WO2017168893A1

WO2017168893A1 - Mold propagation inhibition member

Info

Publication number: WO2017168893A1
Application number: PCT/JP2016/088760
Authority: WO
Inventors: 山下　雄大; 幹雄石川; 伊藤　信行; 正人手塚; 山下　かおり
Original assignee: 大日本印刷株式会社
Priority date: 2016-03-30
Filing date: 2016-12-26
Publication date: 2017-10-05
Also published as: JPWO2017168893A1

Abstract

This mold propagation inhibition member is provided with, in a surface thereof, a recessed portion group including a plurality of recessed portions arranged so as to each have an opening diameter D of 1-100 μm and a depth H of 1-50 μm, wherein the distance P between the adjacent recessed portions is 0.1-10 times as large as the opening diameter D.

Description

Mold breeding suppression member

The embodiment of the present disclosure relates to a mold growth suppression member.

∙ Mold is prone to breed in places with poor ventilation, such as bathrooms and kitchens, and storage spaces. Suppression of mold growth is required from a hygienic point of view. Conventionally, a method using an antifungal agent has been proposed to suppress the growth of mold. For example, Patent Literature 1 describes a method of suppressing the growth of mold at the applied portion by applying a fungicide. Patent Document 2 describes a laminate having an antibacterial / antifungal layer containing an antibacterial / antifungal agent in a synthetic resin as an outermost layer.

In addition, for example, in Patent Document 3, as a material for achieving both high antifouling properties and high antibacterial and antiviral properties even under weak light such as indoor spaces, a water repellent resin binder, A water repellent photocatalyst composition containing a photocatalyst material and cuprous oxide, wherein the photocatalyst material and the cuprous oxide are combined, and a coating film thereof are disclosed.

Also, articles having a superhydrophobic surface are being studied. For example, Patent Document 4 discloses an article having an antibacterial surface that has a specific raised structure on the surface of a substrate and the surface is superhydrophobic.

Japanese Patent Application Laid-Open No. 2014-210739 JP 2004-181652 A JP 2012-210557 A Special table 2013-517903 gazette

As described in Patent Documents 1 to 3 above, antibacterial properties have been imparted to various articles by using antibacterial agents and the like. Further, as in Patent Document 4, it is necessary to use a special material in order to make the surface superhydrophobic.
Under such circumstances, as a result of examining a means different from the method using an antibacterial agent as a means for imparting antibacterial properties, the present inventors have provided a specific recess group on the surface of the article. It has been found that an excellent fungal growth inhibitory effect can be exhibited.

The mold growth inhibiting member of the present disclosure has been completed based on such knowledge, and an object thereof is to provide a mold breeding inhibiting member having an excellent mold growth inhibiting effect.

One embodiment of the present disclosure includes a recess group in which a plurality of recesses having a diameter D of an opening of 1 μm to 100 μm and a depth H of 1 μm to 50 μm are arranged on the surface,
Provided is a mold growth suppressing member in which a distance P between adjacent concave portions is 0.1 to 10 times the diameter D of the opening.

In one embodiment of the present disclosure, the recess provides a mold growth suppressing member in which the ratio (H / D) of the depth H of the recess to the diameter D of the opening of the recess is 0.1 or more and 2 or less. .

In one embodiment of the present disclosure, there is provided a mold growth suppressing member in which a contact angle of water on a surface including the concave group is 0 ° or more and 150 ° or less by a θ / 2 method.

In one embodiment of the present disclosure, there is provided a mold growth suppressing member in which a support is further laminated on a side different from the surface including the concave group.

The embodiment of the present disclosure can provide a mold growth suppression member having an excellent mold growth suppression effect.

FIG. 1 is a perspective view schematically illustrating an example of a mold growth suppressing member according to the present disclosure. FIG. 2 is a schematic plan view schematically illustrating an example of a mold growth suppressing member according to the present disclosure. FIG. 3 is a schematic sectional view schematically showing an example of the A-A ′ sectional view of FIG. 2. FIG. 4 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 5 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 6 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 7 is a schematic plan view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 8 is a schematic plan view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 9 is a diagram for describing a method of determining the contour of the opening of the recess in the present disclosure. FIG. 10 is a diagram for describing a measurement region when measuring a surface having a recess group in the present disclosure. FIG. 11 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 12 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure. FIG. 13 is a diagram schematically illustrating an example of a usage mode of the mold growth suppressing member according to the present disclosure. FIG. 14 is a schematic cross-sectional view schematically showing an example of the B-B ′ cross-sectional view of FIG. 13. FIG. 15 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure. FIG. 16 is a schematic cross-sectional view schematically showing an example of a cross-sectional view taken along the line D-D ′ of FIG. 15. FIG. 17 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure. FIG. 18 is a schematic cross-sectional view schematically showing an example in which a part of the F-F ′ cross section of FIG. 17 is enlarged. FIG. 19 is a diagram schematically illustrating another example of the usage mode of the mold growth suppression member according to the present disclosure. FIG. 20 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure. FIG. 21 is a photomicrograph of the surface of the mold growth inhibiting member after the mold resistance test in Example 1. FIG. 22 is a photomicrograph of the surface of the mold growth inhibiting member after the mold resistance test in Example 2. FIG. 23 is a photomicrograph of the surface of the mold growth inhibiting member after the mold resistance test in Example 3. FIG. 24 is a photomicrograph of the surface of the mold growth inhibiting member after the mold resistance test in Example 4. FIG. 25 is a photomicrograph of the surface of the mold growth inhibiting member after the mold resistance test in Comparative Example 1. FIG. 26 is a photomicrograph of an example of the surface of the mold growth inhibiting member according to the present disclosure after the mold resistance test. FIG. 27 is a photomicrograph of an example of the surface of the mold growth inhibiting member according to the present disclosure after the mold resistance test.

Hereinafter, the mold growth suppression member according to the present disclosure will be described in detail.
In addition, as used in this specification, the shape and geometric conditions and the degree thereof are specified, for example, terms such as “parallel”, “orthogonal”, “identical”, length and angle values, etc. are strictly Without being bound by meaning, it should be interpreted including the extent to which similar functions can be expected. In addition, the “plan view” in this specification means visual recognition from the vertical direction with respect to the upper surface of the mold growth suppressing member. Usually, this corresponds to visual recognition from the direction perpendicular to the surface of the mold growth suppression member having the concave group.
In the present specification, (meth) acryl represents each of acryl and methacryl, (meth) acrylate represents each of acrylate and methacrylate, and (meth) acryloyl represents each of acryloyl and methacryloyl. To express.
Moreover, in this specification, the hardened | cured material of a resin composition means what solidified through or without undergoing a chemical reaction.

The mold growth suppressing member of the present disclosure includes a recess group in which a plurality of recesses having an opening diameter D of 1 μm to 100 μm and a depth H of 1 μm to 50 μm are arranged on the surface,
The distance P between the adjacent recesses is 0.1 to 10 times the diameter D of the opening.

Hereinafter, an embodiment of the present disclosure will be described with reference to the drawings. In the drawings attached to the present specification, for the sake of illustration and ease of understanding, the scale, the vertical / horizontal dimension ratio, and the like are appropriately changed and exaggerated from those of the actual product.
FIG. 1 is a perspective view schematically illustrating an example of a mold growth suppressing member according to the present disclosure. The mold growth suppression member 10 illustrated in FIG. 1 includes a recess group 3 in which a plurality of recesses 2 having the predetermined opening diameter and depth are arranged on one surface of the member 1 at the predetermined distance. It is to be prepared.

