JP2020033700A - Mold propagation suppressing member - Google Patents

Abstract

To provide a mold propagation suppressing member capable of suppressing the propagation of mold without using an antimicrobial agent and capable of mass-producing by a simple method.SOLUTION: A mold propagation suppressing member has a fine uneven surface structure having a projection group in which a plurality of projections are arranged. The projection has an indeterminate form having a diameter φ1 of 1.0 μm or more and 100 μm or less in plan view, a height H of the projection of 1 μm or more and 30 μm or less, and a distance D between adjacent projections of 1 μm or more and 50 μm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a mold propagation suppressing member.

  In places with poor air permeability such as bathrooms, kitchens, and other plumbing facilities, storage spaces, and other places with poor ventilation, it is necessary to suppress the growth of mold from the viewpoint of hygiene and the like. Conventionally, a method using a fungicide has been proposed to suppress the growth of mold. For example, the present applicant discloses in Patent Document 1 a laminated sheet having a foaming agent-containing resin layer containing a fungicide on a substrate.

Patent Document 2 discloses a water-repellent resin binder, a photocatalyst, and a material intended to achieve both high antifouling property and high antibacterial and antiviral properties even under weak light such as indoor space. A water-repellent photocatalyst composition containing a material and cuprous oxide, wherein the photocatalytic material and the cuprous oxide are complexed, and a coating film thereof are disclosed.
On the other hand, Patent Literature 3 discloses an article having a specific raised structure on a surface of a substrate and having an antibacterial surface in which the surface is superhydrophobic.

JP 2014-188940 A JP 2012-210557 A JP-T-2013-517903

However, as the amount of antimicrobial agents such as antifungal agents increases, there arises a problem that microorganisms that do not work are generated. There is a need for a means to control breeding.
On the other hand, the raised structure described in Patent Literature 3 has a honeycomb shape or a brick shape and is formed by photolithography or electrodeposition. In addition, there is a problem that the cost tends to be high. In addition, when performing photolithography or electrodeposition, there is also a problem that the environmental load due to waste liquid is large.

  The present invention has been made in view of the above problems, and it is an object of the present invention to provide a mold propagation suppressing member that can suppress the growth of mold without using an antimicrobial agent and that can be mass-produced by a simple method. With the goal.

  The mold growth suppressing member of the present invention has a fine uneven surface structure having a projection group in which a plurality of projections are arranged, and the projection has a shape in a plan view with a diameter φ1 of 1.0 μm or more and 100 μm or less. It is an irregular shape, wherein the height H of the projection is 1 μm or more and 30 μm or less, and the distance D between adjacent projections is 1 μm or more and 50 μm or less.

  In the mold growth suppressing member of the present invention, the surface having the fine uneven surface structure is preferably a rough surface having an arithmetic mean height (Sa) of 0.1 to 10 μm from the viewpoint of excellent mold growth suppressing effect.

  In the mold growth suppressing member of the present invention, in at least a part of the plurality of protrusions, at least a part of a line defining a shape of the protrusion in a plan view is an irregular curve, and the mold growth suppressing effect is obtained. It is preferable because of its superiority.

  In the mold propagation suppressing member of the present invention, it is preferable that the projection group includes a multimodal projection having one projection having two or more vertices from the viewpoint of excellent mold propagation inhibiting effect.

  The mold growth suppressing member of the present invention preferably has an area occupancy of the projections of 55% or more and 95% or less with respect to the entire area in a plan view of the fine uneven surface structure, from the viewpoint of excellent mold growth suppressing effect. .

  ADVANTAGE OF THE INVENTION According to this invention, the growth of mold can be suppressed without using an antimicrobial agent, and the mold growth suppression member which can be mass-produced by a simple method can be provided.

FIG. 1 is a schematic plan view schematically showing an example of a mold propagation suppressing member according to the present invention. FIG. 2 is a schematic sectional view schematically showing an A-A ′ section in FIG. 1. FIG. 3 is a diagram schematically showing a specific example of a plan view shape of a projection provided on the mold propagation suppressing member according to the present invention. FIG. 4 is a diagram for explaining a measurement region when measuring a surface having a fine uneven surface structure in the present invention. FIG. 5 is a diagram schematically illustrating a specific example of a cross-sectional shape in a height direction of a protrusion provided on a mold propagation suppressing member according to the present invention. FIG. 6 is a diagram schematically illustrating a specific example of a cross-sectional shape in the height direction of a protrusion provided on the mold propagation suppressing member according to the present invention. FIG. 7 is a diagram for explaining a measurement region when measuring a surface having a fine uneven surface structure in the present invention. FIG. 8 is a diagram schematically illustrating an example of a method for manufacturing a mold propagation suppressing member according to the present invention. Drawing 9 is a figure showing typically an example of the mode of use of the mold propagation control member concerning the present invention. FIG. 10 is a schematic cross-sectional view schematically illustrating an example of a cross section taken along line B-B ′ of FIG. 9. FIG. 11 is a view schematically showing another example of a usage mode of the mold propagation suppressing member according to the present invention. FIG. 12 is a schematic cross-sectional view schematically illustrating an example of a D-D ′ cross-section in FIG. 11. FIG. 13 is a view schematically showing another example of a usage mode of the mold propagation suppressing member according to the present invention. FIG. 14 is a schematic cross-sectional view schematically showing an example in which a part of the cross section taken along line F-F ′ of FIG. 13 is enlarged. FIG. 15: is a figure which shows typically an example of the use aspect of the agricultural mold propagation suppression member which concerns on this invention. FIG. 16: is a figure which shows typically another example of the use aspect of the mold-reproduction suppression member for agriculture which concerns on this invention. FIG. 17 is a photomicrograph of the surface of the mold propagation suppressing member obtained in Example 1 magnified 10 times. FIG. 18 (a) is a photomicrograph of the surface of the mold growth suppressing member 1 obtained in Example 1 magnified 20 times, and FIG. 18 (b) is a magnification of the photomicrograph of FIG. 18 (a). Cross-sectional profile obtained by cross-sectional profile analysis using a laser microscope (manufactured by Olympus, LEXT OLS4100) of the three-dimensional surface shape of the fine concavo-convex surface structure magnified at the same magnification as that described above. It is. FIG. 19A is a photomicrograph of the surface of the mold growth suppressing member 1 obtained in Example 1 magnified 50 times, and FIG. 19B is a magnification of the photomicrograph of FIG. Cross-sectional profile obtained by cross-sectional profile analysis using a laser microscope (manufactured by Olympus, LEXT OLS4100) of the three-dimensional surface shape of the fine concavo-convex surface structure magnified at the same magnification as that described above. It is. FIG. 20 is a photomicrograph of the surface of the mold growth suppressing member obtained in Example 1 after the mold resistance test performed without adding a 10% glucose peptone medium. FIG. 21 is a photomicrograph of the surface of the mold growth suppressing member obtained in Example 1 after the mold resistance test performed by adding a 10% glucose peptone medium. FIG. 22 is a micrograph of the surface of the member of Comparative Example 1 after a mold resistance test performed without adding a 10% glucose peptone medium. FIG. 23 is a micrograph of the member surface of Comparative Example 1 after a mold resistance test performed by adding a 10% glucose peptone medium.

Hereinafter, the mold propagation suppressing member according to the present invention will be described in detail.
Further, in this specification, to specify the shape and geometric conditions and their degree, for example, terms such as "identical", "parallel", "orthogonal" and the value of length and angle, etc., strict Without being constrained by the meaning, it should be interpreted to include a range in which a similar function can be expected.
In this specification, "in a plan view" means that the mold growth suppressing member is viewed from a direction perpendicular to the surface having the fine uneven surface structure.
In this 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 .

  The mold growth suppressing member of the present invention has a fine uneven surface structure having a projection group in which a plurality of projections are arranged, and the projection has a shape in a plan view with a diameter φ1 of 1.0 μm or more and 100 μm or less. It is an irregular shape, wherein the height H of the projection is 1 μm or more and 30 μm or less, and the distance D between adjacent projections is 1 μm or more and 50 μm or less.

  FIG. 1 is a schematic plan view schematically illustrating an example of the mold propagation suppressing member of the present invention, and FIG. 2 is a schematic cross-sectional view schematically illustrating a cross section A-A ′ in FIG. 1. The mold propagation suppressing member 10 of the present invention shown in FIGS. 1 and 2 has a fine uneven surface structure including a projection group in which a plurality of projections 1 are arranged. In a plan view of the fine uneven surface structure, portions other than the protrusions 1 are concave portions 2 between the protrusions. As shown in FIG. 2, the mold propagation suppressing member 10 includes a fine uneven layer 4 on one surface of a base material 3, and a projection group in which a plurality of protrusions 1 are arranged on the surface of the fine uneven layer 4. And has a fine uneven surface structure provided with. The microscopic unevenness surface structure of the mold proliferation suppressing member 10 has irregularly arranged projections 1 in a plan view, and has a groove-shaped recess 2 at a portion other than the projections 1 as a boundary between the projections.

