JP6347132B2 - Linear fine concavo-convex structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to a linear fine concavo-convex structure and a manufacturing method thereof.

  In recent years, antireflection has been achieved by utilizing a so-called moth-eye structure in which a large number of minute protrusions are closely arranged on the surface of a transparent substrate and the distance between the minute protrusions is equal to or less than the wavelength of visible light. A method has been proposed (see, for example, Patent Document 1). In this method, the refractive index with respect to incident light is continuously changed in the thickness direction, thereby eliminating the discontinuous interface of the refractive index and preventing reflection.

Further, in Patent Document 2, the moth-eye structure can provide an antireflection function, and by selecting a transparent material having a desired contact angle with water, fine irregularities can be obtained. Controlling the wettability on a surface is disclosed.
Furthermore, in Patent Document 3, the maximum width of the groove on the substrate surface is set to 400 nm or less and the minimum width between adjacent grooves is set to 800 nm or more for the purpose of expressing hydrophilicity, antifogging property, and self-cleaning property. A forming structure is disclosed.

JP2012-128168A JP 2007-187868 A JP 2009-193002 A

A fine concavo-convex structure in which a large number of minute protrusions are closely arranged like the moth eye structure has a problem in terms of durability such as stain resistance due to its surface structure. That is, due to its surface structure, dirt such as sebum is likely to adhere, and the dirt penetrates into the groove between the microprotrusions, so that it is difficult to remove and the surface appearance tends to deteriorate. In addition, the pressure at the time of wiping dirt may cause plastic deformation such as easily crushing the protrusions or sticking the tips of the protrusions, and the wiping marks may remain in the wiped part. There was a problem with durability.
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.
On the other hand, a molded body in which a groove having a predetermined width described in Patent Document 3 is arranged so that a minimum width between adjacent grooves is predetermined is formed on a glass substrate using a reactive etching apparatus. Since it is a production technique, it was difficult to produce a large-area molded body, and the mass productivity was inferior.

  This invention is made | formed in view of the said situation, and it aims at providing the fine uneven structure body which is excellent in durability, and excellent in productivity, and its manufacturing method.

The linear fine concavo-convex structure according to the present invention is a linear fine concavo-convex structure that is a dew condensation suppressing member, and a plurality of linear convex portions that are parallel to each other extend linearly or openly. It has a concavo-convex shape 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, the average value p _AVG of the adjacent linear convex portion intervals p is 500 nm or less, and the contact angle of water on the flat surface of the cured product of the resin composition is 60 degrees or less. Features.
Further, the linear fine concavo-convex structure according to the present invention is a linear fine concavo-convex structure that is a water repellent member, and a plurality of parallel linear protrusions extending linearly or openly. A linear fine concavo-convex layer comprising a cured product of a resin composition, having a fine concavo-convex shape on the surface,
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 contact angle of water on the flat surface of the cured product of the resin composition exceeds 90 degrees. Features.
The linear fine concavo-convex structure according to the present invention is a linear fine concavo-convex structure that is a powder adhesion suppressing member, and a plurality of parallel linear protrusions extend linearly or openly. A linear fine concavo-convex layer made of a cured product of the resin composition having a linear fine concavo-convex shape on the surface,
In the linear fine concavo-convex shape, an average value p _{AVG of} adjacent linear convex portion intervals p is 500 nm or less (except for a linear fine concavo-convex structure applied to an antireflection article). .
The linear fine concavo-convex structure according to the present invention is a linear fine concavo-convex structure which is a transparent conductive film, and a plurality of parallel linear protrusions extending in a straight line or an open curve. A linear fine concavo-convex layer comprising a cured product of a resin composition, having a fine concavo-convex shape on the surface,
In the linear fine concavo-convex shape, an average value p _{AVG of} adjacent linear convex portion intervals p is 500 nm or less, a transparent conductive layer is provided on the surface of the linear fine concavo-convex layer, or the linear fine concavo-convex layer It itself is a transparent conductive layer.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the fine concavo-convex structure body which is excellent in durability and excellent in productivity, and its manufacturing method.

