JP2018196850A - Method for manufacturing antibacterial and antifungal member - Google Patents

Abstract

To provide a method for manufacturing an antibacterial and antifungal member using an antibacterial and antifungal paint which indicates an excellent diffusion stability and an excellent coating property against secular changes by using a low-cost copper oxide as the antibacterial component.SOLUTION: A method for manufacturing an antibacterial and antifungal member includes: a step of coating the surface of a base plate with a paint having copper oxide by using at least one coating method selected from a group consisting of screen printing, spray coating, spin coating, slit coating, die coating, bar coating, knife coating, air doctor coating, roll coating, electrostatic coating, offset coating, reverse coating, flexographic printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and a dipping method; a step of forming coating film by drying the paint after coating; and a step of forming coating film by sintering the copper oxide in the coating film on partial reduction after forming the coating film.SELECTED DRAWING: None

Description

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

Due to the recent increase in hygiene ideas, fungi such as bacteria and fungi in food and pharmaceutical factories, buildings such as hospitals and nursing homes, food kitchen utensils, medical utensils, medical devices and even general household goods Antibacterial agents, antifungal agents, disinfectants, etc. are used to prevent the spread of viruses.
Therefore, it is desired to impart antibacterial and antifungal properties to various members not only in public facilities but also in general households.

In order to solve these problems, organic or inorganic antibacterial agents have been proposed.
In particular, for inorganic antibacterial agents, conventionally, metal ions such as silver ions (Ag ⁺ ), zinc ions (Zn ²⁺ ), and divalent copper ions (Cu ²⁺ ) suppress the growth of microorganisms, or microorganisms It is known that it acts in a bactericidal manner (for example, see Patent Document 1). Based on this knowledge, a number of antimicrobial materials in which these metal ions are supported on a substance such as zeolite or silica gel, and antimicrobial materials combining the above metals with titanium oxide having a photocatalytic action have been developed.

JP 2003-221304 A

Among them, paints using silver have recently been used as antibacterial and antifungal applications, but silver has a problem of high cost.
Therefore, the development of antibacterial and antifungal coatings using metals cheaper than silver as antibacterial and antifungal components is desired.

  Therefore, the problem to be solved by the present invention is to use a low-cost copper oxide as an antibacterial and antifungal component, and to use an antibacterial and antifungal coating that exhibits excellent dispersion stability and excellent coating properties over time. Another object is to provide a method for producing an antibacterial and antifungal member.

  As a result of intensive studies and experiments to achieve the above-mentioned problems, the present inventors applied this paint to the surface of a substrate by a coating method such as printing, and dried to form a coating film, and a part thereof The inventors have found that the above-mentioned problems can be solved by sintering, and have completed the present invention based on such knowledge.

  That is, the present invention is as follows.

The method for producing an antibacterial and antifungal member of the present invention comprises a paint having copper oxide, screen printing, spray coating, spin coating, slit coating, die coating, bar coating, knife coating, air doctor coating, roll coating, electrostatic coating. Applying to the substrate surface using at least one application method selected from the group consisting of offset printing, reverse printing, flexographic printing, inkjet printing, dispenser printing, gravure direct printing, gravure offset printing, and dipping method And a step of drying the paint after coating to form a coating film, and a step of forming a coating film by partially reducing and sintering copper oxide in the coating film after forming the coating film. And
In addition, the method for producing an antibacterial and antifungal member of the present invention includes a step of forming a coating by partially reducing and sintering copper oxide in the coating after forming the coating in a reducing gas atmosphere. Method of heating, air, inert gas, reducing gas, and light, heat rays, and combinations thereof under at least one atmosphere selected from the group consisting of a mixture of two or more of these in any proportion It is preferable to use a method using at least one selected from the group consisting of: or a method in which plasma is generated in a gas containing a reducing gas.

  The method for producing an antibacterial and antifungal member according to the present invention is excellent in dispersion stability of copper oxide particles, which are antibacterial and antifungal components, with respect to changes over time. The antibacterial and antifungal paint that can be used suitably for antibacterial and antifungal applications is used, so that excellent antibacterial and antifungal properties are imparted in a desired pattern to the entire substrate surface or only to a desired portion. An antibacterial and antifungal member can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
First, the antibacterial and antifungal paint of the present invention (hereinafter referred to as “the manufacturing method of the paint of the present invention”) of the present invention (referred to as “ The paint is also described in detail.