Although the action of the mold propagation suppressing member according to the present invention to suppress the growth of mold is still unclear, it is presumed as follows.
Usually, when mold spores adhere to a substrate or the like, they germinate and 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 substrate surface. When the hypha elongates the tip, polymerization of actin at the tip of the hypha, secretion of enzymes, elongation of cells, etc. occur periodically, and the mycelium repeats several stepwise steps periodically. It has recently been shown that it grows slowly. When the hypha grows sufficiently, some of the many tips form a structure related to reproduction, that is, a sporangia or conidium. Then, spores are formed from the structure, and mold grows.
Although the spores attached to the surface of the mold growth suppressing member of the present invention germinate and generate hyphae, the growth of hyphae is inhibited, and branching of hyphae is particularly suppressed. Hyphae tend to grow in moist environments and tend to grow in search of a more moist environment. On the other hand, in the fine uneven surface structure provided in the mold propagation suppressing member of the present invention, the water droplets attached to the projections easily flow into the recesses between the projections, and the tops of the projections are well drained. It is likely to be in an environment where the recesses are more moist. Therefore, the mycelium generated on the surface of the mold growth suppressing member of the present invention is likely to enter the recess between the protrusions. However, it is presumed that the hypha entering the concave portion between the projections inhibits the growth of the hypha by preventing each step that occurs periodically when the hypha extends the tip due to the physical stimulation colliding with the projection. You. Also, it is presumed that sufficient water is not obtained at the tops of the protrusions, so that hyphae are unlikely to grow. For this reason, in the mold proliferation suppressing member of the present invention, the growth of hyphae, in particular, the suppression of branching of hyphae does not increase the number of mycelial tips, and the reproduction at the mycelial tips does not increase. Since the formation of the related structure is suppressed, it is presumed that the reproduction of mold is suppressed.
The mold growth suppressing member of the present invention exerts an effect of suppressing the growth of mold even under conditions that are generally suitable for the growth of mold (for example, a temperature of 20 ° C. or more and 30 ° C. or less and a humidity of 80% RH or more).
In addition, conventionally, there is a technique to obtain an anti-mold effect by making the surface super-hydrophilic or super-water-repellent, but the conventional super-hydrophilic or super-water-repellent surface for anti-mold is slightly contaminated. It is difficult to maintain a super-water-repellent surface or a super-hydrophilic surface because the contact angle changes sensitively only by itself. The mold propagation suppressing member of the present invention exerts the effect of suppressing mold propagation irrespective of the contact angle of water by the above-described action.

  As described above, the mold propagation suppressing member 10 has a fine uneven surface structure including a projection group in which the projections 1 having an irregular shape in plan view are arranged irregularly. As a result, the fine uneven surface structure exhibits a satin finish when the entire fine uneven surface structure is viewed in plan (see FIGS. 1 and 17). In the present specification, the satin finish means a state of a surface having a plurality of irregular and fine spot-like irregularities, such as the epidermis of a pear.

As described above, the projection 1 of the fine uneven surface structure has an irregular shape in plan view, and at least a part of a line (outer contour) defining the shape of the projection 1 in plan view has a curved portion. are doing. More preferably, it is preferable that the line (outer contour) 101 defining the shape of the projection 1 in a plan view includes an irregularly curved curve.
Among them, preferably, 50% or more of the plurality of protrusions, more preferably 70% or more of the plurality of protrusions, and still more preferably 90% or more of the plurality of protrusions, in plan view. It is preferable that at least a part of the line (outer contour) 101 defining the shape is an irregular curve.
It is presumed that, by this, the growth of hyphae that has entered the grooves between the protrusions is likely to be inhibited.

  The mold propagation suppressing member 10 was viewed in plan by exhibiting a matte pattern having a group of protrusions in which the protrusions 1 having an irregular shape in plan view were irregularly arranged when the fine uneven surface structure was viewed in plan. In the fine uneven surface structure, the groove-shaped concave portion 2 serving as a boundary between the projections has a network pattern. The mesh pattern includes a plurality of linear portions intersecting in a mesh shape, and each of the plurality of linear portions may be a straight line or a curved line. Here, the curve includes various curves such as an arc-shaped curve, a wavy curve, and the like, in addition to a curve that bends and proceeds irregularly. As described above, since the concave portion 2 formed in a mesh pattern forms a groove-shaped flow path in the entire fine uneven surface structure, the water droplets flowing into the concave portion 2 are formed by the flow path formed by the concave portion 2. It is easy to discharge to the outside of the fine uneven surface structure, and good drainage can be obtained.

In addition, the mold propagation suppressing member 10 exhibits a satin pattern when the fine uneven surface structure is viewed in a plan view, so that the groove-shaped concave portion 2 serving as a boundary between the projections is formed in the fine uneven surface structure in a plan view. At least a part of the plurality of linear portions constituting the mesh pattern has a curved portion. For this reason, the hypha entering the concave portion 2 between the projections easily collides with the projections 1.
More preferably, when the fine uneven surface structure is viewed in a plan view, at least a part of a plurality of linear portions forming a mesh pattern formed by the concave portions 2 between the projections has an irregular curve. It is preferred that
Thereby, the mycelium that has entered the recess 2 between the projections is more likely to collide with the projections 1, and each step that occurs periodically when the mycelium extends the tip is likely to be hindered by the physical stimulus to collide. And the growth of hyphae is likely to be inhibited.

The surface having the fine uneven surface structure is preferably a rough surface having an arithmetic mean height (Sa) of 0.1 μm or more and 10 μm or less from the viewpoint of improving the effect of suppressing mold growth.
On a rough surface having an arithmetic mean height (Sa) within the above range, it is presumed that physical stimulation prevents the steps that occur periodically when the hypha extends the tip, thereby inhibiting the growth of the hypha. . The arithmetic mean height (Sa) of the surface having the fine uneven surface structure is more preferably 0.5 μm or more and 5 μm or less.
In the present invention, the arithmetic mean height (Sa) of the surface having the fine uneven surface structure is a 3D measurement laser microscope (for example, Olympus Corporation) capable of measuring the surface roughness in a non-contact manner in accordance with ISO25178. It can be measured by a laser microscope OLS4000 (LEXT OLS 4000).
Specifically, Z = f ₁ (x, y), where an average plane of a predetermined measurement target area defined on a three-dimensional surface shape acquired by a 3D measurement laser microscope is an XY plane, and a height direction is a Z axis. ), The value given by the following equation (1) expressed in micrometer (μm) units can be used as the arithmetic mean height (Sa).

  That is, the arithmetic average height (Sa) represents the average of the height difference (absolute value of Z (x, y)) from the average plane in the measurement target area.

The surface having the fine uneven surface structure is preferably a rough surface having a maximum height (Sz) of 1 μm or more and 200 μm or less from the viewpoint of improving the effect of suppressing mold growth.
On a rough surface having a maximum height (Sz) within the above range, it is presumed that the steps that occur periodically when the hypha is stretched by the physical stimulation are hindered, thereby inhibiting the growth of the hypha. The maximum height (Sz) of the surface having the fine uneven surface structure is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 50 μm or less.
In the present invention, the maximum height (Sz) of the surface having the fine uneven surface structure is a 3D measurement laser microscope (for example, manufactured by Olympus Corporation) capable of measuring the surface roughness in a non-contact manner in accordance with ISO25178. It can be measured by a laser microscope OLS4000 (LEX OLS 4000).
Specifically, a value given by the sum of the maximum peak height and the maximum valley depth in a predetermined measurement target area of the three-dimensional surface shape acquired by the 3D measurement laser microscope is expressed in units of micrometers (μm). It can be the maximum height (Sz). Here, the peak refers to a portion above the average plane (XY plane) of the three-dimensional surface shape (direction from the object side to the space side), and the valley refers to the average plane (X-Y plane) of the three-dimensional surface shape. It refers to a portion below (in the direction from the surrounding space toward the object side) below the Y plane.

The surface having the fine uneven surface structure is preferably a rough surface having an arithmetic average height (Ra) of 0.1 μm or more and 10 μm or less from the viewpoint of improving the effect of inhibiting mold propagation.
On a rough surface having an arithmetic mean height (Ra) within the above range, it is presumed that the steps that occur periodically when the mycelium elongates the tip due to physical stimulation are prevented, thereby inhibiting the growth of the mycelium. . The arithmetic average height (Ra) of the surface having the fine uneven surface structure is more preferably 0.5 μm or more and 5 μm or less.
In the present invention, the arithmetic mean height (Ra) of the surface having the fine uneven surface structure is a 3D measurement laser microscope (non-contact) capable of measuring the surface roughness according to JIS B 0601-2001. For example, it can be measured with a laser microscope OLS4000 (LEXT OLS 4000) manufactured by Olympus Corporation.
That is, from the roughness curve (contour curve) obtained by the laser microscope, only the reference length L is extracted in the direction of the average line (X axis) of the contour curve, and the average line of the extracted portion is defined as the X axis and the height direction. When the roughness curve (contour curve) is represented by Z = f ₂ (x), where Z is the Z axis, the value given by the following equation (2) expressed in units of micrometers (μm) is calculated by arithmetic mean The height (Ra) can be used.

  That is, the arithmetic average height (Ra) represents the average of the height difference (the absolute value of Z (x)) from the average line of the roughness curve (contour curve) at the reference length L.

The surface having the fine uneven surface structure is preferably a rough surface having a maximum height (Rz) of 1 μm or more and 30 μm or less, from the viewpoint of improving the effect of suppressing mold growth.
On a rough surface having a maximum height (Rz) within the above range, it is presumed that physical stimulation prevents each step that occurs periodically when the mycelium extends its tip, thereby inhibiting mycelial growth. The maximum height (Rz) of the surface having the fine uneven surface structure is more preferably 5 μm or more and 15 μm or less.
In the present invention, the maximum height (Rz) of the surface having the fine uneven surface structure is a 3D measurement laser microscope capable of measuring the surface roughness in a non-contact manner in accordance with JIS B 0601-2001 (for example, And a laser microscope OLS4000 (LEXT OLS 4000) manufactured by Olympus Corporation.
That is, in the reference length L of the roughness curve (contour curve) obtained by the laser microscope, a value given by the sum of the maximum value of the peak height and the maximum value of the valley depth of the contour curve is expressed in micrometers (μm). ) Unit can be the maximum height (Rz). Here, the peak refers to a portion above the average line (X axis) of the roughness curve (contour curve) (in the direction from the object side to the space side), and the valley refers to the average of the roughness curve (contour curve). It refers to a portion below the line (X axis) (direction from the surrounding space toward the object side).

