JP6706222B2 - Antibacterial and antifungal paint, and method for producing antibacterial and antifungal member using the paint - Google Patents

Description

The present invention relates to an antibacterial/antifungal coating material and a method for producing an antibacterial/antifungal member using the antibacterial/antifungal coating material.

Due to the increasing hygiene in recent years, fungi such as bacteria and fungi can be found in food and pharmaceutical factories, hospitals and nursing homes, buildings such as food kitchen appliances, medical appliances, medical equipment, and even general household products. Antimicrobial agents, antifungal agents, disinfectants, etc. are used to spread and prevent infection.
Therefore, it is desired to give various members antibacterial properties and antifungal properties not only in public facilities but also in general households.

As a solution to these problems, organic or inorganic antibacterial agents have been proposed.
In particular, regarding inorganic antibacterial agents, metal ions such as silver ions (Ag ⁺ ), zinc ions (Zn ²⁺ ), and divalent copper ions (Cu ²⁺ ), have conventionally suppressed the growth of microorganisms, or It is known to act bactericidally (for example, Patent Document 1). Based on this finding, many antimicrobial materials in which these metal ions are supported on a substance such as zeolite or silica gel, and antimicrobial materials in which the above metal and titanium oxide having a photocatalytic action are combined have been developed.

JP, 2003-221304, A

Among them, paints using silver have recently been used for antibacterial and antifungal applications, but silver has a problem of high cost.
Therefore, development of an antibacterial/antifungal coating using a metal, which is cheaper than silver, as an antibacterial/antifungal component is desired.

Therefore, the problem to be solved by the present invention is to use a low-cost copper oxide as an antibacterial antifungal component, an antibacterial antifungal coating showing excellent dispersion stability and excellent coatability with time, and It is intended to provide a method for producing an antibacterial and antifungal member using the antibacterial and antifungal paint.

That is, the present invention is as follows.
The antibacterial and antifungal coating composition of the present invention is a copper oxide particle having an average particle size of 1 nm to 500 nm, an organic compound having a phosphoric acid group, a resin binder having a phosphoric acid group, a solvent, and a fluorine-containing nonionic property. An antibacterial and antifungal coating composition containing a surfactant , wherein 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 organic compound having a phosphoric acid group is 0. 0.05% by mass or more and 20% by mass or less, the content of the resin binder is 0.05% by mass or more and 40% by mass or less, and the phosphoric acid group-containing organic compound and the phosphoric acid group-containing resin binder. The total content of the above is 0.05 mass% or more and 40 mass% or less, and the content of the solvent is 5 mass% or more and 99.4 mass% or less.
In the antibacterial and antifungal coating of the present invention, it is preferable that the resin binder has at least one of an acrylate group and a methacrylate group .

That is, the present invention is as follows.
The antibacterial/antifungal coating composition of the present invention is an antibacterial/antifungal coating composition containing copper oxide particles having an average particle size of 1 nm to 500 nm, an organic compound having a phosphoric acid group, a resin binder, and a solvent. The content of the copper oxide particles is 0.5% by mass or more and 50% by mass or less, the content of the organic compound having a phosphoric acid group is 0.05% by mass or more and 20% by mass or less, and the resin is The content of the binder 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.
In the antibacterial and antifungal coating of the present invention, it is preferable that the resin binder has at least one of an acrylate group and a methacrylate group.
Further, in the antibacterial and antifungal coating composition of the present invention, it is also preferable that the resin binder has a phosphoric acid group.

Further, the method for producing an antibacterial and antifungal member of the present invention comprises the above antibacterial and antifungal paint, screen printing, spray coating, spin coating, slit coating, die coating, bar coating, knife coating, air doctor coating, roll coating. , Electrostatic coating, offset printing, reverse printing, flexo printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and a step of applying to the substrate surface using a method selected from the dipping method and And a step of drying the antibacterial and antifungal coating after application and optionally curing it simultaneously with or after the drying to form a coating film.

The antibacterial and antifungal paint according to the present invention is excellent in dispersion stability of copper oxide particles, which is an antibacterial and antifungal component with respect to aging, and also has excellent coatability, and thus can be applied by printing. It can be preferably used for antibacterial and antifungal applications.
The method for producing an antibacterial and antifungal member according to the present invention uses the above antibacterial and antifungal paint, so that the entire surface of the substrate or only a desired portion is provided with excellent antibacterial and antifungal properties in a desired pattern. An antifungal member can be provided.

