JP3486588B2 - Laminate, method for manufacturing the same, and equipment for manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to bactericidal properties, antibacterial properties,
By dispersing and adhering the photocatalyst particles to the surface of the film containing the antibacterial agent having antifungal and antifouling properties, the photocatalyst particles act, and the antibacterial agent has functions such as antibacterial, antifouling, antifungal and NOx purification. The present invention relates to a functional laminate that can be expressed, a method for producing the same, and an apparatus for producing the same.

[0002]

2. Description of the Related Art As an antibacterial agent exhibiting bactericidal, antibacterial, antifouling and antifungal effects, silver, gold and zinc in a metallic or ionic state have been known. As a method of applying an antibacterial agent to the surface of a molded body or structure, for example, an antibacterial / mold-proofing method of a ceramic or enamel body has been proposed in which the surface of a ceramic or enamel product is coated with silver phosphate powder and baked. (JP-A-6-234584).

The antibacterial agent such as metal or metal ion has an advantage of exhibiting an antibacterial action even in a dark place, but has a drawback that the effect is halved when the surface is soiled or dead bodies of bacteria are accumulated. Further, the metal ions decrease with time due to desorption, peeling, etc., and the activity decreases. Therefore, a system for continuously supplying the metal ions to the surface of the structure or the like is desired.

On the other hand, when a photocatalyst such as titanium oxide is irradiated with a specific wavelength, electrons (-) generated by the photocatalytic function are generated.
Harmful substances due to the reducing or oxidizing power of and holes (+),
Degradation of malodorous substances and organic substances, purification, sterilization and antibacterial action occur. A photocatalyst layer provided on a base material as a photocatalyst is utilized (Japanese Patent Laid-Open No. 7-171408).
No.), or a photocatalyst is supported on the surface of the inner wall material of the building,
A method for antibacterial treatment of the interior of the room by light hitting the wall material has been proposed (JP-A-6-209985). Since the photocatalyst can photoly decompose filth and carcasses, it can maintain a clean surface and sustain the antibacterial action, but if there is not enough light quantity, there is a drawback that the action cannot be exhibited.

Therefore, a method has been proposed in which an antibacterial agent and a photocatalyst are combined to complement each other's disadvantages. For example, an enamel body containing an antibacterial agent and a photocatalyst in the enamel layer,
It is disclosed that a coating agent containing an antibacterial agent and a photocatalyst is applied to the surface of the enamel layer. But,
The photocatalyst buried inside the layer does not work well. Also,
The concentrated and exposed antibacterial agent is liable to be desorbed, so that there is a problem that bactericidal and antibacterial effects are not stably exhibited for a long period of time.

As another example, a highly functional material has been proposed in which a photocatalyst layer is previously formed on the surface of a metal substrate and an antibacterial metal film is formed thereon (Japanese Patent Laid-Open No. 6-209985). However, there is a problem that it does not work at all except those exposed on the surface. That is, all of the conventional techniques have problems that the antibacterial action is insufficient or that the antibacterial action is not sustained, and none of them satisfy the required properties of the antibacterial action and its sustainability at the same time.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the weak points of the prior art, and provides a laminate having sufficient antibacterial action and the like and their durability, a method for producing the laminate, and equipment for producing the same. The purpose is to

[0008]

Means for Solving the Problems As a result of various studies to solve the weaknesses of the prior art, the present inventor formed a film containing an antibacterial agent dispersed on a substrate, and formed an antibacterial agent from the inside of the film. If the agent is gradually exuded to the surface layer, sterilization, antibacterial action can be maintained for a long time, and further, if the photocatalyst particles are dispersed at high density on the surface of the film containing the antibacterial agent, and fixed,
It was found that the sterilization and antibacterial action can be further sustained by the surface purification action by the photocatalyst particles.

Further, a photoreactive antibacterial agent using photocatalyst particles,
It has been found that the NOx purification function is exerted in addition to the effects of antifouling and mildew. Therefore, the present invention, by combining these findings, most effectively exhibits the antibacterial and antifungal effects of the antibacterial agent, the photoreactive antibacterial effect by the photocatalyst particles, the antifouling effect, the NOx purifying effect and the like.

According to the first aspect of the present invention, the photocatalyst particles have a basis weight of 0.5 to 8 on the surface of a film containing an antibacterial agent on a substrate.
The laminate is characterized by being dispersed at a coverage of 20 to 80 area% at g / m ² .

A preferred first invention is (1) a laminate, wherein the antibacterial agent is at least one metal selected from the group consisting of copper, silver, cobalt and zinc, or a compound thereof. .