The mold proliferation suppressing member of the present invention has a fine uneven surface structure including a projection group in which a plurality of projections are arranged. In a plan view of the fine uneven surface structure provided in the mold growth suppressing member of the present invention, portions other than the projections are recesses between the projections.
The projection has an irregular shape having a diameter φ1 of not less than 1.0 μm and not more than 100 μm in plan view.

The shape of the projection 1 in plan view is irregular as described above, may be a shape approximated to a circle or an ellipse, or may be a polygon such as a triangle, a quadrangle, a pentagon, or a hexagon, or a shape approximated thereto. It may be.
In the present invention, the diameter φ1 of the projection in plan view is the maximum value of the distance between two points on the contour of the projection in plan view. (See FIG. 3).
In the present invention, for a three-dimensional shape (for example, see FIG. 18) obtained by enlarging the fine uneven surface structure to a magnification of 20 times that of the real thing, a cross section in the thickness direction of the fine uneven surface structure is obtained by cross-sectional profile analysis. A convex body that is observed between adjacent minimum points and is observed in the obtained cross-sectional profile is defined as one protrusion.
When one projection is defined, for example, when a three-dimensional shape obtained by enlarging the fine uneven surface structure to a magnification of 20 times that of the actual one is viewed in plan, a structure recognized as a convex body is subjected to cross-sectional profile analysis. Of the cross-sections obtained in all directions of 360 ° with respect to the central axis of the structure and cut in the thickness direction of the fine uneven surface structure, that is, in the height direction of the structure, the root position of the structure (structure The convex body existing between the adjacent minimum points and the minimum point, which is observed in the cross section passing through the lowest point of the lowest point among the minimum points of the base of the body), as one projection Can be defined.
In the present invention, the minimum point when defining one protrusion has a height difference of 10% or more of the maximum height (Rz) of the surface having the fine uneven surface structure between the adjacent maximum point. Those not possessed shall not be included.
In the present invention, the cross-sectional profile analysis can be performed using, for example, a laser microscope or a three-dimensional optical profiler, and more specifically, can be performed using, for example, LEXT OLS4100 manufactured by Olympus or ZeGage manufactured by Zygo.

  The diameter φ1 is preferably 1 μm or more, more preferably 2 μm or more, preferably 100 μm or less, and more preferably 50 μm or less, from the viewpoint of improving the effect of inhibiting mold propagation. .

  The diameter φ1 of the shape of the projection in plan view is determined by using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a scanning transmission electron microscope (STEM) in combination with the cross-sectional profile analysis as needed. Can be obtained from a plan-view micrograph of the projection taken.

In the present invention, when measuring the surface having the fine uneven surface structure of the mold growth suppressing member, the surface having the fine uneven surface structure of the mold growth suppressing member to be measured is a square of 1 m square or less. In the case of a rectangle, measurement is performed using the mold propagation suppressing member as a measurement sample as it is, and when it is larger than 1 m square, the measurement is performed using a measurement sample cut into a size of 1 m square, and is not square or rectangular. In this case, the measurement is performed using a measurement sample cut into the largest inscribed square or rectangle.
In the present invention, when measuring the surface of the measurement sample having the fine uneven surface structure, as shown in FIG. 4, of the entire surface A having the fine uneven surface structure of the measurement sample, the central 1 mm square region a, a 1 mm square area b, c, d in the middle from the center to the diagonal end on each diagonal line when a first diagonal line L1 passing through the center and a diagonal line L2 orthogonal to the diagonal line L1 are drawn. It is preferable to perform measurement using a total of five regions of e.

In the mold proliferation suppressing member of the present invention, each of the protrusions constituting the protrusion group is arranged so as to be erected on an envelope surface connecting concave portions between the protrusions.
The height H of the projection is not particularly limited as long as it is 1 μm or more and 30 μm or less. Among them, the height H is preferably 3 μm or more, and more preferably 5 μm or more from the viewpoint of improving the drainage effect and improving the mold propagation suppressing effect. Is more preferable. On the other hand, from the viewpoint of excellent mechanical strength of the projection, the height H of the projection is preferably 20 μm or less, more preferably 15 μm or less.
In the present invention, the height H of the projection is a vertical distance from the lowest point of the root position of the projection to the height of the vertex of the projection, that is, the highest point.
The height H of the protrusion can be measured by acquiring a cross section of the protrusion cut in the height direction in all directions of 360 ° with respect to the center axis of the protrusion by cross-sectional profile analysis. The root position of the protrusion is a minimum point of the root of the protrusion measured using the cross section of the protrusion cut in the height direction. When there are a plurality of minimum points at the base of the protrusion, the lowest point at the lowest position is set as the base position of the protrusion.

The cross-sectional shape of the projection in the height direction is not particularly limited, and examples thereof include a trapezoidal shape, a semi-elliptical shape, and a semi-circular shape. Further, as described above, the cross-sectional shape of the projection in the height direction may be a tapered shape as shown in the example of FIG. 5A, and may be a base material as shown in FIG. 5B. May have a thinner shape (so-called inverted taper shape).
Further, as shown in FIG. 5C, the cross section in the height direction of the protrusion may have a shape showing the maximum width at a position from the upper end surface of the protrusion to the base position.

  Specific examples of the shape of the protrusion include tapered shapes such as conical, elliptical cone, hemisphere, paraboloid of revolution, bell shape, pencil shape, triangular pyramid, quadrangular pyramid, and shapes similar to these. And columnar types such as columnar, elliptical, semi-cylindrical, triangular, quadrangular, hexagonal, and similar shapes.

As shown in FIG. 6, the projection group preferably includes a multimodal projection in which one projection 1 has two or more vertexes 1a, from the viewpoint of improving the effect of suppressing mold propagation.
When the projection group includes multimodal projections, the mycelium generated on the surface of the mold growth suppressing member reaches the top of the multimodal projections and forms two or more vertexes of the multimodal projections. It is presumed that, when trying to pass, the physical stimulus received by the apex inhibits the steps that occur periodically as the hypha elongates the tip, thereby inhibiting hyphal growth.

Further, in the present invention, the average _{H AVG} the ratio of the height H of the projections to the average .phi.1 _AVG diameter .phi.1 of the plan view shape of the protrusion _{(H AVG} / φ1 _AVG) is not particularly limited, to improve the drainage effect In addition, from the viewpoint of improving the effect of suppressing mold propagation, it is preferably at least 0.03, more preferably at least 0.5, and in the present invention, the average φ1 of the diameter φ1 of the shape of the projection in plan view. the average _{H AVG} the ratio of the height H of the protrusion relative to _{AVG (H AVG} / _{φ1 AVG)} is not particularly limited, from the viewpoint of mechanical strength, more is preferably 20 or less, 10 or less preferable.

In the mold growth suppressing member of the present invention, the distance D between the adjacent protrusions is not particularly limited as long as it is 1 μm or more and 50 μm or less, but among them, the top of the protrusion is well drained, and the top of the protrusion is easily put into a dry state. From the viewpoint of easily inhibiting the growth of hypha at the top, it is preferably at least 1.5 μm, more preferably at least 2 μm, even more preferably at least 5 μm, while in the recess between the projections, It is preferably 40 μm or less, more preferably 30 μm or less, in that the growth of hyphae is easily suppressed because each step that occurs periodically when the hyphae extends the tip by physical stimulation is easily hindered. Even more preferably, it is 20 μm or less.
In the present invention, when a region where the protrusions are distributed is viewed in a plan view and the region is subjected to Voronoi division using the center of gravity of the shape of each protrusion in a plan view as a generating point, a Voronoi region adjacent to the Voronoi region of a certain protrusion is obtained. The protrusion belonging to the region is defined as a protrusion adjacent to the protrusion.
In this specification, the distance D between adjacent projections refers to a distance between a certain projection and the center of the projection adjacent to the projection.
In the present specification, the center of the protrusion is the lowest of the root positions of the protrusions in a cross section passing through the lowest point of the root position of the protrusion among the cross sections in the height direction of the protrusions obtained by the cross-sectional profile analysis. The midpoint of the line connecting the point and the minimum point facing the lowest point of the root position of the projection.
For example, in an enlarged view of the fine uneven surface structure shown in FIG. 7 when seen in a plan view, the projections 1-i and the projections 1-ii are adjacent to each other. The distance D between the protrusion 1-i and the protrusion 1-ii shown in FIG. 7 is the distance between the center C1 of the protrusion 1-i and the center C2 of the protrusion 1-ii.
The distance D between the adjacent protrusions can be measured by the cross-sectional profile analysis, if necessary, in combination with a plan view micrograph of the mold growth suppressing member.

In addition, from the viewpoint of improving the effect of suppressing mold growth, the ratio of the average D _AVG of the distance D between adjacent projections to the average φ1 _AVG of the diameter φ1 of the planar shape of the projections (D _AVG / φ1 _AVG ) is particularly preferable. Although not limited, it is preferably 0.06 or more, more preferably 0.5 or more, and still more preferably 1 or more from the viewpoint of improving the drainage effect and suppressing the growth of mold. preferable.
Further, from the viewpoint of improving the drainage effect and further suppressing the growth of mold, the ratio of the average D _AVG of the distance D between the adjacent projections to the average φ 1 _AVG of the diameter φ 1 of the shape of the projections in plan view (D _AVG / (φ1 _AVG ) is preferably 20 or less, more preferably 15 or less, and even more preferably 12 or less.

Further, in the mold growth suppressing member according to the present invention, the number of the protrusions per unit area in plan view of the fine uneven surface structure is appropriately determined by a combination of the size, height, and distance between adjacent protrusions of the protrusions. is adjusted, it is not particularly limited, from the viewpoint of improving the mold breeding inhibiting effect, preferably at 40,000 / cm ² or more, more preferably 100,000 / cm ² or more, 600,000 / cm ² or more, more preferably 5 million pieces / cm ² or less, more preferably 4 million pieces / cm ² or less, and 3 million pieces / cm ² or less. Is even more preferred.

