JP2016087574A - Self-cleaning component and method for manufacturing self-cleaning component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a self-cleaning component which can exhibit an excellent cleaning performance over an extended period, and a method for manufacturing the self-cleaning component.SOLUTION: A self-cleaning component is equipped with a linear fine uneven layer 1 which has, on a surface thereof, a linear fine uneven shape 3 in which plural linear salients 2 parallel to one another are extended in one direction or substantially one direction and which comprises a cured product of a resin composition. In the linear fine uneven shape 3, an average value pof a distance p between adjacent linear salients is equal to or less than 500nm. On the surface having the linear fine uneven shape 3 of the linear fine uneven layer 1, a static contact angle of water is equal to or less than 30°, and is smaller than a static contact angle of n-hexadecane.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a self-cleaning member and a method for manufacturing the self-cleaning member.

In windows, walls, mirrors, and the like of vehicles such as buildings and automobiles, there is a demand for performance that can prevent adhesion of dirt and easily remove the attached dirt.
For example, Patent Document 1 discloses that a light-transmitting and photocatalytic function is provided on the surface of a transparent substrate member such as a glass substrate or mirror glass as a hydrophilic thin film having excellent long-term antifogging and antifouling performance that can be used for automobile mirrors and the like. the TiO ₂ are laminated, the arithmetic average roughness of the unevenness of the crystal shape and the TiO ₂ surface of the TiO ₂ surface is hydrophilic thin film having a specific structure are disclosed.

  Patent Document 2 discloses a method for cleaning a composite material in which the surface of the composite material having a hydrophilic surface layer having a concavo-convex structure without photocatalysis is washed with acidic water. By fixing a surfactant and / or a hydrophilic substance and a sustained release substance having a sustained release property to water on the outermost surface of the material, the surfactant and the hydrophilic substance are gradually prevented from flowing down immediately. It is described that it is possible to keep the hydrophilicity of the composite material for a long period of time while maintaining the hydrophilicity and releasing the dirt easily.

  Patent Document 3 discloses a so-called moth-eye structure in which a surface of a transparent substrate is provided with a fine concavo-convex structure made of a transparent material, and the interval between the convex vertices of the fine concavo-convex structure is shorter than the wavelength of visible light. It is disclosed that the wettability on the fine uneven surface is controlled by using a transparent material that prevents reflection and selects a transparent material having a desired contact angle with water.

  Patent Document 4 includes a base material and a groove formed by removal processing on the surface of the base material for the purpose of expressing hydrophilicity, antifogging property, and self-cleaning property. A molded structure in which the maximum width is equal to or less than the shortest wavelength of visible light and the minimum width between adjacent grooves is equal to or greater than the longest wavelength of visible light is disclosed, as compared with the case where the width between grooves is 300 nm or 500 nm. It is described that light diffraction, refraction, and interference are suppressed when the wavelength is longer than the longest wavelength of visible light such as 1 μm and 4 μm, and transparency is maintained when the substrate is a transparent material. Yes. Patent Document 4 specifically describes a molded structure in which a concavo-convex structure having a recess pitch of 1 μm, a recess groove width of 250 nm, and a depth of 150 nm is formed on a glass plate by a thermal lithography method. Has been.

JP 2002-201045 A JP 2000-308861 A JP 2007-187868 A JP 2009-193002 A

However, since a member using a photocatalyst material such as a hydrophilic thin film described in Patent Document 1 needs to be irradiated with light in order to exhibit cleaning performance, if the light irradiation is insufficient, the cleaning performance is poor. It is not fully demonstrated.
As in the composite material described in Patent Document 2, a member using a component that deteriorates with time, such as a surfactant, has a problem that the cleaning performance also deteriorates as the component deteriorates with time. is there.

  Like the moth-eye structure described in Patent Document 3, the fine concavo-convex structure in which a large number of minute protrusions are closely arranged has a surface structure, so that when another article comes into contact with it or wipes off dirt. There is a problem with durability during use, such as when the pressure at the time of removal causes plastic deformation such as the protrusions to be easily crushed or the tips of the protrusions to adhere to each other, and wiping marks may remain in the wiped place. there were. Further, like the moth-eye structure, the fine concavo-convex structure in which a large number of minute protrusions are arranged closely is not easy to produce a molding die used in production with a large area, Also, when manufacturing using a technique such as anodic oxidation, chemical etching, blasting, etc. to form a plurality of micropores, it is difficult to control the variation of the micro unevenness, and the molding resin is clogged with the micro unevenness. There was also a problem from the viewpoint of productivity, for example, because the life of the molding die was short because it was easy.

  When the width between adjacent grooves is more than 500 nm as in the molded structure described in Patent Document 4, the cleaning performance is inferior as shown in Comparative Example 6 described later, and further, compared with the present invention. Inferior optical properties such as low reflectivity and transparency. In addition, since the molded structure described in Patent Document 4 is a technique for manufacturing a groove in a glass substrate using a reactive etching apparatus, it is difficult to manufacture a molded product with a large area, and mass production is possible. It was inferior to.

  The present invention has been made in view of the above problems, and an object thereof is to provide a self-cleaning member that can exhibit excellent cleaning performance for a long period of time and is excellent in mass productivity, and a method for manufacturing the self-cleaning member. And

The self-cleaning member according to the present invention has a linear fine concavo-convex shape having a plurality of parallel linear protrusions extending in one direction or substantially one direction on the surface, and a line made of a cured product of the resin composition. Provided with a fine uneven layer,
In the linear fine concavo-convex shape, an average value p _{AVG of} adjacent linear convex portion intervals p is 500 nm or less,
The static contact angle of water is 30 ° or less and the static contact angle of water is smaller than the static contact angle of n-hexadecane on the surface of the linear fine unevenness layer having the linear fine unevenness shape. It is characterized by that.

The method for producing a self-cleaning member according to the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear protrusions extend in one direction or substantially one direction on the surface, and a cured product of the resin composition In the linear fine concavo-convex shape, the average value p _AVG of the adjacent linear convex portion intervals p is 500 nm or less, and the linear fine concavo-convex shape of the linear fine concavo-convex layer is provided. A surface having a static contact angle of water of 30 ° or less and a static contact angle of water smaller than that of n-hexadecane,
A step of manufacturing a forming roll mold by sequentially forming a plurality of grooves arranged in parallel along the circumferential direction on the outer peripheral surface of the cylindrical base material by cutting using a cutting tool;
And a step of forming the linear fine concavo-convex shape on the surface by a forming process using the forming roll mold.

  ADVANTAGE OF THE INVENTION According to this invention, the outstanding cleaning performance can be exhibited for a long period of time, and the manufacturing method of the self-cleaning member excellent in mass productivity and the said self-cleaning member can be provided.

It is a perspective view which shows typically an example of the self-cleaning member which concerns on this invention. It is a perspective view which shows typically another example of the self-cleaning member which concerns on this invention. FIG. 2 is a partially enlarged view of a schematic cross-sectional view of the self-cleaning member 10 shown in FIG. 1. 4A to 4E are schematic views of specific examples of vertical cross sections of the linear fine concavo-convex layer with respect to the extending direction Y of the linear fine concavo-convex shape. FIG. 5A to FIG. 5D are schematic views of other specific examples of the vertical cross section of the linear fine uneven layer with respect to the extending direction Y of the linear fine uneven shape. It is a figure where it uses for description of the adjacent linear convex part space | interval p. It is a conceptual diagram for demonstrating the washing | cleaning method by the self-cleaning member which concerns on this invention. It is a figure where it uses for description of the process of manufacturing the roll mold 20 for shaping. It is the typical sectional view which expanded a perpendicular section to the extending direction of the linear fine concavo-convex shape of the cutting edge of a cutting tool partially. It is the schematic which shows an example of the formation method of a linear fine uneven | corrugated layer. 2 is a SEM photograph of a cross section of a self-cleaning member obtained in Example 1. It is a figure where it uses for description of the contact angle of the water of the extension direction of a linear convex part, and the contact angle of the water of the direction perpendicular | vertical to the extension direction of a linear convex part.

In the present invention, (meth) acrylate represents each of acrylate or methacrylate, and (meth) acryloyl represents each of acryloyl or methacryloyl.
Further, as used herein, the shape and geometric conditions and the degree thereof are specified. For example, terms such as “parallel”, “vertical”, “same”, length and angle values, etc., are strictly Without being bound by meaning, it should be interpreted including the extent to which similar functions can be expected.

The self-cleaning member according to the present invention has a linear fine concavo-convex shape having a plurality of parallel linear protrusions extending in one direction or substantially one direction on the surface, and a line made of a cured product of the resin composition. Provided with a fine uneven layer,
In the linear fine concavo-convex shape, an average value p _{AVG of} adjacent linear convex portion intervals p is 500 nm or less,
The static contact angle of water is 30 ° or less and the static contact angle of water is smaller than the static contact angle of n-hexadecane on the surface of the linear fine unevenness layer having the linear fine unevenness shape. It is characterized by that.