Hereinafter, modes 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.
First, the antibacterial and antifungal paint of the present invention (also referred to as the "paint of the present invention" in the present specification) will be described in detail.

[Antibacterial and antifungal paint]
The antibacterial and antifungal coating composition of the present invention is characterized by containing copper oxide particles having an average particle size of 1 nm or more and 500 nm or less, an organic compound having a phosphoric acid group, a solvent, and a resin binder in predetermined contents. Is.

[[Copper oxide particles]]
The coating material of the present invention contains, as an antibacterial/antifungal component, copper oxide particles having a predetermined average particle diameter in a predetermined content. Specific examples of the copper oxide particles, cuprous oxide particles, cupric oxide particles, or other oxide number of copper oxide particles, the core part is copper and the shell part is copper oxide of any oxidation number. Examples include particles having a certain core/shell structure. These particles may contain metal salts and/or metal complexes as minor impurities. Among them, cuprous oxide particles are preferable because they have excellent antibacterial and antifungal 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 "average particle diameter" means the hydrodynamic average diameter of the copper oxide particles under a wet condition, and may be slightly different from the value of "average secondary particle diameter" described later. The “average particle diameter” in the present invention, that is, the hydrodynamic average diameter, is a primary particle that does not constitute a secondary particle and exists alone, and an aggregate formed by collecting a plurality of primary particles. It is the average particle size obtained as a measurement target without distinguishing it from the secondary particles. On the other hand, the "average secondary particle size" described below is an average particle size obtained by assuming that all particles to be measured are secondary particles, and there is a primary particle that does not constitute a secondary particle. Is also excluded from the measurement target.
In the present invention, the average particle diameter of the copper oxide particles can be measured using a dynamic light scattering method. More specifically, copper oxide particles dispersed in the solvent used in the coating is measured, and the signal measured using the dynamic light scattering method is analyzed by the photon correlation method to determine the autocorrelation function. The obtained autocorrelation function can be analyzed by the cumulant method to obtain the average particle size.
Since the copper oxide particles of the present invention have an average particle diameter of 1 nm or more and 500 nm or less, the dispersion stability in the paint is improved, and thus the antibacterial and antifungal performance of the paint can be improved. In addition, the coatability of the paint can be improved, and thus the printing method can be used as a method for applying the paint to the surface of the base material.

The average secondary particle diameter 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 and 500 nm or less, more preferably 200 nm or less, and further preferably 80 nm or less. The average secondary particle diameter is an average particle diameter of aggregates (secondary particles) formed by collecting a plurality of primary particles of copper oxide particles. When the average secondary particle diameter is 500 nm or less, it is easy to form a fine pattern 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 obtained when the copper oxide particles dispersed in diethylene glycol are observed using a transmission electron microscope (TEM), Usually, an arbitrary portion of the image is cut out, and for 100 or more particles contained in this portion, the average value of the secondary particle diameters thereof is calculated, and the average secondary particle diameter is calculated.

The preferable range of the average primary particle diameter of the primary particles constituting the secondary particles is 1 nm or more and 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 and the antibacterial and antifungal performance is improved. When the average primary particle diameter is 1 nm or more, the average particle diameter can be in the range of 1 nm or more and 500 nm or less.
The average primary particle diameter means an average value of primary particle diameters obtained for a plurality of primary particles by image analysis. Here, the primary particle size means particles of primary particles obtained from image data obtained when observing cuprous oxide nanoparticles dispersed in a dispersion medium using a transmission electron microscope (TEM). It is a diameter, and an arbitrary part of the image is usually cut out, and the average primary particle size of 100 or more particles contained in this part is calculated to calculate the average primary particle size.

In the coating material of the present invention, the content of copper oxide particles is 0.5% by mass or more and 50% by mass or less, preferably 1.0 to 40% by mass, and more preferably 2.0, in 100% by mass of the coating material. Is about 35% by mass. When the content of the copper oxide particles is 0.5% by mass or more, the function as the antibacterial and antifungal component can be sufficiently exhibited, and when the content is 60% by mass or less, the aggregation of the copper oxide particles is suppressed. This is because it is easier to do.

