JP2016043030A - Powder cosmetic container and tester display stand for powder cosmetics - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder cosmetic container in which the adherence of powder cosmetics is suppressed.SOLUTION: A powder cosmetic container includes a container body with a storage part for storing cosmetics including powder and a lid for closing the container body. The powder cosmetic container is configured as follows: at least a portion of the internal surface of the powder cosmetic container has a microprotrusion structure with a microprotrusion group formed by closely disposing multiple microprotrusions comprising cured materials of resin composition; an average of distance between the adjacent microprotrusions is 500 nm or less; and the microprotrusions has a structure in which a cross-sectional area occupancy of a material portion forming the microprotrusions in the horizontal section at the time when assuming that it is cut with a horizontal plane perpendicular to the depth direction of the microprotrusions increases continuously and gradually as approaching the deepest part direction from the top part of the microprotrusions.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a powder cosmetic container and a tester display stand for powder cosmetic.

  Powder cosmetics such as foundations and eye shadows are generally accommodated in containers called compacts. As a typical example of the compact, a container main body integrally or individually having a concave portion for accommodating one or more powder cosmetics and a concave portion for accommodating a cosmetic tool such as a brush as needed, and the container main body The container body and the lid are connected to each other via a hinge so as to be opened and closed. In addition, a mirror may be disposed on the inner surface of the lid.

The internal surface of the compact containing the powder cosmetic is in contact with the powder cosmetic at all times or by vibration or the like. As a result, powder cosmetics may adhere to the internal surface. Further, when the powder cosmetic is used, the powder cosmetic flies hollow and may eventually adhere compactly.
In addition, in the case of cosmetics over-the-counter sales, powder cosmetic testers are displayed and customers may be able to try powder cosmetics on the spot. Part of the powder cosmetics tried in such a sales method may adhere to the display stand.
The compact and display stand to which the powder cosmetic is attached deteriorates in appearance, and when the powder cosmetic is attached to the surface on which the mirror is disposed, the visibility of the mirror is deteriorated.

  Conventionally, it is known to arrange a protective sheet between a powder cosmetic and a compact lid or the like. For example, Patent Document 1 discloses a specific compact container with a protective sheet in which a folding surface portion of a protective sheet is sandwiched between a concave portion of a container body and an inner dish filled with cosmetics.

  In Patent Document 2, as a technique for imparting antifogging properties to a mirror provided on the inner surface of a container, a technique for coating a cured product of a coating composition containing polyvinyl alcohol and a crosslinking agent on the surface of the mirror is disclosed. Yes. However, the technique of Patent Document 2 suppresses fogging due to water droplets and does not suppress adhesion of powder.

  Patent Document 3 discloses a specific polyamide system in which a layer made of a specific aliphatic polyamide composition is disposed on the outermost layer as a technique that is excellent in antistatic properties and makes it difficult to electrostatically adhere powder, dust, and the like. A film is disclosed.

JP 2012-143293 A Japanese Utility Model Laid-Open No. 5-18411 JP 2012-61851 A

  An object of the present invention is to provide a powder cosmetic container and a powder cosmetic tester display stand in which adhesion of the powder cosmetic is suppressed.

  The powder cosmetic container according to the present invention is a powder cosmetic container comprising a container body provided with a container for containing cosmetic containing powder, and a lid for closing the container body, At least a part of the inner surface of the powder cosmetic container has a microprojection structure provided with a microprojection group in which a plurality of microprojections made of a cured product of a resin composition are closely arranged, and adjacent to each other. The average distance between the microprotrusions is 500 nm or less, and the material that forms the microprotrusions in a horizontal cross section when the microprotrusions are cut along a horizontal plane perpendicular to the depth direction of the microprotrusions. It is characterized by having a structure in which the cross-sectional area occupancy of the portion continuously and gradually increases from the top of the microprotrusion toward the deepest portion.

  In the powder cosmetic container of the present invention, it is easy to manufacture that a mirror is provided inside the container, and a member having the microprojection structure is attached to the surface of the mirror. From the point of view, it is preferable.

  The powder cosmetic tester display stand according to the present invention is a powder cosmetic tester display stand provided with a tester storage portion for storing a cosmetic tester containing powder, and further capable of opening and closing the upper surface of the tester storage portion. The surface of the display stand and at least a part of the inner and outer surfaces of the lid may be closely arranged with a plurality of minute projections made of a cured resin composition. It has a microprojection structure including a microprojection group, the average distance between adjacent microprojections is 500 nm or less, and the microprojections are cut along a horizontal plane perpendicular to the depth direction of the microprojections. It is characterized by having a structure in which the cross-sectional area occupancy rate of the material portion forming the microprotrusions in the horizontal cross section when assumed is gradually increased gradually from the top of the microprotrusions toward the deepest part.

  According to the present invention, it is possible to provide a powder cosmetic container and a powder cosmetic tester display stand in which adhesion of the powder cosmetic is suppressed.

FIG. 1 is a schematic view showing an example of a powder cosmetic container according to the present invention. FIG. 2 is a schematic view showing an example of a powder cosmetic tester display stand according to the present invention. FIG. 3 is a schematic cross-sectional view showing an example of a member having a microprojection structure on its surface. FIG. 4 is a schematic cross-sectional view showing another example of a member having a microprojection structure on its surface. FIG. 5 is a cross-sectional view (a), a perspective view (b), and a plan view (c) for explaining multi-modal microprotrusions. FIG. 6 is a perspective view (a) and a plan view (b) of a convex protrusion group constituted by a plurality of minute protrusions. FIG. 7 is an enlarged photograph showing an example of a microprojection structure obtained by an atomic force microscope. FIG. 8 is a diagram showing the maximum points of the microprojections in the example of the microprojection structure in FIG. FIG. 9 is a diagram showing a Delaunay diagram in the example of the microprojection structure in FIG. 7. FIG. 10 is a histogram of the frequency distribution of the distance between adjacent maximum points created from the Delaunay diagram of FIG. FIG. 11 is a histogram of the frequency distribution of the microprojection height in the example of the microprojection structure in FIG. FIG. 12 is a schematic cross-sectional view showing another example of the microprojection structure. FIG. 13 is a schematic view showing an example of a method for forming a microprojection structure using a roll mold.

  The powder cosmetic container according to the present invention is a powder cosmetic container comprising a container body provided with a container for containing cosmetic containing powder, and a lid for closing the container body, At least a part of the inner surface of the powder cosmetic container has a microprojection structure provided with a microprojection group in which a plurality of microprojections made of a cured product of a resin composition are closely arranged, and adjacent to each other. The average distance between the microprotrusions is 500 nm or less, and the material that forms the microprotrusions in a horizontal cross section when the microprotrusions are cut along a horizontal plane perpendicular to the depth direction of the microprotrusions. It is characterized by having a structure in which the cross-sectional area occupancy of the portion continuously and gradually increases from the top of the microprotrusion toward the deepest portion.

  The powder cosmetic tester display stand according to the present invention is a powder cosmetic tester display stand provided with a tester storage portion for storing a cosmetic tester containing powder, and further capable of opening and closing the upper surface of the tester storage portion. The surface of the display stand and at least a part of the inner and outer surfaces of the lid may be closely arranged with a plurality of minute projections made of a cured resin composition. It has a microprojection structure including a microprojection group, the average distance between adjacent microprojections is 500 nm or less, and the microprojections are cut along a horizontal plane perpendicular to the depth direction of the microprojections. It is characterized by having a structure in which the cross-sectional area occupancy rate of the material portion forming the microprotrusions in the horizontal cross section when assumed is gradually increased gradually from the top of the microprotrusions toward the deepest part.

In the following, the powder cosmetic container and the powder cosmetic tester display stand according to the present invention will be described first about the microprojection structure, which is a common feature, and then the powder cosmetic container and the powder cosmetic tester display stand Will be described in detail in order.
In the present invention, the term “adhesion” refers to a state in which two substances are in contact with each other and adhered by intermolecular force.

[Microprojection structure]
As described later, the powder cosmetic container of the present invention has a microprojection structure on at least a part of its internal surface. Moreover, the powder cosmetic tester display stand of the present invention, as will be described later, at least a part of the surface of the display stand and the inner and outer surfaces of the lid that the display stand may have a microprojection structure. Have.
The microprojection structure in the present invention includes a microprojection group in which a plurality of microprojections made of a cured resin composition is closely arranged, and the average distance between adjacent microprojections is 500 nm or less. The cross-sectional area occupancy of the material portion forming the microprojection in the horizontal cross section when the microprojection is cut along a horizontal plane perpendicular to the depth direction of the microprojection is from the top of the microprojection. It has a structure that increases gradually and gradually as it approaches the deepest direction.

The microprojection structure will be described with reference to the drawings. 3 and 4 are cross-sectional views each schematically showing an example of a member provided on the surface with a microprojection structure used in the present invention.
In the member 10 provided with the microprojection structure on the surface, the microprojection structure 2 includes a microprojection group in which microprojections 3 made of a cured product of the resin composition are closely arranged, and between adjacent microprojections. The average distance is 500 nm or less. By having such a microprojection structure 2 on the surface, even if it is a powder with a small particle size, adhesion is suppressed.
The member 10 having the microprojection structure on the surface may be formed as a microprojection layer using a material different from the base material 1 on the base material 1 as shown in FIG. Thus, it may be composed of only a microprojection layer. As an example of FIG. 4, the base material 1 and the microprojection layer may be integrally formed. After the microprojection layer is once formed on the base material 1, the base material 1 is removed. It may be a thing.

Since the powder cosmetic container and the powder cosmetic tester display stand according to the present invention of the present invention have the above-mentioned specific microprojection structure on the surface, adhesion of powder is suppressed.
The action of suppressing the adhesion of powder on the surface of the specific microprojection structure is unclear, but is presumed as follows.
Conventionally, there has been known a method for suppressing adhesion of relatively large objects such as dust by imparting antistatic properties. However, the present inventors have obtained the knowledge that the adhesion of powder having a small particle size cannot be sufficiently suppressed even on a surface provided with antistatic properties. As a result of intensive studies, it was found that powders with a small particle size are relatively affected by van der Waals forces as intermolecular forces. Van der Waals force is an agglomeration force generated between electrically neutral atoms and molecules. Therefore, even if antistatic properties are imparted to the surface, it is possible to obtain the effect of suppressing the adhesion of powder with a small particle size. There wasn't.
The microprojection structure used in the present invention has a microprojection structure including a microprojection group in which a plurality of microprojections are closely arranged, and the average distance between adjacent microprojections is 500 nm or less. The cross-sectional area occupancy rate of the material portion forming the microprojection in the horizontal cross section when it is assumed that the microprojection is cut in a horizontal plane orthogonal to the depth direction of the microprojection is the deepest direction from the top of the microprojection It has a structure that gradually increases gradually as it approaches. Since the microprojection group is formed by closely arranging a plurality of microprojections, the powder hardly enters between the microprojections. Further, when the powder comes into contact with the surface of the microprojection structure 2 as described above, the contact area is reduced. As a result, the van der Waals force generated between the surface of the microprojection structure 2 and the powder is relatively It is getting smaller. Therefore, even if it is a powder with a small particle size, adhesion is suppressed.