(2) A laminate characterized in that the film of the base material containing the antibacterial agent comprises at least one coating agent selected from the group consisting of enamel, fluororesin paint and inorganic paint. (3) The optical particle catalyst is
A laminate comprising at least one metal compound selected from the group consisting of titanium oxide, zinc oxide and tin oxide, wherein (4) the film containing the antibacterial agent is an undercoat paint layer or an undercoat enamel. It is a laminated body characterized by being formed on a substrate via layers.

The second aspect of the present invention is: (1) a method for producing a laminate by applying a coating agent containing an antibacterial agent to a substrate to form a film, and spray-coating photocatalyst particles on the surface of the film. The laminated body is characterized in that the substrate on which the film is formed is heated and maintained at a temperature of 100 ° C. or lower, the photocatalyst particles are spray-coated on the surface of the film, and then the obtained laminate is fired. (2) A method for producing a laminate by (2) applying a coating material containing an antibacterial agent to a base material to form a film, and spray-coating photocatalyst particles on the surface of the film. After coating the above-mentioned coating agent on a substrate, baking the substrate, and then heating and holding the substrate having a film formed thereon at a temperature of 100 ° C. or lower, spray-coating photocatalyst particles on the surface of the film, and then obtaining the resulting laminate A method for producing a laminated body, which comprises firing the body.

(3) A method for producing a laminate by applying a coating agent containing an antibacterial agent to a substrate to form a film, and spray-coating photocatalyst particles on the surface of the film to produce a laminate. Is coated with the above coating agent, then baked, and then the substrate on which the coating agent is formed is heated and held at a temperature higher than 100 ° C. and 250 ° C. or lower, and photocatalyst particles are spray-coated on the surface of the coating film. It is a manufacturing method of a layered product.

In a preferred second aspect of the invention, (1) the spray pressure for spray-coating the photocatalyst particles is 1.96 to 19.6.
A method for manufacturing a laminated body characterized by being Pa,
(2) A method for producing a laminate, which comprises subjecting a base material to a surface treatment in advance before forming a film by applying a coating agent containing an antibacterial agent to the base material.

A third aspect of the invention is (1) a coating agent coating device for coating a coating material containing an antibacterial agent on a substrate, and heating for heating and holding the substrate coated with the coating material by the coating agent coating device. A holding device, a spray coating device that spray-coats the photocatalyst particles on the coating surface heated and held by the heating and holding device, and a laminated body baking device that fires the laminated body on which the photocatalyst particles are spray-coated by the spray coating device are provided. It is a facility for manufacturing a laminate, which is characterized in that

(2) A coating agent coating device for coating the substrate with a coating material containing an antibacterial agent, and a substrate burning device for burning the substrate coated with the coating material by the coating agent coating device, A heating and holding device for heating and holding the substrate fired by the substrate firing device, a spray coating device for spray-coating photocatalyst particles on the coating surface heated and held by the heating and holding device, and photocatalyst particles for the spray coating device. Is a laminate manufacturing apparatus, which is provided with a laminate baking apparatus for baking the spray-coated laminate.

Further, (3) a coating material applying device for applying a coating material containing an antibacterial agent to the base material, and a base material baking device for baking the base material coated with the coating material by the coating material applying device, A laminate comprising a heating and holding device for heating and holding the substrate baked by the substrate baking device, and a spray coating device for spray-coating photocatalyst particles on the surface of the coating film heated and held by the heating and holding device. This is a body manufacturing facility.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The first aspect of the present invention is that the antibacterial agent gradually exudes from the inside of the film to the surface of the substrate having the film containing the antibacterial agent, and the antibacterial agent is concentrated and fixed on the surface of the film. A laminate having a structure in which the photocatalyst particles act and the functions of the antibacterial agent, such as the antibacterial effect, can be sufficiently and stably exhibited continuously for a long period of time.

An example of the laminate of the first invention is shown in FIG.
This is the case where the base material is a steel plate, the coating is enameled, and the photocatalyst particles are titanium oxide. There is an undercoat enamel film 2 on a base steel plate 1 and a topcoat enamel film 3 containing an antibacterial agent (silver compound) 5 (antibacterial agent-containing top enamel film) on the surface of the base enamel film 3. It is a laminate having a four-layer structure in which titanium oxide particles 4 are dispersed and fixed. A part of the antibacterial agent 5 in the topcoat enamel film 3 is exposed on the surface of the topcoat enamel film 3. Therefore, the structure is such that the particles of the antibacterial agent 5 are in contact with the titanium oxide particle layer.