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

[[Organic compound having a phosphate group]]
The coating material of the present embodiment contains a phosphoric acid group-containing organic compound as a dispersant at a predetermined content rate. The phosphoric acid groups in the organic compound are adsorbed on the copper oxide particles, and the copper oxide particles can be suppressed from aggregating due to the steric hindrance effect between the organic compounds.
The number average molecular weight of the organic compound is not particularly limited, but is preferably 300 to 30,000. When the number average molecular weight is 300 or more, the dispersion stability of the obtained coating tends to increase, and when it is 30,000 or less, baking after coating the coating is easy.
The number of phosphoric acid groups in one molecule of the organic compound is not particularly limited, but is preferably one. One is preferable because it is excellent in dispersion stability.
Specific examples of the organic compound include "Disperbyk (registered trademark)-142", "Disperbyk-145", "Disperbyk-110", "Disperbyk-111", "Disperbyk-118", and "Disperbyk-" manufactured by Big Chemie. 180", "Byk (registered trademark)-9076", "Daiichi Kogyo Seiyaku Co., Ltd.""Prysurf (registered trademark) M208F", "Prysurf DBS", etc. can be mentioned. These may be used alone or in combination of two or more.
In addition to the above, a resin binder having a phosphoric acid group can be used as the organic compound having a phosphoric acid group. The resin binder having a phosphate group has both a function as a resin binder component and a function as a dispersant for copper oxide particles. The resin binder having a phosphoric acid group may be used alone or in combination of two or more. Moreover, you may use together with the organic compound which has a phosphate group as mentioned above. Details of the resin binder having a phosphoric acid group will be described later.

The content of the organic compound having a phosphoric acid group in 100 mass% of the coating material of the present invention is 0.05 mass% or more and 20 mass% or less, preferably 1.0 mass% or more and 15 mass% or less, and more preferably Is 2.0% by mass or more and 10% by mass or less. When the content of the organic compound is within the above range, aggregation of copper oxide particles can be suppressed, and the coating material has sufficient dispersion stability.

[[solvent]]
The coating material of the present invention contains a solvent as a dispersion medium in a predetermined content. The solvent may be a single solvent or a mixed solvent.
As the single solvent, even a solvent having a vapor pressure of 0.010 Pa or more and less than 20 Pa at 20° C. (hereinafter, also referred to as “solvent (A)”), a solvent having 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 solvent (A), a mixed solvent composed of two or more kinds of solvent (B), or a mixed solvent of solvent (A) and 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 the phosphoric acid group, it is possible to improve the dispersion stability of the coating material of the present embodiment in the air and to improve workability. Can be made

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-dried state, and the workability at the time of manufacturing an antibacterial/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, the content of copper oxide particles in the paint can be easily stabilized even if the solvent volatilization rate is high. When the vapor pressure at 20° C. is 20 Pa or more, the time required to bring the coating film of the coating material to a semi-dried state can be made appropriate.

In the coating material of the present invention, the content of the solvent in 100% by weight 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, more preferably 20% by mass. It is 90 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 presence of the resin binder.

In an embodiment in which 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 0.050% by mass or more and 10% by mass or more. It is preferably the following or less, more preferably 0.10 mass% or more and 9.0 mass% or less, and even more preferably 0.20 mass% or more and 8.0 mass% or less. When the content of the solvent (A) is within the above range, an appropriate drying rate is obtained 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, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol , Dipropylene glycol, hexanediol, octanediol, triethylene glycol, tri-1,2-propylene glycol, organic solvents such as glycerol, and water. Among them, polyhydric alcohols having 10 or less carbon atoms are more preferable. When the polyhydric alcohol has more than 10 carbon atoms, 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 ethyl acetate, normal propyl acetate, isopropyl acetate, pentane, hexane, cyclohexane, methylcyclohexane, toluene, methyl ethyl ketone, methyl isobutyl ketone, dimethyl carbonate, methanol, ethanol, 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-dimethyl- 4-heptanol, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like can be mentioned. 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, volatility, and viscosity are particularly suitable. . When the monoalcohol has more than 10 carbon atoms, it is preferable that the monoalcohol has 10 or less carbon atoms in order to suppress deterioration of the dispersibility of the copper oxide particles. These may be used alone or in combination of two or more.

[[Resin binder]]
The coating material of the present invention contains a resin binder in a predetermined content as an essential component in order to improve processability. The resin binder is a resin soluble in a solvent or water, which can form a coating film only by drying by volatilization of the solvent, polymerization or crosslinking by irradiation with light such as ultraviolet rays or heating simultaneously with or after drying, crosslinking, And, the thing which forms a coating film by condensing and/or hardening can be used. These resin binders are used for holding the copper oxide particles and for providing strength as a coating film and adhesion to the substrate.