Each microprotrusion constituting the microprotrusion structure is formed so as to be planted, and the shape of the microprotrusion in the horizontal cross section when it is assumed that the microprojection is cut along a horizontal plane perpendicular to the depth direction of the microprotrusion. It has a structure in which the cross-sectional area occupancy ratio of the material part forming the protrusions gradually and gradually increases as it approaches the deepest part from the top of the minute protrusions, that is, each minute protrusion is tapered. Since the microprojection structure having such a tapered microprojection can reduce the contact area with the powder, the van der Waals force between the microprojection structure and the powder is reduced to reduce the powder. Body adhesion can be suppressed. Further, in the case of the tapered shape, there is an advantage that even if the powder enters between the fine protrusions, it is easy to come out.
Specific examples of the shape of such microprojections include those having a vertical cross-sectional shape such as a semicircular shape, a semi-elliptical shape, a triangular shape, a parabolic shape, and a bell shape. The plurality of microprotrusions may have the same shape or different shapes.

Furthermore, it is more preferable that the tops of the microprojections have a curved surface. Having a curved surface at the top means that the top has a curved surface shape such as a spherical shape, a spheroid shape, a rotating paraboloid shape, a bell shape, or a curved surface shape that can approximate these curved surface shapes. Say. In addition, in this invention, a top part is the concept which shows a vertex and its vicinity, and means the range of about 10% of the height H of the microprotrusion mentioned later from the vertex of a microprotrusion.
Since the microprotrusions have a curved surface at the top, the contact area of the powder can be made smaller than that having a flat top, which is excellent in the effect of suppressing the adhesion of powder.

In the present invention, a plurality of minute protrusions are closely arranged in the minute protrusion group. Since the minute protrusions are closely arranged, the powder hardly enters between the minute protrusions, and the adhesion of the powder is suppressed. Closely and in the present invention, or base positions of adjacent microprotrusions are in contact, means that close enough in contact, specifically, when the average value of the diameters of the section of the base position of the microprojections has a R _AVG In addition, R _AVG is preferably 80 to 100% of d _AVG , and more preferably 90 to 100%. The above R _AVG is R if the cross section at the base position of the microprojection is a circle, and if it is not a circle, the maximum and minimum values of the cross section width are obtained, and the average value is R. The average value is obtained.

In the present invention, the microprojection structure further has a plurality of apexes as microprojections (hereinafter sometimes referred to as “multimodal microprojections”), which improves the scratch resistance of the surface of the microprojection structure. This is preferable. Note that a microprojection having only one vertex may be referred to as a “unimodal microprojection” in comparison with a multimodal microprojection. Multi-peak microprojections are relatively thicker at the bottom of the apex than the single-peak microprojections, and receive external forces distributed over more vertices. It is considered that the external force applied to the apex can be reduced and the microprotrusions can be hardly damaged. Therefore, in the present invention, the mechanical strength and the scratch resistance are further improved by including multimodal microprojections in the microprojection group. Further, even if the microprojection is damaged, the area of the damaged portion can be reduced, and this can also reduce the local deterioration of the antireflection function and further reduce the appearance failure. Moreover, about half of the multimodal microprotrusions highest peak height (foot height of the highest peaks belonging to the same microprojections) is to produce the average value H _AVG or more microprojections of projection height, the external force First, each peak portion receives and sacrificial damage prevents the wear of the main body portion lower than the peak of the microprojection and the microprojection lower than the multi-peak microprojection. This also reduces local deterioration of the antireflection function and further reduces the occurrence of appearance defects.
In the present invention, the convex portions forming the top portions of the multimodal microprojections and the monomodal microprojections are appropriately referred to as “peaks”.

FIG. 5 is a cross-sectional view (FIG. 5 (a)), a perspective view (FIG. 5 (b)), and a plan view (FIG. 5 (c)) for explaining the multi-modal microprotrusions. Note that FIG. 5 is a diagram schematically showing for easy understanding, and FIG. 5A is a diagram showing a cross section by a broken line connecting the vertices of continuous microprotrusions. In FIG. 5, the xy direction is the in-plane direction of the substrate 1, and the z direction is the height direction of the microprojections. In the microprojection structure 2 shown in FIG. 5A, the unimodal microprojections 5 are, for example, gradually cross-sectional area (surface perpendicular to the height direction (FIG. 5 In FIG. 1, the cross-sectional area when cut along a plane parallel to the XY plane) is reduced, and one vertex is formed. On the other hand, as the multi-peak microprotrusions, for example, a groove g is formed at the tip portion as if a plurality of microprotrusions are combined, and the apex is two (3A), and there are three apexes. (3B), and those having four or more vertices (not shown). The shape of the unimodal microprotrusions 3 can be approximated by a round shape at the top like a paraboloid of revolution or a shape with a sharp apex like a cone. On the other hand, the shape of the multimodal microprotrusions 3A and 3B can be approximated by a shape in which a groove-shaped recess is cut in the vicinity of the top of the single-peak microprotrusion 3 and the top is divided into a plurality of peaks. it can. The shape of the multi-peak microprotrusions 3A and 3B has a plurality of maximal points when the longitudinal cross-sectional shape is cut by a virtual cut surface including a plurality of peaks and including the height direction (Z-axis direction in FIG. 5). The shape is approximated by an algebraic curve Z = a ₂ X ² + a ₄ X ⁴ +... + A _2n X ²ⁿ +.

  The ratio of the number of multimodal microprotrusions in the total microprotrusions existing on the surface of the microprotrusion structure is not particularly limited, but is 10% or more from the viewpoint of further suppressing the adhesion of powder. Is preferable, more preferably 30% or more, still more preferably 50% or more.

In addition, at least a part of the microprojection group constituting the microprojection structure is formed adjacent to the top microprojection and the periphery of the top microprojection, and the height is lower than the top microprojection. You may comprise the group of a group of microprotrusions (it calls a "convex-shaped protrusion group" in this invention) which consists of a some peripheral microprotrusion. By having the aggregate of the fine protrusions, the adhesion of the powder is further suppressed.
FIG. 6 shows a perspective view (FIG. 6 (a)) and a plan view (FIG. 6 (b)) of a convex projection group constituted by a plurality of minute projections. The convex projection group 22 shown in FIG. 6 includes a top microprojection 3C having a relatively high height and a plurality of peripheral microprojections 3D having a relatively low height arranged adjacent to the periphery thereof. FIGS. 6A and 6B are diagrams schematically shown for easy understanding, where the xy direction is the in-plane direction of the substrate, and the z direction is the height of the minute protrusion. Direction.
In the present invention, the top microprotrusion has a relatively higher height than the peripheral microprotrusions, and has a height difference of 10 nm or more, and the height difference is 20 nm or more. Is preferred. In addition, the difference in height is preferably 50 nm or less from the viewpoint of suppressing the feeling of roughness on the surface of the microprojection structure.

  The microprojection structure is not particularly limited, but in view of further suppressing the adhesion of powder, the microprojections arranged around the convex projection group gradually increase as they move away from the top microprojections. It is preferable that they are arranged so as to become lower.

The ratio of the number of the microprojections constituting the convex projection group to the total microprojections present on the surface of the microprojection structure is not particularly limited, but is 10% or more from the viewpoint of exerting the effect. Is preferable, more preferably 30% or more, still more preferably 50% or more.
The convex protrusion group does not include a micro protrusion that is adjacent only to the peripheral micro protrusion and has a height lower than that of the top micro protrusion. Further, when the convex protrusion groups are formed adjacent to each other, the peripheral minute protrusions may be shared by the adjacent convex protrusion groups.
The ratio of the number of the microprojections constituting the convex projection group is, for example, the number of the microprojections out of the number of microprojections whose presence was confirmed by image analysis by observing the surface of the microprojection structure with an SEM or the like. This can be obtained by calculating the ratio of the number of microprojections constituting the group.

In the present invention, the microprojection structure prevents the powder from dropping between the projections and reduces the contact area with the powder. The distance d is referred to as “inter-protrusion distance d”.) The average d _AVG is 500 nm or less. The adjacent minute protrusions related to the distance d between the adjacent protrusions are so-called adjacent minute protrusions, and are protrusions that are in contact with the skirt portions of the minute protrusions that are base portions on the base material side. In the microprojection structure used in the present invention, when microprojections are closely arranged, line segments are created so as to sequentially follow the valleys between the microprojections, and each microprojection is surrounded in plan view. A mesh-like pattern formed by connecting a large number of polygonal regions is formed. The adjacent minute protrusions related to the distance d between the adjacent protrusions are protrusions that share a part of the line segments constituting the mesh pattern.
The average distance between adjacent protrusions d _AVG of the micro protrusions is preferably 500 nm or less, and preferably 50 to 300 nm from the viewpoint of preventing the powder from falling between the protrusions and suppressing the adhesion of the powder. Particularly preferred. When the microprojection structure itself needs to be transparent, the average distance between adjacent projections d _AVG of the microprojections is set to be not more than the shortest wavelength λmin in the visible light band. It is preferable from the viewpoint that reflection of light can be reduced. The shortest wavelength λmin in the visible light band may vary somewhat depending on observation conditions, light intensity (luminance), individual differences, and the like, but is typically λmin = 380 nm. From the viewpoint of ensuring the antireflection property, the average distance d _AVG between the adjacent protrusions of the minute protrusions is preferably 300 nm or less, and more preferably 200 nm or less.

What is necessary is just to set suitably the height H of the microprotrusion which comprises a microprotrusion structure, and the average value _HAVG of the said height. Among these, it is preferable to select the minute protrusion height H so that the aspect ratio of the minute protrusions (average protrusion height H _AVG / average adjacent protrusion interval d _AVG ) is 0.8 to 2.5. It is preferable to select the microprojection height H so that the ratio is 0.8 to 2.1.
The average _{H AVG} height H of the minute projections is preferably at 1μm or less, preferably further 500nm or less, is preferably even more 50～350Nm, particularly preferably 100~250nm .
By setting the aspect ratio to be equal to or higher than the lower limit, the adhesion of the powder is further suppressed. Further, by setting the aspect ratio to be equal to or lower than the lower limit value, it is difficult for the minute protrusions to be bent or collapsed.
Here, the height of the microprotrusions refers to the height of the peak (the highest peak) having the highest height at the top of the microprotrusions. In the case of a unimodal microprojection such as the microprojection 3 in FIG. 5A, the height of the only peak at the top is the height of the microprojection. Further, in the case of a multi-peak microprotrusion such as the microprotrusions 3A and 3B in FIG. 5A, the height of the microprotrusion has the highest peak height among a plurality of peaks sharing the ridge at the top. To do.

