-containing organic compound, an organic compound having a phosphoric acid group is preferable, and a phosphoric acid ester of a high molecular weight copolymer having a group having an affinity for copper oxide particles is more preferable. For example, a phosphoric acid ester having a group having a chemical structure represented by the following chemical formula (1) is preferable because it adsorbs to copper oxide particles, particularly cuprous oxide particles, and has excellent adhesion to a substrate.

(In the above formula, l represents an integer of 1 to 1629, m represents an integer of 1 to 6809, and n represents an integer of 1 to 5166.)

The phosphorus-containing organic compound is preferably one that is easily decomposed or evaporated by light or heat. By using a phosphorus-containing organic compound that is easily decomposed or evaporated by light or heat, the residue of the organic compound is less likely to remain after firing the coating material, and a conductive pattern region having a low resistivity can be obtained.

The decomposition temperature of the phosphorus-containing organic compound is not limited, but is preferably 600 ° C. or lower, more preferably 400 ° C. or lower, and even more preferably 200 ° C. or lower.
The boiling point of the phosphorus-containing organic compound is not limited, but is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and even more preferably 150 ° C. or lower.

The absorption characteristics of the phosphorus-containing organic compound are not limited, but it is preferable that the phosphorus-containing organic compound can absorb the light used for firing the coating material. For example, when laser light is used as a light source for firing, it is preferable to use a phosphorus-containing organic compound that absorbs light having an emission wavelength of, for example, 355 nm, 405 nm, 445 nm, 450 nm, 532 nm, or 1056 nm. When the base material is a resin substrate, a phosphorus-containing organic compound that absorbs light having wavelengths of 355 nm, 405 nm, 445 nm, and 450 nm is particularly preferable.

When the coating material of the present invention is a latex-free embodiment, the content of the organic compound having a phosphate group in 100% by mass of the coating material is 0.05% by mass or more and 20% by mass or less, preferably 0. .1% by mass or more and 17% by mass or less, more preferably 0.20% by mass or more and 15% by mass or less, and further preferably 1.0% by mass or more and 8.0% by mass or less. When the content of the organic compound is within the above range, aggregation of the copper oxide particles can be suppressed, and the coating material has sufficient dispersion stability. Further, in the conductive film obtained by firing the paint, the influence of the residue derived from the dispersant can be suppressed and the conductivity can be improved.

When the coating material of the present invention is an embodiment containing latex, the content of the dispersant in 100% by mass of the coating material is 0.05% by mass or more and 20% by mass or less, preferably 1.0% by mass or more and 15% by mass. It is mass% or less, more preferably 2.0 mass% or more and 10 mass% or less. When the content of the organic compound is within the above range, aggregation of copper oxide particles can be suppressed in the presence of latex, and the coating material has sufficient dispersion stability. Further, in the conductive film obtained by firing the paint, the influence of the residue derived from the dispersant can be suppressed and the conductivity can be improved.

Further, the content of the dispersant is preferably adjusted in consideration of the required dispersion stability according to the content of the copper oxide particles. The mass ratio of the dispersant to the cuprate particles (mass of the dispersant / mass of the cuprate particles) contained in the coating material of the present embodiment is preferably 0.0050 or more and 0.30 or less, and more preferably. It is 0.050 or more and 0.25 or less, and more preferably 0.10 or more and 0.23 or less. When the mass ratio of the dispersant and the copper oxide particles is within the above range, the dispersion stability can be further improved.

[[solvent]]
The coating material of the present invention contains a solvent in a predetermined content as a dispersion medium. The solvent may be a single solvent or a mixed solvent.
As a single solvent, even if the solvent has a vapor pressure of 0.010 Pa or more and less than 20 Pa at 20 ° C. (hereinafter, also referred to as “solvent (A)”), the solvent has a vapor pressure of 20 Pa or more and 150 hPa or less at 20 ° C. (Hereinafter, also referred to as "solvent (B)").
The mixed solvent may be a mixed solvent composed of two or more kinds of solvents (A), a mixed solvent composed of two or more kinds of solvents (B), or a mixed solvent of a solvent (A) and a solvent (B). Above all, it is preferable to use a mixed solvent of the solvent (A) and the solvent (B). By using the mixed solvent of the solvent (A) and the solvent (B) in combination with the organic compound having a phosphoric acid group, both the improvement of the dispersion stability of the coating material of the present embodiment in the atmosphere and the workability are compatible. Can be made to.

The vapor pressure of the solvent (A) at 20 ° C. is 0.010 Pa or more and less than 20 Pa, preferably 0.05 Pa or more and less than 16 Pa, and more preferably 0.1 Pa or more and less than 14 Pa. When the vapor pressure at 20 ° C. is 0.010 Pa or more and less than 20 Pa, the coating film of the paint can be maintained in a semi-dry state, and the workability in manufacturing the antibacterial and antifungal member described later can be improved. it can.

The vapor pressure of the solvent (B) at 20 ° C. is 20 Pa or more and 150 hPa or less, preferably 100 Pa or more and 100 hPa or less, and more preferably 300 Pa or more and 20 hPa or less. When the vapor pressure at 20 ° C. is 150 hPa or less, it is possible to easily stabilize the content of copper oxide particles in the coating material even if the volatilization rate of the solvent is high. When the vapor pressure at 20 ° C. is 20 Pa or more, the time required for the coating film of the paint to be in a semi-dry state can be made appropriate.

When the coating material of the present invention is a latex-free embodiment, the content of the solvent in 100% by mass of the coating material is 20% by mass or more and 99.45% by mass or less, preferably 30% by mass or more and 99.4% by mass. % Or less, more preferably 40% by mass or more and 80% by mass or less. When the coating material of the present invention is a latex-free embodiment, if the solvent content is within the above range, excellent dispersion stability and excellent coatability can be sufficiently imparted to the coating material.