  Further, in a plan view of the fine uneven surface structure, the area occupancy of the projections with respect to the entire area is preferably 55% or more, more preferably 65% or more, from the viewpoint of the effect of suppressing mold growth. The content is further preferably 70% or more, while it is preferably 95% or less, and more preferably 90% or less.

In the fine uneven surface structure, the portion without the specific protrusion, that is, the bottom surface of the concave portion between the protrusions is typically a substantially flat surface, but the surface of the mold growth suppressing member itself is curved. Or may have a ridge. Here, the “substantially flat surface” means that it may have, for example, scratches or minute irregularities derived from a material, such as 1/100 or less of the lower limit of the height of the specific protrusion.
In the present invention, the ridge is a sequence of the minimum points observed in the cross-sectional profile at a magnification of 20 times that of the actual product, obtained by measuring the cross-sectional profile of an arbitrary cross section in the thickness direction of the fine uneven surface structure. Refers to periodic undulations on a curved surface.

In the mold propagation suppressing member of the present invention, a convex portion different from the specific protrusion may be included in a part of the surface as long as the effect of the present invention is not obtained.
In the mold growth suppressing member of the present invention, the area where the plurality of specific projections are arranged at the specific distance D between adjacent projections is 70% or more of the entire area where the projections are arranged. Is preferably 80% or more, more preferably 90% or more.

(Fine irregularities layer)
The mold propagation suppressing member according to the present invention may be configured such that the fine uneven surface structure is formed on the surface of a fine uneven layer made of a material different from the base material described later, or the base material described later. And may be formed on the surface of the fine uneven layer integrated with the base material and may be formed on the surface of the single-layer fine uneven layer without the base material. It may be something. Further, the mold propagation suppressing member according to the present invention may be one in which a plurality of protrusions made of a material different from the base material are arranged on the base material.

The material of the fine unevenness layer is not particularly limited as long as it is a material capable of forming the fine unevenness surface structure, and can be appropriately selected depending on the application. There may be. Examples of the material of the fine unevenness layer include various resin compositions, soda glass, potassium glass, alkali-free glass, glass such as lead glass, ceramics such as lead lanthanum zirconate titanate (PLZT), quartz, fluorite, and various metals. Examples include inorganic materials such as oxides, metals such as silver, copper, and iron, and alloys thereof, and combinations of these materials.
When the mold growth suppressing member according to the present invention is used as a transparent member such as a protective film, for example, as the material of the fine uneven layer, a transparent material such as a colorless and transparent resin composition and glass may be used. preferable. In addition, even when the mold growth suppressing member according to the present invention is used in an embodiment to be attached later, it is preferable to use the transparent material as the material of the fine unevenness layer, since the design property is not hindered.
In the mold growth suppressing member according to the present invention, since the mold growth suppressing effect is obtained by having the fine uneven surface structure, the fine uneven layer has a reduced content of an additive having an antibacterial or antifungal effect. And further contain no additive having an antibacterial or antifungal effect.
The fine uneven layer may be a single layer or a multilayer.

As the material of the fine unevenness layer, among others, those composed of a solidified thermoplastic resin composition, or those composed of a cured product of an ionizing radiation-curable or thermosetting resin composition, This is preferable because the shape can be maintained for a longer period.
The resin composition used in the present invention contains at least a resin and, if necessary, other components. By adjusting the type and content of the resin and various additives contained in the resin composition, the curing conditions such as temperature and time for solidifying or curing the resin composition, and a range in which the protrusion group does not deteriorate. Can be adjusted to

Examples of the resin include, but are not particularly limited to, thermoplastic resins such as polyamide-based, polyolefin-based, polyvinyl chloride-based, (meth) acrylate-based, polyester-based, polycarbonate-based, polyethylene-based, polypropylene-based, and polystyrene-based resins; (Meth) acrylate, epoxy, polyester, etc. ionizing radiation-curable resins; melamine, phenol, polyester, (meth) acrylate, urethane, urea, epoxy, polysiloxane, etc. thermosetting resins Resin.
The (meth) acrylate-based resin can exert an antibacterial effect and an antifungal effect by generating a sterilizing gas. However, in the present invention, the effect of inhibiting the growth of mold is obtained by having the fine uneven surface structure. Therefore, the content of the (meth) acrylate-based resin in the resin composition can be reduced, and the content ratio of the (meth) acrylate-based resin in the total 100 parts by mass of the resin contained in the resin composition is: It can be preferably at most 10 parts by mass, more preferably at most 5 parts by mass, still more preferably at most 1 part by mass, and can be free of a (meth) acrylate-based resin.

The mold growth suppressing member of the present invention can be easily manufactured at a low cost by, for example, molding a thermoplastic resin composition containing a thermoplastic resin into a desired shape and forming the fine uneven surface structure on the surface thereof. Can be.
Further, when the fine uneven surface structure is formed on the surface of the solidified thermoplastic resin composition, the abrasion resistance and the abrasion resistance are excellent, and the durability is improved. Therefore, the mold propagation suppressing member according to the present invention can be suitably used in applications where human hands come into contact with it.
Further, when a thermoplastic resin composition is used as a material of the mold growth suppressing member of the present invention, the content of an elutable additive such as a curing agent can be reduced, and preferably, a curing agent or the like can be eluted. Since it is possible to contain no additives, it can be suitably used in life science-related applications such as food and medicine.
As the thermoplastic resin, among others, from the viewpoint of mechanical strength, heat resistance and scratch resistance, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polyethylene-based high-molecular-weight polyethylene and the like Polyester thermoplastic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, and polyarylate are preferred. Among them, a thermoplastic resin composition containing polyethylene terephthalate is preferable, and among them, a polyethylene-based thermoplastic resin is preferable, and low-density polyethylene is particularly preferable.

  Further, 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 may be used. By using an ionizing radiation-curable resin composition or a thermosetting resin composition, a projection having a desired shape can be accurately formed. In addition, ionizing radiation means an electromagnetic wave or a charged particle having energy capable of polymerizing and curing a molecule, for example, all ultraviolet rays (UV-A, UV-B, UV-C), visible light, and gamma rays. , X-rays, electron beams and the like. The ionizing radiation-curable resin is a mixture of a monomer having a radical polymerizable and / or cationic polymerizable bond in a molecule, a polymer having a low degree of polymerization, and a reactive polymer, and is cured by a polymerization initiator. Is what is done.

The resin composition may further contain other components as long as the effects of the present invention are not impaired. Other components include, for example, a surfactant for controlling wettability, a fluorine compound, a silicone compound, a stabilizer, an antifoaming agent, an anti-repellent agent, an antioxidant, and an anti-agglomeration agent. Agents, viscosity modifiers, release agents and the like.
Since the mold growth suppressing member according to the present invention can obtain a mold growth suppressing effect by the fine uneven surface structure, the resin composition may have a reduced content of an antibacterial agent and an antifungal agent. it can. The total content of the antibacterial agent and the antifungal agent contained in the total solid content of the resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and 0.1% by mass. It is still more preferable that the content is the following, and it is particularly preferable that the resin composition does not contain an antibacterial agent and an antifungal agent.
In addition, in this specification, a solid content represents all the components except the solvent.

When the resin composition contains other components other than the resin, the content of the resin contained in the resin composition is not particularly limited, but is preferably 40% by mass or more and 99% by mass based on the total solid content of the resin composition. It is preferably at most 9.9% by mass, more preferably at least 50% by mass and at most 99.5% by mass.
The resin composition may be composed of only a resin.

When the mold propagation suppressing member according to the present invention is a member on which a plurality of protrusions made of a different material from the base material are arranged, the material of the protrusions is the fine unevenness layer. The same material as the material can be used.
Further, in the mold proliferation suppressing member of the present invention, the surface having the fine uneven surface structure may be further subjected to a surface treatment. For example, a vapor-deposited film of a fluorine-based compound, a silicone-based compound, or the like may be provided on the surface provided with the projection group for wettability adjustment.
In the present invention, the compound used for the surface treatment preferably does not have an antibacterial or antifungal effect.

(Base material)
The mold propagation suppressing member according to the present invention may include a substrate as a support.
The substrate used for the mold growth suppressing member of the present invention can be appropriately selected depending on the application, and may be a transparent substrate or an opaque substrate, and is not particularly limited. Examples of the material of the transparent substrate include acetylcellulose resins such as triacetylcellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, and (meth) acrylic resins. , Polyurethane resins, resins such as polyether sulfone, polycarbonate, polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, soda glass, potassium glass, alkali-free glass, and lead glass And ceramics such as lead lanthanum zirconate titanate (PLZT), and transparent inorganic materials such as quartz and fluorite. Examples of the material of the opaque substrate include metal, paper, fabric, wood, stone, and composite materials thereof, and composite materials of these with the material of the transparent substrate.
Further, when the base and the projection group are formed integrally, as the material of the base, for example, the resin composition that can be used as the material of the fine uneven layer can be used. Thermoplastic resin compositions are preferred from the viewpoint of excellent mechanical strength.
The substrate may be a sheet or a film, and may be any of a rollable material, a material that does not bend enough to be wound up but bends under a load, and a material that does not completely bend. You may. The thickness of the base material can be appropriately selected depending on the application, and is not particularly limited, but is usually 10 μm or more and 5000 μm or less.

  The configuration of the base material used for the mold propagation suppressing member of the present invention is not limited to a configuration including a single layer, and may have a configuration in which a plurality of layers are stacked. In the case of having a structure in which a plurality of layers are stacked, layers having the same composition may be stacked or a plurality of layers having different compositions may be stacked. For example, when the projection group is formed on a fine uneven layer made of a different material from the base material, the adhesion between the base material and the fine uneven layer is improved, and the wear resistance and the scratch resistance are improved. May be formed on a substrate.