[Antimicrobial and antifungal paint]
The antibacterial and antifungal coating of one embodiment of the present invention preferably contains copper oxide particles having an average particle diameter of 1 nm or more and 500 nm or less, an organic compound having a phosphate group, and a solvent at a predetermined content. .

[[Copper oxide particles]]
The coating material of the present invention contains copper oxide particles having a predetermined average particle diameter as an antibacterial and antifungal component in a predetermined content. Specific examples of the copper oxide particles include cuprous oxide particles, cupric oxide particles, or other oxidized copper oxide particles, the core portion is copper, and the shell portion is any oxidized copper oxide. Examples thereof include particles having a certain core / shell structure. These particles may contain metal salts and / or metal complexes as small amounts of impurities. Of these, cuprous oxide particles are preferred because of their excellent antibacterial properties.

The copper oxide particles contained in the paint 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 slightly deviate 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 aggregating a plurality of primary particles. It is an average particle diameter obtained as a measurement object without distinguishing from the secondary particles. On the other hand, the “average secondary particle size” described later is an average particle size obtained on the assumption that all the measurement target particles are secondary particles, and there are primary particles that do not constitute secondary particles. 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 diethylene glycol were measured, and the signal measured using the dynamic light scattering method was analyzed using the photon correlation method to obtain the autocorrelation function. The correlation function can be analyzed by the cumulant method to determine the average particle size.
The copper oxide particles of the present invention have an average particle diameter of 1 nm or more and 500 nm or less, whereby the dispersion stability in the paint is improved, and thus the antibacterial and antifungal performance of the paint can be improved. In addition, the coating property of the paint can be improved, and thus it is possible to use a printing method as a method for applying the paint to the substrate surface.

  The average secondary particle size of the copper oxide particles contained in the paint 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 an aggregate (secondary particle) formed by collecting a plurality of primary particles of copper oxide particles. An average secondary particle size of 500 nm or less is preferable because a fine pattern can be easily formed on the surface of the substrate. The secondary particle size refers to the particle size of the secondary particles obtained from the acquired image data when observing the copper oxide particles dispersed in diethylene glycol using a transmission electron microscope (TEM). Usually, an arbitrary part of the image is cut out, and an average value of the secondary particle diameters is calculated for 100 or more particles contained in the part, and the average secondary particle diameter is calculated.

The preferable range of the average primary particle size 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 still more preferably 20 nm or less. When the average primary particle size is 100 nm or less, the antibacterial and antifungal performance is improved because the surface area is increased. When the average primary particle size is 1 nm or more, the average particle size can be in the range of 1 nm to 500 nm.
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 diameter 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). An average primary particle size is calculated by cutting out an arbitrary portion of an image and calculating an average value of primary particle sizes of 100 or more particles contained in the portion.

  The content of the copper oxide particles of the present invention is 0.5% by mass or more and 60% by mass or less, preferably 1.0 to 60% by mass, more preferably 100% by mass, from the viewpoint of dispersion stability. Is 5.0-50 mass%. When the content is 0.5% by mass or more, the function as an antibacterial and antifungal component can be sufficiently exerted, and when it is 60% by mass or less, aggregation of copper oxide particles can be easily suppressed. is there.

As the copper oxide particles, commercially available products may be used or synthesized. Examples of commercially available products include cupric oxide particles having an average primary particle size of 50 nm manufactured by CIK Nanotech. When synthesized and used, examples of the synthesis method include the following methods (1) to (3).
(1) Water and a copper acetylacetonate complex are added to a polyol solvent, once the organic copper compound is dissolved by heating, then water necessary for the reaction is added afterwards, and the temperature is further raised to reduce the organic copper temperature. The method of heat reduction which heats with.
(2) A method in which an organic copper compound (copper-N-nitrosophenylhydroxylamine complex) is heated 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 the operation is simple and copper oxide particles and cuprous oxide particles having a small particle diameter can be obtained.