FIG. 1 is a perspective view schematically showing an example of a linear fine concavo-convex structure according to the present invention. FIG. 2 is a perspective view schematically showing another example of the linear fine concavo-convex structure according to the present invention. FIG. 3 is a partially enlarged view of the schematic cross-sectional view of the linear fine concavo-convex structure 10 shown in FIG. 4 (A) to 4 (E) are schematic cross-sectional views of specific examples of a vertical cross section with respect to the extending direction Y of the linear fine concavo-convex shape. FIG. 5A to FIG. 5D are schematic cross-sectional views of other specific examples of the vertical cross-section with respect to the extending direction Y of the linear fine concavo-convex shape. FIG. 6 is a diagram for explaining the interval p between adjacent linear protrusions. FIG. 7 is a diagram for explaining the manufacturing process of the forming roll mold 20. FIG. 8 is a schematic cross-sectional view in which a vertical cross section with respect to the extending direction of the linear fine unevenness of the cutting edge of the cutting tool is partially enlarged. FIG. 9 is a schematic view showing an example of a method for producing a linear fine concavo-convex structure according to the present invention. FIG. 10 is an SEM photograph of a cross section of the linear fine concavo-convex structure 1 obtained in Example 1.

Hereinafter, the linear fine concavo-convex structure according to the present invention and the manufacturing method thereof will be described in detail in order.
In the present invention, (meth) acryl represents each of acryl or methacryl, (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.

[Linear fine uneven structure]
The linear fine concavo-convex structure according to the present invention has a linear fine concavo-convex shape having a plurality of parallel linear convex portions extending in one direction or substantially one direction on the surface, and a cured product of the resin composition Comprising a linear fine concavo-convex layer consisting of
In the linear fine concavo-convex shape, an average value _{pAVG of} adjacent linear convex portion intervals p is 500 nm or less.

The linear fine concavo-convex structure according to the present invention will be described with reference to the drawings. 1 and 2 are perspective views each schematically showing an example of a linear fine concavo-convex structure according to the present invention. The linear fine concavo-convex structure 10 shown in FIG. 1 has a linear fine concavo-convex shape 3 in which a plurality of parallel linear ridges 2 extend in a common direction Y on the surface, and the resin composition The linear fine uneven | corrugated layer 1 which consists of hardened | cured material is provided.
The linear fine concavo-convex structure 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 a line may be formed on one surface side of the substrate 4 as shown in FIG. The structure provided with the fine fine uneven | corrugated layer 1 may be sufficient.
Moreover, although the linear fine concavo-convex structure according to the present invention is not shown, the linear fine concavo-convex layer 1 may be provided on both sides of the substrate 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 linear fine concavo-convex structure 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 linear fine concavo-convex structure of the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear convex portions extend in one direction or substantially one direction on the surface, and from a cured product of the resin composition Since the linear fine concavo-convex shape has a specific value in the linear fine concavo-convex shape, it is similar to a so-called moth-eye structure in which minute protrusions are closely arranged. Durability is excellent while obtaining effects. The linear fine concavo-convex structure of the present invention is superior in the structural durability of the convex part itself compared to the fine concavo-convex shape formed by closely arranging so-called moth-eye structures, so that the resin composition 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. Furthermore, the linear fine concavo-convex structure of the present invention has a linear convex portion even when dirt such as sebum adheres, compared to a fine concavo-convex shape in which minute projections called so-called moth-eye structures are closely arranged. It is easy to remove along the surface, and the surface appearance hardly deteriorates.
Further, the linear fine concavo-convex structure of the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear convex portions extend in one direction or substantially one direction on the surface, and the resin composition is cured. Since the linear fine concavo-convex layer made of an object is provided, it can be manufactured by a highly productive manufacturing method as described later. According to the manufacturing method, since a linear fine concavo-convex structure having a large area can be produced in a long shape, it is not necessary to join small concavo-convex structures having a small area as in Patent Document 3. Therefore, even a linear fine concavo-convex structure having a large area can be manufactured with high productivity.
Hereinafter, the linear fine concavo-convex layer which is an essential component of the linear fine concavo-convex structure according to the present invention, the base material which may be included, and other configurations will be described in order.

<Linear fine uneven layer>
The linear fine concavo-convex layer 1 has a linear fine concavo-convex shape in which a plurality of parallel linear convex portions 2 extend in one direction or substantially one direction on the surface. 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). Moreover, a stepped cross section in which the line width becomes narrower in the Z-axis direction as shown in FIG.
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 having a relatively high height are included periodically in directions parallel to each other, a linear fine concavo-convex structure with high productivity and improved stain 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 hydrophilicity and water repellency of the surface of the linear fine irregularities are improved when the shape is such that the specific surface area of the linear convex portions is increased. For example, when the linear protrusions have the same height, the vertical cross-sectional shape is preferably a square rather than a triangle. 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 and water repellency are improved in terms of specific surface area, and optical functions such as antireflection properties are also improved. It is preferable from the point.

  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 | variety w of each linear convex part occupies in the adjacent linear convex part space | interval p is not specifically limited, From a durable point, it is preferable that w / p is 0.3-1.