When the coating material of the present invention is an embodiment containing latex, the content of the solvent in 100% by mass of the coating material is 5% by mass or more and 99.4% by mass or less, preferably 10% by mass or more and 99.0% by mass or less. Hereinafter, it is more preferably 20% by mass or more and 90% by mass or less. When the content of the solvent is within the above range, excellent dispersion stability and excellent coatability can be sufficiently imparted to the coating material in the coexistence of latex.

When the coating material of the present invention does not contain latex and the solvent is a mixed solvent of the solvent (A) and the solvent (B), the content of the solvent (A) in 100% by mass of the coating material of the present invention is. It is preferably 10% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 95% by mass or less, and further preferably 30% by mass or more and 90% by mass or less. When the content of the solvent (A) is within the above range, the drying speed is appropriate in the air, and printing defects tend not to occur, which is preferable.

In the case of the embodiment in which the coating material of the present invention contains a latex and the solvent is a mixed solvent of the solvent (A) and the solvent (B), the content of the solvent (A) in 100% by mass of the coating material of the present invention is 0. It is preferably .050% by mass or more and 10% by mass or less, more preferably 0.10% by mass or more and 9.0% by mass or less, and further preferably 0.20% by mass or more and 8.0% by mass or less. When the content of the solvent (A) is within the above range, the drying speed is appropriate in the air, and printing defects tend not to occur, which is preferable.

Specific examples of the solvent (A) include propylene glycol monomethyl ether acetate, 3methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether. Propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, xylene, mesitylene, ethylbenzene, octane, nonane, decane, ethylene glycol, 1,2-propylene glycol, 1, 3-butylene glycol, 2-pentanediol, 4,2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptandiol, 2-ethylhexane-1,3-diol, diethylene glycol, Examples thereof include organic solvents such as dipropylene glycol, hexanediol, octanediol, triethylene glycol, tri1,2-propylene glycol and glycerol, and water. Of these, a polyhydric alcohol having 10 or less carbon atoms is more preferable. If the number of carbon atoms of the polyhydric alcohol exceeds 10, the dispersibility of the copper oxide particles may decrease. These may be used alone or in combination of two or more.

Specific examples of the solvent (B) include acetic acid, ethyl acetate, normal propyl acetate, isopropyl acetate, pentanol, hexane, cyclohexane, methylcyclohexane, toluene, methylethylketone, methylisobutylketone, dimethylcarbonate, methanol, ethanol and n-propanol. , I-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol , N-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6- Examples thereof include dimethyl-4-heptanol, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like. Of these, monoalcohols having 10 or less carbon atoms are more preferable. Among monoalcohols having 10 or less carbon atoms, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and t-butanol are more preferable because their dispersibility, volatileness, and viscosity are particularly suitable. .. When the carbon number of the monoalcohol exceeds 10, the carbon number of the monoalcohol is preferably 10 or less in order to suppress the decrease in the dispersibility of the copper oxide particles. These may be used alone or in combination of two or more.

[[latex]]
The coating material of the present invention may contain latex in a predetermined content as an optional component for improving processability. Latex is an aqueous resin suspension in which the resin is suspended in an aqueous dispersion medium such as water by an emulsifier.
As the latex, acrylic latex, vinylidene chloride latex, styrene butadiene latex, silicone-modified acrylic latex, organic-inorganic hybrid latex, silicone latex and the like can be used. Of these, acrylic latex or silicone-modified acrylic latex is preferable from the viewpoint of film formation property and durability.
As these latexes, commercially available products may be used, or those prepared by synthesizing a resin may be used.
Examples of commercially available acrylic latex products include Viniblanc (registered trademark) "# 2682", "# 2864", "# 2685", "# 2678" manufactured by Nisshin Chemical Industry Co., Ltd., Polydurex (registered trademark) manufactured by Asahi Kasei Corporation, and Polytron. (Registered trademark) and the like.

Examples of the resin material for synthesizing the resin to prepare the latex include polymerizable monomers such as unsaturated polymers such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane. Vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, acrylic acid, methacrylic acid, crotonic acid , Itaconic acid, maleic acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified (meth) acrylate, polyethylene glycol (meth) Acrylate, polypropylene glycol (meth) acrylate, tetramethoxysilane, tetraethoxysilane, methyltrimethosixisilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, octamethylcyclotetrasiloxane, octa Phenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methylphenylsilane, triphenylethoxysilane, trimethylmethoxysilane, methylchlorosilane, Aromatic monomers such as methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, (meth) acrylic acid ester; styrene, vinyltoluene; vinyl acetate, vinyl propionate, vinyl versaticate, etc. Esters; vinyl cyanide such as (meth) acrylonitrile; vinyl halides such as vinyl chloride and vinylidene chloride; butadiene; and the like, and various functional monomers such as (meth) acrylamide and die. acetone A copolymer obtained by copolymerizing two or more different monomers such as acrylamide, vinylpyrrolidone, glycidyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, divinylbenzene, and methyl vinylketone. Quantum and the like can be mentioned.

As the method for preparing the latex, a usual multi-stage emulsification polymerization method can be adopted. As a typical example, the unsaturated monomer is emulsion-polymerized in water in the presence of an emulsifier, a polymerization initiator, etc., usually under heating at 40 ° C. to 90 ° C., and this step is repeated a plurality of steps. There is a way to do it.