As the resin binder, synthetic resins (polymers), resin materials (monomers, oligomers), natural resins and the like which are generally used in paints can be used.
Specific examples of the synthetic resin include acrylic resin, lacquer, alkyd resin, chlorinated rubber resin, vinyl chloride resin, thermoplastic resin such as vinyl acetate resin, urethane resin, epoxy resin, melamine resin, urea resin, polyester resin, Thermosetting resins such as silicone resin, fluororesin, phenol resin, melamine resin, urea resin, unsaturated polyester, vinyl ester resin and the like can be mentioned.
Specific examples of the resin material include monomers and oligomers that have a functional group reactive with light and heat and that are cured by being polymerized, crosslinked, and/or condensed by irradiation with light or heating, such as an acrylate group. Examples thereof include UV-curable and thermosetting monomers and oligomers having a methacrylate group, an epoxy group, a vinyl ether group, an isocyanate group and the like.
Specific examples of the natural resin include pine resin, shellac, ester gum, tar pitch and the like.

As the resin binder, it is preferable to use a curable resin binder that is cured by polymerization, crosslinking, and/or condensation by light irradiation, heating, or the like. As the curable resin binder, a photocurable or thermosetting synthetic resin (polymer) having a functional group reactive with light or heat, for example, an acrylate group, a methacrylate group, an epoxy group, a vinyl ether group, an isocyanate group, or the like. And resin materials (monomers, oligomers) and the like. By using these curable resin binders, coatability and adhesion of the coating film to the surface of the base material can be improved.
Among them, a photocurable resin binder is more preferable, and a synthetic resin or a resin material having at least one of an acrylate group and a methacrylate group suitable for ultraviolet curing is further preferable.

As the resin binder, those having a phosphoric acid group are also preferable. By having a phosphoric acid group, in addition to the function of a resin binder, it can also have a function as a dispersant for copper oxide particles, and the adhesion strength of oxide particles to a metal substrate can be improved.
Also in the resin binder having a phosphate group, the resin binder portion is preferably a photocurable or thermosetting synthetic resin or resin material as described above, and more preferably a photocurable resin or resin material. A synthetic resin or a resin material having at least one of an acrylate group and a methacrylate group, which is suitable for ultraviolet curing, is more preferable.
The number average molecular weight of the resin binder having a phosphoric acid group is not particularly limited, but is preferably 120 to 30,000 from the viewpoint of also functioning as a dispersant for copper oxide particles, and the number of phosphoric acid groups per molecule is The number is preferably one.

As the resin binder, a commercially available product may be used, or one prepared by synthesizing a resin may be used.
Examples of commercially available curable resin binders having no phosphoric acid group include Kyoeisha Chemical Co., Ltd. light ester E, light ester NB, light ester IB, Light acrylate (registered trademark) IAA, Light acrylate L-A, Light Acrylate S-A, Epolite M-1230, Epolite 40E, Epolite 100E, Urethane Acrylate AH-600, Urethane Acrylate UA-306H, Urethane Acrylate UA-306T, DIC Corporation EPICLON (registered trademark) 840, EPICLON850 , EPICLON 855, EPICLON D-591, Hydran (registered trademark) HW-171 manufactured by DIC Corporation, Burnock (registered trademark) 16-416, Pandex (registered trademark) P-870 and the like.
Commercially available curable resin binders having a phosphoric acid group include Kyoeisha Chemical Co., Ltd. light acrylate P-1A(N), light ester P-M, light ester P-1M, and Toho Chemical Industry phosphorous. Examples thereof include acid ester type acrylate monomers, PhosmerM, PhosmerPE, and PhosmerPP manufactured by Unichemical Co., Ltd.

The resin binder may be used alone or in combination of two or more.
For example, a non-curable resin binder and a curable resin binder may be combined. Moreover, you may combine the curable resin binder which does not have a phosphoric acid group, and the curable resin binder which has a phosphoric acid group.