In the linear fine concavo-convex structure of the present invention, the average value p _AVG of the adjacent linear convex portion intervals p is 500 nm or less, but from the viewpoint of manufacturing, the p _AVG is 10 nm or more, and more preferably 50 nm or more. preferable. 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 enhancement effect of a contact angle (hydrophilicity or water repellency) resulting from the surface of a linear fine unevenness | corrugation 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, various performances are not exhibited, and if it is too large, the 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.
Moreover, in the case of the linear fine uneven | corrugated layer by which the linear fine uneven | corrugated shape was provided in the surface of the base material, the said thickness depends on the thickness of a base material, and is not specifically limited.

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 is not particularly limited, and includes at least a resin and, if necessary, other components such as a polymerization initiator. The resin composition includes those containing only one kind of resin.
The resin is not particularly limited, but, for example, (meth) acrylate-based, epoxy-based, polyester-based ionizing radiation-curable resins, (meth) acrylate-based, urethane-based, epoxy-based, polysiloxane-based thermosetting, etc. Resin, various materials such as thermoplastic resins such as (meth) acrylate-based, polyester-based, polycarbonate-based, polyethylene-based, and polypropylene-based resins, and resins for shaping in various cured forms. 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 preferably used because it is excellent in moldability and mechanical strength of a linear fine uneven shape. The ionizing radiation curable resin is a mixture of monomers having radically polymerizable and / or cationically polymerizable bonds in the molecule, a polymer having a low polymerization degree, and a reactive polymer, and polymerization is started. It is cured by the agent. In addition, you may contain a non-reactive polymer.

Among them, the storage elastic modulus (E ′) at 25 ° C. of the cured product of the resin composition is 300 MPa or less, and the loss elastic modulus with respect to the storage elastic modulus (E ′) at 25 ° C. of the cured product of the resin composition. When the ratio of (E ″) (tan δ (= E ″ / E ′)) is 0.2 or less, the linear fine uneven shape is deformed with a pressure that can be wiped off, and has excellent elastic resilience. From the viewpoint of antifouling properties and durability.
By setting E ′ to 300 MPa or less, the linear fine uneven shape is deformed by the pressure at the time of wiping, and the dirt that has entered the gap between the unevenness can be removed by dry wiping. Among them, the storage elastic modulus (E ′) is preferably 1 to 250 MPa, and more preferably 1 to 100 MPa.
Further, by setting the loss tangent to 0.2 or less, the linear convex portion deformed at the time of wiping is elastically restored and easily returns to the original shape. Thereby, the plastic deformation of the convex portions and the adhesion between the tips of the convex portions are suppressed, and the dirt can be wiped off by dry wiping without deteriorating the function of the linear fine concavo-convex shape. Among them, tan δ is preferably 0.18 or less.

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

From the viewpoint of antifouling properties, the cured product of the resin composition preferably has a contact angle of n-hexadecane on the flat cured film surface of 30 degrees or less, or a contact angle of oleic acid of 25 degrees or less. Even if the oil-based soil adhering to the surface of the linear fine unevenness layer cannot be completely wiped off because the flat cured film surface of the resin composition has the above lipophilicity, the linear fine Since it spreads thinly on the surface of the uneven layer, the dirt becomes inconspicuous and the visibility after wiping is improved.
In addition, the cured product of the resin composition preferably has a water contact angle of 70 degrees or more on the flat cured film surface from the viewpoint of surface wiping.

  Moreover, the surface physical property of hardened | cured material should just be adjusted suitably with a use. For example, when the linear fine concavo-convex structure of the present invention is used as a hydrophilic member, the cured product of the resin composition preferably has a water contact angle of 60 degrees or less on the flat cured film surface, Furthermore, it is preferable that it is 45 degrees or less. When a linear fine concavo-convex shape is formed using such a material, the contact angle emphasizes the hydrophilicity more, and usually depends on the shape, but usually 30 degrees in the extending direction of the linear convex portion and its vertical direction. The following contact angles are shown. As an anti-fogging function, the contact angle appears if it is 30 degrees or less, more preferably 20 degrees or less, and still more preferably 10 degrees or less. The hydrophilic member using the linear fine concavo-convex structure of the present invention is linear even when the contact angle of the material itself is increased due to deterioration or the like as compared with a general antifogging film using a hydrophilic material. There is a feature that an increase in contact angle in a fine uneven shape can be kept low.

  Alternatively, when the linear fine concavo-convex structure of the present invention is used as a water-repellent member, the cured product of the resin composition preferably has a contact angle of water on the flat cured film surface exceeding 90 degrees. Further, it is preferably 100 degrees or more. When a linear fine concavo-convex shape is formed using such a material, the contact angle emphasizes water repellency more, and although it depends on the shape, it is usually 110 degrees in the extending direction of the linear convex portion and its vertical direction. The above water repellency is exhibited.