The emulsifier is not particularly limited, and for example, an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a polymer emulsifier and the like can be used. For example, fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfate ester salts, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxynonyl. Anionic surfactants such as so-called reactive surfactants that have a polymerizable unsaturated double bond in the molecule with phenyl ether sulfonate, polyoxyethylene-polyoxypropylene glycol ether sulfate, sulfonic acid group or sulfate ester group. Agents: Polyoxyethylene alkyl ethers, polyoxyethylene nonylphenyl ethers, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene block copolymers, or the aforementioned skeleton-polymerizable unsaturated double bonds. Nonionic surfactants such as reactive nonionic surfactants contained in the molecule; cationic surfactants such as alkylamine salts and quaternary ammonium salts; (modified) polyvinyl alcohol and the like can be mentioned.

The amount of the emulsifier used is not particularly limited, but is preferably 1.0 to 5.0% by weight based on the total amount of the total polymerizable monomer component used, for example. Increasing the amount of emulsifier used can improve polymerization stability, and decreasing it can improve water resistance. Further, in order to use the high Tg component as the core and the low Tg component as the shell, the amount of the emulsifier used in each stage should be larger than the amount used in the stage for producing the low Tg component. Is preferable.

The polymerization method for emulsion polymerization of the unsaturated monomer is a monomer batch preparation method in which the monomers are collectively charged, a monomer dropping method in which the monomer is continuously dropped, or a monomer. A pre-emulsion method in which water and an emulsifier are mixed and emulsified in advance and then added dropwise, or a method in which these are combined can be mentioned. At this time, the method of using the polymerization initiator is not particularly limited. As a method of using the Si-containing compound, the condensation reaction of the hydrolyzable silane and the radical polymerization of the unsaturated monomer are carried out simultaneously and / or the condensation reaction of the hydrolyzable silane is preceded and then the unsaturated monomer is used. A method of emulsion polymerization in which radical polymerization is allowed to proceed, or a method in which the condensation reaction of hydrolyzable silane is allowed to proceed after the radical polymerization of an unsaturated monomer is allowed to proceed is used.

As the polymerization initiator used when emulsifying and polymerizing the unsaturated monomer, a generally used radical initiator may be used. The radical polymerization initiator is a substance that generates radicals by heat or a reducing substance to cause addition polymerization of a polymerizable monomer, and contains water-soluble or oil-soluble persulfates, peroxides, azobis compounds, etc. is there. Specifically, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis () 2-Diaminopropane) Hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like, preferably water-soluble.
If it is desired to accelerate the polymerization rate or to react at a low temperature, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, or formaldehyde sulfooxylate salt can be used in combination with the radical polymerization initiator.

If necessary, a molecular weight modifier can be used in the emulsion polymerization. Specific examples of the molecular weight adjusting agent include dodecyl mercaptan and butyl mercaptan. The method of use is not particularly limited, but the amount thereof is preferably 2% or less with respect to the total amount of the total polymerizable monomer component used.

In addition, a film-forming aid can be optionally added to the latex.
Specifically, as the film forming aid, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol iso Examples thereof include butyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, and tripropylene glycol methyl ether. These film forming aids can be arbitrarily blended, such as alone or in combination.

The content of latex contained in the coating material of the present invention is preferably 0.05% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 35% by mass or less, and 5% by mass or more and 30% by mass in 100% by mass of the coating material. More preferably, it is by mass or less. Here, the content of latex contained in the paint refers to the content of the solid content (that is, resin and emulsifier) in the latex contained in the paint, and the liquid content in the latex (that is, a dispersion medium such as water). , Molecular weight adjuster, film forming aid) are not included. When the content of the solid content in the latex contained in the coating material is within the above range, the processability of the coating material of the present invention can be sufficiently improved.

The content of the solid content in the latex is not particularly limited, and for example, a latex having a solid content of 20% by mass or more and 60% by mass or less in 100% by mass of latex can be preferably used.

[[Surface energy modifier]]
The coating material of the present invention may contain a surface energy modifier as an optional component in order to improve the coatability. As a result, when the coating film of the coating film is formed on the base material, the smoothness of the applied coating film of the coating film is improved, and a more uniform coating film can be obtained.
Specific examples of surface energy modifiers include Triton® X-45, Triton X-100, Triton X, Triton A-20, Triton X-15, Triton X-114, Triton X-405, and Tween (registered). Trademarks) # 20, Tween # 40, Tween # 60, Tween # 80, Tween # 85, Pluronic® F-68, Pluronic F-127, Span® 20, Span 40, Span 60, Span 80 , Span 83, Span 85, AGC Seimi Chemical's "Surfron® S-221", "Surfron S-221", "Surfron S-231", "Surfron S-232", "Surfron S-233" , "Surflon S-242", "Surfactant S-243", "Surfactant S-611", 3M's "Novec® FC-4430", "Novec FC-4432", DIC's "Mega Fuck (Registration)" Examples thereof include nonionic surfactants such as "F-444" and "Megafuck F-558". Of these, fluorine-containing nonionic surfactants are particularly preferable, and AGC Seimi Chemical's "Surflon S-221", "Surflon S-221", "Surflon S-231", "Surflon S-232", and "Surflon S-233" are particularly preferable. , "Surfron S-242", "Surfron S-243", "Surfron S-611", 3M's "NovecFC-4430", "NovecFC-4432", DIC's "Megafuck F-444", ""Mega Fuck F-558" is preferably used. These may be used alone or in combination of two or more.

The amount of the surface energy adjusting agent added is not particularly limited, but is preferably 0.010% by mass or more and 2.0% by mass or less, more preferably 0.10 to 1.5% by mass, based on 100% by mass of the coating material. Is. When it is 0.010% by mass or more, the paint film tends to be uniform and unevenness is unlikely to occur. Further, in order to improve the coating film formation without causing unevenness in the coating film, the addition amount is preferably 2.0% by mass or less.