[[Organic compound having a phosphate group]]
The coating material of this embodiment contains the organic compound which has a phosphoric acid group with a predetermined content rate as a dispersing agent. The phosphate group in the organic compound is adsorbed on the copper oxide particles, and aggregation of the copper oxide particles can be suppressed by 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. If the number average molecular weight is 300 or more, the dispersion stability of the resulting coating tends to increase, and if it is 30000 or less, baking after coating is easy.
The number of phosphate groups in one molecule of the organic compound is not particularly limited, but is preferably one. This is because when the number of phosphate groups in one molecule is one, the dispersion stability is excellent.
Specific examples of the organic compound include “Disperbyk-142”, “Disperbyk-145”, “Disperbyk-110”, “Disperbyk-111”, “Disperbyk-118”, “Disperbyk-180”, “Disperbyk-180”, Byk-9076 "," Plysurf M208F "," Plysurf DBS "manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can be used. These may be used alone or in combination.

  In the present invention, the content of the organic compound having a phosphate group in 100% by mass of the paint 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, it is 0.20 mass% or more and 15 mass% or less, More preferably, it is 1.0 mass% or more and 8.0 mass% or less. If content of the said organic compound is in the said range, aggregation of copper oxide particles can be suppressed and a coating material has sufficient dispersion stability.

[[solvent]]
The paint 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, a solvent having a vapor pressure of 20 Pa or more and less than 20 Pa at 20 ° C. (hereinafter also referred to as “solvent (A)”) 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). Among these, it is preferable to use a mixed solvent of the solvent (A) and the solvent (B). The mixed solvent of the solvent (A) and the solvent (B) is used in combination with the organic compound having a phosphoric acid group, thereby achieving both improvement in dispersion stability of the paint of the present embodiment in the air and 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, 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 workability at the time of manufacturing an antibacterial and antifungal member described later can be improved. it can.

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

  In the present invention, the content of the solvent in 100% by mass of the paint is 20% by mass to 99.45% by mass, preferably 30% by mass to 99.4% by mass, more preferably 40% by mass to 80% by mass. % Or less. When the content of the solvent is within the above range, it is possible to sufficiently impart excellent dispersion stability and excellent coating properties to the paint.

  In the present embodiment, when 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 paint of the present invention is 10% by mass or more and 99. It is preferable that it is mass% or less, More preferably, it is 20 mass% or more and 99 mass% or less, More preferably, it is 30 mass% or more and 90 mass% or less. It is preferable that the content of the solvent (A) is in the above range because a proper drying speed is obtained in the air and printing tends not to occur.

  In the case of 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. % Is preferably 0.10% by mass or more and 9.0% by mass or less, more preferably 0.20% by mass or more and 8.0% by mass or less. It is preferable that the content of the solvent (A) is in the above range because a proper drying speed is obtained in the air and printing tends not to occur.

  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-di 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, hexanediol, octanediol, triethylene glycol, tri1,2-propylene Examples thereof include organic solvents such as glycol and glycerol, and water. Of these, polyhydric alcohols having 10 or less carbon atoms are more preferred. If the polyhydric alcohol has more than 10 carbon atoms, the dispersibility of the copper oxide particles may be reduced. These may be used alone or in combination.

  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-noni Alcohol, 2,6-dimethyl-4-heptanol, n- decanol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, diacetone alcohol, water 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 dispersibility, volatility, and viscosity are particularly suitable. . When the number of carbon atoms of the monoalcohol exceeds 10, the number of carbon atoms of the monoalcohol is preferably 10 or less in order to suppress a decrease in dispersibility of the copper oxide particles. These monoalcohols may be used alone or in combination.

[[Surface energy regulator]]
The paint of the present invention may contain a surface energy adjusting agent as an optional component in order to improve coatability. Thereby, when forming the coating film of a coating material on a base material, the smoothness of the applied coating film is improved, and a more uniform coating film can be obtained.
Specific examples of the surface energy adjusting agent include Triton (registered trademark) 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 (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 , "Surflon S-2 2 ”,“ Surflon S-243 ”,“ Surflon S-611 ”,“ Nevec (registered trademark) FC-4430 ”,“ NovecFC-4432 ”manufactured by 3M,“ Megafuck F-444 ”,“ Mega ”manufactured by DIC Nonionic surfactants such as “Fuck F-558” can be used. Among these, fluorine-containing nonionic surfactants are particularly preferable. “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 ”,“ NovecFC-4430 ”,“ NovecFC-4432 ”manufactured by 3M,“ Megafac (registered trademark) F- ”manufactured by DIC 444 "and" Megafuck F-558 "are preferably used. These may be used alone or in combination.