In the present invention, the contact angle of the cured product of the resin composition is measured as follows.
First, the resin composition for linear fine unevenness | corrugation layers is apply | coated and hardened on a transparent base material, and the flat cured film which does not have a fine unevenness | corrugation shape is formed. Adhere horizontally to a black acrylic plate with an adhesive layer with the coating side facing up. Next, a droplet of 1.0 μL of solvent (water) whose contact angle is to be measured is dropped onto the fine uneven layer, and the static contact angle 10 seconds after the landing is measured according to the θ / 2 method. For example, the measuring device can measure using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
In addition, the contact angle on the surface of the linear fine concavo-convex structure of the linear fine concavo-convex structure of the present invention can be measured in the same manner. A 1.0 μL drop of solvent (water) is dropped, and static contact is 10 seconds after the landing. The angle is measured according to the θ / 2 method. 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.

The resin composition for the linear fine concavo-convex layer is selected appropriately so as to obtain the above physical properties according to the application.
Among these, a resin composition containing (meth) acrylate that is preferably used as an ionizing radiation curable resin, which is preferably used from the viewpoint of excellent formability and mechanical strength of a linear fine uneven shape, will be specifically described. .

(1) (Meth) acrylate (meth) acrylate is a monofunctional (meth) acrylate having one (meth) acryloyl group in one molecule, but two or more (meth) acryloyl groups in one molecule It may be a polyfunctional acrylate having a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
Among these, the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate are preferable in that the cured product easily satisfies the above storage elastic modulus (E ′) and tan δ, and the linear protrusion has both flexibility and elastic resilience. It is preferable to use together.

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

  When the monofunctional (meth) acrylate is used, the content of the monofunctional (meth) acrylate is preferably 5 to 40% by mass with respect to the total solid content of the ionizing radiation curable resin composition. More preferably, it is mass%.

  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, it is preferable to use a polyfunctional (meth) acrylate containing an alkylene oxide, more preferable to use an ethylene oxide-modified polyfunctional (meth) acrylate, because the linear convex portion is excellent in flexibility and restorability. It is even more preferable that at least one of oxide-modified 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 10-99.2 mass% with respect to the total solid of an ionizing radiation-curable resin composition, and it is 15-99.1 mass%. Is more preferable.

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

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

The ionizing radiation curable resin composition preferably used in the present invention is easy to adjust the storage elastic modulus and loss tangent of the cured product to the above predetermined range, and easily adjust to oleophilic properties, and obtain excellent dry wiping properties. It is particularly preferable that at least a (meth) acrylate having a long-chain alkyl group having 10 or more carbon atoms and a polyfunctional (meth) acrylate containing an alkylene oxide are contained. Especially, it is preferable that the content rate of the (meth) acrylate which has a C10 or more long-chain alkyl group is 5-30 mass parts with respect to 100 mass parts of polyfunctional (meth) acrylate containing an alkylene oxide, More preferably, it is 10-15 mass parts.
In order to increase hydrophilicity, the ionizing radiation curable resin composition preferably used in the present invention is a composition containing a polyfunctional (meth) acrylate containing alkylene oxide. Especially, it is preferable that content of the polyfunctional (meth) acrylate containing the said alkylene oxide is 70-99 mass% with respect to the total solid of an ionizing radiation-curable resin composition, and is 80-99 mass%. More preferably. Moreover, it is preferable that content of the polyfunctional (meth) acrylate containing the said alkylene oxide is 80-100 mass% with respect to all the (meth) acrylate compounds used, and it is 90-100 mass%. Is more preferable.

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

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

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

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

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

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

(6) Other components The resin composition for a linear fine concavo-convex layer used in the present invention may further contain other components as long as the effects of the present invention are not impaired. Other components include, for example, surfactants for wettability adjustment, fluorine compounds, silicone compounds, stabilizers, antifoaming agents, repellency inhibitors, antioxidants, aggregation inhibitors, viscosity modifiers, Examples include mold release agents.

<Base material>
The base material used as needed in the present invention may be appropriately selected and used according to the use of the linear fine concavo-convex structure of the present invention. The base material is not limited to the transparent base material, and may be an opaque base material according to the application.

  The transparent base material used for this invention can be suitably selected and used according to a use from the well-known transparent base materials used for a linear fine concavo-convex structure. Specific examples of materials used for the transparent substrate include, for example, acetyl cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, and acrylic resins. Transparent resins such as resin, polyurethane resin, polyethersulfone, polycarbonate, polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, soda glass, potassium glass, lead glass And glass, ceramics such as PLZT, transparent inorganic materials such as quartz and fluorite, and the like.