[[Other additives]]
In addition to the above-mentioned components, the coating material of the present invention may contain other additives generally used in the coating material as optional components.
Other additives include plasticizers, desiccants, hardeners, anti-skin agents, flattening agents, anti-dripping agents, fungicides, antibacterial agents, UV absorbers, heat ray absorbers, lubricants, and surfactants. Examples thereof include agents, dispersants, thickeners, viscosity modifiers, stabilizers, drying modifiers, colorants, organic binders and the like. Further, other kinds of antiviral compositions, antibacterial compositions, antifungal compositions, antiallergen compositions, catalysts, antireflection materials, materials having heat shielding properties and the like can be mentioned.

<Viscosity>
The viscosity of the coating material of the present invention at 25 ° C. is not particularly limited, but the shear rate measured at 25 ° C. using a cone-plate type rotational viscometer in accordance with JIS K5600-2-3 is 1 × 10 ^-1 s. ^In the region of ^-1 to 1 × 10 ² s ^-1, it is preferably 100 mPa · s or less, more preferably 30 mPa · s or less. The viscosity at 25 ° C. is preferably 100 mPa · s or less because it is easy to form a homogeneous coating film at the time of printing.
In order to adjust the viscosity of the coating material of the present invention at 25 ° C. within the above range, the concentrations of essential components and / or optional components may be appropriately adjusted, or a thickener or the like may be appropriately added, if necessary. .. For example, if it is desired to reduce the viscosity at 25 ° C., the concentration of the solvent may be increased. On the other hand, if it is desired to increase the viscosity at 25 ° C., the concentration of cuprous oxide may be increased or a thickener may be added.
The thickener is not particularly limited, and any thickener usually used in paints can be used.

<Surface free energy>
The surface free energy of the coating material of the present invention at 25 ° C. is not particularly limited, but is preferably 40 mN / m or less, more preferably 35 mN / m or less, and further preferably 30 mN / m or less. In the reverse printing described later, the surface free energy at 25 ° C. is preferably 40 mN / m or less from the viewpoint of the wettability of the paint to the blanket. The surface free energy can be measured using a contact angle meter.
In order to adjust the surface free energy of the coating material of the present invention at 25 ° C. within the above range, the concentrations of the surface energy adjusting agent and various solvents may be appropriately adjusted as necessary. For example, when it is desired to reduce the surface free energy at 25 ° C., a surface energy modifier is added or increased, or a solvent having a low surface free energy (for example, a fluorosolvent, specifically hydrofluoroether) is added. Alternatively, it may be increased, or when a mixed solvent is used, the concentration of the solvent having a high surface free energy may be decreased. On the other hand, when it is desired to increase the surface free energy at 25 ° C., the surface energy modifier is eliminated or reduced, or a solvent having a high surface free energy (for example, water) is added or increased, or a mixed solvent is used. If this is the case, the concentration of the solvent having a low surface free energy may be reduced.

[Paint preparation]
The coating material of the present invention can be produced, for example, by mixing the above-mentioned copper oxide particles, a dispersant, and a solvent. Further, the above-mentioned latex may be mixed.
Each of these essential components is mixed in a predetermined ratio, and for example, an ultrasonic method, a mixer method, a 3-roll method, a 2-roll method, an attritor, a Banbury mixer, a paint shaker, a kneader, a homogenizer, a ball mill, a sand mill, etc. It can be prepared by using and dispersing.
When preparing the coating material of the present invention, additives can be added as needed. As the additive, in addition to the above-mentioned surface energy adjusting agent, a dispersant generally used for paints, an organic binder and the like can be used.

As described above, the coating material of the present invention can be prepared by appropriately adjusting the concentrations of the copper oxide particles, the organic compound having a phosphate group, the solvent, the latex, the surface energy regulator, and other additives. Viscosity and surface energy can be adjusted.

[Use of antibacterial and antifungal paint]
Since the antibacterial and antifungal paint of the present invention has excellent coatability, it can be used for various members. Examples of the member include metal parts, plastic parts, textiles and non-woven fabrics, and more specifically, application examples include plastic parts such as heat transfer tubes and fins of air conditioner heat exchangers and louvers of outlets. , And blower fans, etc .; car air conditioner evaporators, filters and blower fans; masks; air conditioner filters, air purifier filters, vacuum cleaner filters, ventilation fan filters, vehicle filters, air conditioner filters, etc. , Nets for bedding, nets for net doors, nets for poultry houses, etc .; Sheets and films for wallpaper, windows, ceilings, vehicle seats, etc .; Various equipment such as doors, blinds, chairs, sofas, flooring materials (handles viruses) Equipment, trains / vehicles, hospitals, general buildings) interior materials, etc .;
Since the antibacterial antifungal coating material of the present invention can change the wavelength of light absorbed by the coating film by controlling the particle size of the copper oxide particles, it can be applied to an optical component such as an optical filter. It can also impart antibacterial properties.
Since the antibacterial antifungal coating material of the present invention contains copper oxide particles exhibiting conductivity, it can also be applied to electronic parts of electric devices and electronic devices to provide a conductive film having antibacterial properties.

[Use of anti-algae paint]
Since the algae-proof paint of the present invention has excellent coatability, it can be used for various members. As the member, in addition to the above-mentioned antibacterial and antifungal paints, for example, it can be suitably used for building exterior materials, ship exterior materials, and the like.