The action of the mold growth inhibiting member according to the present disclosure has not yet been clarified as to the action of inhibiting mold growth, but is estimated as follows.
Usually, when mold spores adhere to a member or the like, they germinate to generate hyphae. The mycelium usually has a thread-like structure with a diameter of about 1 to 10 μm, and extends by tip growth while branching the surface of the member. When the mycelium grows sufficiently, among the many tips, some tips form a structure related to reproduction, that is, a spore sac or conidia. And a spore is formed from the structure, and mold grows.
Mold and growth require water and oxygen. In a normal member, when a water droplet is formed under a high humidity condition, a large water droplet of millimeter order adheres.
On the other hand, in the case of the mold growth suppressing member of the present disclosure having a specific recess group on the surface, the recesses having an opening diameter D of 1 μm to 100 μm and a depth H of 1 μm to 50 μm are adjacent to each other. Since the distance P between the recesses is arranged in the range of 0.1 to 10 times the diameter D of the opening, each of the water drops grows greatly even under conditions of high humidity and water droplets. It is possible to prevent moisture from entering the recesses and depositing large water droplets on the order of millimeters on the surface of the member.
Although the spores attached to the concave group of the mold growth inhibiting member of the present disclosure germinate and generate mycelia, no large water droplets are adhered to the surface, so that after the mold resistance test in the mold breeding inhibiting member of the present disclosure As shown in the micrograph (FIG. 26) of the mold growth inhibiting member surface, the moisture that has entered the recess group is elongated, but the moisture that has entered the recess group is insufficient as a nutrient. Growth is inhibited, and in particular, mycelial branching is suppressed. In addition, the mold growth inhibiting member of the present disclosure has a recess having a diameter D of 1 μm to 100 μm and a depth H of 1 μm to 50 μm on the surface, and mold spores of about 1 μm to 3 μm are formed on the surface. When entering into each of the recesses, the water is not supplied enough to germinate and generate mycelia, and the germination and generation of mycelia are suppressed. When the opening diameter D is sufficiently large in a predetermined range with respect to the size of the spore, a plurality of mold spores are likely to enter the concave portion, and the plurality of mold spores hold the water together to further germinate. Thus, it was observed that sufficient moisture was not supplied to generate mycelia, and that germination and generation of hyphae itself were suppressed (FIG. 27).
Thus, it is presumed that germination and generation of hyphae itself and hyphal growth, particularly, hyphal branching are suppressed. Therefore, the number of hyphae tips does not increase, and formation of the structure related to reproduction at the tip of the hyphae is suppressed. From such a thing, it is estimated that the mold propagation suppression member of this indication is suppressed mold growth.
It should be noted that the mold growth inhibiting member of the present disclosure exhibits the effect of inhibiting mold growth even under conditions that are generally suitable for mold growth (for example, temperature 20 to 30 degrees, humidity 80% or more).
Conventionally, there is a technique for obtaining an antifungal effect by making the surface super-hydrophilic or super-water-repellent. However, the contact angle of the surface changes sensitively even if it is slightly contaminated. It was difficult to maintain the water surface and the superhydrophilic surface. The mold growth suppressing member of the present disclosure exhibits the effect of suppressing mold growth regardless of the contact angle of water due to the above-described action.
Furthermore, in the prior art, a technique for obtaining an antifungal effect by making the surface super-hydrophilic or super-water-repellent has used a specific raised structure. In some cases, there was a problem with scratch resistance. On the other hand, according to the mold growth inhibiting member of the present disclosure, since it has a concave shape with a concave group on the surface, there are advantages such as excellent scratch resistance and high surface durability.

<Recess group>
The recess group provided on the surface of the mold growth suppressing member of the present disclosure will be further described with reference to the drawings. FIG. 2 is a schematic plan view schematically illustrating an example of a mold growth suppressing member according to the present disclosure. FIG. 3 is a schematic cross-sectional view schematically showing an example of the AA ′ cross-sectional view of FIG.
As shown in the examples of FIGS. 2 and 3, the surface of the member 1 is provided with a recess group 3 in which a plurality of recesses 2 are arranged, and each recess has an opening diameter D of 1 μm to 100 μm. The depth H is not less than 1 μm and not more than 50 μm, and the distance P between the adjacent recesses is not less than 0.1 times and not more than 10 times the diameter D of the opening.

4 to 6 are schematic cross-sectional views schematically showing another example of the mold growth suppressing member of the present disclosure different from FIG. In the present disclosure, the cross-sectional shape of each concave portion, the cross-sectional shape that passes through the deepest portion of the concave portion and is cut in a plane parallel to the depth direction of the concave portion (for example, the vertical direction in FIG. 3), that is, the vertical cross-sectional shape is particularly limited. 3 may be rectangular as shown in the example of FIG. 3, and the cross section of the recess as shown in the examples of FIGS. 4 and 5 may be tapered, as shown in FIG. 6. The shape of the bottom of the concave portion may be larger than the area of the opening.
7 to 8 are schematic plan views schematically showing another example of the mold growth inhibiting member of the present disclosure different from FIG. When each concave portion in the present disclosure is viewed in plan, the planar shape of the concave portion is not particularly limited, and may be a circular shape as shown in the example of FIG. 2 or as shown in FIGS. 7 and 8. It may be a polygonal shape.

Specific examples of the shape of the recess include a columnar shape such as a columnar shape, an elliptical columnar shape, a semicylindrical shape, a triangular columnar shape, a quadrangular columnar shape, and a hexagonal column; Examples include a part of a spheroid, a tapered paraboloid, a bell shape, a tapered shape such as a pencil shape, and shapes similar to these. In the present disclosure, the plurality of recesses may have the same shape or different shapes.

In the mold growth suppressing member of the present disclosure, the diameter D of the opening of the recess is 1 μm or more and 100 μm or less.
The size of the spore is often 1 μm or more, usually about 2 to 3 μm. When the diameter D of the opening of the recess is 1 μm or more, more preferably 3 μm or more, spores can enter the recess to inhibit germination or to inhibit hyphal development. The diameter D of the opening of the recess is further preferably 4 μm or more.
In addition, by setting the diameter D of the opening of the recess to 100 μm or less and the distance P between the recesses described later, it is difficult for water droplets in the order of millimeters to be formed on the mold growth suppression member surface, and the amount of moisture present in the recess Can be suppressed. The diameter D of the opening of the recess is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 20 μm or less, and particularly preferably 10 μm or less.
The plurality of recesses may have the same opening diameter D, or may have different opening diameters.
Here, the diameter of the opening of the recess is the maximum value of the distance between two points on the outline of the opening in plan view of each recess. For example, in the example of FIG. 2 where the planar view of the recess is circular, the diameter D of the opening of the recess is the diameter of the circle. In the example of FIG. 7 where the planar view of the recess is a square, the diameter D of the opening of the recess is the length of the diagonal line of the rectangle. When the concave portion is a polygon other than a quadrangle, the diameter D of the opening is set with the maximum diagonal length. In addition, when the concave portion has an oval shape in plan view, the diameter D of the opening is defined by the major axis of the ellipse. The diameter of the opening of the concave portion can be measured from a plan view micrograph of the mold growth inhibiting member, appropriately combined with a cross-sectional profile analysis.
In the present disclosure, the cross-sectional profile analysis can be performed using, for example, a laser microscope or a three-dimensional optical profiler, and more specifically, for example, can be performed using Olympus LEXT OLS4100 or Zygo ZeGage. . Specifically, for example, in the case of a shape in which it is difficult to determine the contour of the opening, a cross-sectional profile analysis is used to form a recess as shown in FIG. 9 in each cross-section of the recess cut in the height direction. The line L1 passing through the surface of the non-member and the tangent line Lx of the side surface of the recess are drawn, and the angle α formed by L1 and the tangent line Lx of the side surface of the recess is 5 ° or more and the minimum value Let the intersection be a point that forms the outline of the opening. In this way, the contour of the opening in a plan view of each recess can be determined, and the maximum value of the distance between two points on the contour of the opening can be used as the diameter of the opening of each recess.
Further, in the present disclosure, when measuring a surface having a recess group, as shown in FIG. 10, among the entire surface A having a recess group, a central 1 mm square region a and a first diagonal line passing through the center. On each diagonal line when L1 and the diagonal line L2 orthogonal to the diagonal line L1 are drawn, a total of five areas of 1 mm square areas b, c, d, e in the middle from the center to the diagonal end are used. To measure.
Moreover, in this indication, when the surface which has the said crevice group of the mold propagation control member made into a measuring object is larger than 1m square, it measures using a measurement sample cut into the size of 1m square.