  The transparent substrate preferably has a transmittance in the visible light region of 80% or more, and more preferably 90% or more. 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).

  Specific examples of the material used for the opaque substrate include various metals, opaque glass, an opaque resin in which a resin material is mixed with an inorganic pigment and a foaming agent, and the like. Examples include a base material on which a sputtered film, particularly a metal sputtered film is formed.

Examples of the shape of the substrate include a film shape, a sheet shape, a plate shape, a rod shape, and a molded body formed into a predetermined shape. However, the present invention is not limited to such examples.
Moreover, when making it a linear fine concavo-convex structure of a large area, it is preferable to use a long or roll-shaped base material on manufacture.

  Although the thickness of the said base material can be suitably set according to the use and shape of the linear fine concavo-convex structure of this invention, it is not specifically limited, Usually, it is 20-5000 micrometers. The substrate may be one supplied in the form of a roll, one that does not bend to the extent that it can be wound, but one that curves by applying a load, or one that does not bend completely.

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 for improving the adhesiveness of a base material and the linear fine unevenness | corrugation layer mentioned later, and by extension, abrasion resistance (scratch resistance) on a base material. 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 configurations>
The linear fine concavo-convex structure of the present invention may further have other layers as long as the effects of the present invention are not impaired.
For example, for the purpose of imparting hydrophilicity and water repellency, a surface treatment layer containing at least one compound selected from a fluorine-based compound and a silicon-based compound is provided as long as the surface shape of the linear fine irregularities is not impaired. May be. Examples of the method for forming the surface treatment layer include a method in which a solution in which at least one compound selected from a fluorine-based compound and a silicon-based compound is dissolved in a solvent is applied by various application methods and then dried. . Further, there may be mentioned a method in which a fluorine compound or a silicon compound is mixed with an ultraviolet curable resin and applied and then cured by UV irradiation. Alternatively, the surface treatment layer may be formed by an LB method, a PVD method, a CVD method, a self-assembly method, a sputtering method, or the like.

Specifically, for example, a vapor deposition film in which a silicon compound such as hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), hexamethyldisilazane (HMDS), octamethylcyclotetrasiloxane, or the like is reduced in vapor deposition is provided. From the viewpoint of providing a surface with improved water repellency.
Further, using a reactive ion etching apparatus, a compound containing one or more atoms selected from gaseous fluorine atoms such as tetrafluoromethane gas and silicon atoms is deposited on the surface of the linear fine uneven layer by plasma. You may do it.

Among these, vapor deposition using a fluorine compound containing 10 to 10 carbon atoms, which contains a perfluoroalkyl group having 1 to 6 carbon atoms at least at one end and does not contain oxygen atoms, on the surface of the linear fine uneven layer. The provision of a film is preferable from the viewpoint of providing a surface with improved water and oil repellency. Examples of the fluorine compound containing 10 to 6 carbon atoms and containing a perfluoroalkyl group having 1 to 6 carbon atoms at at least one terminal and not containing an oxygen atom include (perfluorohexyl) ethylene and (perfluorobutyl) ethylene. Perfluorohexyl iodide and the like, but are not limited thereto. As a vapor deposition method in this case, a plasma CVD method is particularly preferably used.
In addition, vapor deposition using a fluorine compound containing 10 to 10 carbon atoms, which contains a perfluoroalkyl group having 1 to 6 carbon atoms at least at one end and does not contain oxygen atoms, on the surface of the linear fine uneven layer. A patterned water / oil repellent layer may be provided by patterning the film.

  Furthermore, a conductive film may be provided on the surface of the linear fine uneven layer. For example, a transparent conductive layer containing at least one selected from the group consisting of a conductive metal oxide, a conductive organic polymer, a conductive metal nanoparticle, and a conductive metal nanowire is provided on the surface of the linear fine concavo-convex layer. You may have. In this case, antireflection and conductivity can be expected from the linear fine concavo-convex structure.

Alternatively, a metal thin film may be provided on the surface of the linear fine uneven layer. In this case, an optical effect (for example, viewing angle controllability, wavelength dependency) due to the transmissive or non-transmissive metal thin film can be expected in the linear fine concavo-convex structure.
When a visible light-transmitting metal thin film having a shape following the unevenness is provided, viewing angle controllability can be expected from the linear fine uneven structure. Examples of the visible light transmissive metal thin film include a metal thin film made of at least one of aluminum and an aluminum alloy formed by a sputtering method. When the concavo-convex surface of the linear fine concavo-convex layer is a flat surface and a metal thin film is formed on the flat surface by a sputtering method, an amount of aluminum that forms a metal thin film having a thickness of 5 to 30 nm and A metal thin film made of at least one kind of aluminum alloy is preferable.