[Manufacturing method of parts]
Next, a method for producing the antibacterial antifungal member and the algae-proof member of the present invention will be described in detail.
The antibacterial antifungal member and the algae-proof member of the present invention can be produced by various methods. For example, the base material is immersed in the paint of the present invention, or the paint of the present invention is applied to the surface of the base material by spraying or other coating method or various printing methods, and then the paint is dried to form a coating film. By doing so, the antibacterial antifungal member and the algae-proofing member of the present invention can be produced. In particular, by applying using a printing method, it is possible to apply the entire surface of the base material covered with an antibacterial antifungal material or an algae-proof material only to the area to be coated on the surface of the base material, which is preferable. ..

[[Applying method]]
The method of applying the coating material of the present invention to the surface of the base material to form a coating film is not particularly limited, and screen printing, spray coating, spin coating, slit coating, die coating, bar coating, knife coating, air doctor coating, etc. Coating methods and printing methods such as roll coating, electrostatic coating, offset printing, reverse printing, flexo printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and tampo printing can be used. Further, a dipping method of immersing the paint of the present invention or a coating liquid containing the paint can also be used.
Above all, if the coating is applied by the printing method, the coating material can be directly printed on the surface of the base material in a desired pattern, so that the coating material of the present invention can be applied only where antibacterial and / or algae-proofing properties are required. It is preferable because only the required amount can be applied.

The coating amount of the coating material of the present invention is not particularly limited, and the antibacterial and / or algae-proofing performance of the coating material, that is, the content of copper oxide particles which are antibacterial and antifungal components and / or algae-proofing components, and It can be appropriately determined in consideration of the coating method, the application of the manufactured member, and the like.
From the viewpoint of sufficiently obtaining antibacterial antifungal performance and / or algae-proofing performance, the content of copper oxide particles in the antibacterial antifungal member and the algae-proofing member is 0.001 to 100% by mass. It is preferably applied so as to be 20% by mass, and more preferably 0.1 to 10% by mass.

[[Coating film formation]]
After applying the coating material of the present invention to the substrate, the coating material is dried to form a coating film. The method for drying the paint of the present invention is not particularly limited, and examples thereof include heat drying and natural drying. If necessary, ultraviolet rays, infrared rays, electron beams, γ-rays and the like may be irradiated at the time of drying. ..
The thickness of the coating film formed on the base material is not particularly limited, and can be appropriately determined in consideration of the use of the antibacterial and antifungal member to be produced. From the viewpoint of sufficiently obtaining antibacterial and antifungal properties, the thickness of the coating film on the substrate is preferably 1 μm or more and 10 mm or less, and more preferably 10 μm or more and 5 mm or less.

[[Base material]]
The material of the base material is not particularly limited, and for example, soda lime glass, non-alkali glass, borosilicate glass, high strain point glass, glass such as quartz glass, glass such as silica, ceramic such as alumina, pottery, etc. Examples include baked goods such as porcelain, stone, concrete, and inorganic materials such as copper, steel, brass, titanium, aluminum, stainless steel, and metals such as iron. Further, it may be an organic material such as a polymer material, and for example, a polymer material such as plastic as a base material, paper, wood, fiber or the like derived from a natural raw material can also be used as a base material.

When the base material is plastic, the resin material used for molding the base material is not particularly limited, but for example, polyimide, polyamide, polyamideimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide, and poly. Ether ether ketone, polyether sulfone, polycarbonate, polyetherimide, epoxy resin, phenol resin, glass-epoxy resin, polyphenylene ether, acrylic resin, polyethylene, polypropylene and other polyolefins, polystyrene, polyacetal, ABS resin, polyurethane, polyvinyl chloride , Liquid liquid polymer compounds and the like. Of these, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.
The shape of the base material is not limited to a plate shape, and may be a film, a sheet, a woven fabric, a non-woven fabric, a three-dimensional structure, or the like.

The thickness of the base material is not particularly limited, but in the case of a plastic base material such as a resin film, it is usually in the range of 10 μm or more and 300 μm or less. Further, when the thickness is 300 μm or less, it is preferable in terms of flexibility when the winding process is continuously performed. On the other hand, when the material of the base material is an inorganic material, it is usually about 0.10 mm or more and 10 mm or less, preferably about 0.50 mm or more and 5.0 mm or less.

[Antibacterial antifungal member]
The antibacterial and antifungal member produced by the paint of the present invention has excellent antibacterial and antifungal properties imparted to the entire surface of the base material or only the desired surface portion in a desired pattern, and is therefore used in various applications. be able to. For example, metal parts, plastic parts, textiles, non-woven fabrics, etc. are mentioned, and more specifically, application examples include heat transfer tubes and fins of air conditioner heat exchangers, plastic parts such as louvers of air outlets, and blower fans. Evaporators, filters and blower fans for car air conditioners; Masks; Filters for air conditioners, filters for air purifiers, filters for vacuum cleaners, filters for ventilation fans, filters for vehicles, filters for air conditioners, etc .; For clothing, bedding, blinds, etc. Nets such as nets for air conditioners and poultry houses; seats and films for wallpaper, windows, ceilings, vehicle seats, etc .; various equipment such as doors, blinds, chairs, sofas, flooring materials (equipment that handles viruses, trains / vehicles) , Hospitals, general buildings), etc.;
Further, since the wavelength of the absorbed light can be changed depending on the particle size of the copper oxide particles, it can also be used as an optical filter having antibacterial properties.

[Algae-proof member]
The algae-proof member produced by the paint of the present invention has excellent algae-proof properties imparted to the entire surface of the base material or only the desired surface portion in a desired pattern, and thus can be used for various purposes. it can. For example, woven fabrics, non-woven fabrics, building materials, etc. can be mentioned, and more specifically, application examples include building exterior materials, ship exterior materials, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to such Examples.

Each of the paints of Examples and Comparative Examples was prepared as described later.
The type and content of the copper oxide particles and the average particle size were specifically determined by the methods shown below.