  The addition amount of the surface energy adjusting agent is not particularly limited, but in 100% by mass of the paint, preferably 0.010% by mass to 2.0% by mass, more preferably 0.10 to 1.5% by mass. It is. If it is 0.010% by mass or more, the coating film tends to be uniform and uneven. Further, the coating amount is preferably 2.0% by mass or less so that the coating film is uniform and the coating film formation is good without causing unevenness.

<Viscosity>
Although there is no restriction | limiting in particular in the viscosity at 25 degreeC of the coating material of this invention, The shear rate measured at 25 degreeC using the cone plate type | formula rotational viscometer based on JISK5600-2-3 is 1 * 10 < ^-1 > s. ^-1 to 1 × 10 ² s ⁻¹ 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 at 25 ° C. of the paint of the present invention within the above range, the concentration of essential components and / or optional components may be adjusted as necessary, or a thickener or the like may be added as appropriate. . For example, in order 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 the copper oxide particles may be increased, or a thickener may be added.
The thickener is not particularly limited, and those generally used in paints can be used.

<Surface free energy>
Although there is no restriction | limiting in particular in the surface free energy in 25 degreeC of the coating material of this invention, Preferably it is 40 mN / m or less, More preferably, it is 35 mN / m or less, More preferably, it is 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 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 concentration of the surface energy adjusting agent and various organic solvents may be adjusted as necessary. For example, when it is desired to reduce the surface free energy at 25 ° C., the concentration of the surface energy adjusting agent may be added or increased, or a solvent having a low surface free energy may be added or increased. When there are a plurality of solvents, the concentration of the solvent having a high surface free energy may be reduced. On the other hand, when it is desired to increase the surface free energy at 25 ° C., the surface energy modifier may be eliminated or reduced, or a solvent having a high surface free energy may be added or increased. When there are a plurality of solvents, the concentration of the solvent having a low surface free energy may be reduced.

[Preparation of antibacterial and antifungal paint]
The coating material used for the antibacterial and antifungal member of the present invention can be prepared, for example, by mixing the aforementioned copper oxide particles, an organic compound having a phosphate group, and a solvent.
Furthermore, you may add copper powder to a coating material. The copper powder is preferably larger than the copper oxide particles because it is excellent in antibacterial and antifungal properties. The addition amount of the copper powder is preferably 1/5 to 2 times, more preferably 1/4 to 1 times the mass of the copper oxide particles.
These components are mixed at a predetermined ratio, for example, using an ultrasonic method, a mixer method, a three-roll method, a two-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 dispersing and treating.
When preparing the antibacterial and antifungal coating of the present invention, additives may be added as necessary. As the additive, in addition to the above-mentioned surface energy adjusting agent, a dispersant, an organic binder or the like generally used for paints can be used.

  As described above, the antibacterial and antifungal properties of the present invention are appropriately adjusted by adjusting the concentrations of the copper oxide particles, the organic compound having a phosphate group, the solvent, the surface energy adjusting agent, and other additives. The viscosity and surface energy of the paint can be adjusted.

[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 produced by various methods.
For example, after dipping the base material in the paint or applying the paint to the surface of the base material by spraying or using other coating methods or various printing methods, the paint is dried to form a coating film. The copper oxide in the coating film is partially reduced by heating in a gas atmosphere, using iso-rays or heat rays in a specific atmosphere, or generating and treating plasma in a gas containing a reducing gas. The antibacterial and antifungal member of the present invention can be manufactured by forming a film by sintering.
In particular, it is preferable to apply by using a printing method since the entire surface of the base material so far covered with the antibacterial and antifungal material can be applied only on the surface of the base material.