The method for producing a self-cleaning member according to the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear protrusions extend in one direction or substantially one direction on the surface, and a cured product of the resin composition In the linear fine concavo-convex shape, the average value p _AVG of the adjacent linear convex portion intervals p is 500 nm or less, and the linear fine concavo-convex shape of the linear fine concavo-convex layer is provided. A surface having a static contact angle of water of 30 ° or less and a static contact angle of water smaller than that of n-hexadecane,
A step of manufacturing a forming roll mold by sequentially forming a plurality of grooves arranged in parallel along the circumferential direction on the outer peripheral surface of the cylindrical base material by cutting using a cutting tool;
And a step of forming the linear fine concavo-convex shape on the surface by a forming process using the forming roll mold.

The self-cleaning member according to the present invention will be described with reference to the drawings. 1 and 2 are perspective views schematically showing an example of a self-cleaning member according to the present invention. The self-cleaning member 10 shown in FIG. 1 has a linear fine concavo-convex shape 3 on the surface, in which a plurality of parallel linear protrusions 2 extend in a common direction Y, and a predetermined resin composition is cured. The linear fine uneven | corrugated layer 1 which consists of a thing is provided.
The self-cleaning member according to the present invention may be composed of one layer of the linear fine concavo-convex layer 1 as shown in FIG. 1, or the linear fine concavo-convex on one surface side of the substrate 4 as shown in FIG. A structure including the layer 1 may be used.
Further, although not shown, the self-cleaning member according to the present invention may have a structure in which the linear fine concavo-convex layer 1 is provided on both sides of the base material 4. In this case, the angle formed by the extending directions of the linear fine irregularities on the front and back sides is not particularly limited.

FIG. 3 is a partially enlarged view of the schematic cross-sectional view of the self-cleaning member 10 shown in FIG. FIG. 3 shows a schematic cross-sectional view in a vertical cross section with respect to the extending direction Y of the linear fine concavo-convex shape. In the linear fine concavo-convex shape 3 of the linear fine concavo-convex layer 1, the linear convex portions 2 are parallel to each other, and the interval p between adjacent linear convex portions 2, that is, the end of the linear convex portion 2 in the vertical cross section. The average value p _AVG of the interval p from the portion 5 to the end 5 ′ of the adjacent linear convex portion is 500 nm or less.
The interval (pitch) between these linear protrusions may be the same or different, or may have a predetermined repetition period, but the average value _pAVG needs to be 500 nm or less.

The self-cleaning member according to the present invention has a linear fine concavo-convex shape having a plurality of parallel linear protrusions extending in one direction or substantially one direction on the surface, and a line made of a cured product of the resin composition. In the linear fine concavo-convex shape, the adjacent linear convex interval p has a specific value, and the surface having the linear fine concavo-convex shape (linear fine concavo-convex surface) Even when oil stains adhere to the surface of the linear fine irregularities because the static contact angle is less than the specific value and the static contact angle of water is smaller than the static contact angle of n-hexadecane. The oil stain can be easily removed only with water, and the oil stain is difficult to adhere to the surface of the linear fine irregularities previously covered with water. As described above, the self-cleaning member according to the present invention has a performance that can easily lift and remove the attached oil stain by simply supplying water, and if it is covered with water in advance, the oil stain can be removed. It has excellent performance that is difficult to adhere (referred to as cleaning performance in the present invention). The self-cleaning member according to the present invention is not automatically supplied with water in a use environment, but is used in an environment where the cleaning performance is exhibited at the time of washing with water and in an environment where water is supplied. Therefore, those that exhibit the cleaning performance under the usage environment are included.
The “oil stain” in the present invention is not limited to oil, but also includes lipophilic soil, that is, all soils due to lipophilic substances. In view of the above-described action, the self-cleaning member of the present invention is particularly suitable for use in cleaning the oil stain.
Since the surface of the linear fine irregularities of the self-cleaning member according to the present invention has a smaller static contact angle of water than that of n-hexadecane, The affinity of is greater. Here, it can be said that a liquid having a smaller contact angle generally has a higher affinity, but considering the difference in surface tension, the relationship between the contact angles cannot simply be applied to the affinity relationship. On the other hand, since the surface tension of water is larger than that of n-hexadecane, if the static contact angle of water on the surface of the linear fine irregularities is equivalent to the static contact angle of n-hexadecane, It can be said that the fine uneven surface has a higher affinity for water than the affinity for n-hexadecane. However, the linear fine uneven surface of the present invention has a static water contact angle of n-hexadecane. Smaller than the typical contact angle. Therefore, it can be said that the linear fine uneven surface of the present invention has a greater affinity for water than n-hexadecane and a higher hydrophilicity than lipophilicity. This is because when the surface of the linear fine irregularities has the specific linear fine irregularities, the surface area is increased compared to the flat surface, and a hydrophilic material is used due to the hydrophilic emphasis effect. It is estimated that the water contact angle tends to be smaller. In addition, when water adheres to the periphery of the oil stain on the surface of the linear fine irregularities of the self-cleaning member according to the present invention, water having a higher affinity to the surface of the linear fine irregularities is submerged under the oil stain while the linear fine It is thought that the oily soil can be lifted by water and spread on the uneven surface. This is because the surface of the fine line irregularities is more hydrophilic than lipophilic, so that the water tends to wet and spread. It is estimated that the structure is easy. Furthermore, in the self-cleaning member according to the present invention, the extending direction of the linear convex portion is longer than the direction perpendicular to the extending direction of the linear convex portion by having the specific linear fine uneven surface. Thus, it has been found that water is more likely to spread. Therefore, it is considered that water supplied to the surface of the linear fine irregularities is more likely to sink under oil stains in the extending direction of the linear convex portions.
Moreover, since the self-cleaning member of this invention can flow water easily along the extension direction of a linear convex part, the extension direction of a linear convex part can be made into the flow path of water. Therefore, in this invention, the flow path of water is controllable by adjusting the direction of the extension direction of a linear convex part. For example, when the self-cleaning member according to the present invention is installed so that the extending direction of the linear convex portion is the vertical direction, the water supplied to the surface of the linear fine unevenness is along the extending direction of the linear convex portion. Therefore, the vertical direction is the water flow path. In this case, since water easily wets and spreads even by gravity, water is more likely to sink under the oil stain adhering to the surface of the linear fine irregularities, and the floating oil stain is more likely to be removed.
As described above, the self-cleaning member according to the present invention is considered to exhibit excellent cleaning performance when the surface of the linear fine irregularities has the specific linear fine irregularities and the specific contact angle.
In addition, the self-cleaning member according to the present invention does not require light irradiation in order to exert the cleaning performance unlike the self-cleaning member using the conventional photocatalyst material, so that it is easily excellent even in a dark place. The cleaning performance can be exhibited.
Furthermore, since the self-cleaning member according to the present invention does not include components that deteriorate with time, such as a surfactant, the cleaning performance does not deteriorate due to deterioration of the contained components, and since no photocatalytic material is included, The linear fine irregularities on the surface of the fine irregularities are not decomposed and destroyed by the photocatalytic material.
In addition, the self-cleaning member according to the present invention is superior in the structural durability of the convex portion itself compared to a fine uneven shape in which micro projections called so-called moth-eye structures are closely arranged. Even if it consists of hardened | cured material of this, a convex part is crushed or adhesion of the front-end | tips of a convex part does not arise easily. Further, the self-cleaning member of the present invention is more soiled than a fine uneven surface formed by wiping the surface of the linear fine irregularities along the linear convex portions, so that the so-called moth-eye structure is arranged closely. Is easy to remove and the surface appearance is unlikely to deteriorate. As described above, since contamination and deformation during use are suppressed, the self-cleaning member according to the present invention is not easily deteriorated in cleaning performance and is excellent in sustainability of cleaning performance.
In addition, the self-cleaning member of the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear protrusions extend in one direction or substantially one direction on the surface, and is made of a cured product of the resin composition. Since the linear fine concavo-convex layer is provided, it can be manufactured by a highly productive manufacturing method as described later. According to the manufacturing method, since a large-area self-cleaning member can be manufactured in a long shape, it is not necessary to join small-sized molded structures together as in Patent Document 4. Therefore, even a large-area self-cleaning member can be manufactured with high productivity.
Hereinafter, the linear fine concavo-convex layer that is an essential component of the self-cleaning member according to the present invention, the base material that may be included, and other configurations will be described in order.

<Linear fine uneven layer>
The linear fine concavo-convex layer 1 has on the surface a linear fine concavo-convex shape 3 in which a plurality of parallel linear convex portions 2 extend in one direction or substantially one direction. The linear convex portion 2 is typically a linear convex portion, but may be an open curved convex portion having two end points as long as it extends in substantially one direction. The plurality of linear protrusions are parallel to each other, but in the present invention, “parallel” means that the interval between adjacent linear protrusions is constant. For example, the line of the linear protrusions is curved. When included, it means being at a certain distance in the normal direction from each point on the curve.
Further, in the present invention, assuming that the “one direction” is a direction parallel to the Y axis on the assumption of the XY plane as shown in FIG. 1, the “substantially one direction” means the (x, y) coordinates of the end points. In comparison, the x value may increase or decrease, but the y value gradually increases. That is, the linear convex portion may be a curve such as a meandering curve as long as it does not have a direction to return to the original in the Y-axis direction, that is, a direction in which the y value decreases.