  Further, the linear fine concavo-convex structure of the present invention is stored, transported, traded, post-processed or constructed in a state where a peelable protective film is temporarily bonded to the surface of the linear fine concavo-convex layer, and the protection is performed in a timely manner. It can also be set as the form which peels and removes a film. Thereby, damage and contamination of the surface of the linear fine concavo-convex structure during storage, transportation, etc. can be prevented.

  The linear fine concavo-convex structure of the present invention is an adhesive formed by forming an adhesive layer on a surface that does not have a linear fine concavo-convex shape, and further laminating a release film on the surface of the adhesive layer. It can also be a processed product. 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. . The base material, the adhesive layer, and the arbitrary layer are not limited to one layer, and two or more layers can be appropriately selected depending on the intended use and conditions.

<Physical properties of linear fine concavo-convex structure>
The linear fine concavo-convex structure of the present invention has a specific linear fine concavo-convex surface so that the contact angle of water on the flat cured film surface is 60 ° or less, preferably 45 ° or less. When used on an uneven surface, high hydrophilicity can be obtained. For example, in the linear fine uneven surface, the contact angle of water in the extending direction of the linear protruding portion and the vertical direction thereof is 30 degrees or less, more preferably What is 20 degrees or less, More preferably, it is 10 degrees or less can be obtained. Furthermore, the linear fine concavo-convex structure of the present invention has a specific linear fine concavo-convex surface, whereby hydrophilicity having anisotropy is obtained. Specifically, the direction in which the linear convex portion extends is more likely to wet and spread than the direction in which the linear convex portion extends and the vertical direction.
On the other hand, the linear fine concavo-convex structure according to the present invention has a specific linear fine concavo-convex surface, thereby forming a wire with a contact angle of water exceeding 90 degrees, preferably 100 degrees or more, on the flat cured film surface. When used on the surface of the fine uneven surface, high water repellency can be obtained. For example, on the surface of the fine linear uneven surface, the contact angle of water in the extending direction of the linear protrusion and the vertical direction thereof is 110 degrees or more. What is preferably 140 degrees or more can be obtained. In addition, the linear fine concavo-convex structure of the present invention has a specific linear fine concavo-convex surface, thereby providing water repellency having anisotropy.

<Uses of linear fine concavo-convex structure>
The linear fine concavo-convex structure according to the present invention can be used for various articles.
When the surface of the linear fine irregularities is a surface with improved hydrophilicity, it is suitably used as a hydrophilic member having high hydrophilic sustainability since there is little deterioration in hydrophilicity. The hydrophilic member can function as a defogging member due to condensation, for example. In addition, since the hydrophilicity is not easily deteriorated, it is possible to suppress the adhesion of dirt after long-term use (self-cleaning effect). Moreover, since this invention is equipped with the linear fine uneven | corrugated surface, hydrophilicity has anisotropy and can become a flow path of droplets, such as a water droplet, along a linear uneven structure.
As a dew condensation suppressing member, for example, it can be used for a mirror, a window, a window sash, a car side mirror, a vegetable packaging film, etc. whose visibility is easily deteriorated by dew condensation. Or it is used suitably for a refrigerated freezer showcase. In addition, when used for medical test sheets, the effect of smoothing the flow of reagents and specimens can be expected.

  Moreover, when the said linear fine uneven | corrugated surface is made into the surface which improved water repellency and oil repellency, it is used suitably as a water / oil repellency member. The water / oil repellent member can be used for any application that requires water repellency and / or oil repellency, and is not particularly limited. For example, a window glass or a tempered vehicle or a building such as an automobile, a train, or an aircraft. Glass, mirrors, department store show windows, product and art showcases, PDAs or personal digital assistants, car navigation systems, ticket vending machines, touch panel displays such as ATMs (automatic cash deposit and payment machines), and other liquid crystals LCD protective film used for screens, building materials for outer walls, kitchens, bathrooms, washrooms, toilets, and other water-containing spaces such as transparent and opaque general building materials, soft packaging or the inner surface of retort food packaging, or viscosity In a bag having a high liquid inside, such as the inner surface of a food container, shampoo container, etc., it exhibits a water and oil repellent effect, It prevents the inner surface adhesion of contents thereof, and can be preferably used it is possible to use up to the end.