When the mold proliferation suppressing member according to the present invention is used as a transparent member such as a protective film, it is preferable to use a transparent substrate as the substrate. Further, when the mold propagation suppressing member according to the present invention is used in an embodiment to be attached later, it is preferable to use a transparent base material as the base material, since the design property is not hindered.
Further, when the mold growth suppressing member according to the present invention is installed on a glass portion, the mold growth suppressing member having a thermoplastic resin base material, or a solidified resin composition containing a thermoplastic resin, A mold propagation suppressing member in which the fine uneven layer and the base material are integrated is preferable from the viewpoint of imparting scattering resistance at the time of glass breakage.

Further, the mold propagation suppressing member according to the present invention may have an adhesive layer. The adhesive layer is typically located on a surface that does not have the fine uneven surface structure.
When the mold proliferation suppressing member according to the present invention has an adhesive layer, the adhesive layer is provided on the outermost surface or under a peelable protective film described below in order to attach the mold proliferation suppressing member according to the present invention to another article or the like. Or when the mold growth suppressing member according to the present invention has a layer configuration of two or more layers, the member may be located between the layers for bonding the layers.
In addition, as a material of the adhesive layer, a known adhesive can be used, and there is no particular limitation.

  The mold propagation suppressing member according to the present invention may have a peelable protective film on at least a part of its surface. The mold propagation suppressing member according to the present invention is configured to perform storage, transportation, trading, post-processing or construction in a state where a peelable protective film is temporarily adhered to at least a part of the surface, and to peel off and remove the protective film in a timely manner. It can also be.

  Although the mold propagation suppressing member according to the present invention is not particularly limited, the total light transmittance in the visible region can be 80% or more depending on the application. When the transmittance is equal to or more than the lower limit value, in a mode in which the mold growth control member according to the present invention is used by being attached to another article, it is possible to suppress damage to the design of the base, and Excellent. The transmittance can be measured according to JIS K7361-1 (test method for total light transmittance of plastic-transparent material).

Further, the static contact angle of water on the surface having the fine uneven surface structure of the mold growth suppressing member according to the present invention is not particularly limited, but the contact angle of water on the surface having the fine uneven surface structure is θ / With the two methods, even if the temperature is more than 10 degrees and less than 120 degrees, it is possible to suitably suppress the growth of mold. In general, if the contact angle of water is more than 10 degrees and less than 120 degrees in the θ / 2 method, there is a problem that water easily remains on the surface and mold easily propagates. In addition, the mold propagation suppressing member according to the present invention has a feature that the contact angle of water on the surface having the fine uneven surface structure can be easily determined by the θ / 2 method, because the mold propagation suppressing effect and the strength of the projections are easily compatible. Preferably it is 40 degrees or more and 100 degrees or less.
In the present invention, the static contact angle of water is determined by dropping 1.0 μL of pure water onto the surface of an object to be measured, and after 1 second from the arrival of the droplet, a solid line connecting the left and right end points and the apex of the dropped droplet. The contact angle is measured according to the θ / 2 method of calculating the contact angle from the angle with respect to the surface. As the measuring device, for example, a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. can be used.

  Further, the mold growth suppressing member according to the present invention is not particularly limited, but from the viewpoint of excellent mechanical strength of the mold growth suppressing member, the pencil hardness on the surface having the fine uneven surface structure is H or more. Preferably, it is 2H or more. Note that the pencil hardness was determined by humidifying a measurement sample at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, and then using a test pencil defined by JIS-S-6006 according to JIS K5600-5-4 ( (1999) (a load of 0.98 N) on the surface of the measurement sample having the group of protrusions to evaluate the highest pencil hardness without damage. In the measurement, for example, a pencil scratching film hardness tester manufactured by Toyo Seiki Co., Ltd. can be used.

  In addition, the mold propagation suppressing member according to the present invention is not particularly limited, but in terms of excellent mechanical strength of the mold propagation suppressing member and excellent abrasion resistance, the surface having the fine uneven surface structure is JIS. K 7204: Increased haze value after a 1000-rotational wear test using a wear wheel CS-17 and a 9.8 N load (1,000 gf) in accordance with the wear test method using a plastic-wear wheel specified in 1999. Haze value) is preferably 20% or less, more preferably 10% or less. The wear test can be performed using a Taber abrasion tester such as a rotary abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.).

The mold growth suppressing member of the present invention may have any shape, but typically, may have a fine uneven surface structure on one entire surface of the sheet-like substrate, and may have a sheet-like shape. The base material may have a fine uneven surface structure on both surfaces, or may have a fine uneven surface structure on a part of one surface.
Further, when the mold propagation suppressing member according to the present invention is a molded body molded into a predetermined shape, the mold proliferation suppressing member may have a fine uneven surface structure on the entire surface, or may have a fine uneven surface on a part of the surface. It may have a structure. In the present invention, the sheet shape may be any of a material that bends so that it can be wound, a material that does not bend enough to be wound but is bent by applying a load, and one that does not completely bend.

(Manufacturing method of mold propagation suppressing 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 proliferation suppressing member according to the present invention as described above, and the base material and the fine irregularities of the mold propagation suppressing member are provided. It is appropriately selected depending on the material of the layer. For example, a method of molding a thermoplastic resin composition, forming the fine uneven surface structure on the surface thereof, forming a coating film of a curable resin composition on a substrate, and forming the fine uneven surface on the coating film surface. Method of shaping and curing the structure, method of forming a coating film of the ionizing radiation-curable resin composition on a substrate, forming a cured film having the pattern of the fine uneven surface structure by photolithography, surface of the substrate To form the above-mentioned fine uneven surface structure by cutting a tool.

As a preferred method of manufacturing the mold growth suppressing member of the present invention, among others, the point of simplicity, and mold propagation having high surface hardness, excellent mechanical strength, and excellent durability such as abrasion resistance and abrasion resistance From the viewpoint of obtaining a suppressing member, a production method including a step of forming the fine uneven surface structure on the surface of a previously molded thermoplastic resin layer or a heated and melted thermoplastic resin layer can be preferably used.
Among them, from the viewpoint of production efficiency, as a first manufacturing method, a step of preparing a thermoplastic resin layer made of a solidified thermoplastic resin composition containing a thermoplastic resin,
Forming a fine uneven surface structure on the surface of the thermoplastic resin layer,
The method for producing a mold growth suppressing member, wherein the fine uneven surface structure is the fine uneven surface structure of the mold growth suppressing member of the present invention described above, can be preferably used.
Further, the first manufacturing method may include a step of heating a thermoplastic resin layer forming the fine uneven surface structure, and a step of cooling the thermoplastic resin layer forming the fine uneven surface structure. You may have.

Further, as a second production method of the mold propagation suppressing member of the present invention,
A step of heating and melting a thermoplastic resin composition containing a thermoplastic resin to form a molten thermoplastic resin layer,
Forming a fine irregular surface structure on the surface of the molten thermoplastic resin layer,
While forming the fine uneven surface structure, or after forming the fine uneven surface structure, a step of solidifying by cooling the molten thermoplastic resin layer,
The method for producing a mold growth suppressing member, wherein the fine uneven surface structure is the fine uneven surface structure provided in the above-described mold growth suppressing member of the present invention, can also be preferably used.

  FIG. 8 shows an example of a method for producing the mold propagation suppressing member of the present invention by the second production method. In the method shown in FIG. 8, the thermoplastic resin composition heated and melted by the T-die extruder 5 is extruded from the T-die extruder 5 and formed into a sheet to form a molten thermoplastic resin layer 4a. By passing between a roll-shaped projection group forming original plate 6 having an uneven shape 6a corresponding to the uneven surface structure on the surface and a nip roll 7, a fine uneven surface structure is formed on one surface of the molten thermoplastic resin layer 4a. Is formed and cooled by the cooling roll 8 to obtain the mold propagation suppressing member 10.

Examples of the thermoplastic resin composition used in the first production method and the second production method include the same ones as described above. Further, in the second production method, the resin temperature at the time of heating and melting the thermoplastic resin composition, and the temperature at the time of cooling and solidifying the heated and melted thermoplastic resin composition are not particularly limited, It is appropriately adjusted according to the type of the thermoplastic resin contained in the thermoplastic resin composition.
Further, in the first manufacturing method, when heating the thermoplastic resin layer, the temperature of the thermoplastic resin layer when heating the thermoplastic resin layer, when cooling and solidifying the heated thermoplastic resin layer Is not particularly limited, and is appropriately adjusted according to the type of thermoplastic resin contained in the thermoplastic resin composition.

In the first manufacturing method, in the step of preparing the thermoplastic resin layer, a commercially available thermoplastic resin substrate may be prepared as the thermoplastic resin layer, or the thermoplastic resin composition containing the thermoplastic resin may be heated. The thermoplastic resin layer may be formed by melting to form a molten thermoplastic resin layer, and cooling and solidifying the molten thermoplastic resin layer.
In the step of preparing the thermoplastic resin layer, a method for forming the molten thermoplastic resin layer is not particularly limited, and a known extrusion molding method such as a T-die method can be used.
Further, in the first manufacturing method, as a method for forming a fine uneven surface structure on the surface of the thermoplastic resin layer, a known method can be used, and is not particularly limited. And a high-temperature and high-pressure compression molding method using embossing or embossing.

In the second manufacturing method, the method for forming the molten thermoplastic resin layer is not particularly limited, and a known extrusion molding method such as a T-die method can be used.
Further, in the second manufacturing method, the method of forming a fine uneven surface structure on the surface of the molten thermoplastic resin layer is not particularly limited, but a method of forming using a projection group forming original plate is a method. preferable.

In the present invention, the projection group forming master used when forming the fine uneven surface structure may be a roll-shaped one or a flat plate, but from the viewpoint of production efficiency, A roll-shaped master for forming a projection group is preferable. In addition, as a material of the projection group forming original plate, a known material conventionally used for a plate for imprinting can be used, and it is not particularly limited. Even if it is made of metal, it is made of resin. Although it may be present, a metal projection group forming original plate is preferably used because of its excellent deformation resistance and wear resistance. As the metal material constituting the metal projection group forming master, a known material used as the master can be used, and the type thereof is not particularly limited. For example, copper, SUS, aluminum, steel, nickel and A composite metal or the like obtained by combining these can be used.
As a roll-shaped mold used in the present disclosure, for example, as described above, a roll-shaped mold in which a concavo-convex shape corresponding to the shape of a projection group is formed on a peripheral side surface of a base material.

In the present invention, the projection group forming master used when forming the fine uneven surface structure has an uneven shape corresponding to the fine uneven surface structure.
The concavo-convex shape includes a plurality of holes that are arranged at the same distance as the distance D between adjacent protrusions of the fine concavo-convex surface structure, and the shape of the hole in plan view is the protrusion of the fine concavo-convex surface structure. This is a shape obtained by inverting the shape in plan view.

As a method of forming the concavo-convex shape obtained by inverting the fine concavo-convex surface structure on the projection group forming original plate, a known method can be adopted, and there is no particular limitation, and for example, a polishing treatment such as a sandblasting treatment is preferably performed. Can be used.
In the sand blasting process, unevenness corresponding to the fine unevenness surface structure is formed by spraying the sand blast particles onto the surface of the base material of the projection group forming original plate.

As the sandblast particles used for the sandblast treatment, for example, inorganic particles such as iron, silicon carbide, alumina, titania, chromium oxide, and iron oxide can be used. Among these inorganic particles, at least one of alumina particles and titanium oxide particles can be suitably used.
The shape of the sandblast particles is not particularly limited, but is generally amorphous. The Mohs hardness of the sandblasted particles is not particularly limited, but those having about 6 to 9 can be suitably used.

The average particle size of the sandblast particles is not particularly limited, but is preferably from 1.0 μm to 100 μm, more preferably from 1.0 μm to 50 μm, and still more preferably from 1 μm to 10 μm.
The average particle diameter of the sandblast particles is an average particle diameter measured by a particle size distribution measuring device using a laser diffraction scattering method, and is a volume average particle diameter calculated on a volume basis. As the particle size distribution measuring device, Coulter LS230 manufactured by Beckman Coulter, Inc. or the like can be used.

The sandblasting treatment can be performed by, for example, spraying the above-mentioned sandblasted particles from the tip of the nozzle to the surface of the base material of the master for forming a projection group by the force of compressed air. The base material of the projection group forming original plate to be subjected to the sand blasting treatment may be a flat plate or a roll.
The blast pressure in the sand blasting process is not particularly limited, but can be in the range of 10 to 10000 kPa, preferably 50 to 5000 kPa, and more preferably 100 to 1000 kPa.

  The method for forming the concavo-convex shape obtained by inverting the fine concavo-convex surface structure on the master for forming a protrusion group is not limited to the above-described sand blast treatment, and for example, a known polishing method such as belt polishing or brush polishing may be used. it can. In belt polishing, for example, a sheet-like member with an abrasive such as sandpaper can be used as an endless belt.

For example, when using sandblasting, the material of the sandblasted particles, the average particle size and hardness are appropriately selected, or by appropriately adjusting the blast pressure, the base material of the projection group forming original plate, the fine uneven surface structure A plurality of holes arranged at the same distance as the distance D between adjacent protrusions, and the unevenness of the holes in plan view is a shape obtained by inverting the shape of the protrusions in the fine uneven surface structure in plan view. Shapes can be formed.
Further, by appropriately selecting the material, average particle size, and hardness of the sandblast particles, or adjusting the blast pressure as appropriate, the base material of the projection group forming original plate has a desired range of arithmetic average height (Sa) and the like. Can be formed by inverting the fine uneven surface structure having

  Further, for example, when the composite particles formed by adhering the relatively small particle size sandblast particles to the surface of the relatively large particle size sandblast particles are sprayed on the surface of the base material of the projection group forming original plate, On the base material of the projection group forming original plate, it is possible to form a concavo-convex shape obtained by inverting a multimodal projection (for example, see FIG. 6) in which one projection has two or more vertices.

The method for forming the inverted concavo-convex shape corresponding to the fine concavo-convex surface structure on the original plate for forming the protrusion group is not limited to the above-described polishing method such as sandblasting, and for example, employs a method by dry etching or wet etching. It is also possible.
In the case of employing a method by dry etching, for example, first, a resin layer selected as appropriate is spin-coated on a surface of a base material made of steel or aluminum plated with uniform chrome or copper to form a resist layer. I do. Next, laser drawing is performed using a laser drawing apparatus, and development processing is performed using a predetermined developing solution to form a resist pattern layer.
Next, a 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 etching resistant layers. In this way, it is possible to obtain a projection group forming original plate having a desired uneven shape. In forming a pattern on the resist layer, an electron beam drawing method can be used in addition to the laser drawing method.

In the first manufacturing method, the temperature of the thermoplastic resin layer at the time of forming the fine uneven surface structure on the surface of the thermoplastic resin layer includes the flexibility of the thermoplastic resin layer, the uneven shape of the projection group forming original plate, and the like. The temperature is appropriately adjusted, and is not particularly limited, but is preferably in the range of 150 ° C. or more and 300 ° C. or less from the viewpoint of excellent moldability and handleability.
In the second manufacturing method, the temperature of the molten thermoplastic resin layer when forming a fine uneven surface structure on the surface of the molten thermoplastic resin layer,
The flexibility of the molten thermoplastic resin layer and the unevenness of the projection group forming original plate are appropriately adjusted and are not particularly limited, but from the viewpoint of excellent moldability and handleability, the range of 200 ° C to 280 ° C. Is preferably within the range.

  In the second manufacturing method, for example, by using the above-described sand blasting process, when using a projection group forming original plate formed on the blasted surface of the base material, the projection / recess shape obtained by inverting the fine uneven surface structure is used. The original plate formed in a roll state is placed at the position of the projection group forming original plate 6 in FIG. At this time, the projection group forming original plate 6 is placed so that the unevenness 6a formed on the surface opposite to the blasting surface by sandblasting is opposed to the molten thermoplastic resin layer 4a. In this case, the molten thermoplastic resin layer 4a extruded from the T-die extruder 5 and formed into a sheet shape is passed between the projection group forming original plate 6 and the nip roll 7, so that the molten thermoplastic resin layer 4a On the surface on the side opposite to the contact surface with the projection group forming original plate 6, an uneven shape that follows the uneven shape 6a of the projection group forming original plate 6 (the surface opposite to the blasting surface) is formed. The shape becomes the uneven shape of the fine uneven surface structure.

  Further, in the first manufacturing method, before the step of forming a fine uneven surface structure on the surface of the thermoplastic resin layer, the method may further include a step of stretching the formed thermoplastic resin layer in at least a uniaxial direction. This is preferable from the viewpoint of improving the mechanical strength of the mold propagation suppressing member. The stretching is not particularly limited, but is preferably biaxial stretching. In addition, it is preferable that the temperature of the thermoplastic resin layer at the time of stretching is in the range of 50 ° C. or more and 200 ° C. or less.

  Forming a coating film of the curable resin composition on a substrate, by shaping and curing the fine uneven surface structure on the surface of the coating film, as a method of manufacturing a mold growth suppressing member of the present invention, For example, a projection group forming master having a surface having an uneven shape with a large number of holes corresponding to the fine uneven surface structure is prepared, and the surface of the projection group forming original having the uneven shape is cured. A method in which the curable resin composition is cured after being pressed against the surface of the coating film of the curable resin composition, and then the original plate for forming a projection group is peeled off. Here, as the projection group forming original plate, the same one as described above can be used.

  Forming a coating film of the ionizing radiation-curable resin composition on a substrate, forming a cured film having a pattern of the fine uneven surface structure by photolithography, as a method for producing a mold growth suppressing member of the present invention And a method in which a coating film of the ionizing radiation-curable resin composition is subjected to pattern exposure, development, and formation of a desired pattern, followed by etching as necessary. The pattern exposure may be performed so as to form a pattern corresponding to the shape of the projection group in a plan view. For example, a general method such as a method of exposing through a photomask or a laser drawing method can be used.

<Uses of mold propagation control members>
The mold propagation suppressing member according to the present invention can be used for any application that requires suppression of mold propagation, and is not particularly limited. Since the mold propagation suppressing member according to the present invention is excellent in mechanical strength and durability, it can exert its effects even in applications where human hands come into contact with it, and is suitably used. The mold propagation suppressing member according to the present invention can be suitably used for a part that can be reached by humans in various articles, for example, a bathroom, a washroom, a washing machine place, a kitchen, a toilet (including a unit bath facility), and the like. Interior members such as inner walls, ceilings, interior decorations, etc. used in rooms or spaces provided with plumbing facilities, or rooms or spaces adjacent to plumbing facilities such as dressing rooms, laundry rooms, cafeterias, etc .; gates, fences , Exterior walls, exterior materials such as carports; plant cultivation facilities such as greenhouses and plant cultivation tanks; air conditioners such as air conditioners and air purifiers; household appliances such as refrigerators, washing machines, telephones, and vacuum cleaners; Cooking equipment such as a rice cooker; medical equipment such as medical equipment; office equipment for school equipment and other electronic equipment.
The use when the mold growth suppressing member according to the present invention is used as a transparent member is, for example, a protective film such as an electronic display unit or a touch panel included in these various articles, a surface material used by being pasted on these various articles, And window glass films. On the other hand, the mold propagation suppressing member according to the present invention may be used as an opaque member. For example, by directly forming the fine uneven surface structure on the surface of these various articles, the articles can be used as the mold proliferation suppressing member according to the present invention. In addition, the mold propagation suppressing member according to the present invention can be suitably used for parts that are difficult to reach in various articles, and is preferably used as, for example, a roofing material for a carport, a filter incorporated in the various devices, and the like. Used.
In addition, the container or packaging material for food, medicine, etc. is provided with the projection group on the inside, outside, or both inside and outside surfaces, so that the container or packaging material according to the present invention can be used as a mold. It can also be a propagation control member.

  Specific examples of the container or the packaging material will be described with reference to the drawings. Drawing 9 is a figure showing typically an example of the mode of use of the mold propagation control member concerning the present invention. FIG. 10 is a schematic cross-sectional view schematically showing an example of a cross-sectional view taken along the line B-B 'of FIG. 9, and FIG. 10 also shows an enlarged view of a portion C. 9 and 10 are examples of a container for storing a liquid material, and are examples of a so-called pouch container. The container 40 shown in the example of FIG. 9 and FIG. 10 has a shape in which two pieces of packaging material 31 are overlapped and their peripheral edges are attached, and the bottom is three pieces in order to secure the volume of the container. Packaging material 31 is stuck. In addition, a take-out port 32 that can be sealed is provided at the upper part. In the B-B 'section, as shown in the example of FIG. 10, a space for accommodating the liquid material is formed between the two packaging materials 31. The mold growth suppressing member of the present invention can be provided, for example, inside a space containing a liquid, and can suppress the growth of mold in a liquid state (see FIG. 10C). Further, the mold propagation suppressing member of the present invention may be arranged on the outer surface of the packaging material 31 (not shown).

  FIG. 11 is a view schematically showing another example of a usage mode of the mold propagation suppressing member according to the present invention. FIG. 12 is a schematic cross-sectional view schematically showing an example of the D-D 'cross-sectional view of FIG. 11, and FIG. 12 also shows an enlarged view of a portion E. FIG. 11 and FIG. 12 are examples of a packaging material 50 for storing foods such as bread and vegetables, and are examples of so-called wrapping films. As shown in FIG. 12, in the packaging material 50, an inner surface of a space for storing food is a surface having a group of protrusions. Molds of foods and the like stored in the packaging material start to propagate from the portion that comes into contact with the packaging material, and then spread to the entire storage material, and mold is easily propagated. On the other hand, by using the mold growth suppressing member according to the present invention as a packaging material, the growth of mold on the surface of the packaging material is suppressed. Can be suppressed. For this reason, it is possible to suppress the growth of mold in the whole stored matter. When the mold propagation suppressing member according to the present invention is used as a packaging material, at least a part of the inner surface is preferably a surface having the fine uneven surface structure from the viewpoint of improving the mold propagation suppressing effect, and accommodates a container. More preferably, the inner surface of the space is a surface having the fine uneven surface structure.

  A specific example of the exterior member will be described with reference to the drawings. FIG. 13 is a view schematically showing another example of a usage mode of the mold propagation suppressing member according to the present invention. FIG. 14 is a schematic cross-sectional view schematically showing an example in which a part of the cross section taken along the line F-F ′ in FIG. 13 is enlarged. FIGS. 13 and 14 show examples in which the mold growth suppressing member of the present invention is used as a roofing material 61 of a carport 60. As shown in FIG. The surface has a structure.

  In addition, the mold propagation suppressing member of the present invention can be preferably used for agricultural purposes. Agricultural mold growth suppression member having the mold growth suppression member according to the present invention at least in part, since it can suppress the growth of molds also called phytopathogenic bacteria, it is possible to stably grow agricultural 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 Institute of Horticultural Society (edited), Japanese Hydroponic Culture Research Society (edited), and the present invention. The mold growth suppressing member has a high effect of suppressing the growth of molds such as Pythium and Fusarium.

FIG. 15 is a diagram schematically illustrating an example of a usage mode of the mold-reproduction suppressing member for agriculture according to the present invention, and specifically, a schematic cross-sectional view of the greenhouse 20. The agricultural mold growth suppressing member of the present invention may be, for example, a member disposed on the inner surface side of the ceiling portion 11 or the wall surface portion 12, and is disposed on the surface of the reflection sheet provided on the soil surface 13. It may be something. Further, the mold propagation suppressing member of the present invention may be a sheet-like or plate-like member which itself forms the ceiling portion 11 or the wall surface portion 12, and may be provided on the inner surface side of the ceiling portion 11 or the wall surface portion 12. It may be in the form of a film that is used by bonding.
FIG. 16 is a diagram schematically showing another example of the usage of the agricultural mold propagation suppressing member according to the present invention. Specifically, the plant cultivating unit 30 (also referred to as an LED house) in factory cultivation is shown. It is a typical sectional view showing an example. In the plant cultivation unit 30 shown in the example of FIG. 16, a light source 22 such as an LED light source is arranged on a top plate side of one or more stages of shelves, the shelf efficiently uses light source light, A reflection sheet 21 for maintaining temperature and humidity conditions is provided. The agricultural mold growth suppressing member of the present invention may be, for example, a member arranged on the inner surface side of the reflection sheet 21 or a member arranged on a shelf plate or a top plate constituting a shelf. .
By using the mold propagation suppressing member of the present invention, the amount of pesticides used can be reduced, the yield of agricultural products can be improved, and stable production can be achieved.

Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.
In the following, the diameter φ1 of the shape of the projection in plan view, the height H of the projection, and the distance D between the adjacent projections are based on a three-dimensional shape obtained by enlarging the fine uneven surface structure to a magnification of 20 times that of the actual product. It was measured by a cross-sectional profile analysis using a LEX OLS4100 (manufactured by Olympus) using a cross-sectional profile obtained for a cross section in the thickness direction of the fine uneven surface structure.
Unless otherwise specified below, when measuring a surface having a fine uneven surface structure, a mold sample obtained by cutting the obtained mold growth suppressing member into a 1 m square was used as shown in FIG. In the entire surface A of the measurement sample having the fine uneven surface structure, a 1 mm square area a at the center, a first diagonal L1 passing through the center, and a diagonal L2 orthogonal to the diagonal L1 are drawn. On the diagonal line, the measurement was performed using a total of five regions of 1 mm square regions b, c, d, and e in the middle from the center to the end of the diagonal line.

[Evaluation method]
<Arithmetic average height (Sa), maximum height (Sz)>
In accordance with ISO25178, an area of 644 mm x 644 mm was measured using an Olympus laser microscope OLS4000 (LEX OLS 4000) with an objective lens of 20 times in the laser microscope, and the arithmetic mean height (Sa), the maximum The height (Sz) was calculated. In the laser microscope measurement, when the measurement surface became a curved surface, the arithmetic mean height (Sa) and the maximum height (Sz) were calculated after performing plane correction. In addition, the measurement environmental temperature of the arithmetic mean height (Sa) and the maximum height (Sz) by a laser microscope was 23 to 25 ° C.
<Arithmetic average height (Ra), maximum height (Rz)>
The arithmetic average height (Ra) and the maximum height (Rz) were calculated by cross-sectional profile analysis using a laser microscope (OLYMPUS, LEXT OLS4100) in accordance with JIS B 0601-2001.

(Production Example 1: Production of master for forming projection group)
One surface of the base material was subjected to sandblasting to obtain an original plate 1 for forming projection groups.
The uneven shape of the obtained projection group forming master 1 is such that a plurality of hemispherical to semi-elliptical cone-shaped holes are irregularly arranged at intervals of 0.26 to 70.4 μm. Has an irregular shape in plan view with a diameter φ1 of 0.27 to 81.2 μm and a height H of 0.14 to 39.4 μm, and a distance between adjacent holes of 0.25 to 71.1 μm. Met.

[Example 1: Production of a mold propagation suppressing member]
From a T-die film forming machine, a heated and melted polyethylene terephthalate resin (manufactured by Toyobo Co., Ltd., Byron RF) was extruded at a resin temperature of 260 ° C. onto a roll-shaped projection group forming master 1 obtained in Production Example 1, A mold propagation suppressing member 1 was manufactured.

FIGS. 17 to 19 show plan-view micrographs of the surface of the mold propagation suppressing member 1 obtained in Example 1. FIG. FIG. 17 is a photomicrograph of the surface of the mold propagation suppressing member 1 obtained in Example 1 at a magnification of 10 times, and FIG. 18A is a micrograph of the mold propagation suppressing member obtained in Example 1. FIG. 19A is a micrograph of the surface of the mold growth suppressing member 1 obtained in Example 1 magnified 50 times.
FIG. 18B is a cross-sectional profile of the three-dimensional surface shape of the fine uneven surface structure enlarged to the same magnification as that of the micrograph of FIG. 18A using a laser microscope (OLYMPUS, LEXT OLS4100). FIG. 19B is a cross-sectional profile obtained by analysis of a cross section in the thickness direction of the fine uneven surface structure. FIG. 19B is a cross-sectional profile of the fine uneven surface structure enlarged to the same magnification as the magnification of the micrograph of FIG. This is a cross-sectional profile obtained for a three-dimensional surface shape by a cross-sectional profile analysis using a laser microscope (manufactured by Olympus, LEXT OLS4100) in the thickness direction of the fine uneven surface structure.
Among these, one projection was defined based on the cross-sectional profile shown in FIG. 18B, and the diameter φ1 of the projection in plan view, the height H of the projection, and the distance D between adjacent projections were measured. . That is, in the cross-sectional profile shown in FIG. 18B, a convex body (for example, a symbol A in FIG. 18B) existing between adjacent minimum points is defined as one protrusion, The diameter φ1, the height H of the projection, and the distance D between adjacent projections were measured. In the cross-sectional profile shown in FIG. 18B, the minimum point when defining one protrusion is the maximum height (Rz) of the surface having the fine uneven surface structure between the adjacent maximum point. Points that did not have a height difference of 10% or more were excluded.
The fine uneven surface structure formed on the surface of the mold growth suppressing member 1 includes a projection group in which a plurality of projections are arranged, and the projections have a diameter in plan view of 2.7 to 40.6 μm and an average diameter of φ1. _AVG had an irregular shape of 16.73 μm, and the distance D between adjacent protrusions was 2.7 to 35.2 μm. The height H of the protrusions average _{H AVG} at 1.41 to 19.7 was 9.0 .mu.m.
Further, in the above-described cross-sectional profile, it was confirmed that 38 projections existed per 643.9 μm. That is, the number of the projections per unit area in the planar view of the fine uneven surface structure was approximately 348281 / cm ² . Further, as shown in FIG. 17, at least a part of the line defining the shape of the projection in plan view was an irregular curve.

  In addition, it was confirmed that the projections provided on the mold propagation suppressing member obtained in Example 1 included multi-modal projections in which one projection had two or more vertices.

  The contact angle of water on the surface of the mold growth suppressing member 1 obtained in Example 1 having the fine uneven surface structure was 95 °. Since the present technology does not depend on the contact angle, the antifungal function can be stably maintained.

  Arithmetic average height (Sa), maximum height (Sz), arithmetic average height (Ra), maximum height (Rz) of the surface having the fine uneven surface structure of the mold growth suppressing member 1 obtained in Example 1. Was measured according to the method described in the above [Evaluation method]. Table 2 shows the evaluation results.

[Comparative Example 1]
A PET substrate (Lumirror 50 U34, manufactured by Toray Industries, Inc.) was used as a member of Comparative Example 1.

  Measurement of the arithmetic average height (Sa), the maximum height (Sz), the arithmetic average height (Ra), and the maximum height (Rz) of the PET base material as the member of Comparative Example 1 using the above-described evaluation method. Was measured.

Table 1 shows the measured value and average value φ1 _AVG of the diameter φ1, the measured value of the distance D between the protrusions, and the measured values of the protrusions of the fine uneven surface structure formed on the surface of the mold growth suppressing member 1 obtained in Example 1. Found height H and average H _AVG, and indicates the number of protrusions per unit area, and the evaluation results are shown in Table 2.

[Mold resistance test]
With respect to the mold growth suppressing member obtained in each example, the PET base material of Comparative Example 1, and the member of Comparative Example 1, a mold resistance test was performed according to the following procedure according to JIS Z 2911: 2010 “Test of plastic products”. Was done. The test molds include Aspergillus niger, Aspergillus niger, Penicillium pinophilum, Rhizopus oryzae (Rhizopus oryzae), Chaetemium globosum (Coleoptera) and Cladosporium cladosporium descladosporium. Were used.
In addition, in order to perform an accelerated test for propagating mold in a short time, a test performed by further adding a 10% glucose peptone medium and a test performed without adding a 10% glucose peptone medium were performed. Specifically, the test mold was inoculated on a potato dextrose agar medium, cultured at 26 ± 2 ° C. for 7 to 14 days, and then tested without adding a 10% glucose peptone medium, using sterile water with a humectant, In the test performed with the addition of 10% glucose peptone medium, a single spore suspension of 10 ⁶ CFU / mL of each test mold was prepared using sterile water with a humectant supplemented with 10% glucose peptone liquid medium. . An equal volume of each of the five test mold single spore suspensions was added and mixed to prepare a mixed spore suspension of the five test molds.
A test sample was prepared by disinfecting the surface having an uneven shape in the mold propagation suppressing member 1 obtained in Example 1 and one surface of the PET base material of Comparative Example 1 with ethanol and cutting it into 50 mm square. did.
The whole surface of the test sample was spray-inoculated with 0.5 mL of the mixed spore suspension, placed in a Petri dish, and allowed to stand so that the surface was in a vertical direction, at a temperature of 26 ± 2 ° C. and a humidity of 95% RH. The cells were cultured for 4 weeks under the conditions of not less than 99% RH.
Two weeks and four weeks after the start of the culture, the surface of the test sample was observed with the naked eye and a stereoscopic microscope, and judged based on the following criteria.
0: No hyphal growth was observed 1: Hyphal growth was observed, but the area of the growing part was less than 1/3 of the total area of the sample 2: Hyphal growth was observed, and the area of the growing part was the entire area of the sample In Table 1, a test performed without adding 10% glucose peptone medium was referred to as “without addition of GP broth”, and a test performed using 10% glucose peptone medium was defined as GP. Expressed as 10% broth addition.

Further, FIG. 20 is a plan view micrograph of the surface of the mold growth suppressing member obtained in Example 1 after 4 weeks of culture in a test performed without adding 10% glucose peptone medium in the mold resistance test. FIG. 21 shows a plan-view micrograph of the surface of the mold growth suppressing member obtained in Example 1 after 4 weeks of culture in a test performed with the addition of 10% glucose peptone medium.
On the other hand, FIG. 22 is a plan-view microscopic photograph of the surface of the mold proliferation-inhibiting member obtained in Comparative Example 1 after 4 weeks of culture in a test performed without adding 10% glucose peptone medium in the mold resistance test. FIG. 23 shows a plan-view microscopic photograph of the surface of the mold growth suppressing member obtained in Comparative Example 1 after 4 weeks of culture in a test performed by adding 10% glucose peptone medium.

(Summary of results)
In the mold resistance test performed in a wet state at a temperature of 26 ± 2 ° C. and a humidity of 95% RH to 99% RH, the member having a flat surface of Comparative Example 1 had one level based on the above criteria after 2 weeks of culture. Hyphal growth was observed, and after 4 weeks of culture, two levels of hyphal growth were observed based on the above criteria. On the other hand, the mold growth inhibiting member 1 of the present invention obtained in Example 1 showed that the growth of hypha was 2 weeks after the culture in the mold resistance test performed in the same wet state as in Comparative Example 1. No growth was observed, even after 4 weeks of cultivation, or no level of hyphal growth was observed at 1 level based on the above-mentioned standard. Accordingly, it was clarified that the mold growth suppressing member of the present invention can suppress the growth of mold in a wet state in all types of mold used in the test.

  In addition, for the surface having the fine uneven surface structure of the mold growth suppressing member obtained in each of the examples, the wear wheel CS-17 was formed in accordance with the wear test method using a plastic-wear wheel specified in JIS K 7204: 1999. A 1000-rotation wear test was performed under a load of 9.8 N (1,000 gf), and the difference in haze value before and after the wear test (Δhaze value (%)) was determined. The wear test was performed using a rotary abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.). In the mold propagation suppressing member 1 obtained in Example 1, the increase haze value (△ haze value) after the abrasion test was 20% or less.

[Reference: Antibacterial test]
A test piece cut out from the mold growth suppressing member 1 obtained in Example 1, the PET base material of Comparative Example 1, and a sterilized PET film (Lumirror T60 manufactured by Toray, product name) as a control. I got Escherichia coli was used as a test bacterium. In accordance with JIS Z2801: 2010, the test bacteria were placed on the surface of the test piece of Example 1 having a fine uneven surface structure, one surface of the test piece of Comparative Example 1, and the surface of the control test piece after the sterilization treatment. The solution was dropped, and the viable cell count (pre-test viable cell count) of the test piece immediately after inoculation of the test bacterial solution was measured.
The surface of the test piece to which the test bacterial solution was dropped was covered with a PET film so as to be in close contact with each other, and each test piece was cultured in a culture vessel at a temperature of 35 ° C., a humidity of 90% RH, and irradiation with a fluorescent lamp for 24 hours. Was measured. The number of viable bacteria was measured by a luminescence measurement method. Specifically, an ATP extraction reagent was added to each of the washings, and ATP extracted from the cells was allowed to react with a luminescent reagent (luciferase), and the amount of luminescence was measured with a luminescence photometer to determine the ATP concentration and the viable cell count. Was converted to Table 4 shows the antibacterial activity value calculated from the measured values by the following equation.
Antibacterial activity value = log (viable cell count after cultivation of control test piece) -log (viable cell count after cultivation of test piece to be evaluated)
If the logarithmic value of the antibacterial activity value is 2 or more, it is determined that there is an antibacterial effect.

  From the results in Table 4, it was clarified that the mold growth suppressing member of the present invention obtained in Example 1 did not have the effect of suppressing the growth of Escherichia coli. Therefore, it was clarified that the mold propagation suppressing member of the present invention had an effect of suppressing the propagation of mold specifically among microorganisms.

REFERENCE SIGNS LIST 1 projection 2 recess 3 base 4 fine uneven layer 4a molten thermoplastic resin layer 5 T-die extruder 6 master for forming projection group 7 nip roll 8 cooling roll 10 mold propagation suppressing member 11 ceiling 12 wall 13 soil surface (reflective sheet) )
DESCRIPTION OF SYMBOLS 20 Greenhouse 21 Reflection sheet 22 Light source 30 Plant cultivation unit 31 Packaging material 32 Outlet 40 Container 50 Packaging material 60 Car port 61 Roofing material 101 Line 1a which defines shape of projection 1 in plan view 1a Top of projection 1

Claims (5)

Having a fine uneven surface structure with a projection group in which a plurality of projections are arranged,
The projection has an irregular shape having a diameter φ1 of not less than 1.0 μm and not more than 100 μm in plan view.
A mold propagation suppressing member, wherein a height H of the projection is 1 μm or more and 30 μm or less, and a distance D between the adjacent projections is 1 μm or more and 50 μm or less.   The mold proliferation suppressing member according to claim 1, wherein the surface having the fine uneven surface structure is a rough surface having an arithmetic mean height (Sa) of 0.1 µm or more and 10 µm or less.   The mold proliferation suppressing member according to claim 1, wherein at least a part of a line defining a shape of the projection in a plan view is an irregular curve in at least a part of the plurality of projections.   The mold proliferation suppressing member according to any one of claims 1 to 3, wherein the projection group includes a multimodal projection in which one projection has two or more vertices.   The mold propagation suppressing member according to any one of claims 1 to 4, wherein an area occupation ratio of the protrusion with respect to the entire area is 55% or more and 95% or less in a plan view of the fine uneven surface structure.