Moreover, the microprotrusions may have variations in height. When the height varies, the effect of suppressing the adhesion of powder having a variation in size can be expected more. The variation in the height of the fine protrusion is not particularly limited, but the standard deviation σ _H of the height H of the fine protrusion is preferably 2 to 30% of the average value _HAVG of the protrusion height, and is 5 to 25%. More preferably, it is more preferably 10 to 20%.

  Each microprotrusion of the microprotrusion structure may be regularly arranged or irregularly arranged. FIG. 7 shows an example of an embodiment in which minute protrusions are irregularly arranged. FIG. 7 is an enlarged photograph showing an example of a microprojection structure obtained by an atomic force microscope. When the minute protrusions are regularly arranged, the distance d between the minute protrusions can be defined by the repetition period P of the protrusions. On the other hand, when the minute protrusions are irregularly arranged as shown in the example of FIG. 7, the distance d between adjacent minute protrusions varies. In such a case, the microprojection interval d is calculated as follows.

  (1) That is, first, an in-plane arrangement of projections (projection arrangement) using an atomic force microscope (hereinafter referred to as AFM) or a scanning electron microscope (hereinafter referred to as SEM). ) Is detected. Note that the AFM data has in-plane distribution data of the height of the microprojection structure, and the photograph in FIG. 7 shows the in-plane distribution of height by luminance.

  (2) Subsequently, the maximum point of the height of each protrusion (hereinafter simply referred to as the maximum point) is detected from the obtained in-plane arrangement. The maximum point means a point where the height is larger (maximum value) than any point around the vicinity. There are various methods for obtaining the maximum point, such as a method of sequentially comparing the planar view shape and the enlarged photograph of the corresponding cross-sectional shape to obtain the maximum point, and a method of obtaining the maximum point by image processing of the plan view enlarged photo. Can be applied. FIG. 8 is a diagram showing the maximum points of the microprojections in the example of the microprojection structure in FIG. In FIG. 8, the portions indicated by black dots are the maximum points of the respective protrusions. Each local maximum point can be detected by processing the image data of FIG. In this process, image data is processed in advance by a low-pass filter having a Gaussian characteristic of 4.5 × 4.5 pixels, thereby preventing erroneous detection of the maximum point due to noise. Further, a maximum point was obtained in units of 1 nm (= 1 pixel) by sequentially scanning a filter for detecting a maximum value of 8 pixels × 8 pixels.

  (3) Next, a Delaunay diagram with the detected maximum point as a generating point is created. Here, Delaunay diagram is obtained by dividing the Voronoi region adjacent to the Voronoi region when the Voronoi division is performed with each local maximum as the generating point, and connecting the adjacent generating points with line segments. This is a net-like figure made up of triangular aggregates. Each triangle is called a Delaunay triangle, and a side of each triangle (a line segment connecting adjacent generating points) is called a Delaunay line. FIG. 9 is a diagram showing a Delaunay diagram in the example of the microprojection structure in FIG. 7. The Delaunay diagram has a dual relationship with the Voronoi diagram. Voronoi division means that a plane is divided by a net-like figure made up of a closed polygon aggregate defined by perpendicular bisectors of line segments (Droney lines) connecting between adjacent generating points. A network figure obtained by Voronoi division is a Voronoi diagram, and each closed region is a Voronoi region.

  (4) Next, the frequency distribution of the line segment length of each Delaunay line, that is, the frequency distribution of the distance between adjacent maximum points (distance between adjacent protrusions) is obtained. FIG. 10 is a histogram of the frequency distribution of the distance between adjacent maximum points created from the Delaunay diagram of FIG. In addition, as shown in 5B of FIG. 8, when a concave portion such as a groove exists at the top of the projection or the top is divided into a plurality of peaks, such a projection is obtained from the obtained frequency distribution. The data resulting from the fine structure in which the concave portion is present at the top and the fine structure in which the top is divided into a plurality of peaks are removed, and only the data of the projection body itself is selected to create a frequency distribution.

  Specifically, in the fine structure in which there is a concave portion on the top of the protrusion, or in the fine structure related to the multi-peak microprotrusion in which the top is divided into a plurality of peaks, the single-peak property that does not have such a fine structure From the numerical range in the case of a microprotrusion, the distance between adjacent local maximum points is clearly greatly different. By removing the corresponding data using this feature, only the data of the projection body itself is selected and the frequency distribution is detected. More specifically, for example, about 5 to 20 adjacent single-peaked microprojections are selected from an enlarged photograph of the microprojections (group) as shown in FIG. A value that deviates in a direction that is clearly smaller than the numerical range obtained by sampling this value (usually the value is ½ or less of the average distance between adjacent maximum points obtained by sampling) Frequency distribution is detected. In the example of FIG. 10, data with a distance between adjacent maximal points of 56 nm or less (the leftmost small mountain indicated by arrow A) is excluded. FIG. 10 shows a frequency distribution before performing such exclusion processing. Incidentally, such exclusion processing may be executed by setting the above-described maximum inspection filter.

(5) The frequency distribution of the distance d between adjacent protrusions thus determined is regarded as a normal distribution, and the average value d _AVG and the standard deviation σ _d are determined. In the present invention, the maximum value d _max of the distance d between adjacent protrusions is defined as d _max = d _AVG + 2σ _d and is calculated. In the example of FIG. 10, the average value d _AVG = 158 nm and the standard deviation σ _d = 38 nm. Accordingly, the maximum value d _max = 234 nm of the distance d between adjacent protrusions is calculated.

A similar technique is applied to define the height of the protrusion. In this case, a relative height difference of each local maximum point position from a specific reference position is acquired from the local maximum point obtained by the above (2), and is histogrammed. The average value H _AVG of the projection height and the standard deviation σ _H are obtained from the frequency distribution based on this histogram. If multi-peak microprojections are included, one microprojection has a plurality of vertices, and thus a plurality of data are mixed in a histogram of the projection height H for one projection. . Therefore, in this case, the frequency distribution is obtained by adopting the vertex having the highest height from among the plurality of vertices belonging to the same microprotrusion as the protuberance.
FIG. 11 is a histogram of the frequency distribution of the height H of the microprojections in the example of the microprojection structure in FIG. In the example of FIG. 11, the base position of the minute protrusion is set as a reference (height 0). In the example of FIG. 11, the average value H _AVG = 178 nm and the standard deviation σ = 30 nm. Thus in this example, the height of the projections is an average value _H AVG = 178 nm.

  The reference position for measuring the height of the microprojections is the base position of the projection, that is, the valley bottom (minimum point of height) between the adjacent microprojections is used as the reference for the height 0. However, when the height of the valley bottom itself varies depending on the location, for example, when the envelope surface connecting the valley bottoms between the microprojections has a concavo-convex shape with a large period compared to the distance between adjacent projections of the microprojections ( For example, as shown in the example of FIG. 12, the height of the valley bottom has undulation with a period larger than the distance between adjacent projections of the microprotrusions). The average value of the heights of the valleys measured from the surface opposite to the projection surface 31 is calculated within an area sufficient for the average value to converge. (2) Next, a surface having the average height and parallel to the surface opposite to the microprojection surface 31 of the microprojection structure 30 is considered as a reference plane. (3) Then, the height of each microprotrusion from the reference surface is calculated by setting the reference surface to a height of 0 again.

When the height of the valley between the adjacent microprotrusions 32 varies depending on the location, for example, the periodic undulation as shown in FIG. 12 occurs on a plane parallel to the front and back surfaces of the transparent substrate (XY plane in FIG. 12). The height may be constant in only one direction (for example, the X direction) and in a direction perpendicular to the direction (for example, the Y direction), or in a plane (XY plane in FIG. 12) parallel to the front and back surfaces of the transparent substrate. Both directions (X direction and Y direction) may have undulations.
In order to ensure good smoothness of the surface of the microprojection structure, the height difference (h in FIG. 12) of the concavo-convex surface 33 undulated in the period D is preferably 10 nm or less, and in the range of 1 nm to 5 nm. More preferably, it is within. In addition, the height difference of the uneven surface formed by the uneven surface 33 can be obtained by measuring the height difference of the position of the valley bottom portion of the minute protrusion 32 separated by, for example, 500 nm or more. The position of the valley bottom portion of the microprojection 32 can be obtained by observing the microprojection structure 30 using a TEM photograph or SEM photograph of a vertical section cut in the thickness direction.

  The thickness of the fine uneven layer (T in FIG. 3 or 4) may be adjusted as appropriate, but is preferably 3 μm to 30 μm, and more preferably 5 μm to 10 μm. Note that the thickness T of the fine uneven layer in FIG. 3 is defined by the thickness from the interface of the fine uneven layer to the base material to the top of the highest minute protrusion.

The static contact angle of pure water on the surface of the microprojection structure may be appropriately changed according to the powder cosmetic used, and is not particularly limited. The static contact angle of pure water on the surface of the microprojection structure is 60 ° or less by the θ / 2 method from the viewpoint that the contact area with the powder is reduced and the adhesion of the powder is suppressed. Preferably, it is 3 ° to 40 °, more preferably 3 ° to 25 °.
In addition, since the surface free energy is reduced and the adhesion of powder is further suppressed, the static contact angle of pure water on the surface of the microprojection structure is 90 ° to 170 ° by the θ / 2 method. It is preferably 100 ° to 165 °.
The static contact angle of n-hexadecane on the surface of the microprojection structure is preferably 60 ° or less by the θ / 2 method from the viewpoint of suppressing the adhesion of powder, and 3 ° to 40 °. Is more preferably 3 ° to 25 °.
In the present invention, the static contact angle is a straight line connecting the left and right end points of the dropped liquid and the apex 1 second after the dropping of 1.0 μL of pure water or n-hexadecane on the surface of the measurement object. The contact angle measured in accordance with the θ / 2 method for calculating the contact angle from the angle to the solid surface. As the measuring device, for example, a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. can be used.
The static contact angle can be adjusted by changing the type of resin forming the microprojection structure and the uneven shape of the microprojection structure.

  In the present invention, the storage elastic modulus (E ′) of the cured product of the resin composition may be appropriately adjusted according to the application, and is not particularly limited. The storage elastic modulus (E ′) at 25 ° C. of the cured resin composition is preferably 300 MPa or less from the viewpoint of facilitating wiping off fingerprint stains by dry wiping. By setting E ′ to 300 MPa or less, the minute protrusions are deformed by the pressure during wiping, and the dirt that has entered the gap between the minute protrusions can be removed by dry wiping. Among them, the storage elastic modulus (E ′) is preferably 1 to 250 MPa, and more preferably 1 to 100 MPa.