Further, when the water- and oil-repellent layer is patterned on the surface of the linear fine irregularities, a portion where the water- and oil-repellent layer is not provided may be used as a flow path for discharging droplets attached to the surface of the structure. it can. In particular, by providing a water- and oil-repellent layer in parallel with the extending direction Y of the linear protrusion, it is suitably used as a flow path for discharging droplets due to the synergistic effect of the surface of the linear unevenness and the water- and oil-repellent layer. It is done. For example, by making the structure surface according to the present invention an inclined surface, water droplets and oil droplets attached to the member surface move according to gravity, and at this time, avoid a water / oil repellent layer having water / oil repellent performance, It gathers to the part where the water / oil repellent layer is not provided. As described above, the portion where the water / oil repellent layer is not provided can be used as a flow path for water droplets and oil droplets, and the linear fine concavo-convex structure of the present invention in which the water / oil repellent layer is arranged in a pattern. Can also be used as a drainage oil discharge member.
The linear fine concavo-convex structure according to the present invention having a patterned water- and oil-repellent layer is a printing member such as a printing plate, a color filter, a display member, a lens, and a transportation member, using specific wettability. It can also be used widely for applications such as architectural decoration members. Moreover, the linear fine concavo-convex structure according to the present invention having a patterned water- and oil-repellent layer can realize high sensitivity of antigen-antibody reaction by a DNA array and low-pressure loss of a fluid cell or the like.

  In addition, the linear fine concavo-convex structure can be expected to have an effect of suppressing powder adhesion. In either case of having a hydrophilic surface or having a water-repellent surface, adhesion of organic powder such as inorganic powder and various polymers can be appropriately suppressed. Especially, adhesion of the powder containing metal oxides, such as a titanium oxide, iron oxide, and zinc oxide, can be suppressed suitably. Specific examples of the powder containing a metal oxide include cosmetics such as powder foundation, face powder, blusher, and eye shadow, powder blasting agent, and chalk.

  Furthermore, when the surface of the said linear fine uneven | corrugated layer is equipped with the transparent conductive layer, or when the fine uneven | corrugated layer itself is a transparent conductive layer, the linear fine uneven | corrugated structure of this invention is used as a transparent conductive film. It can be used for a touch panel, a sensor that effectively detects dew condensation, and is difficult to adhere to dirt. When used for a sensor, it is not necessarily transparent.

  Or when the surface of the said linear fine uneven | corrugated layer is equipped with the visible light-permeable metal thin film, it can be used as a transmittance | permeability anisotropic member, for example, can be used as a viewing angle control film. In the case of a metal thin film having a catalytic function, the catalytic activity can be increased.

  Antireflective effect can be expected from the linear fine concavo-convex structure, for example, store windows, exhibition windows of museum exhibits; display windows of various measuring devices such as clocks; road signs, posters, etc. Visibility can be improved by arranging various printed materials on the front or both sides of vehicles such as automobiles and airplanes and windows of various buildings. It can also be used as a window material for various optical devices such as glasses, cameras, telescopes, microscopes, and various illumination devices.

[Method for producing linear fine concavo-convex structure]
The method for producing a linear fine concavo-convex structure of the present invention has a linear fine concavo-convex shape in which a plurality of parallel linear convex portions extend in one direction or substantially one direction on the surface, and the resin composition A method for producing a linear fine concavo-convex structure comprising a linear fine concavo-convex layer made of a cured product, wherein in the linear fine concavo-convex shape, an average value _{pAVG of} adjacent linear convex portion intervals p is 500 nm or less. And
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 with a cutting tool;
A step of forming the surface of the linear fine irregularities by a forming process using the forming roll mold.

<Process for producing a roll mold for shaping>
It has the process of manufacturing the shaping roll metal mold | die by forming sequentially the some groove | channel which was parallel along the circumferential direction in the outer peripheral surface of a cylindrical base material by cutting with a cutting tool.
FIG. 7 is a diagram for explaining the manufacturing process of 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 circumferential surface of the columnar base material 30 using the cutting tool 31 for forming a linear uneven shape. Here, the shape of the cutting edge of the cutting tool 31 for producing the linear uneven shape is appropriately set to a shape corresponding to the linear fine uneven shape to be manufactured. FIG. 8 shows a schematic cross-sectional view in which a vertical cross section with respect to the extending direction of the linear fine unevenness of the cutting edge of the cutting tool is partially enlarged. For example, in the case of forming a rectangular linear convex portion as shown in FIG. 4A, the cutting edge of the cutting tool 31 has a rectangular shape complementary to the linear convex portion as shown in FIG. Further, when the shape and height of the linear protrusions periodically change between the linear protrusions parallel to each other, it is preferable that the cutting edge width S of the cutting tool 31 includes at least the width of the repetition period.
While the cylindrical base material 30 is rotated, the cutting edge of the cutting tool 31 for forming a linear concavo-convex shape is pressed against the outer peripheral surface for cutting, but as indicated by an arrow A, the cutting edge width S 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 S 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 uneven | corrugated shape preparation. As described above, the shaping roll mold 20 can be manufactured.
It should be noted that the production of the cutting tool 31 for forming the linear concavo-convex shape may be performed 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, since such a forming roll mold 20 is used, it is easy to form an arbitrary linear fine uneven shape, and the productivity is further improved.