[Type and content of copper oxide particles]
The type of copper oxide particles contained in the precipitates obtained in Examples and Comparative Examples described later was specified by the X-ray diffraction (XRD) method, and the content thereof was specified by the evaporation dry solid method.
For the type of copper oxide, the precipitate was measured by X-ray diffraction, and it was confirmed that its profile was consistent with that of cuprous oxide. The content of cuprous oxide was determined by drying the precipitate with a vacuum drying device using an evaporation dry method and measuring the weight before drying and the weight after drying to determine the residue as cuprous oxide. From the results of the above-mentioned X-ray diffraction method, it is clear that the residue is cuprous oxide.
[X-ray diffraction method measurement conditions]
Measuring device: Rigaku Co., Ltd. Ultima-IV X-ray source: Cu-Kα
Excitation voltage: Voltage 40kV, Current 40mA Optical system: Centralized optical system Cu-Kβ line filter: Ni foil Absorber: None Detector: D / tex (high-sensitivity detector) Measurement method: θ / 2θ method Slit: DS = 1 ° , SS = release, RS = release, vertical slit = 5 mm,
2θ scan: 2θ = 10-65 ° (0.02 ° / step, 2 ° / min)
[Evaporation-drying method conditions]
Drying method: Vacuum drying Vacuum drying temperature: 160 ° C
Vacuum drying time: 6 hours

[Average particle size of copper oxide particles]
The average particle size of copper oxide particles uses the dynamic light scattering method as the measurement method and the photon correlation method as the method for analyzing the measured signal to obtain the autocorrelation function. FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. The autocorrelation function was measured by the Cumulant method.
The coating materials prepared in the following Examples and Comparative Examples were diluted with ethanol as a diluting solvent for measuring the average particle size so that the copper oxide particles had a concentration of 20% by mass, and were subjected to the above measurement. However, in Comparative Example 2, the particle size could not be measured because the copper oxide particles could not be dispersed and were in an aggregated state.

[Example 1]
96 g of cupric acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in a mixed solvent of 900 g of water and 416 g of 1,2-propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) to dissolve hydrazine monohydrate (Tokyo Kasei Kogyo Co., Ltd.). )) 28 ml was added with stirring, and after the generation of bubbles was completed, the supernatant and the precipitate were separated by centrifugation. The content of cuprous oxide in this precipitate was 0.690.
To 43.5 g of the obtained precipitate, 6.0 g of DISPERBYK-145 (manufactured by Big Chemie, acid value 76 mgKOH / g, phosphoric acid ester having a group having a chemical structure of the chemical formula (1)) as an organic compound having a phosphoric acid group. , 1.5 g of Surflon S-611 (manufactured by Seimi Chemical) as a surface energy modifier and 324 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent were added and dispersed using a homogenizer to obtain a solid content concentration of 10% by mass. 375 g of a coating material (hereinafter referred to as “painting A”) having 8% by mass of cuprous oxide particles as copper oxide particles was obtained.
The average particle size of the copper oxide particles was 25 nm.

[Example 2]
To the paint A prepared in Example 1, water was added to acrylic latex (manufactured by Nisshin Chemical Industries, Ltd., product # 2682, solid content 35% by mass), and an aqueous acrylic latex solution adjusted to a solid content concentration of 10% by mass was mixed. As a result, a coating material containing cuprous oxide particles as copper oxide particles (solid content: 10% by mass, hereinafter referred to as "paint B") was obtained. The mixing ratio of the coating material A and the aqueous acrylic latex solution was 1: 3, and the mixture was mixed so that the content of the copper oxide particles in the solid content of the coating material B was 20% by mass.

[Example 3]
Acrylic latex (manufactured by Nissin Chemical Industry Co., Ltd., product # 2682) is mixed with an aqueous acrylic latex solution adjusted to have a solid content concentration of 10% by mass with the above paint A to obtain cuprous oxide particles as copper oxide particles. (The solid content is 10% by mass, hereinafter referred to as "paint C") was obtained. The mixing ratio of the coating material A and the aqueous acrylic latex solution was 1:39, and the mixture was mixed so that the content of the copper oxide particles in the solid content of the coating material C was 2% by mass.

[Example 4]
96 g of cupric acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in a mixed solvent of 900 g of water and 416 g of 1,2-propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) to dissolve hydrazine monohydrate (Tokyo Kasei Kogyo Co., Ltd.). )) 28 ml was added with stirring, and after the generation of bubbles was completed, the supernatant and the precipitate were separated by centrifugation. The content of cuprous oxide in this precipitate was 0.690.
To 43.5 g of the obtained precipitate, 6.0 g of DISPERBYK-102 (manufactured by Big Chemie, acid value 101 mgKOH / g, copolymer having an acidic group) as a dispersant, and Surflon S-611 (Seimi Chemical) as a surface energy adjuster. (Manufactured by) 1.5 g and ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 99.1 g as a solvent were added and subjected to dispersion treatment using a homogenizer to obtain a dispersion having a solid content concentration of 25% by mass. 10 g of this dispersion is weighed, and 190 g of an acrylic latex aqueous solution adjusted to a solid content concentration of 25% by mass by adding water to acrylic latex (manufactured by Nisshin Chemical Industry Co., Ltd., product # 2682, solid content 35% by mass) is mixed. Then, 200 g of a coating material having 1% by mass of cuprous oxide particles as copper oxide particles (solid content was 25% by mass, hereinafter referred to as "painting D") was obtained.
The average particle size of the copper oxide particles was 19 nm.