  In the present invention, the ratio of the loss elastic modulus (E ″) to the storage elastic modulus (E ′) at 25 ° C. of the cured product of the resin composition (tan δ (= E ″ / E ′) loss tangent) is 0. .2 or less is preferable. By setting the loss tangent to 0.2 or less, the minute protrusions deformed at the time of wiping are elastically restored and easily return to the original shape. Accordingly, the plastic deformation and sticking of the protrusions are suppressed during the fingerprint wiping, and the dirt can be wiped off by dry wiping without deteriorating the powder adhesion suppressing effect. Among them, tan δ is preferably 0.18 or less.

In the present invention, the storage elastic modulus (E ′) and the loss elastic modulus (E ″) are measured by the following method according to JIS K7244.
First, a resin composition for forming a fine uneven layer is sufficiently cured by irradiating ultraviolet rays having an energy of 2000 mJ / cm ² for 1 minute or more, and does not have a substrate and fine uneven shapes, a thickness of 1 mm, a width A single film having a length of 5 mm and a length of 30 mm is used.
Next, by applying a cyclic external force of 25 g at 10 Hz in the length direction of the cured product of the resin composition at 25 ° C. and measuring dynamic viscoelasticity, E ′ and E ″ at 25 ° C. are obtained. As a measuring device, for example, Rhegel E400 manufactured by UBM can be used.

  In the present invention, the microprojection structure is made of a cured product of the resin composition. In the present invention, the cured product of the resin composition includes one obtained by solidifying a component such as a resin in the resin composition through a chemical reaction, or one obtained by solidifying without undergoing a chemical reaction. Furthermore, the resin composition includes those composed of a single resin. Moreover, in this invention, resin is the concept containing a polymer other than a monomer and an oligomer.

In the present invention, the resin composition suitably used for forming the microprojection structure contains at least a resin and, if necessary, other components such as a polymerization initiator.
The resin is not particularly limited, for example, ionizing radiation curable resins such as acrylate, epoxy, and polyester, acrylate, urethane, epoxy, polysiloxane, and other thermosetting resins, acrylate, Various materials such as polyester-based, polycarbonate-based, polyethylene-based, polypropylene-based thermoplastic resins, and various curing resins for shaping can be used. Moreover, you may contain a non-reactive polymer. The ionizing radiation means electromagnetic waves or charged particles having energy that can be cured by polymerizing molecules. For example, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays , X-rays, electron beams and the like.

  As the resin, an ionizing radiation curable resin is preferable from the viewpoint of excellent moldability and mechanical strength of fine protrusions. The ionizing radiation curable resin is a mixture of a monomer having radically polymerizable and / or cationically polymerizable bonds in the molecule, a polymer having a low polymerization degree, and a reactive polymer, depending on the polymerization initiator. It is to be cured. In addition, you may contain a non-reactive polymer.

In the present invention, the resin composition for forming a microprojection structure preferably includes a compound having an ethylenically unsaturated bond as an ionizing radiation curable component, and more preferably includes (meth) acrylate.
In addition, the resin composition contains a compound having a long-chain alkyl group having 10 or more carbon atoms from the viewpoint that the lipophilicity of the cured product surface is improved, the fine protrusions are excellent in flexibility, and the fingerprint wiping property is improved. It is preferable to do. This is because the surface of the microprojection structure is oleophilic, so that it is easy to wipe off dirt by dry wiping, and the microprotrusion is excellent in flexibility, so that the microprotrusions are deformed and easy to scrape off when wiping. .
Hereinafter, each component in the composition containing (meth) acrylate preferably used as the ionizing radiation curable component will be described in order.

(1) (Meth) acrylate (meth) acrylate is a monofunctional (meth) acrylate having one (meth) acryloyl group in one molecule, but two or more (meth) acryloyl groups in one molecule It may be a polyfunctional acrylate having a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
Among these, it is preferable to use a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate in combination from the viewpoint that the cured product satisfies the above physical properties and the microprotrusions have both flexibility and elastic resilience.

  Specific examples of monofunctional (meth) acrylates include, for example, methyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate , Butoxyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate Relate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, biphenyloxyethyl acrylate, bisphenol A diglycidyl (meth) acrylate, biphenylyloxyethyl (meth) acrylate, ethylene oxide modified biphenylyloxyethyl (meth) acrylate, bisphenol A epoxy (meth) acrylate, and the like. Among these, a monofunctional (meth) acrylate having a long-chain alkyl group having 10 or more carbon atoms is preferable from the viewpoint that the lipophilicity of the cured product surface is improved and the microprotrusions are excellent in flexibility. It is even more preferable that it contains at least one of tridecyl (meth) acrylate and dodecyl (meth) acrylate. These monofunctional (meth) acrylic acid esters can be used alone or in combination of two or more. In addition, when using the monofunctional (meth) acrylate which has a C10 or more long-chain alkyl group, it has the characteristic of the compound which has a C10 or more long-chain alkyl group mentioned later.

  The content of the monofunctional (meth) acrylate is preferably 5 to 40% by mass and more preferably 10 to 30% by mass with respect to the total solid content of the ionizing radiation curable resin composition.

  Specific examples of the polyfunctional acrylate include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene di (meth) acrylate, hexanediol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol di (meth) acrylate, di (meth) acrylate phthalate, ethylene oxide modified bisphenol A di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tri (Acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ethylene oxide modified tri Examples include methylolpropane tri (meth) acrylate. Among these, from the viewpoint that the microprotrusions are excellent in flexibility and restorability, it is preferable to use a polyfunctional (meth) acrylate containing an alkylene oxide, more preferably an ethylene oxide modified polyfunctional (meth) acrylate, and an ethylene oxide modified Even more preferably, at least one of bisphenol A di (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and polyethylene glycol di (meth) acrylate is included.

  The content of the polyfunctional (meth) acrylate is preferably 10 to 95% by mass and more preferably 15 to 90% by mass with respect to the total solid content of the ionizing radiation curable resin composition.

(2) Compound having a long-chain alkyl group having 10 or more carbon atoms The resin composition used in the present invention has improved oleophilicity on the surface of the cured product, excellent microprojections, and good fingerprint wiping properties. From the viewpoint, it is preferable to contain a compound having a long-chain alkyl group having 10 or more carbon atoms, and it is more preferable to contain a compound having a long-chain alkyl group having 12 or more carbon atoms.
Specific examples of the compound having a long chain alkyl group having 10 or more carbon atoms include compounds having decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and the like. Moreover, unless the effect of this invention is impaired, you may have a substituent further. Specific examples of the substituent include halogen atoms such as fluorine, chlorine and bromine, hydroxyl groups, carboxy groups, amino groups and sulfo groups, as well as ethylenically unsaturated double bonds such as vinyl groups and (meth) acryloyl groups. Groups and the like. Especially, it is preferable to have an ethylenically unsaturated double bond from the point provided with ionizing radiation curability, and it is more preferable to have a (meth) acryloyl group.
In addition, when the compound which has a C10 or more long-chain alkyl group has a (meth) acryloyl group, the said compound may correspond also to the said (meth) acrylate.

  When using a compound having a long-chain alkyl group having 10 or more carbon atoms, the content of the compound is preferably 5 to 30% by mass with respect to the total solid content of the ionizing radiation curable resin composition. More preferably, it is -20 mass%.

  The ionizing radiation curable resin composition preferably used in the present invention can easily adjust the storage elastic modulus and loss tangent of the cured product to the above preferred ranges, and can easily be adjusted to be oleophilic, thereby obtaining excellent dry wiping properties. It is particularly preferable that at least a (meth) acrylate having a long-chain alkyl group having 10 or more carbon atoms and an ethylene oxide-modified polyfunctional (meth) acrylate are contained. Especially, it is preferable that the content rate of the (meth) acrylate which has a C10 or more long-chain alkyl group is 5-30 mass parts with respect to 100 mass parts of ethylene oxide modified polyfunctional (meth) acrylate. More preferably, it is -15 mass parts.

(3) Photopolymerization initiator In order to initiate or accelerate the curing reaction of the (meth) acrylate, a photopolymerization initiator may be appropriately selected and used as necessary. Specific examples of the photopolymerization initiator include, for example, bisacylphosphinoxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2,2-dimethoxy-1. , 2-Diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenyl -Propane-1-ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis (2,4,6-trimethylbenzene) Benzoyl) - phosphine oxide, phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinic acid and the like. These can be used alone or in combination of two or more.

  When using a photoinitiator, content of the said photoinitiator is 0.8 to 20 mass% normally with respect to the total solid of an ionizing radiation curable resin composition, and 0.9 to 10 mass. % Is preferred.

(4) Antistatic agent In this invention, it is preferable to contain an antistatic agent in the said resin composition. By containing the antistatic agent, it is possible to prevent the dirt from adhering to the surface of the fine concavo-convex layer, and the dirt is easily removed during wiping.
The antistatic agent can be appropriately selected from conventionally known ones. Specific examples of the antistatic agent include, for example, various cationic compounds having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and a primary to tertiary amino group, a sulfonate group, a sulfate ester base, and a phosphate ester. Bases, anionic compounds having an anionic group such as phosphonic acid bases, amphoteric compounds such as amino acid series and aminosulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, tin and titanium alkoxides And metal chelate compounds such as acetylacetonate salts thereof. Of these, cationic compounds are preferred, cationic compounds having a tertiary amino group are more preferred, and trialkylamines such as N, N-dioctyl-1-octaneamine are even more preferred.

  When the antistatic agent is used, the content of the antistatic agent is usually 1 to 20% by mass, preferably 2 to 10% by mass, based on the total solid content of the ionizing radiation curable resin composition. .

(5) Solvent In the present invention, the resin composition may use a solvent from the viewpoint of imparting coatability and the like. In the case of using a solvent, the solvent does not react with each component in the composition, and can be appropriately selected from solvents that can dissolve or disperse each component. Specific examples of such solvents include hydrocarbon solvents such as benzene and hexane, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, tetrahydrofuran, 1,2-dimethoxyethane, propylene glycol monoethyl ether ( PGME) ether solvents such as chloroform and dichloromethane, halogenated alkyl solvents such as methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and other amide solvents such as N, N-dimethylformamide And sulfoxide solvents such as dimethyl sulfoxide, anone solvents such as cyclohexane, and alcohol solvents such as methanol, ethanol, and propanol, but are not limited thereto. Not to. Moreover, the solvent used for a resin composition may be used individually by 1 type, and the mixed solvent of two or more types of solvents may be sufficient as it.

  The ratio of the solid content with respect to the total amount of the resin composition is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. In addition, in this invention, solid content represents all components other than the solvent in a resin composition.

(6) Other components The resin composition for fine concavo-convex layers used in the present invention may further contain other components as long as the effects of the present invention are not impaired. Other components include, for example, a surfactant for adjusting wettability, a silane coupling agent for improving adhesion, a stabilizer, an antifoaming agent, a repellency inhibitor, an antioxidant, an anti-aggregation agent, and a viscosity. A preparation agent, a mold release agent, etc. are mentioned.