As a specific example of the vertical cross-sectional shape with respect to the extending direction Y of the linear convex portion 2, FIGS. 4A to 4E are schematic diagrams of specific examples of the vertical cross-section with respect to the extending direction Y of the linear fine uneven shape. A cross-sectional view is shown. As a vertical cross-sectional shape with respect to the extending direction Y of the linear protrusion 2, for example, a rectangular shape as shown in FIG. 4A, a triangular shape as shown in FIGS. 4B and 4C, FIG. Examples thereof include a parabolic shape such as D) and a vertical cross-sectional shape such as a bell shape, a semicircular shape, a semielliptical shape and a quadrangular shape (not shown). Further, as shown in FIG. 4E, it may have a stepped cross section in which the line width becomes narrower in the Z-axis direction.
In the schematic cross-sectional view in the vertical cross section with respect to the extending direction Y of these linear fine irregularities, the Y direction in which the linear convex portion extends is the depth direction of the drawing.

The vertical cross-sectional shape is not limited to a symmetric structure with respect to the Z axis passing through the apex, and may be an asymmetric structure. As other specific examples of the vertical cross-sectional shape with respect to the extending direction Y of the linear convex portion 2, other specific examples of the vertical cross-section with respect to the extending direction Y of the linear fine concavo-convex shape in FIGS. An exemplary schematic cross-sectional view is shown. For example, a triangular shape as shown in FIG. 5A may be used, or one side is a triangle with respect to the Z-axis direction passing through the apex as shown in FIG. Alternatively, one side is triangular with respect to the Z-axis direction passing through the apex as shown in FIG. 5C, but one side may be semi-elliptical. In addition, although not shown in the figure, in the case of having a stepped cross section whose line width becomes narrower in the Z-axis direction, the central axis after the second step of the stepped cross section is shifted from the central axis of the first step. Also good.
Further, the heights of the linear protrusions 2 may be the same or different. For example, as shown in FIG. 5D, a linear convex portion having a relatively high height, such as one in n adjacent linear convex portions, may be included. Further, although not shown, the heights may be different in the extending direction of the linear protrusions. When linear protrusions that are relatively high in height are included periodically in directions parallel to each other, a self-cleaning member with high productivity and improved contamination resistance and scratch resistance can be obtained.
Further, the plurality of linear convex portions may have the same shape or different shapes.

  For example, when the vertical cross-sectional shape has a structure in which the line width becomes narrower in the Z-axis direction, the refractive index continuously changes in the depth direction of the convex portion, so that the antireflection property Is granted. Moreover, the direction where the specific surface area of a linear convex part becomes large improves the hydrophilic property of a linear fine uneven | corrugated surface, and improves cleaning performance. For example, when the linear protrusions have the same height, the vertical cross-sectional shape is preferably a square rather than a triangle from the viewpoint of cleaning performance. For example, in the case of having a step-like cross section in which the line width becomes narrower in the Z-axis direction, hydrophilicity is improved in terms of specific surface area, cleaning performance is improved, and optical functions such as antireflection properties are provided. It is preferable from the point which improves.

  In the present invention, the linear protrusion interval p and the linear protrusion height H are measured by the following method. First, a vertical cross-sectional shape with respect to the extending direction Y of the linear convex portion is detected using an atomic force microscope (AFM) or a scanning electron microscope (SEM).

Subsequently, in the vertical cross-sectional shape with respect to the extending direction Y of the linear protrusions, an end corresponding to the root position of each linear protrusion is detected. One end portion (5a) on the same side is selected from the end portions (5a, 5b) of each linear convex portion. The distance between one end 5a on the same side of the ends of the linear protrusions and one end 5′a on the same side of the adjacent linear protrusions is the distance between adjacent protrusions, that is, adjacent linear It is set as the convex part space | interval p (refer FIG. 6).
From the enlarged photograph of the vertical cross-sectional shape with respect to the extending direction Y of the linear projections, for example, the value of about 10 to 100 adjacent linear projection intervals p is obtained, and the frequency distribution of the adjacent linear projection intervals p is calculated. To detect. When the adjacent linear protrusion interval p is substantially constant, the number of adjacent linear protrusion intervals p to be obtained may be small, but when the adjacent linear protrusion interval p changes periodically. It is preferable to obtain more adjacent linear convex part intervals p when the adjacent linear convex part interval p changes without a period for at least five periods.
The average value p _AVG and the standard deviation σ are obtained from the frequency distribution of the linear convex portion intervals p thus obtained. In addition, the maximum value of the interval between adjacent convex portions p is set to p _max = p _AVG + 2σ.

  Moreover, the height H of a linear convex part is calculated | required by applying the same method. From the enlarged photograph of the vertical cross-sectional shape with respect to the extending direction Y of the linear convex part, the local maximum point in each linear convex part is detected. Using the base position 7 of each linear projection as a reference (height 0), a relative height difference H of each maximum point position is acquired from the reference position (see FIG. 3) and is histogrammed. In addition, when there are a plurality of vertices in the vertical cross-sectional shape of the linear convex portion, the highest vertex of the plurality of vertices belonging to the same convex portion is the maximal point, and the convex portion Get the height and find the frequency distribution.

  As shown in FIG. 6, in the interval p between adjacent linear protrusions, the width w of each linear protrusion, that is, the distance between the ends (5a and 5b) of each linear protrusion, It may be the same as or different from the convex part interval p. Moreover, although the ratio for which the width w of each linear convex part accounts in the adjacent linear convex part space | interval p is not specifically limited, It is preferable that w / p is 0.3-0.7 from a durable point.

In the self-cleaning member of the present invention, the average value p _AVG of the adjacent linear protrusion interval p is 500 nm or less, but from the viewpoint of production, the p _AVG is 10 nm or more, and preferably 50 nm or more. Especially, the average value _pAVG of the adjacent linear convex part space | interval p is preferably 100 nm or more and 250 nm or less from the viewpoint that expression of various performances described later is improved. When p _AVG exceeds 500 nm, a problem of becoming whitish due to scattering of visible light appears. Moreover, the malfunction that the hydrophilic emphasis effect resulting from the linear fine unevenness | corrugation surface falls appears.

Further, the average height H _AVG of the linear protrusions, which is the average of the heights H of the linear protrusions, is preferably 500 nm or less, and is 10 nm or more from the viewpoint of production, and more preferably 50 nm or more.
Especially, from the point which expression of the various performance mentioned later improves, More preferably, it is 70 nm or more, and is 250 nm or less.

It is preferable that the aspect ratio of the linear convex portions (average height of linear convex portions H _AVG / average interval between adjacent linear convex portions p _AVG ) is 0.4 to 5.0, and further 0.5 to 2 0.5, more preferably 0.5 to 2.1. If the aspect ratio is too small, it is difficult to develop hydrophilicity, and if it is too large, mechanical strength and productivity are lowered.

What is necessary is just to adjust the thickness of a linear fine uneven | corrugated layer suitably. For example, in the case of an aspect provided with a linear fine uneven layer on one surface side of the substrate, the thickness of the linear fine uneven layer can be variously set at a minimum thickness capable of forming a linear fine uneven shape on the substrate surface. Performance can be expressed. However, in consideration of productivity in the molding process described later, appearance defects due to foreign substances are likely to occur when the thickness is thin, and if the thickness is thick, the molding speed is reduced and the concern about curling is increased. Preferably, it is 5 μm to 10 μm. The thickness T of the linear fine concavo-convex layer in this case refers to the thickness from the interface of the linear fine concavo-convex layer to the base material to the top of the highest linear convex portion.
The self-cleaning member according to the present invention may not have a base material, and the linear fine concavo-convex layer is formed by using the same material for the linear fine concavo-convex layer and the base material. And the base material may be integrated. The linear fine uneven layer in this case is not particularly limited because it depends on the thickness of the substrate.

In this invention, a linear fine uneven | corrugated layer consists of the hardened | cured material of a resin composition. In addition, in this invention, hardened | cured material means what solidified through or without passing through a chemical reaction.
The resin composition contains at least a resin and, if necessary, other components such as a polymerization initiator. In addition, in this invention, resin is the concept containing a polymer other than a monomer and an oligomer.
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 resins, polycarbonate resins, polyethylene resins, polypropylene resins, and the like, and various types of curing resins 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 because it is excellent in moldability and mechanical strength. The ionizing radiation curable resin used in the present invention is a mixture of a monomer or a polymer having radically polymerizable and / or cationically polymerizable bonds in a molecule as appropriate, and ionized using a suitable polymerization initiator. It is cured by radiation. Further, in the present invention, being excellent in moldability means that it can be accurately molded into a desired shape.
Among them, the resin composition used in the present invention preferably contains at least one selected from the group consisting of acrylate-based, epoxy-based, and polyester-based ionizing radiation curable resins, and further includes an acryloyl group and / or a methacryloyl group. It is preferable to contain at least one selected from acrylate-based ionizing radiation curable resins.