[[Coating method]]
The method of applying the coating material of the present invention to the substrate surface and forming 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, Coating methods such as roll coating, electrostatic coating, offset printing, reversal printing, flexographic printing, ink jet printing, dispenser printing, gravure direct printing, gravure offset printing, and tampo printing can be used. Moreover, the immersion method immersed in the coating liquid of this invention or the coating liquid containing the said coating material can also be utilized.
Above all, if it is applied by printing method, the paint can be printed directly on the substrate surface in the desired pattern, so only the required amount of antibacterial and antifungal paint is applied where antibacterial and antifungal properties are required. It is preferable because it is possible.

The coating amount of the paint of the present invention is not particularly limited, and the antibacterial and antifungal performance of the paint, that is, the content of the copper oxide particles that are the antibacterial and antifungal components, the coating method, and the antibacterial and antifungal member to be produced It can be determined as appropriate in consideration of the use and the like.
From the viewpoint of sufficiently obtaining antibacterial and antifungal properties, the content of the copper oxide particles in the antibacterial and antifungal member is 0.001 to 70% by mass with the antibacterial and antifungal member being 100% by mass. Preferably, it is applied so that it may become 0.001-40 mass%, it is still more preferable to apply so that it may become 0.001-20%, and it may become 0.001-10% Most preferably, it is applied.

[[Coating 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. When necessary, irradiation with ultraviolet rays, infrared rays, electron beams, γ rays, etc. may be performed during drying. .
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 substrate is not particularly limited, for example, soda lime glass, alkali-free glass, borosilicate glass, high strain point glass, quartz glass, glass such as silica, ceramic such as alumina, ceramics, Examples include ceramics, ceramics, stones, concrete, and other inorganic materials such as aluminum, stainless steel, and iron. Furthermore, it may be an organic material such as a polymer material. For example, a polymer material such as plastic as a substrate, paper derived from natural raw materials, wood, fiber, or the like can be used as the substrate.

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 these, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.
The shape of the substrate is not limited to a plate shape, and may be a film, a sheet, a woven fabric, a nonwoven fabric, a three-dimensional structure, or the like.

  Although there is no restriction | limiting in particular about the thickness of a base material, In the case of plastic base materials, such as a resin film, it is the range of 10 micrometers or more and 300 micrometers or less normally. Moreover, when it is 300 micrometers or less, when winding-up processing is performed continuously, it is suitable at the point of a softness | flexibility. On the other hand, when the material of the base material is an inorganic material, it is usually about 0.10 mm to 10 mm, preferably about 0.50 mm to 5.0 mm.

[Film formation]
The means provided by the present invention utilizes the property that the copper oxide contained in the paint is in the form of fine particles and thus is highly reactive and becomes metallic copper by reduction and can be sintered.
In this method, it is possible to form a film without using a resin component such as a synthetic resin or a natural resin, which is usually necessary for forming a film used as a paint component. Since no resin component is required, there is an advantage that the content in the coating film of copper oxide, which is an active ingredient for antibacterial and antifungal, can be increased. Further, by partially reducing and sintering the coating film, the coating strength is improved by the metallic copper generated thereby, and the falling of the coating film is suppressed. Furthermore, since metallic copper itself has antibacterial and antifungal properties, the function of the antibacterial and antifungal member does not deteriorate.
In the present invention, reduction and sintering are partially performed without complete sintering. In the case of complete reduction / sintering, a smooth copper film is formed and the surface area is reduced, but in the case of partial reduction / sintering, copper oxide particles are present, and a large reduction in surface area is suppressed. Can exhibit antibacterial and antifungal properties. In the present method, it is important that the powder is not completely sintered. This can be achieved by adjusting the conditions in the reduction and sintering processes.
In addition, it is desirable that a resin component other than copper oxide is not included in the paint, but it may be added as long as it is a small amount and does not affect the reduction and sintering.

  The method of partially reducing, sintering, and fixing the coating to the substrate can be performed using a method selected from the following.

[Method of heating in reducing gas atmosphere]
This method is a method of performing reduction and sintering by heating using hydrogen, carbon monoxide or the like as a reducing gas. As the gas, a reducing gas can be used alone or in admixture of two or more. An inert gas such as helium, nitrogen, argon, neon, krypton, or xenon may be mixed with the reducing gas at an arbitrary ratio. Two or more inert gases may be mixed and used. Reduction and sintering may be performed by introducing this gas into an oven, charging a substrate coated with a paint, and heating. In this method, a method of directly heating a mixed gas by heating with a heater, a method of directly heating a substrate with infrared rays, or a method combining these can be used.