(Manufacturing method of microprojection structure)
In the present invention, the method for producing the microprojection structure is not particularly limited, but a method for forming the microprojection structure by shaping on at least one surface of the substrate from the viewpoint of excellent moldability and stable mass production. preferable.
The microprojection structure may be shaped on the surface of another layer made of a material different from the base material provided on the base material, or the base material is made of a shapeable material such as a resin composition. When it becomes, you may shape directly on the said base-material surface.

Examples of the method for producing the microprojection structure include the following methods. That is, first, the resin composition is applied onto a substrate to form a coating film, and the uneven shape of the microprojection structure forming original plate having a desired uneven shape is formed into a coating film of the resin composition. Thereafter, the resin composition is cured to form a microprojection structure, and the original plate for forming the microprojection structure is peeled off.
The concave / convex shape of the original plate for forming a microprojection structure is a shape in which a large number of micropores are densely formed and corresponds to the shape of a group of microprojections provided in the microprojection structure.
Moreover, the method of shaping the concave / convex shape of the original plate for forming a microprojection structure into a resin composition and curing the resin composition can be appropriately selected according to the type of the resin composition.

The original plate for forming the microprojection structure is not particularly limited as long as it is not deformed and worn when repeatedly used, and may be made of metal or resin, Usually, metal is preferably used because it is excellent in deformation resistance and wear resistance.
The surface having the concavo-convex shape of the original plate for forming a microprojection structure is not particularly limited, but is preferably made of aluminum from the viewpoint of being easily oxidized and easily processed by anodization.
Specifically, the original plate for forming the microprojection structure has high purity by sputtering or the like directly on the surface of a metal base material such as stainless steel, copper, or aluminum, or through various intermediate layers. An aluminum layer is provided, and the aluminum layer is formed with an uneven shape. Prior to providing the aluminum layer, the surface of the base material may be made into a super mirror surface by an electrolytic composite polishing method in which electrolytic elution action and abrasion action by abrasive grains are combined.
Examples of a method for forming a concavo-convex shape on the original plate for forming a microprojection structure include, for example, an anodic oxidation step of forming a plurality of micropores on the surface of the aluminum layer by an anodic oxidation method, and etching the aluminum layer. A first etching step for forming a tapered shape in the opening of the microhole, and a second for enlarging the hole diameter of the microhole by etching the aluminum layer at an etching rate higher than the etching rate of the first etching step. It can be formed by sequentially repeating the etching process.
When forming an uneven shape on the original plate for forming a microprojection structure, the purity (impurity amount), crystal grain size, anodizing treatment and / or etching treatment conditions of the aluminum layer are appropriately adjusted to obtain a desired shape. It can be a shape. In the anodic oxidation treatment, more specifically, the micropores can be produced to the desired depth and shape by managing the liquid temperature, the applied voltage, the time for the anodic oxidation, and the like.

Moreover, examples of the shape of the original plate for forming a microprojection structure include a flat plate shape and a roll shape, and are not particularly limited, but a roll shape is preferable from the viewpoint of improving productivity. In the present invention, it is preferable to use a roll-shaped mold (hereinafter sometimes referred to as “roll mold”) as the original plate for forming the microprojection structure.
As the roll mold, for example, as described above, a cylindrical metal material is used as a base material, and the aluminum layer provided on the peripheral side surface of the base material directly or through various intermediate layers, as described above. In other words, the concavo-convex shape is produced by repeating the anodizing treatment and the etching treatment.

  In FIG. 13, a microprojection structure used in the present invention is manufactured by using an ultraviolet curable resin composition as a resin composition for forming a microprojection structure and using a roll mold as an original plate for forming the microprojection structure. An example of how to do this is shown. In this manufacturing method, first, in the resin supplying step, an uncured and liquid ultraviolet curable resin that constitutes the receiving layer 2 ′ on which the microprojection structure 2 is formed on the substrate 1 in the form of a strip film by the die 31. Apply the composition. In addition, about application | coating of an ultraviolet curable resin composition, not only the case by the die | dye 11 but various methods are applicable. Subsequently, the pressing roller 13 presses and presses the base material 1 against the peripheral side surface of the roll mold 12 which is a shaping mold, thereby bringing the uncured receiving layer 2 ′ into close contact with the base material 1, The concave and convex portions formed on the peripheral side surface of the roll mold 12 are sufficiently filled with the ultraviolet curable resin composition constituting the receiving layer 2 ′. In this state, the ultraviolet curable resin composition is cured by irradiation with ultraviolet rays, whereby the microprojection layer 2 having the microprojection structure is formed on the surface of the substrate 1. Subsequently, the base material 1 is peeled from the roll mold 12 through the peeling roller 14 together with the hard microprojection layer 2. If necessary, an adhesive layer or the like is laminated on the substrate 1 and then cut into a desired size. Thereby, the microprojection structure of a desired shape is efficiently mass-produced.

In order to mix multi-peak microprojections and monomodal micro-protrusions, it must be realized by varying the micro-hole intervals of the micro-projection structure forming original plate produced in the anodizing process. Can do. Multi-modal microprotrusions are created by micropores having a concave portion corresponding to the top of the microprotrusions, and such micropores are produced by etching processing. It is thought that they are formed integrally.
In order to make at least a part of the microprojection structure into the convex projection group described above, it is essential that the height of each microprotrusion has a predetermined range. The variation in the height of each microprojection is due to the variation in the depth of the microhole formed in the original plate for forming the microprojection structure. It can be said that it is caused by variation. In this way, a mixture of a relatively high top microprojection and a plurality of relatively low peripheral microprojections can be realized by increasing the variation in anodizing treatment.

  Further, in the above-described embodiment, the case where the forming method of the microprojection structure is produced on the film-shaped base material by the shaping process using the roll mold is described. Depending on the shape of the material, for example, when forming a microprojection structure by processing a flat plate or a single wafer using a mold for shaping with a specific curved surface shape, It can be appropriately changed according to the shape of the material.

  When imparting hydrophobicity to the surface of the microprojection structure, a fluorine atom or a silicon atom may be added to the surface of the obtained microprojection structure by chemical vapor treatment. By adding fluorine atoms or silicon atoms by chemical vapor treatment, fluorine atoms or silicon atoms can be added to the surface of the microprojection structure without impairing the shape of the microprojection structure. By having one or more atoms selected from fluorine atoms and silicon atoms on the surface of the microprojection structure, the hydrophobicity of the surface is increased, and the static contact angle of pure water on the surface on the microprojection structure side is θ In addition to being easily adjusted to 90 ° or more by the / 2 method, the surface free energy is reduced and the adhesion of powder is further suppressed.

The chemical vapor phase treatment used in the present invention is a conventionally known process that can add one or more atoms selected from fluorine atoms and silicon atoms to the surface of a microprojection structure made of a cured product of a resin composition. It can be appropriately selected from chemical vapor processing. As an aspect which has 1 or more types of atoms selected from the fluorine atom and silicon atom which were added to the surface of the said microprotrusion structure by chemical vapor processing, for example, chemical vapor processing is carried out on the surface of the said microprotrusion structure And a mode having a fluorine-containing compound or a silicon-containing compound deposited on the surface of the microprojection structure by chemical modification by chemical vapor treatment.
When a fluorine-containing compound or a silicon-containing compound is added to the surface of the microprojection structure by a solution coating method, the uneven shape on the surface of the microprojection structure is impaired, and the powder adhesion suppressing effect is impaired. On the other hand, according to the method of adding fluorine atoms or silicon atoms to the surface of the microprojection structure by chemical vapor processing, the pure water is static without impairing the irregular shape of the surface of the microprojection structure. The contact angle can be increased. That is, according to the chemical vapor phase treatment, the surface of the microprojection structure can be provided by following the irregularities on the surface of the microprojection structure, whether it is a deposited film or a surface chemical modification. Does not impair the uneven shape. Therefore, when the surface of the microprojection structure has one or more atoms selected from fluorine atoms and silicon atoms added by chemical vapor treatment, the powder adhesion suppressing effect can be enhanced. .

In the present invention, the chemical vapor treatment method is a conventionally known method capable of adding one or more kinds of atoms selected from fluorine atoms and silicon atoms to the surface of a microprojection structure made of a cured product of a resin composition. Can be selected as appropriate.
In the present invention, the chemical vapor deposition method is preferably a chemical vapor deposition (CVD) method or a reactive ion etching method. Hereinafter, each chemical vapor processing method will be described.

(Chemical vapor deposition (CVD) method)
In the present invention, the CVD method can be appropriately selected from conventionally known methods. Specifically, for example, a thermal CVD method, a photo CVD method, a plasma CVD method, an epitaxial CVD method, an atomic layer CVD method, a metal organic chemical vapor deposition method, and the like can be mentioned. The method is preferably used.

  Specifically, for example, the microprojection structure is obtained by evaporating at least one fluorine-containing compound by heating, mixing it with an inert gas such as argon gas or helium gas as a carrier gas, and converting the gas into plasma. A fluorine-containing compound or a silicon-containing compound can be added to the surface of the body.

As the fluorine-containing compound, a conventionally known compound applicable to the CVD method can be used. Among them, at least one terminal contains a perfluoroalkyl group having 1 to 6 carbon atoms and contains an oxygen atom. It is preferable to use a fluorine-containing compound having 10 or less carbon atoms. Specifically, for example, perfluoroalkanes such as tetrafluoromethane, perfluoroethane, perfluoropropane, perfluorobutane, perfluoropentane, and perfluorohexane, hexafluoropropylene, perfluoro (4-methyl-2-pentene). ), Perfluoroalkenes such as perfluoro (2-methyl-2-pentene) and perfluoro-1-hexene. In the present invention, a fluorine-containing compound having a perfluoroalkyl group having 3 to 6 carbon atoms is preferable from the viewpoint of making the surface of the microprojection structure hydrophobic, and further, the number of carbon atoms is 4 to 6 The perfluoroalkyl group is more preferable. In addition, the fluorine-containing compound preferably contains an unsaturated hydrocarbon group or an iodo group in which active species such as ions and radicals are easily generated.
Moreover, what is necessary is just to select suitably from the conventionally well-known silicon-containing compound applicable to CVD method as said silicon-containing compound. Specific examples include hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), hexamethyldisilazane (HMDS), and octamethylcyclotetrasiloxane.
The mixing ratio of the fluorine-containing compound and silicon-containing compound gas to the inert gas is not particularly limited, but is preferably 1:99 to 30:70 (volume ratio), and 2:98 to 10:90. (Volume ratio) is more preferable.

(Reactive ion etching method)
In the present invention, one or more atoms selected from fluorine atoms and silicon atoms may be added using a reactive ion etching method. In the reactive ion etching method, usually, addition of one or more kinds of atoms selected from fluorine atoms and silicon atoms and etching of the substrate surface are simultaneously performed. In the present invention, fluorine atoms and silicon atoms are used. The purpose is to add one or more selected atoms, and the condition is set so that the surface of the microprojection structure is not etched or does not affect the surface shape even if it is etched.