As the resin composition containing at least one selected from acrylate ionizing radiation curable resins having an acryloyl group and / or a methacryloyl group, for example, an ionizing radiation curable resin composition containing (meth) acrylate is preferably used. .
The (meth) acrylate is a polyfunctional acrylate having two or more (meth) acryloyl groups in one molecule, even if it is a monofunctional (meth) acrylate having one (meth) acryloyl group in one molecule. Alternatively, monofunctional (meth) acrylate and polyfunctional (meth) acrylate may be used in combination.

Specific examples of 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.
The content of the monofunctional (meth) acrylate is preferably 0 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.
It is preferable that content of the said polyfunctional (meth) acrylate is 10-99 mass% with respect to the total solid of an ionizing radiation-curable resin composition.

The ionizing radiation curable resin composition is preferably a composition containing a polyfunctional (meth) acrylate containing alkylene oxide from the viewpoint of improving hydrophilicity and consequently improving cleaning performance.
Especially, it is preferable that content of the polyfunctional (meth) acrylate containing the said alkylene oxide is 15-99 mass% with respect to the total solid of an ionizing radiation-curable resin composition. Moreover, it is preferable that content of the polyfunctional (meth) acrylate containing the said alkylene oxide is 20-100 mass% with respect to all the (meth) acrylate compounds used.

In order to start or accelerate the curing reaction of the (meth) acrylate, a photopolymerization initiator may be appropriately selected and used as necessary. Specific examples of the photopolymerization initiator include, for example, 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.

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 the components except a solvent.

  The resin composition used in the present invention may further comprise a polymerization initiator, a release agent, a photosensitizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, and a viscosity adjustment as necessary. An agent, an adhesion improver, etc. can also be contained.

Further, the resin composition used in the present invention is not particularly limited, but from the viewpoint of cleaning performance, it is preferable that the static contact angle of water on the surface as a flat cured film is 80 ° or less, More preferably, it is 60 ° or less, particularly preferably 50 ° or less, and the static contact angle of n-hexadecane is preferably 85 ° or less, more preferably 70 ° or less, particularly preferably 60 ° or less. is there.
The resin composition used in the present invention is not particularly limited, but the static contact angle of water on the surface when a flat cured film is formed is smaller than the static contact angle of n-hexadecane, and water From the viewpoint of cleaning performance, the difference between the static contact angle and the static contact angle of n-hexadecane is preferably 1 ° or more, and more preferably 2 ° or more. As a result, the self-cleaning member of the present invention is capable of easily floating and removing the attached oil stains just by supplying water, and if it is covered with water in advance, the oil stains adhere. Both difficult performance is improved.
In the present invention, the static contact angle is a value calculated by the θ / 2 method. Moreover, a general contact angle meter can be used for the measurement of a static contact angle, for example, the DropMaster series contact angle meter made by Kyowa Interface Science Co., Ltd. can be used.
A flat cured film of the resin composition can be obtained by applying and curing a resin composition for a linear fine concavo-convex layer on a substrate having a flat surface. The cured film was sufficiently dried with a solvent so that the reproducibility of the static contact angle of pure water could be obtained (for example, the standard deviation was within 4 °), and cured sufficiently by reacting as necessary. Shall. For example, when an ionizing radiation curable resin is used, a coating film made of a resin composition for a linear fine concavo-convex layer having a thickness of 5 μm is formed on a transparent substrate, and ultraviolet rays are accumulated in an amount of 940 mJ / cm ² or more. Irradiation is performed to form a cured film that is sufficiently reacted and cured.

The transmittance of the linear fine concavo-convex layer can be appropriately adjusted depending on the application, and is not particularly limited. The transmittance in the visible light region may be 80% or more, or less than 80%. It may be translucent or opaque.
When the self-cleaning member according to the present invention is used as a transparent member, the transmittance of the linear fine concavo-convex layer in the visible light region is preferably 80% or more, more preferably 90% or more, and 95%. It is still more preferable that it is above.

<Base material>
The self-cleaning member according to the present invention may include a base material as a support. The base material used for this invention can be suitably selected according to a use, and is not specifically limited. 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, Polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer and other resins, soda glass, potassium glass, alkali-free glass, lead glass, etc., lead lanthanum zirconate titanate (PLZT) ), Etc., inorganic materials such as quartz and fluorite, metals, paper, wood, and composite materials thereof. According to the production method of the present invention, not only a substrate having high heat resistance but also a resin substrate having relatively low heat resistance can be suitably used.

The shape of the base material is not particularly limited, and may be a sheet shape, a rod shape, or a molded body formed into a predetermined shape. In the present invention, the sheet shape means a flat shape whose thickness is small for the length and width, and is supplied in the form of a roll, which does not bend to the extent that it can be wound, but is curved by applying a load. It includes meanings that do and those that do not bend completely. Further, when a self-cleaning member having a large area is used, it is preferable to use a long or roll-shaped base material in terms of production.
The thickness of the sheet-like substrate used in the present invention can be appropriately set according to the use of the self-cleaning member of the present invention, and is not particularly limited, but is usually 10 to 5000 μm.

The transmittance in the visible light region of the substrate used in the present invention can be appropriately adjusted depending on the application, and is not particularly limited. A transparent substrate having a transmittance in the visible light region of 80% or more may be used. It is also possible to use less than 80% translucent or opaque substrates. Here, the transmittance | permeability of a transparent base material can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).
When the self-cleaning member according to the present invention is used for a transparent member such as a window or a liquid crystal protective film, a transparent substrate is preferably used as the substrate.
Moreover, when installing the self-cleaning member which concerns on this invention in a glass part, it is preferable to use polyester-type resin base materials, such as a polyethylene terephthalate (PET), from the point which provides the scattering resistance at the time of glass breakage.

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.
Moreover, you may form the primer layer on a base material for improving the adhesiveness of a base material and a linear fine uneven | corrugated layer, and, thereby improving abrasion resistance (scratch resistance). This primer layer preferably has adhesiveness to both the base material and the linear fine concavo-convex layer and transmits visible light. If interference unevenness occurs due to the difference in refractive index between the substrate and the linear fine uneven layer, the unevenness can be reduced by adjusting the refractive index of the primer layer to an intermediate value between the substrate and the linear fine uneven layer. .

<Other layers>
The self-cleaning member according to the present invention may further have other layers as long as the effects of the present invention are not impaired. For example, it can further have various conventionally known layers for optical film use on the side of the substrate that does not have the linear fine uneven layer. Specific examples of the other layers include, for example, a single layer or multilayer antireflection layer, a layer imparting antiglare properties by light diffusion, a hard coat layer for preventing scratches, an ultraviolet absorbing layer (UVA layer). ), A heat dissipation layer (thermal conductive layer), and the like.

  In the self-cleaning member according to the present invention, a peelable protective film may be temporarily bonded to the surface of the linear fine unevenness. Thereby, in a state where the protective film is temporarily bonded to the surface of the linear fine irregularities, the self-cleaning member according to the present invention is stored, transported, traded, post-processed or constructed, and the protective film is peeled and removed in a timely manner. Therefore, damage and contamination of the surface of the linear fine irregularities during storage, transportation, etc. can be prevented.

  In addition, the self-cleaning member according to the present invention is an adhesive processed product in which an adhesive layer is formed on a surface that does not have a fine uneven shape, and a release film is further laminated on the surface of the adhesive layer in a peelable manner. You can also. As the adhesive, various types of known adhesive forms such as a pressure-sensitive adhesive (pressure-sensitive adhesive), a two-component curable adhesive, an ultraviolet curable adhesive, a thermosetting adhesive, and a hot-melt adhesive can be used. .