In the mold growth suppressing member of the present disclosure, the depth H of the recess is 1 μm or more and 50 μm or less. The depth H of the recess is a distance from the surface where the opening of the recess exists to the deepest portion of the recess. Specifically, the depth of the recess can be measured using the cross-sectional profile analysis.
When the depth H of the recess is 2 μm or more, more preferably 4 μm or more, spores enter the recess to inhibit germination, and it is difficult to form millimeter-order water droplets on the surface of the mold growth suppression member. Moreover, if the recessed part depth H is 30 micrometers or less, it will become difficult to form a water droplet of a millimeter order on the mold growth suppression member surface, and the moisture content which exists in a recessed part can be suppressed. The depth H of the recess is further preferably 20 μm or less, and particularly preferably 10 μm or less.
The plurality of recesses may have the same depth or different depths.
Further, in the mold growth inhibiting member according to the present disclosure, the ratio of the depth H of the recess to the diameter D of the opening of the recess (H / D) is preferably 0 or more and 2 or less. It is preferably from 1 to 1.5, more preferably from 0.1 to 1.2 from the viewpoint of suitably suppressing mold growth.

Moreover, in the mold growth suppressing member of the present disclosure, the distance P between the adjacent recesses is 0.1 to 10 times the diameter D of the opening. In addition, the distance P between the said recessed parts adjacent is defined as follows. For a planar area where depressions are distributed, when the area is divided by Voronoi with the center of gravity of the shape of each depression in plan view as a generating point, a depression belonging to a Voronoi area adjacent to a Voronoi area of a certain depression is adjacent to the depression. It is defined as a recess. And about the recessed parts contained in this adjacent Voronoi area | region, it defines as the distance P between the said adjacent recessed parts by the minimum value of the distance between the outer contours of the opening part of both recessed parts. When the recesses are regularly arranged, the distance P between the recesses can be defined by the repetition period of the recesses.
In the present disclosure, when the distance P between the adjacent recesses is within the above range, it is difficult for water droplets in the order of millimeters to be formed on the surface of the mold growth suppression member, and the spores or mycelium attached to the mold growth suppression member And the growth of mycelia growing between the recesses can be easily inhibited, and mold growth can be suppressed.
In the present disclosure, the distance P between the adjacent recesses is preferably 0.6 times or more the diameter D of the opening, and more preferably 1.2, from the viewpoint of improving the effect of suppressing the growth of mold. It is preferably at least twice, on the other hand, preferably at most 5 times the diameter D of the opening, and more preferably at most 3 times.
In addition, the distance P between the said adjacent recessed part should be measured from the planar view micrograph of a mold growth suppression member suitably combining with the said cross-sectional profile analysis as needed similarly to the diameter D of the opening part of the said recessed part. Can do.
Further, the arrangement of the concave portions in plan view is not particularly limited as long as the distance P between the adjacent concave portions is 0.1 to 10 times the diameter D of the opening. The arrangement may be regular as shown in FIGS. 2, 7, and 8, and the distance P between the adjacent recesses is in the range of 0.1 to 10 times the diameter D of the opening. It may be randomly arranged (not shown).

In addition, the ratio of the total area of the openings of the recesses to the area of the region having the recess group is 1% or more and 50% or less from the viewpoint of improving the effect of suppressing the growth of mold. It is preferably 5% or more and 50% or less, and more preferably 10% or more and 50% or less.

Moreover, in the mold growth suppressing member according to the present disclosure, the number of the concave portions per unit area in a plan view of the surface having the concave group is the diameter D of the opening, the depth H of the concave portion, and between the adjacent concave portions. It is appropriately adjusted depending on the combination with the distance P, and is not particularly limited, but is preferably 10,000 pieces / cm ² or more, preferably 50,000 pieces / cm ² or more from the viewpoint of improving the effect of inhibiting mold growth. still more preferably, more further preferably 100,000 / cm ² or more, preferably at 10 million / cm ² or less, more preferably 500 million pieces / cm ² or less 2 million More preferably, the number is not more than pieces / cm ² .

In the mold growth inhibiting member of the present disclosure, the portion without the specific recess is typically a substantially flat surface, but the surface of the mold breeding inhibiting member itself is curved or has a curvature. May be. A substantially flat surface means that it may have, for example, scratches or fine irregularities derived from a material, such as 1/100 or less than the lower limit of the depth of the specific recess.

In addition, in the mold growth suppressing member of the present disclosure, a concave portion different from the specific opening D and the depth H may be included in a part of the surface unless the effects of the present disclosure can be obtained. . Moreover, in the mold growth suppression member of the present disclosure, the specific recess or the different recess may be arranged at a distance different from the specific distance P between adjacent recesses unless the effects of the present disclosure can be obtained. good.
In the mold growth inhibiting member of the present disclosure, the area where a plurality of concave portions having the specific opening D and the depth H are arranged at the specific distance P between adjacent concave portions is the total area where the concave portions are arranged. Is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

<Member>
Next, a member having the concave group on the surface will be described. The mold growth inhibiting member according to the present disclosure may be, for example, a member in which the concave group is provided on the surface of a single layer member as shown in the schematic cross-sectional views of FIGS. FIG. 11 is a schematic cross-sectional view schematically showing another example of the mold growth inhibiting member of the present disclosure. As shown in FIG. 11, the mold propagation suppressing member 10 of the present disclosure is a member having a multilayer structure composed of two or more layers, a member 5 having a plurality of through holes constituting the recess 2, a member 6 constituting the bottom of the recess 2. 1 may be used. The member 5 itself having a through hole constituting the concave portion may be composed of multiple layers.

The material of the member is not particularly limited as long as it is a material capable of forming a recess, and can be appropriately selected depending on the application, and may be a transparent material or an opaque material. Materials for the members include various resin compositions, glass such as soda glass, potassium glass, alkali-free glass, lead glass, ceramics such as lead lanthanum zirconate titanate (PLZT), quartz, fluorite, and various metal oxides. Inorganic materials such as silver, copper, and iron, and alloys thereof, and combinations of these materials.