In the present invention, the reactive ion etching method uses one or more gaseous compounds selected from fluorine-containing compounds and silicon-containing compounds, and adds a fluorine-containing compound to the surface of the microprojection structure by plasma. .
In the reactive ion etching method, oxygen may be further mixed with the gaseous compound. The mixing ratio of one or more gaseous compounds selected from fluorine-containing compounds and silicon-containing compounds and oxygen is preferably 100: 0 to 80:20 (volume ratio), and 100: 0 to 85: More preferably, it is 15 (volume ratio). When the proportion of oxygen is increased, the surface of the microprojection structure may be etched.

As the fluorine-containing compound, a fluorinated alkyl compound is preferably used. Specific examples thereof include tetrafluoromethane, trifluoromethane, hexafluoroethane, and the like. Among these, tetrafluoromethane is preferably used from the viewpoint of making the surface of the microprojection structure hydrophobic.
Examples of the silicon-containing compound include hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), hexamethyldisilazane (HMDS), and octamethylcyclotetrasiloxane.

  When a chemical vapor deposition (CVD) method or a reactive ion etching method is used, a fluorine-containing compound is deposited on the surface of the microprojection structure. Even in this case, the outermost surface of the microprojection structure has an uneven shape due to the uneven shape of the microprojection structure, and is selected from fluorine atoms and silicon atoms added by chemical vapor processing. The film thickness of the portion including one or more kinds of atoms is appropriately selected so that the outermost surface of the microprojection structure has an uneven shape due to the uneven shape of the microprojection structure. For example, when a chemical vapor deposition (CVD) method or a reactive ion etching method is used, the film thickness of the portion containing fluorine atoms is preferably 5 nm to 50 nm, and preferably 10 nm to 40 nm. More preferred.

<Base material>
As shown in the example of FIG. 3, the microprojection structure used in the present invention may be a laminate having a base material on the surface side not having the microprojection structure. When using a base material, the base material can be appropriately selected from conventionally known base materials, and has a curved surface according to the shape of the powder cosmetic container or the powder cosmetic tester display stand. It may be a base material having an arbitrary three-dimensional shape.
Examples of the material used for the base material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, acrylic resins, polyurethane resins, polyethersulfone and polycarbonate, Resins such as polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, glass such as soda glass, potassium glass, lead glass, ceramics such as PLZT, inorganic such as quartz and fluorite Examples include materials, metals, paper, wood, and composite materials thereof.
Further, the substrate may be any of those supplied in the form of a roll, those that do not bend enough to be wound, but that are curved by applying a load, and those that do not bend completely. You can choose.

The structure of the base material used in the present invention is not limited to a structure composed of a single layer, and may have a structure in which a plurality of layers are laminated. When it has the structure by which the several layer was laminated | stacked, the layer of the same composition may be laminated | stacked, and the several layer which has a different composition may be laminated | stacked.
In addition, when the microprojection structure to be described later is formed on a microprojection layer made of a material different from the substrate, the surface performance of the substrate such as adhesion between layers, coating suitability, and surface smoothness is improved. From the above, an intermediate layer may be formed on the substrate.
What is necessary is just to select an intermediate | middle layer suitably from a conventionally well-known thing according to a use. For example, the material for the intermediate layer can be appropriately selected from fluorine-based coating agents and silane coupling agents. Examples of commercially available fluorine-based coating agents include Fluorosurf FG-5010Z130 manufactured by Fluoro Technology, and examples of commercially available silane coupling agents include Durasurf Primer DS-PC-3B manufactured by Harves. Is mentioned.

  The transmittance in the visible light region of the substrate used in the present invention can be appropriately adjusted according to the use, and a transparent substrate having a transmittance of 80% or more may be used, and the transmittance is less than 80%. An anti-transparent substrate or an opaque substrate may be used. When the microprojection structure is used for a mirror surface, it is preferable to use a transparent substrate from the viewpoint of excellent specular reflection. The transmittance can be measured by JIS K7361-1 (Plastic—Testing method for total light transmittance of transparent material).

  What is necessary is just to set the thickness of a base material suitably according to a use. When using a film-like base material, it can be set to, for example, about 1 μm to 5000 μm.

  In the present invention, the microprojection structure is preferably provided by a member having the microprojection structure on the surface. For example, an adhesive layer (not shown) is further provided on the surface of the member having the microprojection structure as shown in FIGS. The powder cosmetic container according to the present invention or the powder cosmetic tester display stand according to the present invention can be obtained by sticking to the cosmetic tester display stand through the adhesive layer. Adhesives used for the adhesive layer include known adhesives such as pressure-sensitive adhesives (pressure-sensitive adhesives), two-component curable adhesives, ultraviolet curable adhesives, thermosetting adhesives, and hot melt adhesives. Various forms can be used.

[Powder cosmetic container]
The powder cosmetic container according to the present invention is a powder cosmetic container comprising a container body provided with a container for containing cosmetic containing powder, and a lid for closing the container body, At least a part of the inner surface of the powder cosmetic container has the microprojection structure.

An example of the embodiment of the powder cosmetic container of the present invention is shown in FIG. In the example of FIG. 1, the powder cosmetic container 100 includes a container main body 101 including storage units 102 </ b> A and 102 </ b> B that store the powder cosmetic, and a lid 103.
In the container body 101, a cosmetic tool such as a powder puff may be housed in one of the housing portions 102A and 102B in place of the powder cosmetic material. You may provide the recessed part which accommodates cosmetic tools, such as. Further, in the container main body 101, an engaging protrusion 105A is protruded in a recess formed in the center of the front surface, and a push button 105B is pivotally mounted in the recess so as to swing.
Further, the lid 103 has a rear part rotatably connected to the rear part of the container main body 101 so that the upper surface of the container main body can be opened and closed, and a mirror 104 is fixed to the rear surface thereof. Further, the hook 105C suspended from the lower surface of the center of the front part is configured so as to be able to engage with the engaging protrusion 105A when the cover is closed, so that the closed state can be maintained, and the hook 105C is pushed by pressing the push button 105B. The engagement is released by pushing up.
FIG. 1 is an example of the powder cosmetic container according to the present invention, and any other configuration is not particularly limited as long as it has an essential configuration of the powder cosmetic container according to the present invention. Can be adopted.

In the powder cosmetic container of the present invention, since at least a part of the inner surface has the microprojection structure, the adhesion of the powder cosmetic is suppressed on the inner surface having the microprojection structure, It can be kept clean all the time. The internal surface having the microprojection structure is not particularly limited. For example, when a mirror is provided inside the container, the surface of the mirror, the peripheral surface of the powder cosmetic container, the surface of the cosmetic tool container, and In the case where an inner lid is further provided in the peripheral edge surface of the makeup tool accommodating portion, the back surface of the lid, and the inside of the container, the front surface and the back surface of the inner lid are exemplified. The method for disposing the microprojection structure on the inner surface of the powder cosmetic container is not particularly limited. For example, a method in which a member provided on the surface of the microprojection structure manufactured by the method of manufacturing the microprojection structure is attached to the inner surface of the powder cosmetic container via an adhesive or the like. It is done.
In the powder cosmetic container of the present invention, the resin surface itself constituting the inside of the container main body may be shaped by the above-described method to have a microprojection structure.

  Among these, the powder cosmetic container of the present invention is preferably in a mode in which a mirror 104 is provided inside the container, and a member 106 having a microprojection structure on the surface is attached to at least the surface of the mirror. Such a powder cosmetic container is excellent in the visibility of the mirror because the powder cosmetic is suppressed from adhering to the mirror surface.

Examples of the powder cosmetic include cosmetics containing powder, and powders and solid powders are preferable. Examples thereof include makeup cosmetics such as foundations, eye shadows, and cheeks, care cosmetics, body cosmetics, and the like.
The microprojection structure has an effect of suppressing adhesion regardless of the particle size of the powder, and among these, it can be suitably used for a powder having a particle size of 0.1 to 30 μm. A powder having a particle size of 25 μm can be preferably used.

[Powder cosmetic tester display stand]
The powder cosmetic tester display stand according to the present invention is a powder cosmetic tester display stand provided with a tester storage portion for storing a cosmetic tester containing powder, and further capable of opening and closing the upper surface of the tester storage portion. The lid may be provided, and at least a part of the surface of the display stand and the inner and outer surfaces of the lid have the microprojection structure.

An example of the embodiment of the powder cosmetic tester display stand of the present invention is shown in FIG. In the example of the tester display stand 200 in FIG. 2, a plurality of tester accommodating portions 201 are provided, and a work table 202 is disposed in front of the tester display unit 200. The tester accommodating portion accommodates a tester unit 204 including one or more testers, and includes a mirror 203 at the top of the display stand. The tester accommodating part 201 may be provided with a lid (not shown) for storing the tester, and the tester unit 204 may have the lid.
FIG. 2 is an example of the powder cosmetic tester display stand of the present invention, and other configurations are not particularly limited as long as the powder cosmetic tester display stand according to the present invention has an essential configuration. A known configuration can be adopted as appropriate.

The tester display stand of the present invention has a microprojection structure on at least a part of the surface of the display stand, such as the peripheral portion of the tester housing, the peripheral portion of the tester unit, the work table, the surface of the mirror, or the inner and outer surfaces of the lid. Since the body is provided, the adhesion of the powder cosmetic can be suppressed and kept clean at all times.
As a method of arranging the microprojection structure on the surface of the tester display stand, a member provided on the surface with the microprojection structure manufactured by the method for manufacturing the microprojection structure is ground with an adhesive or the like. The method of sticking on the said surface of a body cosmetics tester display stand etc. are mentioned.
In the powder cosmetic tester display stand of the present invention, the resin surface itself constituting the surface of the display stand may be shaped by the above-described method to have a microprojection structure.
FIG. 2 is an example of the powder cosmetic tester display stand of the present invention, and other configurations are not particularly limited as long as the powder cosmetic tester display stand according to the present invention has an essential configuration. A known configuration can be adopted as appropriate.

  Hereinafter, it demonstrates more concretely using an Example. In addition, this invention is not limited to an Example.