<Physical properties of self-cleaning member>
The self-cleaning member according to the present invention has a static contact angle of water of 30 ° or less on the surface of the linear fine concavo-convex layer having the linear fine concavo-convex shape, that is, the surface of the linear fine concavo-convex layer, and the static The target contact angle is smaller than the static contact angle of n-hexadecane. Moreover, from the point which is excellent in cleaning performance, it is preferable that the static contact angle of the water in the said linear fine uneven | corrugated surface is 20 degrees or less, and it is more preferable that it is 15 degrees or less.
Moreover, it is preferable that the static contact angle of the water in the said linear fine uneven | corrugated surface is 5 degrees or more. When the static contact angle of water on the surface of the linear fine irregularities is less than 5 °, water attached to the surface of the linear fine irregularities is likely to evaporate. In an environment where it is not supplied, it becomes difficult to retain water on the surface of the linear fine irregularities for a long time, which may result in poor cleaning performance.
The static contact angle is a value calculated by the θ / 2 method, and can be measured using a general contact angle meter, for example, a DropMaster series contact angle meter manufactured by Kyowa Interface Science Co., Ltd. . At this time, since the contact angle on the surface of the linear fine unevenness of the present invention has anisotropy, for example, the extension direction of the linear protrusion at the point where the droplet is dropped and the extension direction of the linear protrusion Measure the static contact angle in the vertical direction. If the static contact angle of water in the extending direction of the linear protrusions and in the direction perpendicular thereto is 30 ° or less on the surface having the linear fine uneven surface, water in all directions of the linear fine uneven surface It can be considered that the static contact angle is 30 ° or less.
Here, the contact angle of water in the extending direction Y of the linear convex portion is a contact angle in a direction extending along the linear convex portion, as shown in FIGS. Assuming a plane (plane parallel to the YZ plane) that is perpendicular to the surface of the fine irregularities (plane parallel to the XY plane) and parallel to the extending direction Y of the linear projections, This refers to the angle formed between the surface of the fine uneven surface (plane parallel to the XY plane) and water. Further, the contact angle of water in the vertical direction X with respect to the extending direction Y of the linear convex portion is such that the linear convex portion extends across the linear convex portion as shown in FIGS. 12 (C) and (D). A contact angle, which is a surface perpendicular to the linear fine irregular surface (plane parallel to the XY plane) and parallel to the direction X perpendicular to the extending direction Y of the linear convex portion (plane parallel to the XZ plane). It is assumed that the angle between the surface of the linear fine irregularities (a plane parallel to the XY plane) and water in a cross section obtained by cutting a water drop on the surface.

  From the viewpoint of cleaning performance, the difference between the static contact angle of water and the static contact angle of n-hexadecane on the surface of the linear fine irregularities is preferably 3 ° or more, and preferably 5 ° or more. It is more preferable that the angle is 6 ° or more. As a result, the self-cleaning member of the present invention is capable of easily floating and removing the attached oil stains just by supplying water, and if it is covered with water in advance, the oil stains adhere. Both difficult performance is improved.

  Further, from the viewpoint of cleaning performance, the ratio of the static contact angle of n-hexadecane to the static contact angle of water on the surface of the linear fine irregularities (the static contact angle of n-hexadecane / the static contact angle of water) is 1.2 or more, and more preferably 1.5 or more.

Further, the static contact angle of n-hexadecane on the surface of the linear fine irregularities is not particularly limited as long as it is larger than the static contact angle of water, but it is preferably 9 ° or more from the viewpoint of cleaning performance, More preferably, it is 12 ° or more.
The static contact angle of the solvent on the surface of the linear fine unevenness can be adjusted by the component of the resin composition used for forming the linear fine unevenness layer, the linear fine unevenness shape of the linear fine unevenness surface, and the like. .

  From the point that oil stains are less likely to adhere when the surface of the linear fine unevenness is previously covered with water, the oil-in-water contact angle on the linear fine uneven surface is preferably 165 ° or more, and 170 ° or more It is more preferable that The oil-in-water contact angle is determined by placing the self-cleaning member according to the present invention in water so that the surface of the linear fine irregularities is on the lower side, and n-hexadecane 5.0 μL from the lower side of the self-cleaning member placed in water. The droplet is deposited on the surface of the linear fine irregularities, and the static contact angle one second after the droplet deposition is measured according to the θ / 2 method.

  Since the self-cleaning member of the present invention has a specific linear fine uneven surface, hydrophilicity having anisotropy can be obtained. Specifically, the direction in which the linear convex portion extends is more likely to wet and spread than the direction perpendicular to the direction in which the linear convex portion extends. When controlling the flow path of the water supplied to the surface of the linear fine irregularities, the contact angle and linearity of the water in the extending direction of the linear convex portion at the point where water is dropped on the linear fine irregularities surface. The difference from the contact angle of water in the direction perpendicular to the direction in which the protrusions extend is preferably 1.0 ° or more, and more preferably 1.5 ° or more. On the other hand, the difference in the contact angle is usually in the range of 20 ° or less.

  The self-cleaning member of the present invention is preferably a highly transparent member depending on the application. That is, the transmittance in the visible light region of the self-cleaning member is preferably 85% or more, more preferably 90% or more, and further 92% or more from the viewpoint that the design properties of the base are not damaged. It is preferable. In addition, the said linear transmittance can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

  The self-cleaning member of the present invention is preferably a highly transparent member depending on the application. That is, the haze value of the self-cleaning member is preferably 3% or less, and more preferably 1% or less, from the viewpoint that the design properties of the base are not damaged. Here, the haze value of the self-cleaning member can be measured according to JIS K-7136.

The self-cleaning member of the present invention is preferably a member having a reflection Y value of 4% or less depending on the application. Here, the reflection Y value is a software that measures a 5 ° regular reflectance in a wavelength range from 380 to 780 nm with a spectrophotometer (MPC3100, manufactured by Shimadzu Corporation), and then converts the brightness as perceived by human eyes. The luminous reflectance calculated by (MPC3100 built-in) is shown.
Specifically, the self-cleaning member of the present invention preferably has a reflection Y value of 2.5% or less.

<Cleaning method using self-cleaning member>
The self-cleaning member according to the present invention can be cleaned by floating and removing the oil stain by supplying water to the surface of the linear fine irregularities to which the oil stain has adhered.
As a method for supplying water to the surface of the linear fine irregularities, the linear fine irregularities on the surface of the linear fine irregularities of the self-cleaning member according to the present invention can be easily maintained, and the cleaning performance can be easily maintained for a long time. From, for example, a method of pouring water using a shower, a method of spraying water using a spray, etc., a method of spraying water such as rain or water used in water surroundings, etc. A method in which a solid object does not directly touch the uneven surface is preferable.

The cleaning method using the self-cleaning member according to the present invention includes, for example, a step of preparing a self-cleaning member, a step of attaching oil stains to the surface of the linear fine irregularities of the self-cleaning member, and the linear fine irregularities There is a method including a step of supplying water to a portion of the surface where the oil stain is attached and a step of washing and removing the oil stain.
The process of supplying water to the part where the oil stain is attached on the surface of the linear fine irregularities and the process of cleaning and removing the oil stain will be described with reference to FIG. In the step of supplying water, as shown in FIG. 7 (a), when water 42 is supplied to the portion where the oil stain 41 is attached to the surface of the linear fine uneven surface 3a, it is shown in FIG. 7 (b). Thus, the water 42 covers the periphery of the oil stain 41, and as shown in FIG. 7C, the water 42 sinks under the oil stain 41 and causes the oil stain 41 to rise. Thereafter, in the step of washing and removing the oil stain, the oil stain 41 flows over the water 42 and is removed as shown in FIG. The step of supplying water to the portion of the surface of the linear fine irregularities where the oil stain is attached and the step of washing and removing the oil stain may be performed simultaneously. In the step of washing and removing the oil stain, there is no particular limitation, but the self-cleaning member according to the present invention is arranged so that the extending direction of the linear protrusions is in the horizontal direction so that the oil stain is easily washed and removed. You may incline so that it may have an inclination with respect to it. Further, the self-cleaning member according to the present invention may be appropriately vibrated, or oil stains that have flowed on the water may be wiped off by an appropriate method. The direction of wiping off the surface of the linear fine irregularities is preferably a direction along the extending direction of the linear convex portions from the viewpoint of suppressing deformation of the shape of the surface.
Examples of the method of supplying water in the cleaning method include the same method as the method of supplying water to the above-described linear fine uneven surface.

Further, as another cleaning method using the self-cleaning member according to the present invention, for example, a step of preparing a self-cleaning member and a step of covering at least a part of the linear fine uneven surface of the self-cleaning member with water And a step of leaving the surface of the linear fine irregularities coated with water in an environment where oil stains come into contact, and further, if necessary, a method of washing and removing the oil stains. As described above, the surface of the linear fine unevenness of the self-cleaning member according to the present invention has the performance that oil stains are difficult to adhere when it is covered with water in advance. Therefore, in the another linear method, even if oil stains are brought into contact with the surface of the linear fine unevenness previously covered with water, the oil stain is difficult to adhere to or adheres to the surface of the linear fine unevenness. Since peeling is easy, the self-cleaning member according to the present invention maintains a state in which adhesion of oil stains is suppressed.
As the step of washing and removing the oil stain, for example, by removing the water containing the oil stain, and by tilting the self-cleaning member according to the present invention, giving vibration, or performing a wiping operation, etc. The process etc. which remove | eliminate the oil stain which adhered to the self-cleaning member which concerns on this invention easily peeled are mentioned, You may carry out combining several types of processes as needed.

<Use of self-cleaning member>
The self-cleaning member according to the present invention is required to be imparted with an antifouling property, and can be used for any application where washing of dirt with water or prevention of adhesion of dirt can be performed, and is not particularly limited. Further, since the self-cleaning member according to the present invention has little deterioration in cleaning performance, it can be used for various articles as a self-cleaning member having excellent cleaning performance.
Examples of applications in which the self-cleaning member according to the present invention can exert a cleaning action include, for example, automobiles, trains, airplanes, and other vehicles, as well as building materials used in spaces where oil stains are likely to adhere, such as open kitchens and kitchens of restaurants. And window glass or tempered glass for buildings and the like, building materials for outer walls, bathroom materials, bathrooms, toilets, and other building materials used in watering spaces. In these applications, oil stains attached to the surface of the linear fine irregularities can be washed and removed by rain when used outdoors, and by water used in indoor water spaces when used outdoors. In addition, among the building materials used in the water space, portions that are in contact with water, such as portions that are immersed in the usage environment, are prevented from being attached with dirt in advance. Examples of applications in which the self-cleaning member according to the present invention is used in contact with water include an inner wall of a water tank and an inner wall of a water pipe. For example, when the self-cleaning member according to the present invention is attached to the inner wall of the aquarium, oil stains are less likely to adhere to the inner wall of the aquarium and algae are less likely to grow. In addition, when the self-cleaning member according to the present invention is attached to the inner wall of a water pipe, oil stains are less likely to adhere to the inner wall, so that the water pipe can be prevented from being clogged with dirt. .
In addition to the above, examples of the use of the self-cleaning member according to the present invention include, for example, a store window of a store such as a department store, a showcase of goods and artworks, a PDA or a portable information terminal, a car navigation system, a ticket machine, an ATM. A liquid crystal protective film used for a touch panel display such as an automatic cash deposit payment machine and other liquid crystal screens can be given.

  In addition, the self-cleaning member of the present invention having hydrophilicity having anisotropy can be installed in a portion where condensation is likely to occur, and can be used using condensed water. For example, by using the self-cleaning member of the present invention as a member that constitutes the ceiling inside the refrigerated showcase, it is possible to prevent water droplets from dropping onto the product and to clean oil stains inside the refrigerated showcase. Specifically, for example, the self-cleaning member of the present invention is provided inside the refrigerated showcase so that the linear fine uneven layer side is the surface and the extending direction of the linear convex portion is inclined with respect to the horizontal direction. Install on the ceiling. As a result, the extending direction of the linear protrusions of the linear fine uneven layer in which water is more likely to spread and spread becomes the flow path of the water droplets. It is moved and discharged. In addition to the refrigerated showcase, the self-cleaning member according to the present invention can be used, for example, on the ceiling of a bathroom or the ceiling of an agricultural greenhouse using the same principle.

In addition, the self-cleaning member according to the present invention may be used in an aspect in which it is later attached to a portion where cleaning performance is desired, or may be used as a member itself that requires cleaning performance.
When the self-cleaning member according to the present invention is used in an aspect that is applied later, the self-cleaning member having a transmittance in the visible light region of 80% or more imparts cleaning performance without disturbing the design. It is preferable because it can be performed.

Furthermore, in addition to the cleaning performance, the self-cleaning member according to the present invention can also exhibit antireflection performance by the method described above. The self-cleaning member according to the present invention having antireflection performance can be preferably used as a window glass, a show window, a showcase, a liquid crystal protective film, etc., which require particularly excellent visibility among the above uses.
The application object to which the self-cleaning member according to the present invention is attached or formed as the self-cleaning member according to the present invention may be appropriately selected according to various uses as described above, and has a transmittance in the visible light region. It may be used by adhering to an opaque adherend of less than 30%, or an opaque self-cleaning member having a transmittance in the visible light region of less than 30%.

<Method for manufacturing self-cleaning member>
The method for producing a self-cleaning member according to the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear protrusions extend in one direction or substantially one direction on the surface, and a cured product of the resin composition In the linear fine concavo-convex shape, the average value p _AVG of the adjacent linear convex portion intervals p is 500 nm or less, and the linear fine concavo-convex shape of the linear fine concavo-convex layer is provided. A self-cleaning member according to the present invention, wherein the static contact angle of water is 30 ° or less and the static contact angle of water is smaller than the static contact angle of n-hexadecane. If it is a method that can be, there is no particular limitation, among others, by sequentially forming a plurality of grooves parallel in the circumferential direction on the outer peripheral surface of the cylindrical base material by cutting using a cutting tool, Mold roll gold A step of producing, by shaping process using the embossing roll mold, the method comprising the step of forming the linear fine irregularities on the surface is preferable from the viewpoint of excellent productivity.

(Process for manufacturing a mold for forming)
FIG. 8 is a diagram for explaining a process of manufacturing the forming roll mold 20. In this manufacturing process, first, a columnar base material 30 is prepared. The columnar base material 30 is not particularly limited as long as it is not deformed and worn when repeatedly used, and may be made of metal or resin, but usually metal The product is preferably used. This is because it is excellent in deformation resistance and wear resistance.

  Nickel, chrome, stainless steel, iron, aluminum, copper or their alloys can be used as the material of the metal columnar base material, but the surface of the metal columnar base material is easy to reuse. Alternatively, a cylindrical base material that has been subjected to metal plating with the above material may be used. The columnar base material may be hollow, that is, cylindrical. Moreover, you may have the process of smoothing the outer peripheral surface of the columnar base material 30 initially by a cutting process. In this case, while rotating the columnar base material 30, the cutting edge of the smoothing tool is pressed against the outer peripheral surface and moved in the direction of the rotation axis, as indicated by the arrow A, so that the outer periphery of the columnar base material 30 Smooth the surface. A polishing step such as buffing or electrolytic polishing may be added as necessary. In addition, on the surface of the cylindrical base material, a coating such as silicone, fluorine-based resin or DLC (diamond-like carbon), vapor deposition, or the like is applied so that the linear fine concavo-convex resin is easily peeled from the cylindrical base material during transfer. You may perform the combined mold release process.

Subsequently, a plurality of grooves arranged in parallel along the circumferential direction are sequentially formed on the outer peripheral surface of the columnar base material 30 using the cutting tool 31 for producing a linear fine uneven shape. Here, the shape of the cutting edge of the cutting tool 31 for producing the linear fine concavo-convex shape is appropriately set to a shape corresponding to the linear fine concavo-convex shape to be manufactured. FIG. 9 is a schematic cross-sectional view partially enlarging a vertical cross section with respect to the extending direction of the linear fine unevenness of the cutting edge of the cutting tool. For example, when the vertical cross section as shown in FIG. 4 (A) forms a linear projection having a rectangular shape, the cutting edge of the cutting tool 31 is complementary to the linear projection in the vertical cross section as shown in FIG. The shape has a rectangular groove. Moreover, when the shape and height of a linear convex part change periodically between the linear convex parts parallel to each other, it is preferable that the cutting edge width of the cutting tool 31 includes at least a repetition period.
While the cylindrical base material 30 is rotated, the cutting edge of the cutting tool 31 for producing the linear fine unevenness is pressed against the outer peripheral surface for cutting, but as indicated by the arrow A, the cutting edge width of the cutting tool 31 is increased in the direction of the rotation axis. A plurality of grooves arranged in parallel along the circumferential direction are sequentially formed by intermittently feeding and moving with the pitch.
The cutting edge width of the cutting tool 31 can be, for example, about 20 to 100 μm, but is not limited thereto.

In addition, for example, when the height is periodically different in the extending direction of the linear convex portion, when a shape complementary to the linear fine uneven shape to be manufactured cannot be created by a single cutting process, You may have the cutting process of multiple times using the bit for another linear fine uneven | corrugated shape preparation. As described above, the shaping roll mold 20 can be manufactured.
The cutting tool 31 for forming the linear fine concavo-convex shape may be prepared by appropriately selecting a conventionally known method so as to have a shape corresponding to the linear fine concavo-convex shape to be manufactured.
In the present invention, a mold having a shape corresponding to the linear fine concavo-convex shape is formed on the outer peripheral surface of the columnar base material by cutting using such a tool for producing the linear fine concavo-convex shape. Since the roll die 20 is used, it is easy to form an arbitrary linear fine uneven shape, and the productivity is further improved.

(Process of forming linear fine irregularities on the surface)
In the step of forming the linear fine uneven shape on the surface, the linear fine uneven shape is formed on the surface by a forming process using the forming roll mold.
For example, first, a resin composition for forming a linear fine concavo-convex layer is applied on a substrate to form a linear fine concavo-convex shape forming layer (receiving layer), and the surface of the receiving layer and a desired linear fine After forming the said linear fine uneven | corrugated shape in the metal mold | die side surface of the said receiving layer by contacting and arrange | positioning with the shaping | molding roll metal mold | die which has an uneven | corrugated shape, this resin composition is suitably used. By curing and peeling from the shaping roll mold, a linear fine uneven layer is formed. The method for curing the resin composition can be appropriately selected according to the type of the resin composition.

In FIG. 10, when the ionizing radiation curable resin composition is used as the resin composition for forming the linear fine uneven layer and the shaping roll mold 20 is used, the linear fine uneven layer is formed on the transparent substrate. An example of a forming method is shown.
In the method shown in FIG. 10, in the resin supplying step, an uncured and liquid ionizing radiation curable resin composition is applied to the transparent substrate 6 in the form of a belt-like film by the die 11, and the linear fine uneven receiving layer 1. 'Form. In addition, about application | coating of an ionizing radiation curable resin composition, not only the case by the die | dye 11 but various methods are applicable. Subsequently, the transparent substrate 6 is pressed and pressed by the pressing roller 12 onto the peripheral side surface of the shaping roll mold 20 which is the original for forming the linear fine uneven layer, whereby the receiving layer 1 ′ is applied to the transparent substrate 6. The ionizing radiation curable resin composition constituting the receiving layer 1 ′ is sufficiently filled in the concave portions of the linear fine irregularities formed on the peripheral side surface of the shaping roll mold 20. In this state, the ionizing radiation curable resin composition is cured by irradiation with ultraviolet rays, whereby the linear fine uneven layer 1 is produced on the surface of the transparent substrate 6. Subsequently, the transparent base material 6 is peeled from the shaping roll mold 20 through the peeling roller 13 integrally with the cured linear fine uneven layer 1. If necessary, an adhesive layer or the like is formed on the transparent substrate 6 and then cut into a desired size to prepare a self-cleaning member in which the linear fine uneven layer 1 is formed on the transparent substrate 6. In this way, the linear fine concavo-convex shape produced on the peripheral side surface of the shaping roll mold 20 which is the original plate for forming the linear fine concavo-convex layer is sequentially molded on the long transparent substrate 6 made of the roll material. Thus, the self-cleaning member in which the linear fine uneven layer 1 is formed on the transparent substrate 6 is efficiently mass-produced.

  Further, in the above-described method for forming the linear fine uneven layer used in the present invention, the case where the linear fine uneven layer is produced by the forming process using the forming roll mold 20 has been described. The linear fine concavo-convex layer used is not limited to this method, and may be manufactured. For example, in accordance with the shape of the base material related to the shape of the self-cleaning member according to the present invention, for example, a linear fine concavo-convex layer is created by processing a sheet using a flat plate or a mold for molding with a specific curved surface shape. In some cases, the process related to the shaping process and the original plate for forming the linear fine uneven layer can be appropriately changed according to the shape of the base material related to the shape of the self-cleaning member.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

(Production Example 1 Production of roll mold 1 for shaping)
An iron columnar base material having a width of 1300 mm and a diameter of 298 mm and having a surface plated with copper was prepared. On the other hand, on the surface having a cutting edge width of 30 μm, the vertical cross-sectional shape with respect to the extending direction Y of the linear convex portions is a rectangular linear concave and convex portion as shown in FIG. 9 (the average value p _{AVG of} adjacent linear convex portion intervals p). 150 nm, average width of linear convex part width 75 nm, average width of linear concave part 75 nm, height of linear convex part _HAVG is 70 nm).
While rotating the columnar base material, the cutting edge of the cutting tool is pressed against the outer peripheral surface and cut, and intermittently fed at a pitch of a cutting edge width of 30 μm of the cutting tool 31 and moved in the direction of the rotation axis, thereby causing a circumferential direction. A plurality of grooves arranged in parallel with each other were sequentially formed, and a shaping roll mold 1 was produced.

(Production Example 2 Production of Forming Roll Mold 2)
As a cutting tool, on the surface having a cutting edge width of 30 μm, the vertical cross-sectional shape with respect to the extending direction Y of the linear convex portion is a rectangular linear concave and convex portion as shown in FIG. 9 (the average value of adjacent linear convex portion intervals p) Except that a cutting tool having a p _AVG of 200 nm, an average width of linear convex portions of 100 nm, an average width of linear concave portions of 100 nm, and a height of linear convex portions _HAVG of 100 nm is prepared, Similarly, a mold roll 2 was produced.

(Production Example 3 Production of Forming Roll Mold 3)
As a cutting tool, on the surface having a cutting edge width of 30 μm, the vertical cross-sectional shape with respect to the extending direction Y of the linear convex portion is a rectangular linear concave and convex portion as shown in FIG. 9 (the average value of adjacent linear convex portion intervals p) Except for preparing a cutting tool having a p _AVG of 800 nm, an average width of linear convex portions of 400 nm, an average width of linear concave portions of 400 nm, and a height of linear convex portions of _HAVG of 400 nm) Similarly, a mold roll 3 was produced.

(Production Example 4 Preparation of Resin Composition A for Forming Linear Fine Uneven Layer)
The following components were mixed, and a resin composition A for forming a linear fine concavo-convex layer having a solid content of 45% by mass was prepared using methyl ethyl ketone and methyl isobutyl ketone as dilution solvents.
<Resin composition A for forming a linear fine uneven layer>
Pentaerythritol triacrylate 30 parts by mass Polyethylene glycol diacrylate 20 parts by mass 1,4-butanediol diacrylate 50 parts by mass Diphenyl (2,4,6-trimethoxybenzoyl) fosifine oxide (Lucirin TPO) 1 part by mass Part

(Production Example 5 Preparation of Resin Composition B for Forming Linear Fine Irregular Layer)
The following components were mixed, and a resin composition B for forming a linear fine concavo-convex layer having a solid content of 45% by mass was prepared using methyl ethyl ketone and methyl isobutyl ketone as diluent solvents.
<Linear fine uneven layer forming resin composition B>
-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

(Production Example 6 Preparation of Resin Composition C for Forming Linear Fine Concavity and Concavity Layer)
The following components were mixed, and a resin composition C for forming a linear fine unevenness layer having a solid content of 45% by mass was prepared using methyl ethyl ketone and methyl isobutyl ketone as dilution solvents.
<Linear fine uneven layer forming resin composition C>
-EO-modified bisphenol A diacrylate 50 parts by mass-EO-modified trimethylolpropane triacrylate 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

(Manufacture example 7 Preparation of resin composition D for linear fine uneven | corrugated layer formation)
The following components were mixed, and a resin composition D for forming a linear fine unevenness layer having a solid content of 45% by mass was prepared using methyl ethyl ketone and methyl isobutyl ketone as dilution solvents.
<Linear fine uneven layer forming resin composition D>
-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 mass-Silica gel 5 parts by mass

Example 1
A self-cleaning member was manufactured by the method shown in FIG.
As the forming roll mold 20, the forming roll mold 1 of Production Example 1 was used, and as the transparent substrate 6, 75 μm thick polyethylene terephthalate (PET) (manufactured by Toyobo Co., Ltd.) was used. Moreover, the resin composition for linear fine uneven | corrugated layer formation obtained by manufacture example 3 was set so that the thickness of the linear fine uneven | corrugated layer after hardening may be set to 20 micrometers in the transparent base material 6 of a strip | belt-shaped film form with the die | dye 11. A was applied. The resin composition A for forming a linear fine concavo-convex layer was cured by irradiating ultraviolet rays with energy of 2000 mJ / cm ² from the transparent substrate side. Then, it peeled from the shaping roll metal mold | die and the self-cleaning member of Example 1 was obtained. Linear fine uneven surface having a rectangular cross section perpendicular to the extending direction Y of the linear protrusions (average value _{pAVG of} adjacent linear protrusion intervals p is 150 nm, average width of linear protrusions is 75 nm, line the average width of the Jo recess 75 nm, the linear protrusion height _{H AVG} 70 nm) was obtained.
A SEM photograph of a cross section of the self-cleaning member 1 obtained in Example 1 is shown in FIG.

(Example 2)
In Example 1, in place of the resin composition A for forming a linear fine concavo-convex layer, the self composition of Example 2 was used in the same manner as in Example 1 except that the resin composition B for forming a linear fine concavo-convex layer was used. A cleaning member was obtained.

(Example 3)
In Example 1, in place of the resin composition A for forming a linear fine concavo-convex layer, the self-resin of Example 3 was used in the same manner as in Example 1 except that the resin composition C for forming a linear fine concavo-convex layer was used. A cleaning member was obtained.

Example 4
In Example 2, a triacetyl cellulose (TAC) film (manufactured by FUJIFILM Corporation, product number: TD80UF, thickness 80 μm) was used instead of the PET film. A self-cleaning member was obtained.

(Example 5)
In Example 4, a self-cleaning member of Example 5 was obtained in the same manner as in Example 4 except that the forming roll mold 2 was used in place of the forming roll mold 1. Linear fine uneven surface having a rectangular cross section perpendicular to the extending direction Y of the linear protrusions (average value p _{AVG of} adjacent linear protrusion intervals p is 200 nm, average width of linear protrusions is 100 nm, line average width 100nm of Jo recess, the line-shaped protruding portion height _{H AVG} 100nm) was obtained.

(Comparative Example 1)
In Example 4, a comparative member of Comparative Example 1 was obtained in the same manner as in Example 4 except that instead of the shaping roll mold 1, a columnar base material having no irregularities on the surface was used. The surface of the obtained comparative member was a flat surface, and no linear fine uneven shape was formed.

(Comparative Example 2)
In Example 1, it replaced with the resin composition A for linear fine uneven | corrugated layer formation, it replaced with the resin composition D for linear fine uneven | corrugated layer formation, and compared with Comparative Example 2 like Example 1 except having used it. A member was obtained.

(Comparative Example 3)
A comparative member of Comparative Example 3 was obtained by attaching a self-cleaning film (manufactured by Kimoto Co., Ltd., Laclean AT2) to a glass plate (made by Vixen, product number: 24041-2, thickness 1 mm).

(Comparative Example 4)
A triacetyl cellulose (TAC) film (manufactured by FUJIFILM Corporation, product number: TD80UF, thickness 80 μm) was used as a comparative member of Comparative Example 4.

(Comparative Example 5)
A glass plate (manufactured by Vixen, product number: 24014-2, thickness 1 mm) was used as a comparative member of Comparative Example 5.

(Comparative Example 6)
In Example 4, a comparative member of Comparative Example 6 was obtained in the same manner as in Example 4 except that the forming roll mold 3 was used instead of the forming roll mold 1. Linear fine concavo-convex surface in which the vertical cross-sectional shape with respect to the extending direction Y of the linear protrusions is rectangular (the average value p _{AVG of} adjacent linear protrusion intervals p is 800 nm, the average width of the linear protrusions is 400 nm, the line average width 400nm of Jo recess, the line-shaped protruding portion height _{H AVG} 400nm) was obtained.

(Evaluation)
<Measurement of contact angle>
A coating film is formed on polyethylene terephthalate (PET) so that the film thickness after drying the resin composition A to D for forming a linear fine uneven layer is 5 μm in thickness, and ultraviolet light has an integrated light quantity of 940 mJ / cm ^2. In this way, a cured film having no linear fine irregularities was formed. A liquid of 1.0 μL of pure water is dropped on a surface of the cured film side surface, which is attached to a black acrylic plate with an adhesive layer, and 10 seconds after the landing, contact made by Kyowa Interface Science Co., Ltd. The static contact angle was measured using an angle meter DM 500 according to the θ / 2 method. Moreover, the static contact angle was similarly measured using n-hexadecane (n-HD) instead of pure water. The measurement results are shown in Table 1.

In the self-cleaning members of Examples 1 to 5 and the comparative members of Comparative Examples 2 and 6, the surface of the linear fine irregularities was used. In the comparative member of Comparative Example 1, the surface of the cured film of the flat resin composition was used. Self-cleaning film surface in the comparative member, and one surface in the comparative members of Comparative Examples 4 and 5, with 1.0 μL of pure water (distilled water for liquid chromatography (manufactured by Pure Chemical Co., Ltd.)) A droplet was dropped from above, and after 1 second of landing, a static contact angle was measured according to the θ / 2 method using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. In addition, in the self-cleaning member of Examples 1 to 5 and the comparative members of Comparative Examples 2 and 6, with respect to the extending direction of the linear convex portion at the point where the droplet was dropped and the extending direction of the linear convex portion The static contact angle in the vertical direction was measured. Since the comparative members of Comparative Examples 1, 3, 4 and 5 had a flat surface, the target contact angle was measured from an arbitrary direction.
Moreover, the static contact angle was similarly measured using n-hexadecane (n-HD) instead of pure water. The measurement results are shown in Table 1.

<Decontamination evaluation>
As for the self-cleaning members of Examples 1 to 5 and the comparative members of Comparative Examples 1 to 6, the surface of the resin composition side, or the one not using the resin composition, on one side, colored cooking oil (Nisshin Oillio Group ( Co., Ltd., trade name: Nissin Salad Oil) was attached to a range of 1 cm in diameter at 1200 g / m ^{2 and} placed under conditions of a temperature of 25 ° C. and a humidity of 60% RH for 5 minutes. After that, pure water was sprayed on the part where the cooking oil was adhered by spraying. Based on the number of sprays until the cooking oil was removed, the decontamination property was evaluated under the following evaluation criteria. Table 1 shows the evaluation results and the number of sprays until the edible oil is removed.
[Evaluation criteria]
A: Edible oil was completely removed by spraying less than 30 times.
B: Edible oil was completely removed by spraying 30 times or more and less than 50 times.
C: Edible oil was not completely removed even after spraying 50 times or more.

<Sustainability evaluation>
The surface of the linear fine irregularities of the self-cleaning members of Examples 1 to 5 for which the decontamination evaluation was performed was wiped by 10 reciprocations with a force of about 3 kg / cm ^{2 with} Zavina Minimax (manufactured by Fuji Chemical). The appearance after removal was evaluated.

<Measurement of oil-in-water contact angle>
The self-cleaning members of Examples 1 to 5 and the comparative members of Comparative Examples 1 to 6 were placed in water. In addition, about the member which has the layer which consists of hardened | cured material of a resin composition, the said hardened | cured material side surface was made to become a lower side. Next, a droplet of 5.0 μL of n-hexadecane was deposited on the lower surface of the member from the lower side of the member placed in water, and contacted by Kyowa Interface Science Co., Ltd. after 1 second. The static contact angle was measured using an angle meter DM 500 according to the θ / 2 method. As the oil-in-water contact angle is closer to 180 °, oil stains are less likely to adhere in water.

(Summary of results)
The self-cleaning member obtained in Examples 1 to 5 includes a linear fine concavo-convex layer made of a cured product of a resin composition having a specific linear fine concavo-convex surface, and static water on the linear fine concavo-convex surface. Since the self-cleaning member according to the present invention has a contact angle of 30 ° or less and a static contact angle of water smaller than that of n-hexadecane, it has excellent antifouling properties and has an oil-in-water contact angle. Is large, that is, it is difficult for oil stains to adhere in water, and the performance can be easily lifted and removed by simply supplying water, and if it is covered with water in advance, the oil stains It had excellent cleaning performance in the present invention, which had the performance of being difficult to adhere. Moreover, in the evaluation of the decontamination property, the state that the water sprayed on the linear fine uneven surface of the self-cleaning member obtained in Examples 1 to 5 flows along the extending direction of the linear convex portion is observed. We were able to. Further, in the self-cleaning members obtained in Examples 1 to 5, in the sustainability evaluation, the linear protrusions are excellent in flexibility and restorability, and when wiping off, the linear protrusions are crushed or between the tips. No adhesion occurred. In addition, since the self-cleaning member obtained in Examples 1 to 5 did not contain a component that deteriorates with time, it can be used for a long period of time.
On the other hand, the comparative member of Comparative Example 1 did not have a specific linear fine uneven shape. In the comparative member of Comparative Example 2, the static contact angle of water was larger than that of n-hexadecane. The comparative member of Comparative Example 3 was a member using a self-cleaning film by photocatalytic action, and light irradiation was insufficient. The comparative members of Comparative Example 4 and Comparative Example 5 did not have a fine uneven shape, and the static contact angle of water was larger than that of n-hexadecane. In the comparative member of Comparative Example 6, the average value p _AVG of the linear protrusion interval p was over 500 nm. Therefore, the comparative members of Comparative Examples 1 to 6 were inferior in antifouling property as compared with the self-cleaning members obtained in Examples 1 to 5. In addition, the comparative members of Comparative Examples 2 and 3 in which the oil-in-water contact angle was measured had a smaller oil-in-water contact angle than the self-cleaning members obtained in Examples 1 to 5, that is, oil stains in water. It was relatively easy to adhere.

DESCRIPTION OF SYMBOLS 1 Linear fine uneven | corrugated layer 1 'Receptive layer 2 Linear convex part 3 Linear fine uneven | corrugated shape 3a Linear fine uneven | corrugated surface 4 Base material 5, 5' End part 5a of a convex part 5'a One end of a convex part Part 5b, 5'b The other end 6 of the convex part 6 Transparent base material 10 Self-cleaning member 11 Die 12 Pressing roller 13 Peeling roller 20 Molding roll mold 30 Cylindrical base material 31 Byte 41 Oil stain 42 Water X, Y, Z XYZ coordinate axes when the extending direction of the linear convex portion is Y

Claims (2)

A plurality of mutually parallel linear protrusions have a linear fine concavo-convex shape extending in one direction or substantially one direction on the surface, and a linear fine concavo-convex layer made of a cured product of the resin composition,
In the linear fine concavo-convex shape, an average value p _{AVG of} adjacent linear convex portion intervals p is 500 nm or less,
The static contact angle of water is 30 ° or less and the static contact angle of water is smaller than the static contact angle of n-hexadecane on the surface of the linear fine unevenness layer having the linear fine unevenness shape. A self-cleaning member. A plurality of parallel linear protrusions having a linear fine concavo-convex shape extending in one direction or substantially one direction on the surface, and comprising a linear fine concavo-convex layer made of a cured product of the resin composition, In the surface fine uneven shape, the average value p _AVG of the adjacent linear protrusion interval p is 500 nm or less, and the surface having the linear fine uneven shape of the linear fine uneven layer has a static contact angle of water. A method for producing a self-cleaning member, wherein the static contact angle of water is 30 ° or less and the static contact angle of water is smaller than that of n-hexadecane,
A step of manufacturing a forming roll mold by sequentially forming a plurality of grooves arranged in parallel along the circumferential direction on the outer peripheral surface of the cylindrical base material by cutting using a cutting tool;
A method for producing a self-cleaning member, comprising a step of forming the linear fine concavo-convex shape on a surface by a forming process using the forming roll mold.