[Example 5]
A precipitate containing cuprous oxide at a content of 0.690 was prepared in the same manner as in Example 1. With respect to the obtained precipitate, DISPERBYK-145 (manufactured by Big Chemie) as an organic compound having a phosphoric acid group and Surflon S-611 (manufactured by Seimi Chemical) as a surface energy adjuster were added at the same ratio to precipitate as in Example 1. In addition, only the amount of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent was adjusted and added, and the mixture was dispersed using a homogenizer to have a solid content concentration of 25% by mass and cuprous oxide particles as copper oxide particles of 20% by mass. (Hereinafter referred to as "paint E") was obtained.

[Example 6]
Acrylic latex aqueous solution and ethanol (manufactured by Nissin Chemical Co., Ltd., product # 2682, solid content 35% by mass) adjusted to a solid content concentration of 30% by mass by adding water to the paint E prepared in Example 5 Wako Pure Chemical Industries, Ltd.) was added and mixed to obtain a paint containing 5% by mass of cuprous oxide particles as copper oxide particles (solid content was 25% by mass, hereinafter referred to as "paint F").

[Example 7]
Acrylic latex aqueous solution and ethanol (manufactured by Nissin Chemical Industry Co., Ltd., product # 2682, solid content 35% by mass) adjusted to a solid content concentration of 30% by mass by adding water to the paint E prepared in Example 5. Wako Pure Chemical Industries, Ltd.) was mixed to obtain a paint containing 0.5% by mass of cuprous oxide particles as copper oxide particles (solid content is 25% by mass, hereinafter referred to as "paint G").

[Comparative Example 1]
As Comparative Example 1, a sample filter was prepared as described later using an automobile air conditioner filter that had not been impregnated with the paint and dried.

[Comparative Example 2]
96 g of cupric acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in a mixed solvent of 900 g of water and 416 g of 1,2-propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) to dissolve hydrazine monohydrate (Tokyo Kasei Kogyo Co., Ltd.). )) 28 ml was added with stirring, and after the generation of bubbles was completed, the supernatant and the precipitate were separated by centrifugation. The content of cuprous oxide in this precipitate was 0.690.
To 43.5 g of the obtained precipitate, 6.0 g of DISPERBYK-170 (manufactured by Big Chemie, acid value 11 mgKOH / g) as a dispersant, 1.5 g of Surflon S-611 (manufactured by Seimi Chemical) as a surface energy modifier, and 324 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent was added and dispersion treatment was performed using a homogenizer, but the copper oxide particles aggregated and could not be converted into ink, and the particle size could not be measured.

[Antibacterial and antifungal evaluation]
Sample filters were prepared for each of the paints (paints A to G) of Examples 1 to 7 and the following tests were carried out to evaluate the antibacterial and antifungal properties. Preparation of a sample filter, antibacterial test, antifungal test method, and test results will be described below.

<1. Preparation of sample filter>
As a filter material for evaluation of each of the paints A to G of Examples 1 to 7 and Comparative Example 1, an automobile air conditioner filter (Aerist Comfort high dust collection type manufactured by BOSCH) is made into a solution of 76% ethanol and 24% water. The one which was immersed at room temperature for about 10 minutes, sterilized, and then dried was used. In Examples 1 to 7, the paint was immersed in each of the paints A to G for about 5 minutes, the filter was taken out from the paint, left to dry at room temperature, and further in a dryer set at 60 ° C. for 1 hour. It was dried. The paint impregnated filter of Examples 1 to 7 and the paint non-coated filter of Comparative Example 1 prepared in this manner are left at room temperature for one week to allow microorganisms (bacteria, fungi, etc.) in the air to naturally adhere to the filter. It was. These filters were used as sample filters of Examples 1 to 7 and Comparative Example 1 in the following antibacterial and antifungal tests.

<2. Antibacterial test method>
The antibacterial property test was carried out by the following viable cell count test membrane filter method in accordance with the 17th revised Japanese Pharmacopoeia Microbial Limit Test Method.
The sample filters of Examples 1 to 3 and Comparative Example 1 were immersed in physiological saline, and the microorganisms adhering to the sample filters were shaken and extracted. The obtained extract was filtered through a membrane filter having a pore size of 0.45 μm. The colony filter was placed on a tryptosome agar medium and cultured in an incubator at 32 ° C. for 5 days, and the number of colonies was visually counted.
The above test was carried out twice to determine the average number of colonies.

<3. Antifungal test method>
The antifungal test was carried out in accordance with "6, Testing of general industrial products" of JIS Z 2911: 2010 "Mold resistance test method". As the mold species, Cladosporium cladosporioides (NBRC 6348 strain, obtained from the National Institute of Technology and Evaluation) was used. The sample filters of Examples 1 to 7 and Comparative Example 1 prepared in 1 above were used as test pieces. The size of the test piece was 30 mm square.
The antifungal property was evaluated by visually examining the growth state of hyphae formed on the surface of the test piece cultured for 4 weeks. The method of displaying the test results is as follows.
(Evaluation criteria for antifungal properties)
0: No hyphal growth is observed in the inoculated part of the sample or test piece.
1: The area of the hyphal growth part observed in the inoculated part of the sample or test piece does not exceed 1/3 of the total area.
2: The area of the hyphal growth part observed in the inoculated part of the sample or test piece exceeds 1/3 of the total area.

<4. Test result>
The test results are shown in Table 1 below.

As can be seen from Table 1, the paints A to G of Examples 1 to 7 showed remarkable antibacterial performance and antifungal performance as compared with the filter alone of Comparative Example 1.