The base material is not particularly limited, but may be metal, resin, ceramics, ceramics, glass or a composite thereof (for example, a metal surface coated with resin, ceramics, glass, etc.). It is illustrated. When a film containing an antibacterial agent is formed or when photocatalyst particles are dispersed and fixed, firing is usually performed, so that the base material is preferably a metal capable of withstanding firing, enamel, or ceramics. The metal is preferably ultra-low carbon steel, stainless steel, aluminum steel, galvanized steel, zinc-aluminum alloy steel and the like. The base material is a plate-shaped body, a rod-shaped body, a structure of various shapes, or the like, and is preferably a plate-shaped body although it is not limited to the structure. The size and thickness of the plate-like body are not particularly limited.

An undercoat paint layer or an undercoat enamel layer (hereinafter also referred to as an undercoat layer) is preferably provided between the substrate and the film containing the antibacterial agent. The undercoat layer is a base material for the purpose of improving the adhesion between the base material and the film containing the antibacterial agent, and improving the durability (weather resistance, corrosion resistance) of the base material for adhering the base material and the film. And a film containing an antibacterial agent. The thickness of the undercoat layer is sufficient as long as the above object can be achieved, and is usually 10 to 120 μm, preferably 20 to 80 μm.

The undercoat paint is not particularly limited, but is a commonly used undercoat paint containing a resin such as a polyester resin, an epoxy resin, an acrylic resin as a main component, and includes a curing agent, a curing accelerator, and other Common compounding ingredients may be included. The undercoat enamel is a commonly used undercoat glaze containing a metal such as Co, Ni or Mn in a borosilicate glaze, and a mill additive may be a general formulation.

The coating agent containing the antibacterial agent is applied to the surface of the base material directly or on the undercoat layer to improve the corrosion resistance, weather resistance and adhesion of the base material to form a film. The film preferably comprises at least one coating agent selected from the group consisting of enamel, fluororesin paint and inorganic paint. The film thickness is appropriately determined in consideration of the type of base material, thickness, application, etc., but is generally 10 to 150 μm.
m, preferably 60-120 μm for enamel,
In the case of paint, it is 20 to 60 μm.

As the fluororesin coating material as the coating agent, one generally used as a fluororesin coating material for the top coat is used, and resins such as difluoride, trifluoride and tetrafluoride fluororesin are mainly used. Examples of the component are given. Fluororesin coatings include curing agents, curing accelerators, viscosity modifiers, pigments,
It does not matter even if it contains the usual compounding ingredients, such as other coloring agents.

Enamel used as a coating agent is TiO ₂ , S
MO ₂ compounds such as iO ₂ and ZrO ₂ , P ₂ O ₅ , V
M ₂ O ₅ based compounds such as _{2 O 5, Sb 2 O 3} , Al 2 O
₃ , M ₂ O ₃ based compounds such as B ₂ O ₃ , Na ₂ O, K ₂
O, Li ₂ O and other M ₂ O-based compounds, ZnO, BaO,
Examples thereof include MO compounds such as CaO and fluoride compounds such as ZrF ₄ and AlF ₃ . M ₂ O ₄ compounds, especially glazes containing 50% by weight or more of P ₂ O ₅ are preferable because the baking temperature can be lowered. The inorganic coating material as a coating material is glass glaze, alkali silicate, silicone resin, metal alkoxide resin, cement, mortar and the like.

The antibacterial agent is a substance exhibiting actions and functions such as bactericidal property, antibacterial property and antifungal property, and it may be inorganic or organic. When baking a substrate having a film containing an antibacterial agent, the antibacterial agent also needs to have heat resistance and is preferably an inorganic compound, particularly a metal or a metal compound.

For example, at least one selected from the group consisting of silver, zinc, copper, cobalt, titanium and tungsten.
Seed metal or metal compound, zeolite, apatite, silica, glass, titania, zirconium phosphate,
Some of them are supported on a carrier such as aluminum phosphate and calcium phosphate, and silver zeolite, silver calcium phosphate and silver zirconium phosphate are preferable.

Examples of the organic antibacterial agents include ammonium salts such as benzalnicome chloride, fatty acid esters, and nitrogen-containing / sulfur-containing heterocyclic compounds. The organic antibacterial agent is suitable when the coating material is a fluororesin paint.
When the antibacterial agent is used by being mixed with the coating agent, the content of the antibacterial agent is 0.1 to 20% by weight of the coating agent, and preferably 0.1.
It is 5 to 5% by weight. The particle size of the antibacterial agent should be such that it can be intimately and satisfactorily mixed with the coating agent, and is preferably about 0.5 to 10 μm.