When a curable resin binder is used, a reaction initiator suitable for the resin binder used may be added, if necessary. These reaction initiators can be appropriately selected from commercial products.
Specifically, when using a photocurable resin binder, a photopolymerization initiator is used. For example, as a photocurable resin binder having an acrylate group or a methacrylate group as a functional group, a photo radical polymerization initiator such as an alkylphenone such as BASF Japan Ltd. IRGACURE (registered trademark) 651, IRGACURE 127, IRGACURE 184, and IRGACURE 369E is used. You can use it. The photocurable resin binder having an epoxy group or a vinyl ether group as a functional group includes CPI (registered trademark)-101A, CPI-200K, CPI-210S manufactured by San-Apro Co., Ltd. and San-Aid (registered trademark) manufactured by Sanshin Chemical Industry Co., Ltd. A cationic photopolymerization initiator such as an aromatic sulfonium salt such as trademark (trademark) Si-45L and San-Aid Si-60L may be used. The photocurable resin binder having an epoxy group or an isocyanate group as a functional group includes a photobase initiator that generates a base such as a tertiary amine by light irradiation such as WPBG-266 and WPBG-300 manufactured by Wako Pure Chemical Industries, Ltd. Such as a photoanionic polymerization initiator.
When using a thermosetting resin binder, a thermal polymerization initiator is used. For example, thermosetting resin binders such as unsaturated polyester and vinyl ester resins include t-butylperoxy-2-ethylhexanoate manufactured by Arkema Yoshitomi Co., Ltd. and organic materials such as BPO-SP manufactured by Kawaguchi Yakuhin Co., Ltd. Thermal radical polymerization initiators such as peroxides, the thermosetting resin binder having an epoxy group as a functional group, ST11, LV11 manufactured by Mitsubishi Chemical Co., Ltd., Tomeide (registered trademark) 423 manufactured by T&K TOKA, A curing agent such as an amine compound such as Fujicure 7001 (registered trademark) or an amide compound is used.

In the coating composition of the present invention, the content of the resin binder is 0.05% by mass or more and 40% by mass or less, preferably 1% by mass or more and 30% by mass or less, and 2% by mass or more, in 100% by mass of the coating composition. It is more preferably 20% by mass or less.

The content of the resin binder having a phosphoric acid group, when used in combination with an organic compound having a phosphoric acid group, is 0.05% by mass or more in 100% by mass of the coating material. It is preferably 40% by mass or less, and more preferably 1% by mass or more and 30% by mass or less.
Further, when only the resin binder having a phosphoric acid group is used as the organic compound having a phosphoric acid group, it is preferably 0.05% by mass or more and 40% by mass or less in 100% by mass of the paint. It is more preferably not less than 30% by mass.

[[Surface energy modifier]]
The coating material of the present invention may contain a surface energy modifier as an optional component in order to improve coatability. Thereby, when the coating film of the coating material is formed on the substrate, the smoothness of the applied coating material coating film is improved, and a more uniform coating film can be obtained.
Specific examples of the surface energy modifier include Triton (registered trademark) X-45, Triton X-100, Triton X, Triton A-20, Triton X-15, Triton X-114, Triton X-405, Tween (registered). Trademark) #20, Tween #40, Tween #60, Tween #80, Tween #85, Pluronic (registered trademark) F-68, Pluronic F-127, Span (registered trademark) 20, Span 40, Span 60, Span 80. , Span 83, Span 85, "Surflon (registered trademark) S-211", "Surflon S-221", "Surflon S-231", "Surflon S-232", "Surflon S-233" manufactured by AGC Seimi Chemical Co., Ltd. , "Surflon S-242", "Surflon S-243", "Surflon S-611", 3M "Novec (registered trademark) FC-4430", "Novec FC-4432", DIC "Megafuck (registered Nonionic surfactants such as "Trademark) F-444" and "Megafuck F-558". Among them, fluorine-containing nonionic surfactants are particularly preferable, and "Surflon S-211", "Surflon S-221", "Surflon S-231", "Surflon S-232", "Surflon S-233" manufactured by AGC Seimi Chemical Co., Ltd. , "Surflon S-242", "Surflon S-243", "Surflon S-611", 3M's "Novec FC-4430", "Novec FC-4432", DIC's "Megafuck F-444", " Megafac F-558" is preferably used. These may be used alone or in combination of two or more.

The amount of the surface energy modifier 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 in 100% by mass of the coating material. Is. If it is 0.010% by mass or more, the coating film of the paint is uniform and unevenness tends not to occur. Further, in order to make the paint coating film uniform and without unevenness and to improve the coating film formation, the addition amount is preferably 2.0% by mass or less.