[Method of using light rays, heat rays, etc.]
This method is a method using light rays or heat rays, for example, a method in which copper is generated and sintered by a reduction reaction by energy generated by a xenon flash or a laser. In the xenon flash, the light emission output and the light emission time may be adjusted, or the output and the light emission time may be adjusted as necessary, and these pulsed lights may be combined continuously. As the gas constituting the atmosphere for carrying out this method, an inert gas such as air, nitrogen or argon, or a reducing gas such as hydrogen or carbon monoxide may be used alone or in combination of two or more. These gases and an inert gas may be mixed and used. When laser light is used for firing, the wavelength of the laser light is preferably 355 nm, 405 nm, 445 nm, 450 nm, 532 nm, 1056 nm, or the like. When the substrate is a resin, the wavelengths are particularly preferably 355 nm, 405 nm, 445 nm, and 450 nm.

[Method of generating and treating plasma in a gas containing reducing gas]
As an example of this method, a reducing gas or a mixed gas of reducing gas and inert gas is introduced under reduced pressure, and microwave energy is supplied thereto to generate microwave-excited surface wave plasma. A method of activating the introduced gas and treating the coating surface applied on the substrate can be mentioned. This can be used to reduce and sinter copper oxide in the coating. When the heat resistance of the substrate is inferior, the substrate is cooled, the heat resistance of the substrate is excellent, and when further reduction and sintering are desired, the substrate may be heated. As the reducing gas, one kind of hydrogen, carbon monoxide, ammonia or the like, or a mixture of two or more kinds may be used, and helium, argon, neon, krypton, xenon, nitrogen or one or more kinds of nitrogen may be used. A mixture of active gases may be employed from the viewpoint of facilitating plasma generation.

[Antimicrobial 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 or only the desired surface portion of the substrate. Can be used for Examples include woven fabrics and non-woven fabrics. More specifically, application examples include masks; filters for air conditioners, filters for air cleaners, filters for vacuum cleaners, filters for ventilation fans, filters for vehicles, filters for air conditioning, etc. Filters; nets for clothes, bedding, nets for screen doors, nets for poultry houses, etc .; sheets and films for wallpaper, windows, ceilings, vehicle seats; various facilities such as doors, blinds, chairs, sofas, flooring Interior materials for (equipment for handling viruses, trains / vehicles, hospitals, buildings in general) and the like.

  When this member contains copper oxide particles and metallic copper, the antibacterial property is improved. Further, in the antibacterial and antifungal member, when more metal copper is unevenly distributed near the surface, the antibacterial and antifungal property is further improved. Further, in the antibacterial and antifungal member, when the particle size of the metallic copper is larger than the average primary particle size of the copper oxide particles, the film has excellent long-term stability. It is preferable for the antibacterial and antifungal properties that the metal copper is exposed on the surface.

  The method for producing an antibacterial and antifungal member according to the present invention can be suitably used for the production of antibacterial and antifungal members of home appliances such as homes, automobiles, and air conditioners, such as filters, and has excellent antibacterial and antifungal properties. In addition, it is possible to provide an antibacterial and antifungal member imparted in a desired pattern only to the entire surface or a desired surface portion of the substrate.

Claims (2)

Paint with copper oxide, 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, flexographic printing, inkjet printing, Applying to the substrate surface using at least one application method selected from the group consisting of dispenser printing, gravure direct printing, gravure offset printing, and dipping method;
A step of drying the paint after application to form a coating film;
A method for producing an antibacterial and antifungal member, comprising: forming a coating film by partially reducing and sintering copper oxide in the coating film after forming the coating film. In the step of forming a coating film by partially reducing and sintering copper oxide in the coating film after forming the coating film,
A method of heating in a reducing gas atmosphere, at least one atmosphere selected from the group consisting of air, an inert gas, a reducing gas, and a gas obtained by mixing two or more of these in an arbitrary ratio; The antibacterial antifungal according to claim 1, wherein a method using at least one selected from the group consisting of heat rays and combinations thereof, or a method of generating and treating plasma in a gas containing a reducing gas is used. A method for manufacturing a structural member.