(Preparation of resin composition A)
The following components were mixed to prepare a resin composition A for forming a microprojection structure.
-EO-modified bisphenol A diacrylate 70 parts by mass-Polyethylene glycol diacrylate 30 parts by mass-Diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (Lucillin TPO) 1 part by mass

(Preparation of resin composition B)
The following components were mixed to prepare a resin composition B for forming a microprojection structure.
-EO-modified bisphenol A diacrylate 50 parts by mass-EO-modified trimethylolpropane acrylate 30 parts by mass-tridecyl acrylate 5 parts by mass-dodecyl acrylate 5 parts by mass-methyl methacrylate 5 parts by mass-hexyl methacrylate 5 parts by mass-diphenyl (2, 4,6-trimethoxybenzoyl) phosphine oxide (Lucillin TPO) 1 part by mass

(Preparation of comparative resin composition C)
The following components were mixed to prepare a comparative resin composition C for forming a microprojection structure.
-EO-modified bisphenol A diacrylate 70 parts by mass-Polyethylene glycol diacrylate 30 parts by mass-Diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (Lucirin TPO) 1 part by weight-Silica gel 5 parts by mass

(Production of mold 1)
The polished aluminum plate having a purity of 99.50% was polished and then anodized in an electrolyte solution of 0.02 M oxalic acid aqueous solution at an applied voltage of 40 V and 20 ° C. for 100 seconds. Next, as a first etching process, an etching process was performed for 50 seconds with the electrolytic solution after anodization. Subsequently, as the second etching treatment, a pore size treatment was performed for 120 seconds with a 1.0 M phosphoric acid aqueous solution. Furthermore, the said process was repeated and these were added and implemented 5 times in total. As a result, an anodized aluminum layer having minute holes formed densely on the aluminum substrate was formed. Finally, a mold release agent for forming a microprojection structure was obtained by applying a fluorine-based release agent and washing away the excess release agent. In addition, the fine uneven | corrugated shape formed in the aluminum layer of the metal mold | die 1 was the average distance between adjacent micropores of 100 nm, and the average depth of 160 nm. In addition, a part of the microholes which become microprotrusions having a plurality of vertices are present, and the part of the microholes has a variation in depth.

(Production of mold 2)
Except that the first etching treatment time was 60 seconds, the second etching treatment time was 130 seconds, and the repeating operation was additionally performed seven times, the average distance between adjacent micro-holes was 200 nm, the average A mold 2 for forming a microprojection structure having a depth of 160 nm was obtained. Note that the fine uneven shape formed on the aluminum layer of the mold 2 has a part of micro holes that become micro projections having a plurality of apexes, and some micro holes have variations in depth. It was a shape.

(Production of mold 3)
Except that the first etching treatment time was 70 seconds, the second etching treatment time was 170 seconds, and the repeating operation was additionally performed five times, in the same manner as in the fabrication of the mold 1, the average distance between adjacent micropores was 400 nm, the average A mold 3 for forming a microprojection structure having a depth of 210 nm was obtained. Note that the fine uneven shape formed in the aluminum layer of the mold 3 has a part of micro holes that become micro projections having a plurality of vertices, and some micro holes have variations in depth. It was a shape.

(Production of mold 4)
Except that the first etching treatment time was 70 seconds, the second etching treatment time was 170 seconds, and the repeating operation was additionally performed seven times, the average distance between adjacent micropores was 500 nm and the average was the same as in the manufacture of the mold 1. A mold 4 for forming a microprojection structure having a depth of 230 nm was obtained. In addition, the fine uneven shape formed in the aluminum layer of the mold 4 has a part of micro holes which become micro protrusions having a plurality of apexes, and some micro holes have variations in depth. It was a shape.

<Chemical vapor phase processing method>
As a chemical vapor treatment method for the surface of the microprojection structure, chemical vapor treatment was performed by the following treatment method.

(Chemical vapor phase processing method 1: CVD method)
The CVD method was performed in combination with RF GENERATOR PRF-153B (ANELVA) and processing unit DEA-506 (ANEVAVA) as energy control devices. A base material on which a microprojection structure to be described later was formed was installed on the reaction stage in the processing apparatus, and the degree of vacuum in the reaction chamber was set to 5 × 10 ⁻³ Pa or less.
Hexamethyldisiloxane (HMDSO; manufactured by Tokyo Chemical Industry Co., Ltd.) was put into a stainless steel container and connected to an argon (Ar) gas line. The stainless steel container containing HMDSO was heated on a 50 ° C. warm bath and vaporized to mix with Ar gas and perform the treatment. At this time, the temperature control and the throttle were adjusted so that the vaporization amount could be mixed by 3% with respect to the total Ar flow rate. The mixed gas was flowed at a flow rate of 100 sccm, the internal pressure in the reaction chamber was set to 50 mTorr, and plasma was generated at an energy of 100 W, followed by a CVD process for 3 minutes.
Argon gas having a purity of 99.999% (manufactured by Taiyo Nippon Sanso) was used.

(Chemical vapor phase treatment method 2: reactive ion etching method)
The reactive ion etching method was performed by combining RF GENERATOR PRF-153B (ANELVA) and processing device DEA-506 (ANELVA) as an energy control device in the same manner as the CVD method. A base material on which a microprojection structure to be described later was formed was installed on the reaction stage in the processing apparatus, and the degree of vacuum in the reaction chamber was set to 5 × 10 ⁻³ Pa or less. Next, tetrafluoromethane gas (produced by Showa Denko, purity: 100.00%) was flowed at a flow rate of 100 sccm, the internal pressure in the reaction chamber was changed to 50 mTorr, and plasma was generated at an energy of 100 W, followed by a reactive ion etching treatment for 2 minutes.

[Example 1]
The resin composition A is applied and filled so that the surface of the mold 2 having the concavo-convex shape is covered, and the thickness of the microprojection layer on which the microprojection structure is formed is 20 μm after curing. After a base material (material: PET, thickness: 25 μm, trade name: Lumirror, manufactured by Toray Industries, Inc.) was bonded from an oblique direction, the bonded body was pressed with a rubber roller under a load of 10 N / cm ² . After confirming that the uniform composition was applied to the entire mold, the resin was cured by irradiating ultraviolet rays with energy of 2000 mJ / cm ² from the substrate side. Thereafter, it was peeled from the mold to obtain a member 1 having a sheet-like microprojection structure on its surface (hereinafter, a member having a sheet-like microprojection structure on its surface was simply referred to as a sheet-like microprojection. Sometimes called a structure.)
When the cross section of the surface of the microprojection structure 1 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 200 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, the microprojection structure 1 was adhered to the surface of a mirror of a commercially available powder cosmetic container using an adhesive, whereby the powder cosmetic container 1 of Example 1 was obtained.

[Example 2]
In Example 1, except that the resin composition B was used in place of the resin composition A and the mold 1 was used in place of the mold 2, the sheet-like microprojection structure 2 was formed in the same manner as in Example 1. Obtained.
When the cross section of the surface of the microprojection structure 2 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 100 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, a powder cosmetic container 2 of Example 2 was obtained in the same manner as Example 1 except that the microprojection structure 2 was used instead of the microprojection structure 1.

[Example 3]
A sheet-like microprojection structure 3 was obtained in the same manner as in Example 1 except that the resin composition B was used in place of the resin composition A in Example 1.
When the cross section of the surface of the microprojection structure 3 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 200 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, a powder cosmetic container 3 of Example 3 was obtained in the same manner as Example 1 except that the microprojection structure 3 was used instead of the microprojection structure 1.

[Example 4]
A sheet-like microprojection structure 4 was obtained in the same manner as in Example 1 except that the mold 3 was used instead of the mold 2 in Example 1.
When the cross section of the surface of the microprojection structure 4 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 400 nm and an average microprojection height of 210 nm was formed. Moreover, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference of standard deviation 25 nm.
Next, a powder cosmetic container 4 of Example 4 was obtained in the same manner as Example 1 except that the microprojection structure 4 was used instead of the microprojection structure 1.

[Example 5]
In Example 1, except that the resin composition B was used instead of the resin composition A and the mold 3 was used instead of the mold 2, the sheet-like microprojection structure 5 was formed in the same manner as in Example 1. Obtained.
When the cross section of the surface of the microprojection structure 5 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 400 nm and an average microprojection height of 210 nm was formed. Moreover, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference of standard deviation 25 nm.
Next, a powder cosmetic container 5 of Example 5 was obtained in the same manner as Example 1 except that the microprojection structure 5 was used instead of the microprojection structure 1.

[Example 6]
A sheet-like microprojection structure 6 was obtained in the same manner as in Example 1 except that the mold 4 was used instead of the mold 2 in Example 1.
When the cross section of the surface of the microprojection structure 6 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 500 nm and an average microprojection height of 230 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 35 nm.
Next, a powder cosmetic container 6 of Example 6 was obtained in the same manner as Example 1 except that the microprojection structure 6 was used instead of the microprojection structure 1.

[Example 7]
In Example 1, except that the resin composition B was used instead of the resin composition A and the mold 4 was used instead of the mold 2, the sheet-like microprojection structure 7 was formed in the same manner as in Example 1. Obtained.
When the cross section of the surface of the microprojection structure 7 was observed by SEM, a microprojection group having an average distance between adjacent microprojections of 500 nm and an average microprojection height of 230 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 35 nm.
Next, a powder cosmetic container 7 of Example 7 was obtained in the same manner as Example 1 except that the microprojection structure 7 was used instead of the microprojection structure 1.

[Example 8]
The resin composition A is applied and filled so that the surface of the mold 2 having the concavo-convex shape is covered, and the thickness of the microprojection layer on which the microprojection structure is formed is 20 μm after curing. After a base material (material: PET, thickness: 25 μm, trade name: Lumirror, manufactured by Toray Industries, Inc.) was bonded from an oblique direction, the bonded body was pressed with a rubber roller under a load of 10 N / cm ² . After confirming that the uniform composition was applied to the entire mold, the resin was cured by irradiating ultraviolet rays with energy of 2000 mJ / cm ² from the substrate side. Then, it peeled from the metal mold | die and the sheet | seat 8 in which the microprotrusion group was formed was obtained.
When the cross section of the surface of the obtained sheet 8 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 100 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, the surface of the sheet 8 having the microprojection group was treated by the chemical vapor treatment method 1 to obtain a sheet-like microprojection structure 8.
Next, a powder cosmetic container 8 of Example 8 was obtained in the same manner as Example 1 except that the microprojection structure 8 was used instead of the microprojection structure 1.

[Example 9]
In Example 8, except that the resin composition B was used in place of the resin composition A, and the mold 1 was used in place of the mold 2, the sheet 9 on which the microprojection group was formed in the same manner as in Example 8. Got.
When the cross section of the surface of the obtained sheet 9 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 100 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 1 to obtain a sheet-like microprojection structure 9.
Next, a powder cosmetic container 9 of Example 9 was obtained in the same manner as Example 1 except that the microprojection structure 9 was used instead of the microprojection structure 1.

[Example 10]
In Example 8, except that the resin composition B was used instead of the resin composition A, a sheet 10 on which microprojections were formed was obtained in the same manner as in Example 8.
When the cross section of the surface of the obtained sheet 10 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 200 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 1 to obtain a sheet-like microprojection structure 10.
Next, a powder cosmetic container 10 of Example 10 was obtained in the same manner as Example 1 except that the microprojection structure 10 was used instead of the microprojection structure 1.