[[Other additives]]
The coating composition of the present invention may contain, in addition to the above-mentioned components, other additives as generally used in coating compositions, if necessary.
Other additives include plasticizers, desiccants, curing agents, anti-skin agents, flattening agents, anti-sagging agents, antifungal agents, antibacterial agents, ultraviolet absorbers, heat ray absorbers, lubricants, surfactants. , A dispersant, a thickener, a viscosity modifier, a stabilizer, a drying modifier, a coloring agent, a latex, and the like, and further, another kind of antiviral composition, antibacterial composition, antifungal composition, antiallergen composition. , A catalyst, an antireflection material, a material having a heat-shielding property, and the like.

<Viscosity>
The viscosity of the coating composition 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 from the viewpoint of easy formation of a uniform coating film during printing.
In order to adjust the viscosity of the coating composition of the present invention at 25° C. within the above range, the concentrations of the essential components and/or the optional components may be appropriately adjusted, or a thickener may be appropriately added, if necessary. .. For example, when it is desired to reduce the viscosity at 25°C, the concentration of the solvent may be increased. On the other hand, when it is desired to increase the viscosity at 25° C., the concentration of copper oxide particles may be increased or a thickener may be added.
The thickener is not particularly limited, and any of those commonly used in paints can be used.

<Surface free energy>
The surface free energy at 25° C. of the coating material of the present invention 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 below, 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 at 25° C. of the coating material of the present invention 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 lower the surface free energy at 25° C., a surface energy adjusting agent is added or increased, or a solvent having a low surface free energy (for example, a fluorinated solvent, specifically hydrofluoroether, etc.) 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 adjusting agent is eliminated or reduced, or a solvent having a high surface free energy (such as water) is added or increased, or a mixed solvent is used. In that case, the concentration of the solvent having a low surface free energy may be reduced.

[Preparation of antibacterial and antifungal paint]
The antibacterial/antifungal coating composition of the present invention can be produced, for example, by mixing the above-mentioned copper oxide particles, an organic compound having a phosphoric acid group, and a solvent. Further, the above-mentioned resin binder is mixed.
These essential components are mixed in predetermined proportions, and for example, ultrasonic method, mixer method, three-roll method, two-roll method, attritor, Banbury mixer, paint shaker, kneader, homogenizer, ball mill, sand mill, etc. It can be prepared by subjecting it to dispersion treatment.
When preparing the antibacterial and antifungal paint of the present invention, additives can be added as necessary. As the additive, in addition to the above-mentioned surface energy adjusting agent, the above-mentioned additives generally used in paints, such as a thickener, a colorant, a dispersant and a latex, can be used. When a resin or resin material having a reactive functional group is used as the resin binder, a reaction initiator compatible with them is also added, if necessary.

As described above, the viscosity and surface energy of the antibacterial and antifungal coating composition of the present invention can be adjusted by appropriately adjusting the concentrations of the essential component and/or the optional component.

[Method for producing antibacterial and antifungal member]
Next, the method for producing the antibacterial and antifungal member of the present invention will be described in detail.
The antibacterial and antifungal member of the present invention can be manufactured by various methods. For example, by immersing the base material in the coating material of the present invention, or by applying the coating material of the present invention to the surface of the base material using a spray or other coating method or various printing methods, the coating material is dried, and simultaneously with the drying. Alternatively, the antibacterial and antifungal member of the present invention can be produced by forming a coating film by subsequently optionally curing. In particular, it is preferable to apply the method using a printing method, since the entire surface of the base material, which has been covered with the antibacterial and antifungal material until now, can be applied only where desired on the surface of the base material.

[[Application method]]
The method of applying the coating composition of the present invention on the surface of the substrate, 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, A coating method and a printing method 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. Also, a dipping method of immersing in the coating material of the present invention or a coating liquid containing the coating material can be used.
In particular, if the coating method is used, the paint can be directly printed on the surface of the base material in a desired pattern, so the antibacterial and antifungal paint is applied only to the places where the antibacterial and antifungal properties are required. It is preferable because it is possible.