It is preferable that the material of the member is made of a cured product of the resin composition because the concave group can be easily formed and the shape of the concave group can be maintained for a longer period of time. The resin composition contains at least a resin and optionally contains other components such as a polymerization initiator. Further, in the present disclosure, by forming the recess group from a cured product of the resin composition, by appropriately adjusting the composition of the resin composition, molding when forming the recess group by molding It is possible to easily improve the fungal growth suppression effect by improving the properties and adding various additives. Furthermore, in the combination of various additives and the said recessed part group, the effect that the additive for obtaining sufficient antifungal effect can be reduced can be anticipated. In addition, even if the mold growth inhibitory member of this indication does not contain an antibacterial agent, a favorable mold reproduction inhibitory effect can be acquired.
Moreover, even when various additives are contained in the resin composition, the temperature and time for curing the resin composition can be adjusted by adjusting the type and content of the resin and the polymerization initiator. The curing conditions can be adjusted so as to be in a range where the recesses are not altered.

Examples of the resin include, but are not limited to, ionizing radiation curable resins such as (meth) acrylate, epoxy, and polyester, melamine, phenol, polyester, (meth) acrylate, urethane, and urea. , Epoxy, polysiloxane, and other thermosetting resins, polyamide, polyolefin, polyvinyl chloride, (meth) acrylate, polyester, polycarbonate, polyethylene, polypropylene, polystyrene, etc. Examples thereof include resins. The ionizing radiation means electromagnetic waves or charged particles having energy that can be cured by polymerizing molecules. For example, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays , X-rays, electron beams and the like. An ionizing radiation curable resin is a mixture of a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer, and is cured by a polymerization initiator. It is what is done.
As the resin composition, an ionizing radiation curable resin composition containing an ionizing radiation curable resin and a thermosetting resin composition containing a thermosetting resin are preferable because the moldability and mechanical strength of the recesses are excellent. .
Moreover, it is preferable that the said resin composition contains (meth) acrylate type resin. Since the (meth) acrylate resin can generate a sterilization gas, antibacterial properties can be improved.

(Ionizing radiation curable resin composition)
Among ionizing radiation curable resins that are preferably used from the viewpoint of excellent moldability, mechanical strength, and scratch resistance of the recesses, an ionizing radiation curable resin composition containing (meth) acrylate that is particularly preferably used as an example, This will be specifically described below.

The (meth) acrylate is a polyfunctional acrylate having two or more (meth) acryloyl groups in one molecule, even if it is a monofunctional (meth) acrylate having one (meth) acryloyl group in one molecule. Alternatively, monofunctional (meth) acrylate and polyfunctional (meth) acrylate may be used in combination.

Specific examples of the polyfunctional acrylate include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene di (meth) acrylate, hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and bisphenol. A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, etc. Can be mentioned.

It is preferable that content of the said polyfunctional (meth) acrylate is 40 mass% or more and 99.9 mass% or less with respect to the total solid of the said ionizing radiation-curable resin composition, and 50 mass% or more and 99.99 mass%. It is preferable that it is 5 mass% or less. When used in combination with a monofunctional (meth) acrylate described later, it is preferably 40% by mass or more and 98.9% by mass or less, and 50% by mass or more and 96.5% by mass or less based on the solid content. Is preferred. In the present disclosure, the solid content represents all components excluding the solvent.

Specific examples of monofunctional (meth) acrylates include, for example, methyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate , Butoxyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) Chryrate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, biphenyloxyethyl acrylate, bisphenol A diglycidyl (meth) acrylate, biphenylyloxyethyl (meth) acrylate, ethylene oxide modified biphenylyloxyethyl (meth) acrylate, bisphenol A epoxy (meth) acrylate, and the like. These monofunctional (meth) acrylic acid esters can be used alone or in combination of two or more.

In the case of using a monofunctional (meth) acrylate, the content of the monofunctional (meth) acrylate is preferably 1% by mass or more and 30% by mass or less with respect to the total solid content of the ionizing radiation curable resin composition. More preferably, the content is 3% by mass or more and 15% by mass or less.

In order to start or accelerate the curing reaction of the (meth) acrylate, a photopolymerization initiator may be appropriately selected and used as necessary. Specific examples of the photopolymerization initiator include, for example, in the case of a radical polymerization type ionizing radiation curable resin such as (meth) acrylate, bisacylphosphinoxide, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy -2-Methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2,4,6-trimethylben Diphenylphosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) - phosphine oxide, phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinic acid and the like. In the case of a cationic polymerization type ionizing radiation curable resin such as epoxy, aromatic iodonium salts, metallocene compounds and the like can be mentioned. These can be used alone or in combination of two or more.

When using a photopolymerization initiator, the content of the photopolymerization initiator is usually preferably 0.1% by mass or more and 10% by mass or less based on the total solid content of the ionizing radiation curable resin composition. More preferably, the content is 0.5% by mass or more and 5% by mass or less.

The ionizing radiation curable resin composition may further contain other components as long as the effects of the present disclosure are not impaired. Other components include, for example, surfactants for adjusting wettability, fluorine compounds, silicone compounds, stabilizers, antifoaming agents, anti-repellent agents, antioxidants, and aggregation prevention. Agents, viscosity modifiers, release agents and the like.

Further, the surface of the member provided with the concave group on the surface may be further subjected to surface treatment. For example, in order to adjust wettability, a vapor deposition film such as a fluorine-based compound or a silicone-based compound may be provided on the surface including the concave group.

The mold growth suppressing member of the present disclosure may have an arbitrary shape, but typically, one having a concave group on one entire surface of the sheet-like member is exemplified, and the entire surface of both sides of the sheet-like member is exemplified. It may have a recess group, or may have a recess group on a part of one surface. In addition, when the mold growth suppressing member according to the present disclosure is a molded body molded into a predetermined shape, the entire surface may have a concave group, or a part of the surface may have a concave group. It may be. Here, the sheet-like shape may be any one that bends so that it can be wound, one that does not bend enough to be wound, but that is bent by applying a load, or one that does not bend completely.

(Support)
As shown in FIG. 12, the mold growth suppressing member 10 according to the present disclosure has a structure in which a support 11 is further laminated on the surface 8 side different from the surface 7 including the concave group 3. Also good. The support used in the present disclosure can be appropriately selected depending on the application, and may be a transparent support or an opaque support, and is not particularly limited. Examples of the material for the transparent support include acetyl cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, and (meth) acrylic resins. , Polyurethane resin, polyethersulfone and polycarbonate, polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, resin, soda glass, potassium glass, alkali-free glass, lead glass Glass, ceramics such as lead lanthanum zirconate titanate (PLZT), and transparent inorganic materials such as quartz and fluorite. As the material of the opaque support, for example, paper, fabric, wood, ceramics, metal, stone, and two or more of these containing a colorant such as a pigment and a dye as needed are combined by mixing, mixing, or the like. Examples thereof include composite materials, and composite materials of these materials with the transparent support.
Moreover, as a material of a support body, the resin composition mentioned above may be used, for example.
The support may be a sheet or a film, and may be any of those that can be wound, those that do not bend enough to be wound, but that can be bent by applying a load, and those that do not bend completely. May be. Although the thickness of a base material can be suitably selected according to a use and is not specifically limited, Usually, they are 10 micrometers or more and 5000 micrometers or less.

The structure of the support used for the mold growth inhibiting member according to the present disclosure is not limited to a structure composed of a single layer, and may have a structure in which a plurality of layers are laminated, or a molded body. There may be. When it has the structure by which the several layer was laminated | stacked, the layer of the same composition may be laminated | stacked, and the several layer which has a different composition may be laminated | stacked. Further, for example, a primer layer may be formed on the support for improving the adhesion between the member having the concave group and the support, and thus improving the wear resistance (scratch resistance).

When the mold growth suppressing member according to the present disclosure is used as a transparent member such as a protective film, it is preferable to use a transparent member as the member. Moreover, when using the mold growth suppression member according to the present disclosure in an aspect to be attached later, it is preferable to use a transparent member as the member so as not to disturb the design.
Moreover, when installing the mold growth inhibiting member according to the present disclosure on a glass part, it is preferable to use a polyester-based resin base material such as polyethylene terephthalate (PET) from the viewpoint of imparting scattering resistance when the glass is broken. .

Moreover, the mold growth suppressing member according to the present disclosure may be a laminate with an adhesive layer. The adhesive layer is typically located on the surface side that does not have the concave group. When the mold growth inhibiting member according to the present disclosure has an adhesive layer, the adhesive layer is provided on the outermost surface or under a peelable protective film, which will be described later, in order to attach the mold propagation inhibiting member according to the present disclosure to another article or the like. In the case where the mold propagation suppressing member according to the present disclosure has two or more layers, it may be located between the layers in order to bond the layers.
In addition, as a material of the said contact bonding layer, a well-known adhesive agent can be used and it does not specifically limit.

The mold growth inhibiting member according to the present disclosure may have a peelable protective film on at least a part of its surface. The mold growth inhibiting member according to the present disclosure is a form in which a protective film that can be peeled at least partially is temporarily attached, stored, transported, traded, post-processed or constructed, and the protective film is peeled and removed in a timely manner. It can also be.

The mold growth suppressing member according to the present disclosure is not particularly limited, but the total light transmittance in the visible region can be 80% or more depending on the application. When the transmittance is equal to or higher than the lower limit value, in the aspect of using the mold growth suppressing member according to the present disclosure attached to another article, it is possible to suppress damage to the design property of the base, and visibility Can be excellent. The transmittance can be measured by JIS K7361-1 (Plastic—Testing method for total light transmittance of transparent material).

Further, the static contact angle of water on the surface provided with the concave group of the mold propagation suppressing member according to the present disclosure is not particularly limited, but the contact angle of water on the surface having the concave group is 0 degree by the θ / 2 method. The case of 150 degrees or less is mentioned, and the case of exceeding 10 degrees and less than 120 degrees by the θ / 2 method is preferable. In addition, in the mold growth suppressing member according to the present disclosure, the contact angle of water on the surface having the concave group is preferably 20 degrees or more and 115 degrees or less, more preferably 45 degrees or more and 115 degrees, by the θ / 2 method. In the following, it is more preferable that the angle is 70 degrees or more and 115 degrees or less from the viewpoint of achieving both mold growth inhibition and shaping.
In general, when the contact angle of water is more than 10 degrees and less than 120 degrees by the θ / 2 method, there is a problem that water tends to remain on the surface and mold tends to propagate. The mold growth suppressing member can suitably suppress mold growth even if the contact angle of water on the surface having the concave group is greater than 10 degrees and less than 120 degrees by the θ / 2 method.
In the present disclosure, the static contact angle of water is defined as a straight solid that connects 1.0 μL of pure water to the surface of the object to be measured, and one second after the landing, connecting the left and right end points and the vertex of the dropped liquid. The contact angle measured according to the θ / 2 method for calculating the contact angle from the angle to the surface is used. As the measuring device, for example, a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. can be used.

Further, the pencil hardness of the surface having the concave group of the mold growth suppressing member according to the present disclosure is not particularly limited, but is H or more from the viewpoint of excellent mechanical strength and scratch resistance of the mold growth suppressing member. Is preferable, and 2H or more is more preferable. The pencil hardness is measured according to JIS K5600-5-4 (Test pencil specified in JIS-S-6006) after the measurement sample is conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. 1999) can be performed by performing a pencil hardness test (0.98N load) as defined in 1999) on the surface of the measurement sample having the concave group and evaluating the highest pencil hardness without scratches. In the measurement, for example, a pencil scratch coating film hardness tester manufactured by Toyo Seiki Co., Ltd. can be used.

(Manufacturing method of mold growth suppression member)
The method for producing the mold growth suppressing member is not particularly limited as long as it is a method capable of producing the mold propagation inhibiting member according to the present disclosure as described above. The surface is appropriately selected according to the material of the member having a recess group on the surface. For example, a method for shaping the concave / convex shape of the original plate for forming a concave group, a photolithography method, a cutting tool method, and a combination thereof, among others, from the point that the concave group can be easily formed, A method for forming an uneven shape, a photolithography method, and a combination thereof are preferable.
As a method for producing the mold growth inhibiting member of the present disclosure by photolithography, for example, a coating film of a resin composition for forming a recess layer is subjected to pattern exposure and development to form a desired pattern, and then as necessary. And a method of performing etching. The pattern exposure may be performed so as to be a pattern corresponding to the shape of the concave group in plan view. For example, a general method such as a method of exposing through a photomask or a laser drawing method can be used.
Examples of the method for producing the mold growth suppressing member of the present disclosure by shaping the concave / convex shape of the original plate for forming the concave group include, for example, the concave / convex shape obtained by inverting the shape of the desired concave group of the mold growth suppressing member according to the present disclosure. On the other hand, a resin composition for forming a recess layer is applied on a support, and the surface having the concavo-convex shape of the recess group forming original plate is prepared. Examples include a method of pressing the surface of the coating film of the resin composition, curing the resin composition, peeling from the original plate for forming the concave group, and forming a desired concave group by molding. The method for curing the resin composition can be appropriately selected according to the type of the resin composition.
In addition, when a thermoplastic resin is used as a material for a member having a concave group on the surface, instead of a curable resin composition, the concave group is formed by heating at a temperature appropriately selected according to the softening temperature of the thermoplastic resin. By pressing the surface of the original plate having the uneven shape onto the surface of the thermoplastic resin to form a recess group, and cooling and fixing, a desired recess group is formed on the thermoplastic resin surface by molding. And the like.
In addition, the uneven | corrugated shape of the original plate for concave group formation is a shape in which many convex parts were formed and the shape of the desired concave group was reversed.

The original plate for forming a recess group is not particularly limited as long as it is not deformed and worn when repeatedly used, and may be made of metal or resin, A metal is preferably used. This is because it is excellent in deformation resistance and wear resistance.
Specifically, the concave group forming original plate can be formed, for example, as follows. First, an appropriately selected resin resist is spin-coated on the surface of a steel or aluminum base material subjected to uniform chrome plating or copper plating to form a resist layer. Next, laser drawing is performed using a laser drawing apparatus, and development processing is performed using a predetermined developer to form a resist pattern layer. Next, the metal pattern layer is formed by dry etching the chromium or copper metal film exposed from the opening of the resist pattern layer. Next, dry etching of the base material is performed using the resist pattern layer and the metal pattern layer as an etching resistant layer. Thereby, the original plate for concave group formation in which the desired uneven | corrugated shape was formed can be obtained. In forming a pattern on the resist layer, an electron beam drawing method can be used in addition to the laser drawing method.
Further, in order to improve the durability of the plate, a thin film such as a DLC (diamond-like carbon) thin film may be further uniformly coated on the plate.

As the original plate for forming the recess group, a high-purity aluminum layer is provided by sputtering or the like on the surface of a metal base material such as stainless steel, copper, or aluminum directly or through various intermediate layers. It is also possible to mention a layer in which the uneven shape is formed by an anodic oxidation method. When an aluminum layer is provided on the surface of the base material, the surface of the base material may be made into a super-mirror surface by an electrolytic composite polishing method that combines electrolytic elution action and abrasion action by abrasive grains before providing the aluminum layer.
When forming the concavo-convex shape on the concave group forming original plate by an anodic oxidation method, the purity (amount of impurities), crystal grain size, anodizing treatment and / or etching conditions of the aluminum layer are appropriately adjusted. Thus, a desired shape can be obtained.

In addition, the shape of the original plate for forming a concave group is not particularly limited as long as a desired shape can be formed. For example, a plate shape may be used, and a roll shape may be used. Also good. From the viewpoint of easy mass production, a roll shape is preferable. In the present disclosure, a plate-shaped mold can also be suitably used as the concave group forming original plate because the concave group can be easily formed. By using a flat metal mold, deformation of the concave portion can be easily suppressed when the metal mold is peeled from the cured product of the resin composition.
As the roll-shaped mold used in the present disclosure, for example, a mold in which a concave / convex shape in which a shape of a desired concave group is inverted is formed on the peripheral side surface of a base material as described above.

In addition, when an inorganic compound material or a metal material is used as a material for a member having a concave group on the surface, a method of providing a large number of holes on the surface may be appropriately selected from known methods. For example, as described above, anodizing treatment, etching treatment, and the like can be given.

<Use of mold growth suppression member>
The mold growth suppression member according to the present disclosure can be used for any application that requires suppression of mold growth, and is not particularly limited. Examples of applications in which the mold growth suppressing member according to the present disclosure can exert an effect include, for example, a room provided with water facilities such as a bathroom, a washroom, a washing machine storage place, a kitchen, and a toilet (including unit bath equipment) Interior materials such as interior walls, ceilings, and interior decorations used in spaces or rooms or spaces adjacent to watering facilities such as dressing rooms, clothes drying places, canteens; exterior members such as gates, fences, exterior walls, and carports ; Plant cultivation facilities such as greenhouses and plant cultivation tanks; Air conditioning equipment such as air conditioners and air purifiers; Household appliances such as refrigerators, washing machines, telephones, and vacuum cleaners; Cooking equipment such as microwave ovens and rice cookers; Medical Medical equipment such as equipment, medical screens and partitions; office equipment for school equipment, and other electronic equipment. Specific examples of these various devices include filters incorporated in these various devices, protective films such as electronic display units and touch panels provided in these various articles, casings, and films for window glass. it can. The mold growth inhibiting member according to the present disclosure can be suitably used for, among other things, parts that are difficult for humans to reach, for example, carport roofing materials, and preferably used as filters incorporated in the various devices. It is done. In addition, about the container or packaging material, such as a foodstuff and a pharmaceutical, it can also be set as the form which comprised this recessed part group in the surface of the inner side, the outer side, or both inside and outside.

Specific examples of the container or the packaging material will be described with reference to the drawings. FIG. 13 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure. FIG. 14 is a schematic cross-sectional view schematically showing an example of the B-B ′ cross-sectional view of FIG. 13, and FIG. 14 also shows an enlarged view of a portion C. FIG. 13 and FIG. 14 are examples of containers for storing the liquid material, and are examples of so-called pouch containers. The container 40 shown in the example of FIG. 13 and FIG. 14 has a shape in which two packaging materials 31 are overlapped and the peripheral part is bonded together, and the bottom part is three pieces to secure the volume of the container. The packaging material 31 is bonded together. In addition, an extraction port 32 that can be sealed is provided at the top. In the B-B ′ cross section, as shown in the example of FIG. 14, a space for accommodating the liquid material is formed between the two packaging materials 31. The mold growth suppressing member of the present disclosure can be provided, for example, inside a space that stores liquid, and can suppress mold growth in a liquid state (see C in FIG. 14). Moreover, the mold growth suppressing member of the present disclosure may be disposed on the outer surface of the packaging material 31 (not shown).

FIG. 15 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure. FIG. 16 is a schematic sectional view schematically showing an example of the D-D ′ sectional view of FIG. 14, and FIG. 16 also shows an enlarged view of an E portion. FIG.15 and FIG.16 is an example of the packaging material 50 for preserving foodstuffs, such as bread and vegetables, and is an example of what is called a wrapping film. As shown in FIG. 16, in the packaging material 50, the inner surface of the space that accommodates food is a surface having a recess group. Contained items such as foods contained in the packaging material start to propagate mold from the portion that comes into contact with the packaging material, and then spread to the entire stored item and mold tends to propagate. On the other hand, since the growth of mold on the surface of the packaging material is suppressed by using the mold growth suppression member according to the present disclosure as a packaging material, the growth of mold in a portion that comes into contact with the packaging material in food or other contained items is prevented. Can be suppressed. Therefore, mold growth can be suppressed even in the entire contents. When using the mold growth suppressing member according to the present disclosure as a packaging material, it is preferable that at least a part of the inner surface is a surface having the concave group, in order to improve the mold growth suppressing effect. More preferably, the inner surface is a surface having the recess group.

A specific example of the exterior member will be described with reference to the drawings. FIG. 17 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure. FIG. 18 is a schematic cross-sectional view schematically showing an example in which a part of the F-F ′ cross section of FIG. 17 is enlarged. 17 and 18 are examples in which the mold propagation suppressing member of the present disclosure is used as the roofing material 61 of the carport 60. As shown in FIG. 18, both surfaces of the roofing material 61 of the carport 60 have a recess group. It is a surface.

Moreover, the mold growth inhibiting member of the present disclosure can be preferably used for agricultural applications. An agricultural mold growth inhibitory member having at least a part of the mold growth inhibitory member according to the present disclosure can suppress the growth of bacteria and molds, which are also called plant pathogenic bacteria, and enables stable growth of crops. It is also possible to increase the yield. Specific examples of plant pathogens include those described in “All of Hydroponic Culture-Basic Technology Supporting Plant Factories Japan Facility Horticultural Association (edit), Japan Hydroponic Culture Research Association (edit)”. The disclosed fungal growth inhibiting member for agriculture has an improved fungal growth inhibiting effect on fungi such as Pythium and Fusarium.

The usage mode of the mold growth inhibiting member of the present disclosure will be described with reference to the drawings. FIG. 19 is a diagram schematically illustrating an example of a usage mode of the mold growth suppressing member according to the present disclosure, and specifically, a schematic cross-sectional view of the greenhouse 20. The mold growth suppression member of the present disclosure may be disposed on the inner surface side of the ceiling portion 12 or the wall surface portion 13, for example, and is disposed on the surface of the reflection sheet provided on the soil surface 14. There may be. Further, the mold propagation suppressing member of the present disclosure may be a sheet or plate that itself forms the ceiling 12 or the wall surface 13, and is provided on the inner surface side of the ceiling 12 or the wall surface 13. The film-like thing used by bonding may be used.

Moreover, FIG. 20 is a figure which shows typically another example of the usage condition of the mold reproduction suppression member which concerns on this indication, and specifically, an example of the plant cultivation unit 30 (it is also called LED house) in factory cultivation It is a typical sectional view shown. The plant cultivation unit 30 shown in the example of FIG. 20 has a light source 22 such as an LED light source disposed on the top plate side of one or more shelves, the shelf efficiently uses light source light, and A reflection sheet 21 for maintaining temperature and humidity conditions is disposed. The mold growth suppressing member of the present disclosure may be, for example, disposed on the inner surface side of the reflection sheet 21 or may be disposed on a shelf board or a top board constituting the shelf.
By using the mold growth inhibiting member of the present disclosure, it is possible to reduce the amount of agricultural chemicals used, improve the crop yield, and enable stable production.

Next, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the spirit of the present disclosure.
Hereinafter, the present disclosure will be specifically described with reference to examples. These descriptions do not limit the present disclosure. In the following, the diameter D of the opening of the recess, the depth H of the recess, and the distance P between the adjacent recesses are a cross-sectional profile analysis using a laser microscope (manufactured by Olympus, LEXT OLS4100), and a planar view microscope. Measured by photographs.

(Production example: Production of original plate for forming each recess group)
A resist pattern is formed on the surface of the roll plate coated with chrome plating with a uniform thickness by laser beam drawing, which is a reversal pattern of the diameter D and depth H of the following predetermined recess opening and the distance between adjacent recesses. An original was made by etching the layer. In order to secure the peelability of the plate and resin, which will be described later, and the durability of the plate, a 2 μm thick DLC thin film was uniformly coated on the plate.

(Preparation Example 1: Preparation of resin composition for forming concave layer)
The following components were dissolved in 200 parts by mass of ethyl acetate to prepare a resin composition for forming a concave layer.
-23 parts by mass of dipentaerythritol hexaacrylate (DPHA)-72 parts by mass of Aronix M-260 (manufactured by Toa Gosei Co., Ltd., polyethylene glycol diacrylate)-5 parts by mass of hydroxyethyl acrylate-Photoinitiator (Lucirin TPO, manufactured by BASF) 3 parts by mass

[Example 1: Production of mold growth inhibiting member]
The concave layer forming resin composition is applied and filled so that the concave surface of the concave group forming original plate is covered, and the thickness of the concave layer in which the concave group is formed is 20 μm after curing. A base material (material: PET, thickness: 100 μm, product name: Lumirror U34, manufactured by Toray Industries, Inc.) was bonded to the substrate diagonally, and the bonded body was bonded with a rubber roller at a load of 10 N / cm ² . Crimped. After confirming that the uniform composition was applied to the entire original plate for forming the concave group, the resin composition was cured by irradiating ultraviolet rays with energy of 2000 mJ / cm ² from the substrate side. Then, it peeled from the original plate for concave group formation, and the mold growth inhibitory member of Example 1 was obtained.
When the surface of the obtained mold growth inhibiting member was observed with a SEM (Hitachi High Technologies SU8010) and a laser microscope (OLYMPUS, LEXT OLS4100), the diameter D of the recess opening was 15 μm, the depth H was 4 μm, and the adjacent recess A recess group was formed in which a plurality of recesses having an inter-distance P of 35 μm were arranged. Moreover, the contact angle with respect to the water of the surface provided with a recessed group was 52 degree | times. Since the present technology does not depend on the contact angle, the antifungal function can be stably maintained.

[Example 2: Production of mold growth inhibiting member]
In Example 1, a recess group was formed in which a plurality of recesses having a diameter D of the recess opening of 20 μm, a depth H of 8 μm, and a distance P between adjacent recesses of 30 μm were arranged. The contact angle with respect to water of the surface provided with the recess group was 102 degrees.

[Example 3: Production of mold growth inhibiting member]
In Example 1, a recess group was formed in which a plurality of recesses having a recess opening diameter D of 30 μm, a depth H of 4 μm, and a distance P between adjacent recesses of 30 μm were arranged. The contact angle with respect to water of the surface provided with the recess group was 65 degrees.

[Example 4: Production of mold growth inhibiting member]
In Example 1, a recess group was formed in which a plurality of recesses having a recess opening diameter D of 35 μm, a depth H of 20 μm, and a distance P between adjacent recesses of 25 μm were arranged. The contact angle with respect to water of the surface provided with the recess group was 92 degrees.

[Comparative Example 1]
On the base material (material: PET, thickness: 100 μm, trade name: Lumirror U34, manufactured by Toray Industries, Inc.), the concave layer forming resin composition was applied so that the thickness after curing was 20 μm. By irradiating ultraviolet rays with energy of 2000 mJ / cm ² from the material side to cure the resin composition, a member of Comparative Example 1 having a flat surface was obtained.

<Evaluation>
[Mold resistance test 1]
The fungus growth inhibition member obtained in the examples and the member obtained in the comparative example were subjected to a fungus resistance test according to the following procedure in accordance with “Test of plastic products” of JIS Z 2911: 2010. However, in order to make an accelerated test in which mold was propagated in a short time, the test was further conducted by adding 10% glucose peptone medium.
Potato dextrose agar medium is inoculated with each test fungus listed in Table 1 and cultured at 25 ° C. for 7 to 14 days. Then, 10% glucose peptone medium is further added so that the number of spores becomes 10 ⁶ CFU / mL. By doing so, a spore solution was prepared.
The test sample was prepared by disinfecting the surface of each member made of the cured product of the resin composition for forming a concave layer with ethanol, and cutting it into 50 mm squares.
Spray the whole surface of the test sample by spray inoculation to the extent that water droplets are attached, suspend the test sample so that the surface is in the vertical direction, and culture for 4 weeks under conditions of temperature 24 ± 1 ° C. and humidity 95% RH. did.
The surface of the test sample after culturing was observed with the naked eye and a stereomicroscope, and judged according to the following criteria. The determination results are shown in Table 1.
0: No growth of mold was observed with the naked eye or under the microscope 1: No growth of mold was observed with the naked eye, but clearly visible under the microscope 2: Growth of mold was observed with the naked eye, and the area of the growth area was Less than 25% of the total area of the sample 3: Growth of mold was observed with the naked eye, and the area of the growth part was 25% or more and less than 50% of the total area of the sample 4: Mycelia grew well, and the area of the growth part was More than 50% of the total area 5: Mycelium grows vigorously and covers the entire surface of the sample

21 to 25 show micrographs of the surface of the cultured test sample used in the mold resistance test. FIGS. 21 to 24 are microphotographs of the surface of the Aspergillus oryzae test sample of Examples 1 to 4, respectively. FIG.

[Mold resistance test 2]
The mold resistance test 2 was performed in the same manner as the mold resistance test 1 except that the mold was Pythium vanterpoolii, Fusarium solani, Fusarium oxysporum, and Fusarium moniliforme. The results are shown in Table 2.

(Summary of results)
The member having a flat surface obtained in Comparative Example 1 was found to have 5 levels of mold growth in the above-mentioned criteria in the mold resistance test conducted in a wet state at a temperature of 24 ± 1 ° C. and a humidity of 95% RH. It was.
On the other hand, all the mold growth suppression members obtained in the examples, in the mold resistance test conducted in the same wet state as in Comparative Example 1, the mold growth was only at 1 or 2 level based on the standard. It was not recognized, and the growth of mold was able to be suppressed in all types of mold used in the test.

[Examples 5 to 24: Production of mold growth inhibiting member]
In Example 1, the concave group forming original plate was changed so that the diameter D, depth H, and the distance P between adjacent concave parts of the concave part had the values shown in Table 3, respectively. Mold growth inhibiting members of Examples 5 to 24 were produced in the same manner as in Example 1 except that the thickness after curing was 200 μm.
With respect to the mold growth inhibitory members of Examples 5 to 24, the contact angle with water on the surface provided with the recess group was measured, and the mold resistance test 1 was conducted. Table 3 shows the measurement results and test results.

(Manufacturing example: Production of each concave group forming master, container mold, and sheet forming die)
A resist pattern is formed on the surface of an aluminum lithographic plate having a uniform thickness of chrome plating by laser beam drawing to be a reversal pattern of the diameter D, depth H, and the distance between adjacent recesses as shown below. The original plate was prepared by etching the plating layer. In order to ensure the peelability of the plate and the resin and the durability of the plate, a 2 μm thick DLC thin film was uniformly coated on the plate. The prepared lithographic original was prepared and used in the shape of a container mold of an injection molding machine or a sheet forming die of an extrusion molding machine.

[Example 25: Production of mold growth inhibiting member]
Using the container mold having the concave-convex shape of the concave group forming original plate obtained above, a high-density polyethylene (HDPE, Nippon Polyethylene Co., Ltd., Novatec ^TM HD HJ580N) is injected into an injection molding machine (Nissei Plastic Industry Co., Ltd.). ) Made by NEX50III), an injection molding cylinder temperature of 250 ° C., a mold temperature of 40 ° C., an injection molding pressure of 1100 kgf / cm ² , and a cup-type cylindrical container having a thickness of 1 mm, a height of 10 mm, and an outer diameter of 35 mmφ The mold growth inhibiting member of Example 25 was obtained.
When the surface of the obtained mold growth inhibitory member was observed with an SEM (Hitachi High Technologies SU8010) and a laser microscope (OLYMPUS, LEXT OLS4100), the diameter D of the concave opening was 5 μm, the depth H was 10 μm, and the adjacent concave A recess group was formed in which a plurality of recesses having an inter-distance P of 10 μm were arranged.

[Example 26: Production of mold growth inhibiting member]
Implementation was carried out except that the original plate for forming a concave group used in the mold in Example 25 was changed so that the diameter D, depth H, and distance P between adjacent concave portions were the values shown in Table 4, respectively. In the same manner as in Example 25, the mold growth inhibiting member of Example 26 was produced.

[Example 27: Production of mold growth inhibiting member]
In Example 25, the concave group forming original plate used for the mold was changed so that the diameter D, depth H, and the distance P between adjacent concave portions of the concave opening became the values shown in Table 4, respectively. Instead, polypropylene (PP, Nippon Polypro Co., Ltd., Novatec ^TM PP) was used, and the mold growth inhibiting member of Example 27 was produced in the same manner as in Example 25 except that the mold temperature was changed to 50 ° C.

[Example 28: Production of mold growth inhibiting member]
Implementation was carried out except that the concave group forming master used in the mold in Example 27 was changed so that the diameter D, depth H, and distance P between adjacent concave portions were the values shown in Table 4, respectively. In the same manner as in Example 27, the mold growth inhibiting member of Example 28 was produced.

[Example 29: Production of mold growth inhibiting member]
In Example 25, the concave group forming original plate used for the mold was changed so that the diameter D, depth H, and the distance P between adjacent concave portions of the concave opening became the values shown in Table 4, respectively. Instead of using polycarbonate (PC, Idemitsu Kosan Co., Ltd., Toughlon A2200) and changing to an injection molding cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. A member was manufactured. The polycarbonate was used after drying resin pellets at 120 ° C. for 5 hours using a vacuum oven for the purpose of removing moisture absorbed in the resin.

[Example 30: Production of mold growth inhibiting member]
Implementation was carried out except that the original plate for forming a recess group used in the mold in Example 29 was changed so that the diameter D, depth H, and distance P between adjacent recesses of the recess opening became values shown in Table 4, respectively. In the same manner as in Example 29, the mold growth inhibiting member of Example 30 was produced.

[Example 31: Production of mold growth inhibiting member]
In Example 25, the concave group forming original plate used for the mold was changed so that the diameter D, the depth H, and the distance P between adjacent concave portions of the concave opening became the values shown in Table 4, respectively. Implemented except that polymethyl methacrylate (PMMA, Mitsubishi Rayon Co., Acrypet VH) was used instead of Nippon Polyethylene Co., Ltd. and Novatec ^TM HD HJ580N), and the injection molding cylinder temperature was changed to 240 ° C and the mold temperature to 60 ° C. In the same manner as in Example 25, the mold growth inhibiting member of Example 31 was produced. The polymethylmethacrylate was used after drying the resin pellets at 85 ° C. for 4 hours using a vacuum oven for the purpose of removing moisture absorbed inside the resin.

[Example 32: Production of mold growth inhibiting member]
Implementation was performed except that the original plate for forming a concave group used in the mold in Example 31 was changed so that the diameter D, depth H, and distance P between adjacent concave portions of the concave opening became the values shown in Table 4, respectively. In the same manner as in Example 31, the mold growth inhibiting member of Example 32 was produced.

[Example 33: Production of mold growth inhibiting member]
Using the sheet forming die having the concave and convex shape of the concave group forming original plate obtained as described above, polymethyl methacrylate (Mitsubishi Rayon Co., Ltd., Acrypet VH) is used as an extrusion molding machine (manufactured by IHI Machine System Co., Ltd.). Then, extrusion molding was performed at a cylinder temperature of 220 ° C., a die temperature of 220 ° C., a molding pressure of 140 MPa, and a screw shape L / D30 to obtain a mold growth inhibiting member of Example 33 having a thickness of 200 μm.
When the surface of the obtained mold growth inhibitory member was observed with an SEM (Hitachi High Technologies SU8010) and a laser microscope (OLYMPUS, LEXT OLS4100), the diameter D of the concave opening was 10 μm, the depth H was 20 μm, and the adjacent concave A recess group was formed in which a plurality of recesses having an inter-distance P of 10 μm were arranged.

[Example 34: Production of mold growth inhibiting member]
Except for changing the concave group forming original plate used for the sheet forming die in Example 33, the diameter D of the concave opening, the depth H, and the distance P between adjacent concaves are the values shown in Table 4, respectively. In the same manner as in Example 33, the mold growth inhibiting member of Example 34 was produced.

For the mold growth inhibiting members of Examples 25 to 34, the contact angle with water on the surface provided with the recesses was measured, and the mold resistance test 1 was performed. Table 4 shows the measurement results and test results.

DESCRIPTION OF SYMBOLS 1 Member 2 Concave part 3 Concave group 5 Member which has multiple through-holes which comprise a recessed part 6 Member which comprises the bottom part of a recessed part 10 Mold growth suppression member 11 Support body 12 Ceiling part 13 Wall surface part 14 Soil surface (reflective sheet)
20 greenhouse 21 reflective sheet 22 light source 30 plant cultivation unit 31 packaging material 32 outlet 40 container 50 packaging material 60 car port 61 roofing material

Claims

Provided with a recess group in which a plurality of recesses having a diameter D of an opening of 1 μm to 100 μm and a depth H of 1 μm to 50 μm are arranged on the surface,
The mold growth suppressing member, wherein the distance P between the adjacent recesses is 0.1 to 10 times the diameter D of the opening.
The mold propagation suppressing member according to claim 1, wherein the recess has a ratio (H / D) of the depth H of the recess to the diameter D of the opening of the recess, which is 0.1 or more and 2 or less.
The mold growth inhibiting member according to claim 1 or 2, wherein a contact angle of water on a surface including the concave group is 0 ° or more and 150 ° or less by a θ / 2 method.
The mold growth suppressing member according to any one of claims 1 to 3, wherein a support is further laminated on a side different from the surface including the concave group.