[Example 11]
In the same manner as in Example 9, a sheet 11 on which microprojections were formed was obtained.
When the cross section of the surface of the obtained sheet 11 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 100 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 2 to obtain a sheet-like microprojection structure 11.
Next, a powder cosmetic container 11 of Example 11 was obtained in the same manner as Example 1 except that the microprojection structure 11 was used instead of the microprojection structure 1.

[Example 12]
In the same manner as in Example 10, a sheet 12 on which microprojections were formed was obtained.
When the cross section of the surface of the obtained sheet 12 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 200 nm and an average microprojection height of 160 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 30 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 2 to obtain a sheet-like microprojection structure 12.
Next, a powder cosmetic container 12 of Example 12 was obtained in the same manner as Example 1 except that the microprojection structure 12 was used instead of the microprojection structure 1.

[Example 13]
In Example 8, except that the mold 3 was used in place of the mold 2, a sheet 13 on which microprojections were formed was obtained in the same manner as in Example 8.
When the cross section of the surface of the obtained sheet 13 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 400 nm and an average microprojection height of 210 nm was formed. Moreover, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference of standard deviation 25 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 2 to obtain a sheet-like microprojection structure 13.
Next, a powder cosmetic container 13 of Example 13 was obtained in the same manner as Example 1 except that the microprojection structure 13 was used instead of the microprojection structure 1.

[Implementation 14]
In Example 8, except that the resin composition B was used instead of the resin composition A, and the mold 3 was used instead of the mold 2, the sheet 14 on which the microprojection group was formed in the same manner as in Example 8. Got.
When the cross section of the surface of the obtained sheet 14 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 400 nm and an average microprojection height of 210 nm was formed. Moreover, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference of standard deviation 25 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 1 to obtain a sheet-like microprojection structure 14.
Next, a powder cosmetic container 14 of Example 14 was obtained in the same manner as Example 1 except that the microprojection structure 14 was used instead of the microprojection structure 1.

[Example 15]
In Example 8, except that the mold 4 was used instead of the mold 2, a sheet 15 on which microprojections were formed was obtained in the same manner as in Example 1.
When the cross section of the surface of the obtained sheet 15 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 500 nm and an average microprojection height of 230 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 35 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 1 to obtain a sheet-like microprojection structure 15.
Next, a powder cosmetic container 15 of Example 15 was obtained in the same manner as Example 1 except that the microprojection structure 15 was used instead of the microprojection structure 1.

[Example 16]
In Example 8, except that the resin composition B was used instead of the resin composition A, and the mold 4 was used instead of the mold 2, the sheet 16 on which the microprojection group was formed in the same manner as in Example 1. Got.
When the cross section of the surface of the obtained sheet 16 was observed with an SEM, a microprojection group having an average distance between adjacent microprojections of 500 nm and an average microprojection height of 230 nm was formed. Further, a part of the microprotrusions are microprotrusions having a plurality of vertices, and the height of each microprotrusion has a height difference with a standard deviation of 35 nm.
Next, the surface of the sheet having the microprojection group was treated by the chemical vapor treatment method 1 to obtain a sheet-like microprojection structure 16.
Next, a powder cosmetic container 16 of Example 16 was obtained in the same manner as Example 1 except that the microprojection structure 16 was used instead of the microprojection structure 1.

[Comparative Example 1]
The resin composition A was applied onto a substrate (material: PET, thickness: 25 μm, trade name: Lumirror, manufactured by Toray Industries, Inc.) so that the thickness after curing was 20 μm, and 2000 mJ / from the substrate side. By irradiating ultraviolet rays with an energy of cm ² to cure the resin, a comparative structure 1 having no microprojection structure was obtained.
Next, a powder cosmetic container 17 of Comparative Example 1 was obtained in the same manner as in Example 1 except that the comparative structure 1 was used instead of the microprojection structure 1.

[Comparative Example 2]
In Comparative Example 1, a comparative structure 2 having no microprojection structure was obtained in the same manner as in Comparative Example 1, except that the resin composition B was used instead of the resin composition A.
Next, a powder cosmetic container 18 of Comparative Example 2 was obtained in the same manner as in Example 1 except that the comparative structure 2 was used instead of the microprojection structure 1.

[Comparative Example 3]
Acrylic EX502 manufactured by Mitsubishi Rayon Co., Ltd. was attached to the surface of the mirror of a commercially available powder cosmetic container using an adhesive to obtain the powder cosmetic container 19 of Comparative Example 3 having no microprojection structure. .

[Comparative Example 4]
First, the anti-glare film which has an uneven | corrugated shape on the surface was produced by hardening the comparative resin composition C on a 25-micrometer-thick film. Next, the antiglare sheet of Comparative Example 4 is obtained by pasting the antiglare film on a base material (material: PET, thickness: 25 μm, trade name: Lumirror, manufactured by Toray Industries, Inc.) via an adhesive layer. It was.
When the cross section of the surface of the anti-glare sheet of Comparative Example 4 was observed with an SEM, the surface on the anti-glare film side had a minute protrusion with a variation in height within a height range of 10 to 800 nm, and the distance between adjacent minute protrusions. Irregular uneven | corrugated shape with which the average value of the distance of adjacent protrusions is 740 nm was irregularly arrange | positioned in the range of 500 nm-1 micrometer.
Next, a powder cosmetic container 20 of Comparative Example 4 was obtained in the same manner as in Example 1 except that the above antiglare sheet was used instead of the microprojection structure 1.

[Comparative Example 5]
Similar to Comparative Example 1, a structure 21 having no microprojection structure was obtained.
Next, the surface having the microprojections of the structure 21 was processed by the chemical vapor processing method 1 to obtain a sheet-like comparative structure 21.
Next, a powder cosmetic container 21 of Comparative Example 5 was obtained in the same manner as in Example 1 except that the comparative structure 21 was used instead of the microprojection structure 1.

[Comparative Example 6]
In Comparative Example 1, except that the resin composition B was used in place of the resin composition A, a structure 22 having no microprojection structure was obtained in the same manner as in Comparative Example 1.
Next, the surface having the microprojections of the structure 22 was treated by the chemical vapor treatment method 1 to obtain a sheet-like comparative structure 22.
Next, a powder cosmetic container 22 of Comparative Example 6 was obtained in the same manner as in Example 1 except that the comparative structure 22 was used instead of the microprojection structure 1.

<Measurement of contact angle>
The substrate-side surface of the sheet-like microprojection structure obtained in each Example and Comparative Example was attached to a black acrylic plate via an adhesive layer, and the microprojection structure on the side opposite to the black acrylic plate A drop of 1.0 μL of pure water (distilled water for liquid chromatography (manufactured by Junsei Chemical Co., Ltd.)) was dropped on the surface. The static contact angle was measured according to the θ / 2 method. The results are shown in Table 1.

<Powder cosmetic adhesion suppression evaluation>
The substrate-side surface of the sheet-like microprojection structure obtained in each example and comparative example is fixed on a 50 mm × 50 mm acrylic plate (Acrylite EX502) via an adhesive layer, and the fixed sheet Was cut into the same size as the acrylic plate. The charge on the surface of each sheet obtained by an ionizer (manufactured by ASONE, SFV-3000) was neutralized.
Each of the following five types of powder cosmetics (cosmetics A to E) is applied to the entire surface of the microprojection structure side surface of each sheet using a puff attached to each cosmetic, and the like, approximately 10 g / cm ^2. It was applied at a pressure of
Thereafter, the adhesion state of the powder was evaluated according to the following criteria by five test subjects.

(Powder cosmetic)
Cosmetic A: Kanebo Cosmetics Foundation, Cofredor Premium Silky Pact UV
Cosmetic B: Shiseido Foundation, Maquillage True Powder UV
Cosmetic C: Kanebo Cosmetics Eyeshadow, Coffredoll Full Smile Eyes Cosmetic D: Kao Co., Ltd. Eyeshadow Cosmetic, Orb Couture Designing Impression Eyes II
E: Teak manufactured by Kose Co., Ltd., Esprik Blend Creation Eye & Teak (Bitter Line)

(Powder cosmetic adhesion prevention evaluation criteria)
A: Powder adhesion was not recognized.
○: Slight adhesion of the powder was recognized, but it did not affect the visibility of the acrylic plate.
X: Adherence of the powder was recognized, and the visibility of the acrylic plate was deteriorated.
If the evaluation results are ◎ and ○, it is judged that the powder adhesion suppressing effect is excellent. The results are shown in Table 1.

[Summary of results]
From the results of Table 1, it is clear that the powder cosmetic containers of Examples 1 to 16 having fine protrusion structures having an average distance (pitch) between the protrusions of 500 nm or less suppress the adhesion of powder. It became.

DESCRIPTION OF SYMBOLS 1 Base material 2 Microprotrusion structure 2 'Receptive layer 3 Microprotrusion 3A, 3B Multimodal microprotrusion 3C Top microprotrusion 3D Peripheral microprotrusion 5, 5A, 5B Microprotrusion 10 Member 11 which provided the microprotrusion structure on the surface Die 12 roll mold (original)
13 Pressing roller 14 Peeling roller 22 Convex protrusion group 30 Microprotrusion structure 31 Microprotrusion structure surface 32 Microprotrusion 33 Uneven surface due to undulation 100 Powder cosmetic container 101 Container body 102A, 102B Container 103 Lid 104 Mirror 105A Engagement projection 105B Push button 105C Hook 106 Member 200 having a microprojection structure on its surface Powder cosmetic tester display stand 201 Tester receiving portion 202 Work table 203 Mirror 204 Tester unit

Claims (3)

  A powder cosmetic container comprising a container main body having a container for containing cosmetic containing powder, and a lid for closing the container main body, wherein at least an inner surface of the powder cosmetic container A part has a microprojection structure provided with a microprojection group in which a plurality of microprojections made of a cured product of a resin composition are closely arranged, and the average distance between adjacent microprojections is 500 nm. The cross-sectional area occupancy rate of the material portion forming the microprojection in a horizontal cross section when the microprojection is cut along a horizontal plane orthogonal to the depth direction of the microprojection is The powder cosmetic container which has a structure which increases gradually gradually as it approaches the deepest part direction from the top part.   The powder cosmetic container according to claim 1, wherein a mirror is provided inside the container, and a member having the microprojection structure on the surface is attached to the surface of the mirror.   It is a powder cosmetic tester display stand provided with a tester storage part for storing a cosmetic tester containing powder, and may further comprise a lid provided with an openable / closable upper surface of the tester storage part, At least a part of the surface of the display stand and the inner and outer surfaces of the lid body has a microprojection structure provided with a microprojection group in which a plurality of microprojections made of a cured resin composition are closely arranged. The average distance between adjacent microprotrusions is 500 nm or less, and the microprotrusions are formed in a horizontal cross section when it is assumed that the microprotrusions are cut along a horizontal plane perpendicular to the depth direction of the microprotrusions. A powder cosmetic tester display stand having a structure in which a cross-sectional area occupancy ratio of a material portion to be continuously increased gradually from the top of the microprotrusion toward the deepest portion.