<4. Algae resistance test / results>
Chlamydomonas (species name: Chlamydomonas reinhardtii, Japanese name: Chlamydomonas chinensis, building wall surface growing strain was collected) was liquid-cultured under the following culture conditions.
(Culture conditions)
Medium: Made by Hyponex Japan Co., Ltd. Fine powder Hyponex 0.2% aqueous solution (liquid culture in a bottle)
Culture temperature: 23 ° C
Light irradiation: Sunlight (indirect light near the window) irradiation Culture atmosphere: Normal atmosphere

3 mL of the liquid-cultured Chlamydomonas culture solution was added dropwise to an 8 cm × 5 cm Asahi Kasei BEMCOT “AZ-8” stored in a case with a lid. Further, another 2 cm × 2 cm BEMCOT was impregnated with the paint A of Example 1 and dried at 60 ° C. for 1 hour to prepare a sample piece. The sample piece was placed on BEMCOT in which the culture solution of Chlamydomonas was previously added dropwise (Fig. 1). This sample was allowed to stand for 2 weeks in a temperature: 23 ° C., light irradiation: sunlight (indirect light near the window) irradiation, and a normal atmospheric environment.
When the sample was observed two weeks later, the green color around the sample piece disappeared (Fig. 2).
From this test result, it was confirmed that it is also effective for algae.

The antibacterial antifungal paint and the algae-proof paint according to the present invention can be provided as low-cost paints having excellent dispersion stability against changes over time. Further, it can be suitably used for imparting antibacterial and antifungal properties to antibacterial and antifungal members such as filters in building materials, automobiles, and home appliances such as air conditioners.
The method for producing an antibacterial antifungal and / or algae-proof member according to the present invention provides excellent antibacterial antifungal and / or algae-proof properties only on the entire surface or a desired surface portion of a base material in a desired pattern. It is possible to provide an antibacterial antifungal and / or algae-proof member imparted in 1.

Claims (11)

An antibacterial and antifungal paint containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, and a solvent.
The acid value of the dispersant is 73 mgKOH / g or more and 130 mgKOH / g or less.
The content of the copper oxide particles is 0.5% by mass or more and 60% by mass or less.
The content of the dispersant is 0.05% by mass or more and 20% by mass or less.
An antibacterial and antifungal coating material, wherein the content of the solvent is 20% by mass or more and 99.45% by mass or less. An algae-proof paint containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, and a solvent.
The acid value of the dispersant is 73 mgKOH / g or more and 130 mgKOH / g or less.
The content of the copper oxide particles is 0.5% by mass or more and 60% by mass or less.
The content of the dispersant is 0.05% by mass or more and 20% by mass or less.
An algae-proof coating material, characterized in that the content of the solvent is 20% by mass or more and 99.45% by mass or less. An antibacterial and antifungal paint containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, latex, and a solvent.
The acid value of the dispersant is 73 mgKOH / g or more and 130 mgKOH / g or less.
The content of the copper oxide particles is 0.5% by mass or more and 50% by mass or less.
The content of the dispersant is 0.05% by mass or more and 20% by mass or less.
The content of the latex is 0.05% by mass or more and 40% by mass or less.
An antibacterial and antifungal coating material, wherein the content of the solvent is 5% by mass or more and 99.4% by mass or less. The antibacterial and antifungal paint according to claim 3, wherein the latex is an acrylic latex. An algae-proof paint containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, a dispersant, latex, and a solvent.
The acid value of the dispersant is 73 mgKOH / g or more and 130 mgKOH / g or less.
The content of the copper oxide particles is 0.5% by mass or more and 50% by mass or less.
The content of the dispersant is 0.05% by mass or more and 20% by mass or less.
The content of the latex is 0.05% by mass or more and 40% by mass or less.
An algae-proof coating material, characterized in that the content of the solvent is 5% by mass or more and 99.4% by mass or less. The algae-proof paint according to claim 5, wherein the latex is an acrylic latex. The antibacterial antifungal paint according to any one of claims 1, 3 and 4, or the antibacterial antifungal paint according to any one of claims 2, 5 and 6, wherein the dispersant is an organic compound having a phosphoric acid group. Algae-proof paint. The antibacterial antifungal paint according to any one of claims 1, 3 and 4, or any of claims 2, 5 and 6, which contains 0.010% by mass or more and 2.0% by mass or less of a surface energy modifier. Or the antifungal paint according to item 1. The antibacterial antifungal paint or algae-proof paint according to claim 8, wherein the surface energy modifier is a fluorine-containing nonionic surfactant. The antibacterial antifungal paint according to any one of claims 1, 3 and 4, the antibacterial antifungal paint according to claim 7, which cites any one of claims 1, 3 and 4. The antibacterial antifungal paint according to claim 8 or the antibacterial antifungal paint according to claim 9 which cites any one of 1, 3 and 4 is applied to screen printing, spray coating, spin coating and slit coating. , Die coat, bar coat, knife coat, air doctor coat, roll coat, electrostatic coating, offset printing, reverse printing, flexo printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and dipping method. A step of applying to the surface of the substrate using at least one coating method, and
After application, the antibacterial and antifungal paint is dried to form a coating film.
A method for producing an antibacterial and antifungal member, which comprises. The algae-proof paint according to any one of claims 2, 5 and 6, the algae-proof paint according to claim 7, which cites any one of claims 2, 5 and 6, the claim 2. The algae-proof paint according to claim 8 or the algae-proof paint according to claim 9, which cites any one of 5 and 6, is used for screen printing, spray coating, spin coating, slit coating, die coating, and bar. At least one selected from coat, knife coat, air doctor coat, roll coat, electrostatic coating, offset printing, reverse printing, flexo printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and immersion method. The process of applying to the surface of the substrate using the application method,
The step of drying the algae-proof paint after application to form a coating film, and
A method for producing an algae-proof member, which comprises.