The photocatalyst particles are particles that exhibit a photocatalytic action by receiving light, and are dispersed and fixed on the surface of the antibacterial agent-containing film. Therefore, the photocatalyst particles are not aggregated substantially and are mutually dispersed with the antibacterial agent particles and exposed on the surface of the film. The area ratio in which the photocatalyst particles are exposed and dispersed is the coverage ratio, and the coverage ratio is preferably 20 to 80 area%, particularly 40 to 60 area%. The coverage is determined by observing the surface of the coating containing the antibacterial agent and the surface of the laminate having the photocatalyst particles dispersed and fixed on the surface thereof with a scanning electron microscope. If the coverage is less than 20% by area, there are few photocatalyst particles exposed on the surface, so that antibacterial properties and antifungal properties are exhibited, but photoreactive antibacterial properties, antifouling properties, antifungal properties,
NOx purification performance is not fully exerted. On the other hand, when the coverage is more than 80% by area, the antibacterial and antifungal properties of the antibacterial agent do not last for a long time.

The basis weight of the photocatalyst particles is 0.5 to 8 g / m ^2.
Is. If it is less than 0.5 g / m ² , the dispersion of the photocatalyst particles on the film is poor, and the long-term sustainability such as antibacterial property may be poor. If it exceeds 8 g / m ² , the photocatalyst particle layer becomes thick and the film is not formed. In some cases, the adhesiveness of the product deteriorates, and the effect of the antibacterial agent may not be fully exhibited. The primary particles of the photocatalyst particles have a particle size of 1 to 100 nm, preferably 5 to 100 n.
m. If it is less than 1 nm, the dispersion with the binder is poor and the photocatalyst particles cannot be spray-coated uniformly.
If it exceeds 00 nm, the activity of the photocatalyst particles decreases, and the function as a photoreactive photocatalyst cannot be sufficiently exhibited.

The photocatalyst particles generate active oxygen by receiving light.
If it shows photoactivity, it is known as a photocatalyst.
TiO₂, SnO₂, ZnO₂, SrTiO₃, Fe
₂O ₃, WO₃, KNbO₃, KTaO₃Metal acids such as
Of metal compounds such as GaP, CdS, CdSe, MoS
An example is a compound. Among these, titanium oxide TiO
₂Is preferred, and especially anatase type titanium oxide has high activity.
Yes, it is preferable. The photocatalyst particles are distributed on the surface of the antibacterial agent-containing film.
Use a UV-transparent binder when fixing
Titanium oxide sol and / or powder, and
It is possible to use a titanium oxide sol solution mixed with an inder.
Wear. More specifically, commercially available CZG220 (Taki Chemical
Company) is exemplified.

The second invention relates to a production method, in which a substrate having a film containing an antibacterial agent is heated and held at a predetermined temperature, and photocatalyst particles are spray-coated, and the photocatalyst particles have a basis weight of 0.5. -8 g / m < ² > and a coverage of 20-80% by area are obtained. Spray pressure is 1.
Particularly preferably, it is 96 to 19.6 Pa. When the substrate having the coating containing the antibacterial agent is heated and maintained at a temperature of 100 ° C. or lower, the photocatalyst particles are applied by spraying and then the obtained laminate is fired, and the substrate is heated at a temperature of more than 100 ° C.
When heating and holding at a temperature of 50 ° C. or lower, it is not necessary to bake the photocatalyst particles after spray coating. It is preferable that a coating material containing an antibacterial agent is applied on the substrate and baked to form a film on the substrate, and then the photocatalyst particles are spray-coated.

When forming a film containing an antibacterial agent on the base material, it is preferable to pre-treat the base material. The surface treatment includes degreasing, chemical conversion treatment, surface roughening treatment and the like which are usually carried out, and they are carried out in combination as necessary. As the chemical conversion treatment, phosphate treatment, chromate treatment, etc.
Examples of the roughening treatment include a chemical etching method, an electrolytic etching method, a barrel grinding method, a hairline method, and a shot brush method.

The coating material containing the antibacterial agent is applied to the substrate by a conventionally known method such as roll coater coating or spray coating. The undercoat paint is generally baked at a temperature of 200 ° C. to room temperature for 5 to 30 minutes, but is not limited thereto.

The firing of the substrate on which the coating film is formed depends on the type of the coating material. When a fluororesin coating material is used, the temperature is between the melting point of the coating material and a temperature 50 ° C. higher than the melting point. For 5 to 30 minutes. When enamel is used, the temperature is generally 500 to 800 ° C. and the time is from several seconds to several minutes. It should be noted that an undercoat paint or enamel enamel may be applied and baked before applying the coating agent containing the antibacterial agent. The coating and firing conditions can be the same as those for the above-mentioned coating agent.

The first mode of heat retention of the coating containing the antibacterial agent is to heat and retain the base material having the coating containing the antibacterial agent at a temperature of 100 ° C. or lower, and photocatalyst particles on the coating. Is spray applied and fired. The substrate having a coating is heated to 100 ° C. or lower, preferably 50 to 10
The formation of a layer by spray-coating the photocatalyst particles while maintaining the temperature of 0 ° C. for 2 to 10 minutes improves the adhesion between the photocatalyst particle layer and the coating film and the dispersibility of the photocatalyst particles. At the same time, it is intended to prevent the photocatalyst particle layer from settling inside the film so that the photocatalyst particles are exposed on the outermost surface of the film as shown in FIG. That is, the coverage is 20
This is to maintain -80 area%.

The second embodiment of the heating and holding of the film containing the antibacterial agent is performed by baking the film of the substrate having the film containing the antibacterial agent and then heating the substrate having the film with a heating and holding facility.
More than 00 ° C and 250 ° C or less, more preferably 120 to 200
This is a case of heating and holding at a temperature of 2 ° C. for 2 to 10 minutes, spray-coating photocatalyst particles on the surface of the coating, and then cooling as it is.

The base material having the film is heated to more than 100 ° C. and 250 ° C.
The reason why the layer is formed by spray-coating the photocatalyst particles while maintaining the temperature at the following temperature is also to achieve the same purpose as in the first case. This is because if the temperature is less than 100 ° C, the adhesion of the photocatalyst particles to the coating is poor, and if it exceeds 250 ° C, the photocatalyst particles are buried in the coating and the coverage does not fall within the above specified range.

The photocatalyst particles are spray-coated on the coating surface of the base material having the coating heated and maintained at the above temperature.
The spray temperature is not particularly limited, but is generally room temperature. The thickness of the photocatalyst particle layer is preferably 0.01 to 5 μm. Since the photocatalyst particles may accelerate the decomposition of organic substances, when an inorganic coating material containing an organic resin coating material is used as a coating agent containing an antibacterial agent, a film made of an inorganic coating material containing an organic resin coating material is used as necessary. It is desirable to spray-coat the surface with photocatalyst particles via a primer layer of an inorganic resin.

In order to form a photocatalyst particle layer having a coverage of 20 to 80 area% by spray coating on the surface of the base material film by adjusting the spray pressure, it is preferable to optimize the spray conditions. Spread the spray pattern flat and wide to a width of 300 to 500 mm, and spray pressure to 1.9.
It may be adjusted to 6 to 19.6 Pa. In this case, the spray nozzle has a diameter of 0.4 to 2 mm, preferably 0.4 to 2 mm.
It is 0.8 mm. If it is less than 1.96 Pa, the adhesion of photocatalyst particles to the coating is small and the coverage is likely to be 20 area% or less. Conversely, if it exceeds 19.6 Pa, the coverage is likely to exceed 80 area%, and the antibacterial effect of the antibacterial agent is high. Does not last for a long time.

The laminate having the photocatalyst particle layer formed thereon is subsequently fired in a furnace. The firing conditions are the type of base material (metal,
(Ceramics, glass, enamels, coatings, etc.)
Less than 100 to 600 ° C. for several seconds to several minutes. The firing conditions vary depending on the type of photocatalyst particles, but when titanium oxide is used, it changes to rutile type at 800 ° C. or higher, so it is preferably performed at 800 ° C. or lower.

However, the laminate having the photocatalyst particle layer obtained by spray-coating the photocatalyst particles on the surface of the coating film containing the antibacterial agent on the base material is baked at a temperature of 100 ° C.
Only when spray-coating is performed by heating and holding at 250 ° C. or less, cooling is performed instead of firing. Cooling conditions are not specifically regulated.

A third aspect of the present invention is a coating material coating device for coating a base material with a coating material containing an antibacterial agent, a heating and holding device for heating and holding a base material having a coating film containing an antibacterial agent, and a coating surface. It is a manufacturing facility of a laminated body including a facility row provided with a spray coating device for spray coating the photocatalyst particles. If necessary, a device for treating the surface of the substrate, a device for applying a base coating material or enamel for the substrate, and a device for baking the base coating material or enamel may be provided before the coating device for the coating material. Further, a base material baking device for baking the base material may be provided after the coating material coating device. Furthermore, after the spray coating device for photocatalyst particles, a stacked body baking device for baking the stacked body to which the photocatalyst particles are spray applied may be provided.

There is no particular restriction on the structure, method, etc. of each equipment, and known equipment can be used. For example, as the heating and holding device, an electric furnace, an induction heater (IH furnace),
A gas furnace and the like can be mentioned, but an electric furnace and an IH furnace are preferable. It is preferable that each device and the furnace are arranged in a straight line or a curved line, and the equipment and the furnace in which the base materials are arranged are sequentially moved to proceed.

The manufacturing equipment of the third invention will be described with reference to FIGS. First, the first manufacturing facility (FIG. 2) is a facility corresponding to the first manufacturing method, and includes a surface treatment device 12 for performing a surface treatment on a substrate 11, and an undercoat coating for applying an undercoat paint or an undercoat enamel to the substrate. Device 13, undercoat baking device 1 for baking the applied undercoat paint or undercoat enamel
4, coating agent applying device 15 for applying a coating material containing an antibacterial agent, heating holding device 16 for heating and holding a base material coated with a coating material containing an antibacterial agent, spray for spray-coating photocatalyst particles on the coating surface This is a laminated plate manufacturing facility including a coating device 17 and a laminate firing device 18 for firing a laminate in which photocatalyst particles are dispersed. It is also possible to omit the undercoat coating device 13 for applying the undercoat paint or the undercoat enamel, and the undercoat baking device 14 for baking the applied undercoat paint or the undercoat enamel.

The second manufacturing equipment (FIG. 3) is equipment corresponding to the second manufacturing method, and includes a surface treatment device 12 for surface-treating the base material 11 and an undercoat coating device for applying an undercoat paint or an undercoat enamel. 13, an undercoat baking device 14 for baking the applied undercoat paint or undercoat enamel, a coating device application device 15 for applying a coating material containing an antibacterial agent, and a base material coated with a coating material containing an antibacterial agent Lamination comprising a base material firing device 19, a heating and holding device 16 for heating and holding a base material having a coating, a spray coating device 17 for spray-coating photocatalyst particles, and a laminate firing device 18 for firing a laminate in which photocatalyst particles are dispersed. It is a board manufacturing facility. It is also possible to omit the undercoat coating device 13 for applying the undercoat paint or the undercoat enamel, and the undercoat baking device 14 for baking the applied undercoat paint or enamel.

The third manufacturing equipment (FIG. 4) is equipment corresponding to the third manufacturing method, and includes a surface treatment device 12 for surface-treating the base material 11 and an undercoat coating device for applying undercoat paint or enamel. 13, an undercoat baking device 14 for baking the applied undercoat paint or undercoat enamel, a coating device application device 15 for applying a coating material containing an antibacterial agent, and a base material coated with a coating material containing an antibacterial agent This is a laminated plate manufacturing facility comprising a base material baking device 19, a heat holding device 16 for heating and holding a base material having a coating, and a spray coating device 17 for spray coating photocatalyst particles. It is also possible to omit the undercoat coating device 13 for applying the undercoat paint or the undercoat enamel, and the undercoat baking device 14 for baking the applied undercoat paint or the undercoat enamel. A cooling device (not shown) may be provided after the spray device 17.

[0049]

EXAMPLES Examples of the present invention will be shown below and will be described more specifically. (Example 1) In the first laminate manufacturing facility shown in FIG. 2, the undercoat paint shown in Table 1 was spray-coated on the steel plate shown in Table 1 as a base material, and baked at the baking temperature shown in Table 1,
Subsequently, the coating material containing the antibacterial agent shown in Table 1 was spray-coated to obtain a steel sheet having a film. After heating and holding the steel sheet in the furnace shown in Table 1 at the temperature and time shown in Table 1,
Photocatalyst particles (titanium oxide) were spray-coated with a spray gun (nozzle hole diameter: 0.8 μm) at a basis weight and pressure shown in Table 1, and baked at a baking temperature shown in Table 1. Table 2 shows the appearance, adhesion (interlayer between the coating film and the photocatalyst particle layer), antibacterial property, antifungal property, outdoor antifouling property, and NO _x purification property of the obtained laminate. In the table, numbers 6 to 12 are examples, and numbers 1 to 5 are comparative examples.