The coating amount of the coating material of the present invention is not particularly limited, the antibacterial and antifungal performance of the coating material, that is, the content of the copper oxide particles which are the antibacterial and antifungal components, the coating method, and the antibacterial and antifungal member to be produced. It can be appropriately determined in consideration of the application.
From the viewpoint of sufficiently obtaining antibacterial and antifungal properties, the content of the copper oxide particles in the antibacterial and antifungal member is set to 0.001 to 20% by mass with the antibacterial and antifungal member being 100% by mass. It is preferable to apply it, and it is more preferable to apply it in an amount of 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 remove the solvent. When a photocurable or thermosetting resin or resin material is used as the resin binder, it is optionally cured to form a coating film.
The method for drying the coating material of the present invention is not particularly limited, and examples thereof include heat drying and natural drying. Then, if necessary, at the same time as or after drying, irradiation with light such as ultraviolet rays, infrared rays, electron beams, and γ rays or heating is performed to cause a photopolymerization reaction or a thermal polymerization reaction, whereby a resin binder component is obtained. Let it harden.
The thickness of the coating film formed on the substrate is not particularly limited and can be appropriately determined in consideration of the application 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, for example, soda lime glass, alkali-free glass, borosilicate glass, high strain point glass, glass such as quartz glass, glasses such as silica, ceramics such as alumina, pottery, Examples include porcelain and other pottery, stone materials, concrete, and inorganic materials such as metals such as aluminum, stainless steel, and 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 polyimide, polyamide, polyamideimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide, polyether ether ketone, polyether sulfone. , Polycarbonate, polyetherimide, epoxy resin, phenol resin, glass-epoxy resin, polyphenylene ether, acrylic resin, polyolefin such as polyethylene and polypropylene, and liquid crystalline polymer compound. Among them, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.
The shape of the base material is not limited to the 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 substrate is not particularly limited, but in the case of a plastic substrate such as a resin film, it is usually in the range of 10 μm or more and 300 μm or less. Further, when it 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 about 10 mm or less, preferably about 0.50 mm or more and about 5.0 mm or less.

[Antibacterial and antifungal material]
The antibacterial and antifungal member produced by the production method of the present invention can have excellent antibacterial and antifungal properties imparted in a desired pattern to the entire surface of the substrate or only a desired surface portion, and thus has various applications. Can be used for Examples include woven fabrics and non-woven fabrics, and more specifically, application examples include masks; air conditioner filters, air cleaner filters, vacuum cleaner filters, ventilation fan filters, vehicle filters, air conditioning filters, and the like. Filters; clothes, bedding, nets for screen 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, etc. Interior materials for (equipment handling viruses, trains/vehicles, hospitals, buildings in general) and the like.

INDUSTRIAL APPLICABILITY The antibacterial and antifungal coating composition according to the present invention can be provided as a low-cost coating composition having excellent dispersion stability against aging. Further, it can be suitably used for imparting antibacterial and antifungal properties to antibacterial and antifungal members of homes, automobiles, and home electric appliances such as air conditioners, such as filters.
The method for producing an antibacterial/antifungal member according to the present invention provides an antibacterial/antifungal member having excellent antibacterial/antifungal properties, which is imparted in a desired pattern only to the entire surface of a substrate or a desired surface portion. You can

Claims (3)

For an antibacterial and antifungal agent containing copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, an organic compound having a phosphoric acid group, a resin binder having a phosphoric acid group, a solvent, and a fluorine-containing nonionic surfactant . It’s paint,
The content of the copper oxide particles is 0.5 mass% or more and 50 mass% or less,
The content of the organic compound having a phosphate group is 0.05% by mass or more and 20% by mass or less,
The content of the resin binder is 0.05% by mass or more and 40% by mass or less,
The total content of the organic compound having a phosphoric acid group and the resin binder having a phosphoric acid group is 0.05% by mass or more and 40% by mass or less,
Content of the said solvent is 5 mass% or more and 99.4 mass% or less, The antibacterial and antifungal coating material characterized by the above-mentioned. The antibacterial and antifungal coating composition according to claim 1, wherein the resin binder has at least one of an acrylate group and a methacrylate group. The antibacterial and antifungal paint according to claim 1 or 2 is screen-printed, spray-coated, spin-coated, slit-coated, die-coated, bar-coated, knife-coated, air doctor-coated, roll-coated, electrostatically coated, offset-printed, Reverse printing, flexographic printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, using a coating method selected from the dipping method, a step of applying to the substrate surface,
A step of drying the antibacterial and antifungal coating after application and optionally curing it simultaneously with or after the drying to form a coating film;
A method for producing an antibacterial/antifungal member, comprising: