JP2020032542A - Member suppressing proliferation of fungi - Google Patents

Abstract

To provide a member suppressing proliferation of fungi capable of suppressing a proliferation of fungi without using an antimicrobial agent and capable of mass-producing by a simple method.SOLUTION: A member suppressing proliferation of fungi comprising a concave-convex surface structure in which a plurality of concave portions surrounded by convex portions are arranged, and in said concave portion, a major axis φ1 of an open is 100 μm or more and 1500 μm or less, and a minor diameter φ2 is 100 μm or more and 1500 μm or less, and major axis φ1≥minor axis φ2 is satisfied, and an average dof a distance between adjacent concave portions is 110 μm or more and 3000 μm or less, an opening area of said concave portion gradually decreases from the opening toward the deepest portion, and a depth H of said concave portion is 10 μm or more and 500 μm or less, and provided with a microprojection group constituted by arranging a plurality of microprojections on the inner surface of said concave portion, and said microprojections have a width w of 0.1 μm or more and 20 μm or less, a height h of 0.1 μm or more and 100 μm or less, and the average dof the distance between adjacent microprojections is 0.1 μm or more and 20 μm or less, and Sa on the inner surface of the concave portion is 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 an antimicrobial surface having a plurality of raised structures on a surface of a substrate, wherein the width of a distal end of the raised structures is less than about 50 μm.
In addition, the present applicant discloses that, in Patent Document 4, the growth of mold is suppressed on a fine uneven surface having a so-called moth-eye structure in which the average d _AVG of the distance d between adjacent microprojections is 50 nm or more and 500 nm or less. Is disclosed.

JP 2014-188940 A JP 2012-210557 A JP-T-2013-517903 JP 2016-210164 A

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 Document 3 has a distal end width of a honeycomb shape or a brick shape having a width of less than about 50 μm, and is formed by photolithography or electrodeposition. Not suitable for mass production.
In the micro-textured surface disclosed in Patent Document 4, although mold growth can be suppressed to such an extent that mold growth to the naked eye is not observed or hardly observed, mold growth is suppressed to such an extent that it cannot be confirmed even by microscopic observation. It is difficult to do.

  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 propagation suppressing member of the present invention has an uneven surface structure in which a plurality of concave portions surrounded by convex portions are arranged,
In the concave portion, the major axis φ1 of the opening is 100 μm or more and 1500 μm or less, the minor axis φ2 of the opening is 100 μm or more and 1500 μm or less. The average D _AVG of the distance D between the concave portions is 110 μm or more and 3000 μm or less,
The opening area of the recess gradually decreases from the opening of the recess toward the deepest portion, and the depth H of the recess is 10 μm or more and 500 μm or less,
On the inner surface of the concave portion, there is provided a microprojection group in which a plurality of microprojections are arranged, and the microprojections have a width w of 0.1 μm or more and 20 μm or less, and a height h of 0.1 μm or more and 100 μm or less. The average d _AVG of the distance d between the adjacent minute projections is 0.1 μm or more and 20 μm or less;
The arithmetic mean height (Sa) of the inner surface of the recess is 1 μm or more and 50 μm or less.

  In the mold growth suppressing member of the present invention, when the area occupancy of the concave portion with respect to the entire area of the concave-convex surface structure is 55% or more and 95% or less in plan view of the concave-convex surface structure, It is preferable because of its superiority.

  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 schematic plan view schematically showing a specific example of the mold propagation suppressing member according to the present invention. FIG. 4 is a view schematically showing a specific example of the shape in plan view of the opening of the recess provided in the mold propagation suppressing member according to the present invention. FIG. 5 is a diagram schematically illustrating a specific example of a cross-sectional shape in a depth direction of a concave portion provided in the mold propagation suppressing member according to the present invention. FIG. 6 is a schematic cross-sectional view schematically showing an example of the inner surface of the concave portion provided in 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 an 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 the line F-F ′ in 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 an optical microscope photograph of the surface of the mold growth suppressing member obtained in Example 1. FIG. 18 is an optical micrograph 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. 19 is an optical micrograph of the surface of the mold growth suppressing member obtained in Example 1 after the mold resistance test performed by adding 10% glucose peptone medium. FIG. 20 is an optical micrograph of the member surface of Comparative Example 1 after a mold resistance test performed without adding a 10% glucose peptone medium. FIG. 21 is an optical 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.
Note that, in the present specification, to specify the shape and geometric conditions and the degree thereof, for example, terms such as "identical", "parallel", "orthogonal" and the value of the 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 propagation suppressing member is viewed from a direction perpendicular to the surface having the 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 propagation suppressing member of the present invention has an uneven surface structure in which a plurality of concave portions surrounded by convex portions are arranged,
In the concave portion, the major axis φ1 of the opening is 100 μm or more and 1500 μm or less, the minor axis φ2 of the opening is 100 μm or more and 1500 μm or less. The average D _AVG of the distance D between the concave portions is 110 μm or more and 3000 μm or less,
The opening area of the recess gradually decreases from the opening of the recess toward the deepest portion, and the depth H of the recess is 10 μm or more and 500 μm or less,
On the inner surface of the concave portion, there is provided a microprojection group in which a plurality of microprojections are arranged, and the microprojections have a width w of 0.1 μm or more and 20 μm or less, and a height h of 0.1 μm or more and 100 μm or less. The average d _AVG of the distance d between the adjacent minute projections is 0.1 μm or more and 20 μm or less;
The arithmetic mean height (Sa) of the inner surface of the recess is 1 μm or more and 50 μm or less.

FIG. 1 is a schematic plan view schematically showing an example of the mold propagation suppressing member of the present invention, and FIG. 2 is a schematic cross-sectional view schematically showing an AA ′ section in FIG. The mold propagation suppressing member 10 of the present invention shown in FIGS. 1 and 2 has an uneven surface structure in which a plurality of concave portions 2 surrounded by convex portions 1 are arranged. As shown in the plan view of FIG. In a plan view of the uneven surface structure of the mold propagation suppressing member 10, the shape of the opening of the recess 2 is rhombic, and the plurality of recesses 2 are regularly arranged. Further, as shown in the cross-sectional view of FIG. 2, the mold growth suppressing member 10 includes the fine uneven layer 4 on one surface of the base material 3, and is surrounded by the convex portions 1 on the surface of the fine uneven layer 4. It has an uneven surface structure in which a plurality of concave portions 2 are arranged.
FIG. 3 is a schematic plan view showing a specific example of the mold propagation suppressing member of the present invention different from FIG. The mold propagation suppressing member 10a has a concave-convex surface structure in which a plurality of concave portions 2a surrounded by the convex portions 1a are arranged. The planar shape of the opening portion of the concave portion 2a is hexagonal, and the plurality of concave portions 2a are regular. It is arranged in a way. The mold propagation suppressing member 10b has a concave-convex surface structure in which a plurality of concave portions 2b surrounded by the convex portions 1b are arranged. The opening of the concave portion 2b has a rectangular shape in plan view, and the plural concave portions 2b are regularly arranged. Are located in The mold propagation suppressing member 10c has an uneven surface structure in which a plurality of recesses 2c surrounded by the protrusions 1c and a plurality of recesses 2d surrounded by the protrusions 1c are provided. Is a parallelogram, the planar shape of the opening of the recess 2d is a triangle, and the plurality of recesses 2c and the plurality of recesses 2d are regularly arranged.

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. Further, in the case of a member having a flat surface, if a water droplet is formed on the surface under a high humidity condition, a large water droplet on the order of millimeters may occur. On the other hand, in the uneven surface structure provided in the mold propagation suppressing member of the present invention, since a plurality of concave portions having a predetermined size are arranged, even under a condition where water droplets are formed with high humidity, before water droplets grow large. In addition, it is possible to suppress the entry of moisture into each concave portion and the attachment of large water droplets on the order of millimeters to the member surface. Since no large water droplets adhere to the surface of the member, it is considered that the mycelium generated on the surface of the mold proliferation suppressing member of the present invention elongates in search of the water entering the concave portion. However, the moisture that has entered the recess is insufficient as a nutrient. Furthermore, since each concave portion has a shape in which the opening area gradually decreases from the opening portion of the concave portion toward the deepest portion, at least a part of the inner surface of the concave portion is a slope or a curved surface, and a specific minute surface is formed on the inner surface of the concave portion. An arithmetic mean height (Sa) of the inner surface of the recess is provided within a specific range. Therefore, it is considered that when the hypha extends to the inner surface of the concave portion, it receives a specific physical stimulus. Hyphae that have entered the recesses are subjected to a specific physical stimulus in a water-deficient environment, preventing the steps that occur periodically when the hyphae extends its tip, thereby inhibiting the growth of hyphae. It is estimated that. 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 an effect of suppressing the propagation of mold irrespective of the contact angle of water by the above-mentioned action.

(Uneven surface structure)
The mold propagation suppressing member of the present invention has an uneven surface structure in which a plurality of concave portions surrounded by convex portions are arranged. The entire concave portion in the concave-convex surface structure is surrounded by a convex portion, and the concave portion is a concave portion as compared with an envelope surface connecting the tops of the convex portions. The envelope surface connecting the tops of the protrusions is an envelope surface connecting the flat surfaces when the tops of the protrusions are flat surfaces, and the ridgeline when the tops of the protrusions have ridges. Is an envelope surface. The planar shape of the opening of the recess has a contour without an open end.

The concave portion has a major axis φ1 of 100 μm or more and 1500 μm or less, a minor axis φ2 of 100 μm or more and 1500 μm or less, and satisfies a major axis φ1 ≧ minor axis φ2 at the opening of the concave portion. The shape of the opening of the concave portion is not particularly limited as long as the major axis φ1 and the minor axis φ2 are within the above range and the major axis φ1 ≧ the minor axis φ2, but is not particularly limited, from the viewpoint of improving the effect of suppressing mold propagation. , All interior angles are preferably polygons, ellipses or circles of less than 180 degrees. In the present invention, the shape of the opening of the concave portion is the shape of the opening of the concave portion in plan view when the surface structure of the concave and convex portion is viewed in plan.
Further, in the present invention, the major axis φ1 is the maximum value of the distance between two points on the contour of the opening of the concave portion, and the minor axis φ2 is a perpendicular line passing through the midpoint of the line segment indicating the major axis φ1 and the concave portion. The distance between intersections with the contour of the opening.
For example, when the shape of the opening of the concave portion is a polygon having all interior angles less than 180 degrees, the major axis φ1 is the maximum diagonal length in the case of a polygon other than a triangle, and the maximum side in the case of a triangle. Length.
FIG. 4 shows a major axis φ1 and a minor axis φ2, respectively, in a specific example of a polygon that can be the shape of the opening of the recess. As shown in FIG. 4, in the case of a rhombus, the major axis φ1 is the maximum diagonal length, and the minor axis φ2 is the minimum diagonal length. In the case of a rectangle, the major axis φ1 is the maximum diagonal length, and the minor axis φ2 is the distance between the intersection of a perpendicular passing through the midpoint of the line segment indicating the major axis φ1 and the outline of the rectangle. In the case of a hexagon, the major axis φ1 is the maximum diagonal length, and the minor axis φ2 is the distance between the intersections of a perpendicular passing through the midpoint of the line indicating the major axis φ1 and the outline of the hexagon. In the case of a triangle, the major axis φ1 is the length of the longest side, and the minor axis φ2 is the distance between the intersection of a perpendicular passing through the midpoint of the side indicating the major axis φ1 and the outline of the triangle. Although not shown, in the case of a square, the major axis φ1 and the minor axis φ2 each have a diagonal length and have the same value.

The major axis φ1 is preferably 300 μm or more, more preferably 400 μm or more, still more preferably 500 μm or more, and on the other hand, 1000 μm or less, from the viewpoint of improving the effect of inhibiting mold propagation. It is more preferable that the thickness be 900 μm or less.
The minor axis φ2 is preferably 300 μm or more, more preferably 400 μm or more, and on the other hand, 1000 μm or less, and preferably 900 μm or less, from the viewpoint of improving the effect of inhibiting mold propagation. Is more preferred.

  Further, in each recess, the ratio of the minor diameter φ2 of the opening to the major diameter φ1 of the opening (φ2 / φ1) is not particularly limited. However, from the viewpoint of improving the effect of suppressing mold growth, it is 0.3 to 1.0. Is preferably 0.4 or less, more preferably 0.4 or more and 1.0 or less, and even more preferably 0.5 or more and 1.0 or less.

  In plan view of the uneven surface structure, the shapes of the openings of the plurality of concave portions may be the same or different, but the uneven surface structure excellent in the viewpoint of production efficiency and the effect of suppressing mold growth can be easily formed. From the viewpoint, it is preferable that they have the same shape, and it is more preferable that they have the same shape.

  Further, in the uneven surface structure provided in the mold propagation suppressing member of the present invention, the arrangement of the concave portions in plan view may be arranged regularly, or may be arranged randomly, Although not particularly limited, those arranged regularly are preferable from the viewpoint of production efficiency and the point that an uneven surface structure excellent in the effect of suppressing mold growth can be easily formed.

In the mold propagation suppressing member of the present invention, the average D _AVG of the distance D between the adjacent concave portions is not particularly limited as long as it is 110 μm or more and 3000 μm or less. Is more preferably 300 μm or more, while it is preferably 1500 μm or less, more preferably 1000 μm or less, and even more preferably 900 μm or less.
In the present invention, when the area having the concave-convex surface structure is planarly viewed with an optical microscope, and when the area is subjected to Voronoi division using the center of gravity of the planar shape of the opening of each recess as a generating point, one A concave portion belonging to the Voronoi region adjacent to the Voronoi region of the concave portion is defined as a concave portion adjacent to the concave portion. The distance D between the adjacent concave portions is determined by calculating the planar shape of the opening of the concave portion adjacent to the concave portion from the center of gravity of the planar portion of the opening portion of one concave portion when the concave-convex surface structure is viewed in a plan view with an optical microscope. Distance to the center of gravity. The average D _AVG of the distance D between the adjacent concave portions is obtained from the frequency distribution of the distance D between the adjacent concave portions.

  The major axis φ1 and the minor axis φ2 in the opening of the concave portion and the distance D between the adjacent concave portions can be measured from an optical microscope photograph of the region having the concave-convex surface structure of the mold growth suppressing member in plan view. As the optical microscope, a general one can be used, and there is no particular limitation. For example, a BX series manufactured by Olympus Corporation can be used.

The opening area of the recess gradually decreases from the opening of the recess toward the deepest portion.
As the cross-sectional shape in the depth direction of the concave portion, for example, a tapered shape as shown in FIG. 5A, a bowl shape as shown in FIG. 5B, and a sectional shape as shown in FIG. And a V-shape as shown in FIG. 5D. Above all, from the viewpoint of improving the effect of suppressing mold propagation, it is preferable that the concave portion has a flat surface or a curved surface at the deepest portion. Specifically, for example, the concave portion is deep in all directions of 360 ° with respect to the central axis of the concave portion. It is preferable that the cross section of the concave portion cut in the vertical direction has any of a tapered shape, a bowl shape, and an elliptical arc shape.

The depth H of the concave portion is not particularly limited as long as it is 10 μm or more and 500 μm or less, but among them, from the viewpoint of improving the effect of inhibiting mold growth, it is preferably 50 μm or more, more preferably 100 μm or more, Even more preferably, it is 130 μm or more. On the other hand, it is preferably 400 μm or less, more preferably 300 μm or less.
In the present invention, the depth H of the concave portion is, as shown in FIG. 2, a vertical distance from an envelope surface 1 _{top connecting} the tops of the convex portions 1 surrounding the concave portion 2 to a deepest portion 2 _bottom of the concave portion 2. And

The depth H of the concave portion and the opening area of the concave portion at a predetermined depth H can be confirmed by cross-sectional profile analysis. Specifically, in all directions of 360 ° with respect to the central axis of the concave portion, by obtaining a cross section of the concave portion cut in the depth direction, the depth H of the concave portion, and the depth of the concave portion at a predetermined depth H The opening area can be measured. Note that the opening area of the concave portion at the predetermined depth H refers to the cut surface when the concave portion is cut at a predetermined depth H and parallel to the envelope surface 1 _{top connecting} the tops of the convex portions 1. This is the opening area of the recess.
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 mold growth suppressing member of the present invention includes a group of microprojections on which a plurality of microprojections are arranged on the inner surface of the recess. FIG. 6 is a schematic cross-sectional view schematically illustrating an example of the inner surface of the concave portion provided in the mold propagation suppressing member according to the present invention, and is an enlarged view of the cross section of the concave portion 2 on the surface of the fine uneven layer 4. On the inner surface of the concave portion 2 shown in FIG. 6, there is provided a small projection group in which a plurality of small projections 8 are arranged.
The shape of the fine projections arranged on the inner surface of the concave portion is not particularly limited, but is preferably tapered from the viewpoint of improving the effect of suppressing mold growth. Examples of the shape of the cross section obtained by cutting the microprojection in the planting direction include a semi-ellipse, a parabola, a bell, a triangle, a semicircle, and a trapezoid. Further, the fine projections may have finer irregularities with a height difference of less than 0.1 μm on the top and side surfaces.

The fine projections have a width w of 0.1 μm or more and 20 μm or less, a height h of 0.1 μm or more and 100 μm or less, and an average d _AVG of a distance d between the adjacent fine projections of 0.1 μm or more and 20 μm or less. It is.
The average d _AVG of the distance d between the adjacent microprojections is preferably 1 μm or more and 10 μm or less, and more preferably 1.5 μm or more and 8 μm or less, from the viewpoint of improving the effect of suppressing mold growth.
Here, the width w of the microprojections is measured using the mold growth suppressing member as a measurement sample as it is when the mold growth suppressing member is a sheet having a uniform thickness, and when the mold growth suppressing member is not a sheet having a uniform thickness. The measurement is performed using a measurement sample obtained by cutting a sheet having a uniform thickness along the surface to be measured. In addition, the measurement is performed by placing the measurement sample on a horizontal table so that the surface to be measured is the upper surface, and the fine protrusions are obtained by cutting the fine protrusions on the reference surface as shown in FIG. The maximum diameter of the cut surface is defined as the width w of the minute projection.
The height h of the microprojections is measured by acquiring a plurality of cross sections of the microprojections cut in the direction of planting in all directions of 360 ° with respect to the central axis passing through the vertices of the microprojections. In each cross-section, as shown in FIG. 6, the base 8a of the minute projections 8, determine the distance from the line segment at the midpoint 8c to the apex 8 _top of microprojection connecting 8b, among the distance measured from each section , The maximum value is the height h of the minute projections. In the case with the fine irregularities on top of microprojection, the vertex height h is the highest measured to determine the height h as the vertex 8 _top of microprojections.
Among the plurality of minute projections arranged on the inner surface of the recess, the minute projections adjacent to each other refers to the cross section of the inner surface of the plurality of recesses obtained in the same manner as the case where the height h is obtained for a certain minute projection. The microprojection located adjacent to the certain microprojection in at least one cross section is defined as a microprojection adjacent to the certain microprojection.
The distance d between adjacent microprojections is, as shown in FIG. 6, the distance between adjacent microprojections in the cross section of the inner surface of the concave portion cut in the direction of planting the microprojections so as to pass through each vertex 8 _top of the adjacent microprojections. the distance between the vertices _{8 top} of the protrusion.
When there is fine unevenness at the base of the fine projections with a height difference of less than 0.1 μm, the fine unevenness is assumed to be a plane connecting the valleys of the unevenness, and the width w and the height h of the fine projections are assumed. Ask for.
The width w and height h of the microprojections and the distance d between the adjacent microprojections can be measured by cross-sectional profile analysis. The average d _AVG of the distance d between adjacent microprojections is obtained from the frequency distribution of the distance d between adjacent microprojections.
On the inner surface of one recess, the plurality of microprojections may have the same shape or different shapes.

The inner surface of the concave portion has an arithmetic mean height (Sa) of 1 μm or more and 50 μm or less, and particularly preferably 5 μm or more and 40 μm or less, and more preferably 10 μm or more and 35 μm or less from the viewpoint of improving the effect of inhibiting mold growth. Is more preferred.
In the present invention, the arithmetic mean height (Sa) of the inner surface of the concave portion is a 3D measuring laser microscope (for example, Olympus) capable of performing a plane correction and 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) manufactured by the company. In the present invention, the arithmetic mean height (Sa) of the inner surface of the concave portion is a square region located closest to the center of the concave portion among the largest squares inscribed in the outline of the opening portion of the concave portion in plan view. Is the arithmetic average height (Sa) measured in.

In the present invention, when measuring the surface having the uneven surface structure of the mold growth suppressing member, the surface having the uneven surface structure of the mold growth suppressing member to be measured is a square or rectangular within 1 m square. In the case, the measurement is performed using the mold proliferation 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. Preferably, the measurement is performed using a measurement sample cut into the largest inscribed square or rectangle.
In the present invention, when measuring the surface having the uneven surface structure of the measurement sample, as shown in FIG. 7, of the entire surface A having the uneven surface structure of the measurement sample, the central area 1 mm square area a 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, a 1 mm square region b, c, d, e in the middle from the center to the diagonal end portion The measurement is preferably performed using a total of five regions.

Further, in the mold propagation suppressing member according to the present invention, the number of the recesses per unit area in plan view of the uneven surface structure is appropriately determined by a combination of the size, depth, and distance between adjacent recesses of the recesses. Although it is adjusted and not particularly limited, it is preferably at least 20 cells / cm ^2, more preferably at least 50 cells / cm ^{2, and at} least 150 cells / cm ² from the viewpoint of improving the effect of inhibiting mold reproduction. more preferably more that it is, also 1 preferably thousands at / cm ² or less, more preferably 5000 / cm ² or less, and still further preferably 1000 / cm ² or less.

  Further, in a plan view of the uneven surface structure, the area occupancy of the concave portion with respect to the entire area of the uneven surface structure is preferably 55% or more, and more preferably 65% or more, from the viewpoint of the effect of suppressing mold growth. Is more preferably 70% or more, and on the other hand, it is preferably 95% or less, and more preferably 93% or less.

  In the uneven surface structure, the top of the projection surrounding the entire periphery of the recess is typically a substantially flat surface, but may have a ridge. The substantially flat surface means that the concave portion may have, for example, scratches or fine irregularities derived from a material, such as 1/100 or less of the lower limit of the depth of the concave portion. Further, the mold propagation suppressing member of the present invention may have a curved surface or ridges on the surface of the member itself.

In addition, the surface having the uneven surface structure of the mold growth suppressing member of the present invention may include a concave portion different from the specific concave portion as long as the effect of the present invention is not impaired.
In the mold growth suppressing member of the present invention, in the region having the concave-convex surface structure, the area where the specific concave portion is arranged at the specific distance between the concave portions is preferably 70% or more, and more preferably 80% or more. %, More preferably 90% or more.

(Fine irregularities layer)
The mold growth suppressing member according to the present invention may be configured such that the 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. It may be formed of the same material and formed on the surface of a fine uneven layer integrated with the base material, or may be formed on the surface of a single-layer fine uneven layer without a base material It may be. In addition, the mold proliferation control member according to the present invention may be one in which the protrusion made of a material different from the base material is disposed on the base material.

The material of the fine uneven layer is not particularly limited as long as the material can form the uneven surface structure, and can be appropriately selected depending on the application. You may. 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 uneven surface structure, the fine uneven layer has a reduced content of an additive having an antibacterial or antifungal effect. And further do not contain additives having an antibacterial or antifungal effect.
The fine uneven layer may be a single layer or a multilayer.

Among them, a resin composition is preferable as the material of the fine uneven layer, from the viewpoint of forming a fine uneven layer capable of maintaining the shape of the uneven surface structure for a longer period of time.
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, curing conditions such as temperature and time for solidifying or curing the resin composition, the uneven surface structure does not change. It can be adjusted to be within the range.
The fine irregularities layer, among others, is formed of a solidified thermoplastic resin composition, or may be formed of a cured product of an ionizing radiation-curable or thermosetting resin composition, the shape of the irregular surface structure Is preferable in that it can be held for a longer period of time, and in particular, it is preferably made of a solidified thermoplastic resin composition in terms of simplicity of production, and abrasion resistance, scratch resistance, and durability. .

Examples of the resin include, but are not particularly limited to, thermoplastic resins such as polyamide, polyolefin, polyvinyl chloride, (meth) acrylate, polyester, polycarbonate, polyethylene, polypropylene, and polystyrene; Ionizing radiation curable resins such as meth) acrylate, epoxy, and polyester; thermosetting resins such as melamine, phenol, polyester, (meth) acrylate, urethane, urea, epoxy, and polysiloxane Resins.
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 uneven surface structure. 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 of 100 parts by mass of the resin contained in the resin composition is preferably Can be not more than 10 parts by mass, more preferably not more than 5 parts by mass, still more preferably not more than 1 part by mass, and may not contain a (meth) acrylate-based resin.

As the resin composition used in the present invention, among others, a thermoplastic resin composition containing a thermoplastic resin is preferable. For example, by molding the thermoplastic resin composition into a desired shape and forming the uneven surface structure on the surface thereof, the surface of the fine uneven layer made of the solidified thermoplastic resin composition has the uneven surface structure. The mold propagation suppressing member of the present invention can be easily manufactured at low cost. Furthermore, when the mold growth suppressing member of the present invention has the above-mentioned uneven surface structure on the surface of the fine uneven layer made of a solidified thermoplastic resin composition, the abrasion resistance and the scratch resistance are excellent, and the durability is improved. I do. Therefore, the mold propagation suppressing member according to the present invention having the fine uneven layer made of the solidified thermoplastic resin composition is suitably used even in applications where human hands come into contact.
Further, the thermoplastic resin can be solidified without using a dissolvable additive such as a curing agent. Therefore, when the mold growth suppressing member of the present invention has a fine uneven layer made of a solidified thermoplastic resin composition, in the fine uneven layer, the content of an elutable additive such as a curing agent is reduced. And preferably contains no dissolvable additive such as a curing agent. Therefore, the mold growth suppressing member according to the present invention having the fine uneven layer made of the solidified thermoplastic resin composition is suitably used in life science-related applications such as food and medicine. The same effect as described above can be obtained also when the mold growth suppressing member of the present invention has the above-mentioned uneven surface structure on the surface of a molded product made of a solidified thermoplastic resin composition.
Examples of the thermoplastic resin include, among others, low-density polyethylene, linear low-density polyethylene (linear polyethylene), medium-density polyethylene, high-density polyethylene, and ultra-high-molecular-weight polyethylene from the viewpoint of mechanical strength, heat resistance, and scratch resistance. Polyethylene, such as, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyesters such as polyarylate, among others, polyethylene-based thermoplastic resin is preferred, Low density polyethylene or linear low density polyethylene (linear polyethylene) is particularly preferred.

  As the resin composition, an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin or a thermosetting resin composition containing a thermosetting resin may be used. By using the ionizing radiation-curable resin composition or the thermosetting resin composition, a concave portion 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. Examples of the other components include a stabilizer, an antifoaming agent, an anti-repellent agent, an antioxidant, an anti-agglomeration agent, a viscosity modifier, and a release agent.
Since the mold growth suppressing member according to the present invention can obtain a mold growth suppressing effect by the uneven surface structure, the resin composition can have a reduced content of an antibacterial agent and an antifungal agent. . 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.

  In the resin composition, the content of the component containing fluorine or silicon is preferably 1% by mass or less, and more preferably 0.1% by mass or less based on the total solid content of the resin composition. More preferably, it is even more preferably 0.01% by mass or less. If the component containing fluorine or silicon contained in the resin composition is too large, it may be difficult to form the minute projections on the inner surface of the recess.

  The resin composition may be composed of only a resin. As the thermoplastic resin composition, the one composed of only the thermoplastic resin has no elution of the additive from the solidified product, and can be suitably used for life science-related applications such as food and medical treatment. It is also preferable from the viewpoints of abrasion resistance, abrasion resistance and durability of the solidified product.

When the mold proliferation suppressing member according to the present invention is such that the convex portion made of a material different from that of the substrate is arranged on a substrate, the material of the convex portion may be, for example, the fine The same material as the material of the uneven layer can be used.
Further, in the mold propagation suppressing member of the present invention, the surface having the 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 having the uneven surface structure 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.
When the base and the fine uneven layer or the convex portion 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 is used. Among them, a thermoplastic resin composition is 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 uneven surface structure is formed on a fine uneven layer made of a material different from the base material, the adhesion between the base material and the fine uneven layer is improved, and abrasion resistance and scratch resistance are improved. A primer layer for improvement may be formed on the 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.

In addition, when the mold growth suppressing member according to the present invention is installed on a glass portion, the base material or the entire mold growth suppressing member may be formed of a solidified thermoplastic resin composition, and may have shatter resistance at the time of glass breakage. Is preferred from the viewpoint of imparting
The mold growth suppressing member made of a solidified thermoplastic resin composition is excellent in abrasion resistance and scratch resistance, has improved durability, and is preferable in that it is suitably used in applications where human hands come into contact with it. .

The mold propagation suppressing member according to the present invention may further include an adhesive layer. The adhesive layer is typically located on a surface that does not have the 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).

  In addition, the mold propagation suppressing member according to the present invention is not particularly limited, but from the viewpoint of excellent mechanical strength of the mold propagation suppressing member, the pencil hardness on the surface having the uneven surface structure is preferably H or more. And more preferably 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) can be performed by performing a pencil hardness test (load: 0.98 N) on the surface of the measurement sample having the above-mentioned uneven surface structure, and evaluating the highest pencil hardness without scratching. In the measurement, for example, a pencil scratching film hardness tester manufactured by Toyo Seiki Co., Ltd. can be used.

  In addition, the mold growth suppressing member according to the present invention is not particularly limited, but from the viewpoint of excellent mechanical strength and excellent wear resistance, the surface having the uneven surface structure is JIS K 7204: Increased haze after performing a 1000-rotational wear test with a wear wheel CS-17 at a 9.8 N load (1,000 gf) in accordance with the wear test method using a plastic-wear wheel specified in 1999. The value (△ 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 the above-mentioned uneven surface structure on one surface of a sheet-like substrate or a fine uneven layer, The substrate may have the above-mentioned uneven surface structure on both sides of a sheet-like substrate or a fine uneven layer. In addition, 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 the uneven surface structure on the entire surface, or may have the uneven surface structure 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 forming a thermoplastic resin composition, forming the uneven surface structure on the surface thereof, forming a coating film of the curable resin composition on a base material, and forming the uneven surface structure on the coating film surface. A method of shaping and curing, a method of forming a coating film of the ionizing radiation-curable resin composition on a substrate, a method of forming a cured film having the pattern of the uneven surface structure by photolithography, and cutting a surface of the substrate by cutting tool To form the uneven surface structure.

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 uneven surface structure on the surface of a thermoplastic resin layer formed in advance or a molten thermoplastic resin layer heated and melted can be preferably used.
Among them, from the viewpoint of production efficiency, as the first manufacturing method,
A step of preparing a thermoplastic resin layer made of a solidified thermoplastic resin composition containing a thermoplastic resin,
Forming a concave-convex surface structure on the surface of the thermoplastic resin layer,
The method for producing a mold growth suppressing member, wherein the uneven surface structure is the uneven surface structure of the mold growth suppressing member of the present invention described above, can be preferably used.

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 an uneven surface structure on the surface of the molten thermoplastic resin layer,
While forming the uneven surface structure, or after forming the uneven surface structure, a step of solidifying by cooling the molten thermoplastic resin layer,
A method for producing a mold growth suppressing member, wherein the uneven surface structure is the uneven surface structure of 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. When the thermoplastic resin layer 4a passes through the surface structure forming masters 6a and 6b having a surface shape for forming the uneven surface structure, the uneven surface structure is formed on at least one surface of the molten thermoplastic resin layer 4a. The mold propagation suppressing member 10 is obtained by cooling the formed thermoplastic resin layer 4a. The obtained mold propagation suppressing member 10 is taken up by the take-up roll 7. In the method shown in FIG. 8, the surface structure forming original plates 6a and 6b may also function as cooling rolls. In this case, while forming the uneven surface structure on the molten thermoplastic resin layer 4a, The molten thermoplastic resin layer 4a can be cooled and solidified.

  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 first production method and 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, It is not particularly limited, and is appropriately adjusted according to the type of the 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 can be a known method, and is not particularly limited, and for example, a T-die method or the like can be used.
Further, in the first manufacturing method, as a method of forming an uneven surface structure on the surface of the thermoplastic resin layer, a known method can be used, and is not particularly limited. For example, a surface structure forming original plate may be used. The high-temperature high-pressure compression molding method or embossing used is used.

In the second manufacturing method, as a method for forming the molten thermoplastic resin layer, a known method can be used, and there is no particular limitation. For example, a T-die method or the like can be used.
In the second manufacturing method, the method of forming the uneven surface structure on the surface of the molten thermoplastic resin layer is not particularly limited, but a method of shaping using a surface structure forming original plate is preferable. .

In the present invention, the surface structure forming master used in forming the uneven surface structure may be in the form of a roll or a flat plate, but from the viewpoint of production efficiency, a roll may be used. Is preferred.
As the material for the surface structure forming original plate, a known material that has been conventionally used for a printing plate can be used, and it is not particularly limited. Even if it is made of metal, it can be made of resin. However, a metal surface structure forming master is preferably used because of its excellent deformation resistance and abrasion resistance.
Further, it is preferable that the surface structure forming original plate has not been subjected to a release treatment on its surface. For example, it is preferable that the material of the surface of the original plate and the material of the base material are the same. By using a surface structure forming master not subjected to a mold release treatment on the surface, the peelability when the surface structure forming master is separated from the molten thermoplastic resin layer or the thermoplastic resin layer is appropriately deteriorated. In addition, the minute projections are easily formed on the inner surface of the recess formed in the thermoplastic resin layer, and the uneven surface structure can be easily formed.

In the first manufacturing method, the temperature of the thermoplastic resin layer at the time of forming the uneven surface structure on the surface of the thermoplastic resin layer includes the flexibility of the thermoplastic resin layer, the uneven shape of the surface structure forming original plate, and the like. It is preferably adjusted within the range of 100 ° C. or more and 400 ° C. or less from the viewpoint of excellent moldability and handleability.
In the second manufacturing method, the temperature of the molten thermoplastic resin layer at the time of forming the uneven surface structure on the surface of the molten thermoplastic resin layer, the flexibility of the molten thermoplastic resin layer, the unevenness of the surface structure forming original plate The temperature is appropriately adjusted depending on the shape and the like, and is not particularly limited, but is preferably in the range of 150 ° C. or more and 400 ° C. or less from the viewpoint of excellent moldability and handleability.

  Further, in the first manufacturing method, before the step of forming an uneven surface structure on the surface of the thermoplastic resin layer, further comprising a step of stretching the formed thermoplastic resin layer at least uniaxially, It 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 120 ° C. or less.

  Forming a coating film of the curable resin composition on a substrate, by shaping and curing the uneven surface structure on the coating film surface, as a method for producing a mold growth suppressing member of the present invention, for example, Prepare a surface structure forming master having a surface having an uneven shape corresponding to the uneven surface structure, and prepare the surface having the uneven shape of the surface structure forming master on a coating surface of a curable resin composition. After pressing, the curable resin composition is cured, and then the surface structure forming master is peeled off.

  Forming a coating film of the ionizing radiation-curable resin composition on a substrate, by forming a cured film having a pattern of the uneven surface structure by photolithography, as a method for producing a mold propagation suppressing member of the present invention For example, there is 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 required. The pattern exposure may be performed so as to form a pattern corresponding to the planar shape of the uneven surface structure, for example, a method of exposing through a photomask, a laser drawing method, or the like may be used. it can.

<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 uneven surface structure on the surface of these various articles, the articles can be used as the mold propagation 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, for a container or packaging material for foods, medicines, etc., the inside, outside, or both inside and outside surfaces are provided with the uneven surface structure so that the container or packaging material suppresses mold propagation according to the present invention. It can also be a 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, the inner surface of the space for accommodating food is a surface having the uneven surface structure. 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 uneven surface structure, from the viewpoint of improving the mold propagation suppressing effect, and a space for accommodating a container. Is more preferably a surface having the 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. 13 and 14 show an example in which the mold growth suppressing member of the present invention is used as the roofing material 61 of the carport 60. As shown in FIG. 14, both surfaces of the roofing material 61 of the carport 60 have the uneven surface structure. Surface.

  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 Cultivation-Basic Technology Supporting Plant Factories Japan Institute of Horticulture Association (edited), Japan 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 planar shape of the opening of the concave portion, the major axis φ1, the minor axis φ2, and the distance D between adjacent concave portions were photographed in a plan view using an optical microscope (manufactured by Olympus Corporation, product name BX53M). It was measured from an optical micrograph.
The depth H of the concave portion, the width w, the height h, and the distance d between the adjacent fine protrusions of the fine protrusions arranged on the inner surface of the concave portion are cross-sectional profiles using a laser microscope (OLYMPUS Corporation, LEXT OLS4100). Measured by analysis. The average D _AVG of the distance D between adjacent concave portions and the average d _AVG of the distance d between adjacent microprojections were determined from the frequency distribution of the measured values.
The arithmetic average height (Sa) of the inner surface of the concave portion is 20 × in an environment of 23 ° C. to 25 ° C. using a laser microscope (manufactured by Olympus Corporation, LEXT OLS 4000) according to ISO25178. Measured using The measurement area of the arithmetic average height (Sa) was a square area located closest to the center of the recess among the largest squares inscribed in the contour of the opening of the recess. When the measurement surface was a curved surface in the laser microscope measurement, the arithmetic mean height (Sa) was calculated after performing plane correction.
Further, when measuring the surface having the uneven surface structure, the uneven surface structure of the measurement sample was measured as shown in FIG. 7 using a measurement sample obtained by cutting the obtained mold growth suppressing member into a size of 1 m square. From the center to the diagonal end on each diagonal line when the area a of 1 mm square at the center, the first diagonal line L1 passing through the center, and the diagonal line L2 orthogonal to the diagonal line L1 are drawn out of the entire surface A having The measurement was performed using a total of five areas of 1 mm square areas b, c, d, and e in the middle of the above. Further, the inner surface of the concave portion was measured for five concave portions arbitrarily selected from the region. The arithmetic average height (Sa) of the inner surface of the concave portion was obtained as an average value of Sa measured in a plurality of concave portions. At the time of microscopic observation, the measurement sample was placed on a horizontal table and observed.

[Example 1: Production of a mold propagation suppressing member]
Using a manufacturing apparatus as shown in FIG. 8, a low-density polyethylene (Novatec LD, manufactured by Nippon Polyethylene Co., Ltd.) heated and melted from a T-die film forming machine into a 80 μm thick sheet at a resin temperature of 205 ° C. The mold was extruded to form an uneven surface structure on one surface by using a surface structure forming master not subjected to a mold release treatment, thereby obtaining a mold growth suppressing member of Example 1 consisting of a solidified thermoplastic resin. .
FIG. 17 shows an optical microscope photograph of the surface having the uneven surface structure of the mold growth suppressing member obtained in Example 1. The photographing conditions of the optical microscope photograph shown in FIG. 17 are as follows.
Scanning mode: XYZ high accuracy + color Image size [pixel]: 1024 × 1024
Image size [μm]: 644 × 647
Objective lens: MPLAPONLEX20
Zoom: 1X
The concave-convex surface structure formed on the surface of the mold propagation suppressing member obtained in Example 1 has a plurality of concave portions arranged, and the planar shape of the opening of each concave portion has a major axis φ1 of 850 μm ± 42.5 μm. (Average: 850 μm), the minor axis φ2 is a rhombus of 460 μm ± 23 μm (average: 460 μm), the average D _AVG of the distance D between adjacent concave portions is 533 μm, and the depth H of the concave portions is 135 μm ± 13.5 μm (average). 135 μm). The major axis φ1 and minor axis φ2 of the shape of the opening of the recess shown in Table 1 in plan view and the depth H of the recess are average values, respectively. The arithmetic mean height (Sa) of the inner surface of the recess was 13.2 μm.
In addition, the mold propagation suppressing member obtained in Example 1 has, on the inner surface of each recess, a width w in the range of 0.3 μm to 10 μm and a height h in the range of 1 μm to 70 μm. And the average d _AVG of the distance d between the adjacent micro projections was 2.1 μm.
In the mold propagation suppressing member obtained in Example 1, the area occupation ratio of the concave portion to the entire area of the uneven surface structure was 89.2% in plan view of the uneven surface structure.

[Examples 2 to 6, Comparative Example 2]
Using a manufacturing apparatus as shown in FIG. 8, linear polyethylene (LLDPE) is extruded from a T-die film forming machine at a resin temperature of 205 ° C. into a sheet having a thickness of 50 to 100 μm, and a release treatment is performed. Example 2 comprising a solidified thermoplastic resin, using a master for forming a surface structure having no irregularities, on one surface, forming an uneven surface structure in which a plurality of recesses are arranged in the shape and arrangement shown in Table 1. 6 and a member of Comparative Example 2 were obtained.
Table 1 shows the concave-convex surface structures of the mold propagation suppressing member obtained in Examples 2 to 6 and the member obtained in Comparative Example 2 in plan view of the opening of the concave portion, the major axis φ1, the minor axis φ2, and the concave portion. Of the depth H, the average D _AVG of the distance D between adjacent recesses, the arithmetic average height (Sa) of the inner surface of the recess, the range of the width w of the microprojections on the inner surface of the recess, the range of the height h, and the adjacent The average d _AVG of the distance d between the small projections and the area occupancy of the concave portion with respect to the entire area of the uneven surface structure in plan view are shown. In addition, in the mold propagation suppressing member obtained in Examples 2 to 6, the variation of the major axis φ1 and the minor axis φ2 is 10% or less of the average value, and the variation of the depth H of the concave portion is 30% or less of the average value. there were.

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

[Comparative Example 3]
A member of Comparative Example 3 was obtained in the same manner as in Example 1 except that the surface of the surface structure forming original plate was subjected to a release treatment. In the member obtained in Comparative Example 3, the shape of the opening of the concave portion, the depth of the concave portion, and the arrangement of the concave portion were the same as those in Example 1, but the inner surface of the concave portion was the mold propagation obtained in Example 1. Unlike the suppression member, the surface was smooth.

[Comparative Example 4]
In the same manner as in Example 1 of JP-A-2016-210164, a member of Comparative Example 4 having a so-called moth-eye structure on the surface was obtained. The member obtained in Comparative Example 4 has, on its surface, a microprojection structure provided with a group of microprojections in which a plurality of microprojections having an average height of 160 nm are closely arranged, and a distance between adjacent microprojections. Was 200 nm, and the envelope surface connecting the valley bottoms between the microprojections had a wavy shape.

[Mold resistance test]
The following procedure was followed for the mold propagation suppressing member obtained in each example, the PET base material of Comparative Example 1, and the member obtained in Comparative Examples 2 to 4 in accordance with JIS Z 2911: 2010 "Test of plastic products". A mold resistance test was conducted. 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 members obtained in each of Examples and Comparative Examples 2 to 4, and disinfecting one surface of the PET substrate of Comparative Example 1 with ethanol, and cutting the surface into 50 mm square. Was prepared.
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 mold growth was observed with the naked eye and under the microscope 1: Mold growth was not observed under the naked eye, but was clearly confirmed under the microscope 2: Mold growth was observed under the naked eye, and the area of the developed portion was Less than 25% of the total area of the sample 3: Mold growth was observed with the naked eye, and the area of the growing part was 25% or more and less than 50% of the total area of the sample 4: Mycelium grew well, and the area of the growing part was 50% or more of the total area 5: Mycelia grew vigorously and covered the entire surface of the sample. In Table 1, a test performed without adding 10% glucose peptone medium was referred to as "without addition of GP broth". The test performed with the addition of the% glucose peptone medium is indicated as GP broth addition 10%.

In addition, FIG. 18 shows an optical microscope photograph of the surface of the mold proliferation suppressing member obtained in Example 1 after 4 weeks of culture in a test performed without adding a 10% glucose peptone medium in the mold resistance test. FIG. 19 shows an optical micrograph of the surface of the mold growth suppressing member obtained in Example 1 after 4 weeks of culture in a test performed by adding 10% glucose peptone medium.
On the other hand, FIG. 20 shows an optical micrograph of the surface of the PET substrate of Comparative 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 an optical micrograph of the surface of the PET substrate of Comparative Example 1 after 4 weeks of culture in a test in which a glucose peptone medium was added.

(Summary of results)
In the above mold resistance test performed in a wet state at a temperature of 26 ± 2 ° C. and a humidity of 95% RH or more and 99% RH or less, the members of Comparative Examples 1 to 3 showed two levels of hypha based on the above criteria after 2 weeks of culture. After 4 weeks of cultivation, three levels of hyphal growth were observed on the basis of the above criteria. In the member of Comparative Example 4, two weeks after culturing, one level of mycelial growth was observed on the basis of the above criteria. After 4 weeks, 1-2 levels of hyphal growth were observed based on the above criteria.
On the other hand, the mold growth suppressing member of the present invention obtained in each of the examples shows that in the mold resistance test performed in the same wet state as the comparative example, no growth of hypha was observed after 2 weeks of culture. Even after 4 weeks of culturing, no hyphal growth was observed or at one level based on the above criteria. 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 uneven surface structure of the mold propagation suppressing member obtained in each of the examples, a wear wheel CS-17 was used in accordance with a wear test method using a plastic-wear wheel specified in JIS K 7204: 1999. , 9.8 N load (1,000 gf), a 1000-rotation wear test was performed, and the difference in haze value before and after the wear test (△ haze value (%)) was determined. The wear test was performed using a rotary abrasion tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.). Each of the mold propagation suppressing members obtained in each of the examples had an increased haze value (△ haze value) after the abrasion test of 20% or less.

[Reference: Antibacterial test]
The mold growth suppressing member obtained in Example 1 and the PET base material of Comparative Example 1 were cut to obtain test pieces each having a size of 5 cm square. Escherichia coli was used as a test bacterium. In accordance with JIS Z2801: 2010, the test bacterial solution was dropped on the surface of the test piece of Example 1 having an uneven surface structure and one surface of the test piece of Comparative Example 1, respectively, and the test immediately after inoculation of the test bacterial solution The viable cell count (viable cell count before the test) of each piece 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 2 shows the antibacterial activity value calculated from the measured values by the following formula.
Antibacterial activity value = log (viable cell count after culture of test piece of Comparative Example 1) -log (viable cell number after culture 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.

  As shown in Table 2, 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 as compared with a flat PET substrate. Accordingly, it was revealed that the mold propagation suppressing member of the present invention has an effect of suppressing propagation specifically for mold among microorganisms.

REFERENCE SIGNS LIST 1 convex portion 2 concave portion 3 base material 4 fine uneven layer 4a molten thermoplastic resin layer 5 T-die extruder 6a, 6b original plate for surface structure formation 7 take-up roll 8 minute protrusion 10 mold growth suppressing member 11 ceiling portion 12 wall portion 13 Soil surface (reflective sheet)
Reference Signs List 20 greenhouse 21 reflection sheet 22 light source 30 plant cultivation unit 31 packaging material 32 take-out port 40 container 50 packaging material 60 car port 61 roofing material

Claims (2)

Having a concave-convex surface structure in which a plurality of concave portions surrounded by convex portions are arranged,
In the concave portion, the major axis φ1 of the opening is 100 μm or more and 1500 μm or less, the minor axis φ2 of the opening is 100 μm or more and 1500 μm or less. The average D _AVG of the distance D between the concave portions is 110 μm or more and 3000 μm or less,
The opening area of the recess gradually decreases from the opening of the recess toward the deepest portion, and the depth H of the recess is 10 μm or more and 500 μm or less,
On the inner surface of the concave portion, there is provided a microprojection group in which a plurality of microprojections are arranged, and the microprojections have a width w of 0.1 μm or more and 20 μm or less, and a height h of 0.1 μm or more and 100 μm or less. The average d _AVG of the distance d between the adjacent minute projections is 0.1 μm or more and 20 μm or less;
A mold propagation suppressing member, wherein an arithmetic average height (Sa) of an inner surface of the concave portion is 1 μm or more and 50 μm or less.   2. The mold propagation suppressing member according to claim 1, wherein, in a plan view of the uneven surface structure, an area occupancy of the concave portion with respect to the entire area of the uneven surface structure is 55% or more and 95% or less. 3.