[0050]

[Table 1]

[0051]

[Table 2]

The physical properties, quality and functionality of the laminate were investigated by the following methods. (1) Appearance The color tone of the surface of the laminated body was visually observed and evaluated in four levels. ◎: No iris color ○: Almost no iris color △: Irregular color unevenness ×: Many iris color unevenness

(2) Adhesiveness The adhesiveness of the laminate was examined by a cross-cut cellophane tape test (100 cross-cuts) in accordance with JIS K 5400 (paint general test method) and evaluated in 6 levels. Primarily, the delamination strength between the film made of the top coat coating and the photocatalyst particle layer will be investigated. 10: No peeling of photocatalyst particle layer 8: Peeling of photocatalyst particle layer is 5% or less 6: Peeling of photocatalyst particle layer is more than 5% and 15% or less 4: Peeling of photocatalyst particle layer is more than 15% and 35% or less 2: Photocatalyst Exfoliation of particle layer exceeds 35% and 65% or less 0: Exfoliation of photocatalyst particle layer exceeds 65%

(3) Coverage The surface of the laminated body was observed with a scanning electron microscope to measure the area of the photocatalyst particles dispersed and exposed in the observed area, and the ratio to the observed area was obtained as an area ratio.

(4) A fixed amount of E. coli-containing liquid according to the voluntary standard for antibacterial inorganic antibacterial agents such as silver and antibacterial test method (antibacterial test method for past antibacterial products I film adhesion method) The film was placed on three laminated plates on which SCD was dropped, and stored at a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more, and after 24 hours, SCD
Surviving bacteria were washed out using LP medium, and the viable cell count was measured by the agar plate culture method using SA medium.

(5) Antifungal property According to JIS Z 2911 (mold resistance test method), a mixed spore suspension (after culturing the test solution in an agar medium, 3% by weight of sucrose) was placed on three laminated plates. After being suspended and mixed in the added solution), the temperature was 28 ± 1 ° C. and the relative humidity was 97.
% For 28 days. After 14 days and 28 days, the following three criteria were used for evaluation. 3: No growth of hyphae was observed on the surface of the laminate 2: Growth of mycelia was not observed in more than 1/3 of the total area of the surface of the laminate 1: Growth of mycelia was less than that of the total area of the surface of the laminate Approved over 1/3

(6) The outdoor antifouling laminate was placed on the roof of a building in a factory area, and the degree of pollution (ΔE) after 1 month and 3 months was measured by a color difference meter (“MINOLTA” CR-33).
It was measured in 1). The larger the value of ΔE, the greater the degree of contamination.

(7) The laminated plate was set in a box with a NOx purifying glass window and a capacity of about 190 l, and a predetermined amount of NOx / air (initial NO concentration 50
ppm) is introduced. After irradiation with BLB for 12 hours, the laminate was taken out and the surface was washed with water, and the nitrate ion in the aqueous solution obtained was measured by an ion chromatograph.
It was converted to 1 / m ² ).

(Example 2) In the second manufacturing facility shown in FIG. 3, the undercoat paint (undercoat paint, glaze for enamel) shown in Table 3 was spray applied to the steel plate shown in Table 3 as in Example 1. Coating material containing antibacterial agents shown in Table 3 (top coating, glaze)
Was spray-coated, baked, heated and held, and further, photocatalyst particles were spray-coated and baked to produce a laminated plate.
The manufacturing conditions are shown in Table 3. The evaluation results are shown in Table 4. In the table, numbers 15 to 18 and numbers 21 to 23 are examples,
The numbers 13 to 14 and the numbers 19 to 20 are comparative examples.

[0060]

[Table 3]

[0061]

[Table 4]

(Example 3) A laminated board was manufactured in the same manner as in Example 1 in the third manufacturing facility shown in FIG. Table 5 shows the production conditions of steel plate, paint, antibacterial agent, coating agent, furnace and each process. The evaluation results are shown in Table 6. Number 2 in the table
6 to 29 are examples, and numbers 24 to 25 are comparative examples.

[0063]

[Table 5]

[0064]

[Table 6]

[0065]

EFFECTS OF THE INVENTION The layered product of the present invention has excellent functions such as antibacterial properties, antifungal properties, outdoor antifouling properties, and NOx purification properties due to the action of photocatalyst particles, and these functions last for a long period of time.
In addition, since the laminate can be manufactured by combining existing equipment and furnaces, the economical effect that the equipment investment is small is remarkable.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a cross-sectional structure of a laminate of the present invention.

FIG. 2 is an explanatory view showing an example of a facility for manufacturing a laminate of the present invention.

FIG. 3 is an explanatory view showing an example of a facility for manufacturing a laminate of the present invention.

FIG. 4 is an explanatory view showing an example of a facility for manufacturing a laminate of the present invention.

[Explanation of Codes] 1 ... Steel plate 2 ... Undercoat enamel film 3 ... Topcoat enamel film 4 containing antibacterial agent ... Titanium oxide particles 5 ... Antibacterial agent 11 ... -Substrate 12-Surface treatment device 13-Undercoat paint or enamel application device 14-Undercoat paint or enamel baking device 15-Coating agent application device 19 containing antibacterial agent- Firing device 16 for the substrate coated with the coating material contained therein ... Heating and holding device 17 ... Spray coating device 18 for photocatalyst particles 18 ...

Front page continuation (72) Hideo Takamura Inventor Hideo Takamura 2-18-13 Higashi Narashino, Narashino, Chiba Prefecture Technical Research Institute, Kawatetsu Construction Materials Co., Ltd. (72) Tomoyuki Tahara, 1 Kawasaki-cho, Chuo-ku, Chiba-shi Technical Research Institute (72) Inventor Toshihide Suzuki 1 Kawasaki-cho, Chuo-ku, Chiba, Chiba Prefecture Technical Research Laboratory, Kawasaki Steel Co., Ltd. (56) Reference JP-A-10-264297 (JP, A) JP-A-9-314743 (JP, A) JP-A-10-71666 (JP, A) JP-A-8-98876 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00 -35 / 00 B01J 21/00-37/36

Claims (13)

(57) [Claims] 1. A film surface containing an antibacterial agent on a substrate,
A laminate, wherein the photocatalyst particles are dispersed at a basis weight of 0.5 to 8 g / m ² and a coverage of 20 to 80% by area. 2. The laminate according to claim 1, wherein the antibacterial agent is at least one metal selected from the group consisting of copper, silver, cobalt and zinc, or a compound thereof. 3. A film containing the antibacterial agent is enamel,
The laminate according to claim 1 or 2, comprising at least one coating material selected from the group consisting of fluororesin paints and inorganic paints. 4. The laminate according to claim 1, wherein the photocatalyst is at least one metal compound selected from the group consisting of titanium oxide, zinc oxide and tin oxide. body. 5. The laminate according to claim 1, wherein the film containing the antibacterial agent is formed on the substrate via an undercoat paint layer or an undercoat enamel layer. body. 6. A method for producing a laminate by applying a coating agent containing an antibacterial agent to a base material to form a film, and spray-coating photocatalyst particles on the surface of the film to form a laminate. The method for producing a laminate, comprising heating and holding the obtained substrate at a temperature of 100 ° C. or lower, spray-coating the surface of the coating with photocatalyst particles, and then firing the obtained laminate. 7. A method for producing a laminate by applying a coating agent containing an antibacterial agent to a substrate to form a film, and spray-coating photocatalyst particles on the surface of the film to produce a laminate. After applying the coating agent, bake it, and then set the film-formed substrate to 1
A method for producing a layered product, which comprises heating and holding at a temperature of 00 ° C or lower, spray-coating photocatalyst particles on the surface of the film, and then firing the resulting layered product. 8. A method for producing a laminate by applying a coating agent containing an antibacterial agent to a substrate to form a film, and spray-coating photocatalyst particles on the surface of the film to produce a laminate. After applying the coating agent, bake it, and then set the film-formed substrate to 1
A method for producing a laminate, which comprises heating and holding at a temperature higher than 00 ° C. and 250 ° C. or lower and spray-coating photocatalyst particles on the surface of the film. 9. The method for producing a laminate according to claim 6, wherein a spray pressure for spray-coating the photocatalyst particles is 1.96 to 19.6 Pa. 10. The substrate according to any one of claims 7 to 9, wherein the substrate is surface-treated in advance before a coating containing an antibacterial agent is applied to the substrate to form a film. A method for producing the laminated body described. 11. A coating agent coating device for coating a coating material containing an antibacterial agent on a substrate, a heating and holding device for heating and holding the substrate coated with the coating material by the coating material coating device, and the heating and holding device. A spray coating device for spray-coating the photocatalyst particles onto the surface of the coating material heated and held by the device, and a laminate firing device for firing the laminate coated with the photocatalyst particles by the spray coating device are provided. Equipment for manufacturing laminates. 12. A coating material coating device for coating a coating material containing an antibacterial agent on a substrate, a substrate burning device for burning a substrate coated with the coating material by the coating material coating device, and the substrate. A heating and holding device that heats and holds the base material baked by the baking device, a spray coating device that spray-coats the photocatalyst particles on the surface of the coating material that is heated and held by the heating and holding device, and photocatalyst particles are sprayed by the spray coating device. A laminated body manufacturing facility comprising a laminated body baking device for baking the applied laminated body. 13. A coating material coating device for coating a coating material containing an antibacterial agent on a substrate, a substrate burning device for burning a substrate coated with the coating material by the coating material coating device, and the substrate. A heating and holding device for heating and holding a substrate baked by a baking device, and a spray coating device for spray-coating photocatalyst particles on the surface of the coating material heated and held by the heating and holding device. production equipment.