<Step of forming a linear fine uneven surface>
In this invention, in the said process, the said linear fine uneven | corrugated surface is formed by the shaping process using the said roll mold for shaping.
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 surface forming layer (receiving layer), and the surface of the linear fine concavo-convex surface forming layer And the forming roll mold having a desired linear fine uneven shape are placed in contact with each other, and the linear fine unevenness is applied to the mold side surface of the linear fine uneven surface forming layer by applying pressure. Examples thereof include a method of forming a linear fine concavo-convex layer by appropriately curing the resin composition after the surface is formed, and then peeling from the mold roll mold. The method for curing the resin composition can be appropriately selected according to the type of the resin composition.

In FIG. 9, 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. 9, in the resin supply step, an uncured and liquid ionizing radiation curable resin composition is applied to the transparent base material 6 in the form of a belt-shaped 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 plate for forming the fine uneven layer, whereby the receiving layer 1 ′ is brought into close contact with the transparent substrate 6. At the same time, the ionizing radiation curable resin composition constituting the receiving layer 1 ′ is sufficiently filled into 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 prepared on the transparent substrate 6 and then cut into a desired size to produce a linear fine concavo-convex structure 10. Thereby, the linear fine concavo-convex structure 10 is formed on the long transparent base material 6 made of a roll material on the peripheral side surface of the shaping roll mold 20 which is a master for forming the fine concavo-convex layer. Are mass-produced efficiently.

  Moreover, in the manufacturing method of the linear fine concavo-convex structure according to the present invention described above, the case where the linear fine concavo-convex structure is produced by the forming process using the forming roll mold 20 has been described. The linear fine concavo-convex structure is not limited to this method, and may be manufactured. For example, according to the shape of the substrate related to the shape of the linear fine concavo-convex structure, for example, a linear fine concavo-convex structure 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 concavo-convex structure can be appropriately changed according to the shape of the substrate related to the shape of the linear fine concavo-convex structure.

  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 protrusions is a rectangular linear uneven part as shown in FIG. 8 (the average value p _{AVG of} adjacent linear convex part 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 a 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 uneven portion as shown in FIG. 8 (the average value of the spacing p between adjacent linear convex portions) 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 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 diluent solvents.
<Composition of Resin Composition A>
-65 parts by mass of ethylene oxide-modified (EO-modified) bisphenol A diacrylate-35 parts by mass of EO-modified trimethylolpropane triacrylate-1 part by mass of diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (lucillin TPO)

Example 1
The linear fine concavo-convex structure 1 was manufactured by the method shown in FIG.
As the mold roll 20, the mold roll 1 of Production Example 1 was used, and as the transparent substrate 6, a 80 μm thick triacetyl cellulose film (TAC) (manufactured by Fuji Film 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 original plate and obtained the linear fine concavo-convex structure 1 of Example 1. 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.
The SEM photograph of the cross section of the linear fine concavo-convex structure 1 obtained in Example 1 is shown in FIG.

(Example 2)
In Example 1, the implementation was performed except that the shaping roll die 2 obtained in Production Example 2 was used as the shaping roll die 20 instead of the shaping roll die 1 in Production Example 1. In the same manner as in Example 1, a linear fine concavo-convex structure 2 was obtained. 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.

[Evaluation]
<Measurement of contact angle on flat cured film surface of resin composition>
The resin composition A for forming a linear fine uneven layer was applied on a triacetyl cellulose film and cured to form a coating film having no fine uneven shape. The surface of the coating film side was used as the upper surface, and a 1.0 μL drop of water was dropped on the surface adhered to a black acrylic plate with an adhesive layer, and the contact angle of water 10 seconds after the drop was measured.
The contact angle of water on the flat cured film surface of the resin composition A was 50 degrees.

<Measurement of the contact angle on the surface of the cured film of the linear fine relief structures 1 and 2>
On the surface of the linear fine concavo-convex structure 1 and 2 obtained in Examples 1 and 2 with the surface of the linear fine concavo-convex layer on the top, and affixed to a black acrylic plate with an adhesive layer, 1.0 μL of water A droplet was dropped, and the contact angle of water 10 seconds after landing was measured. As a result, the contact angle of water in the extending direction of the linear protrusions of the linear fine concavo-convex structure 1 is 16 degrees, and the contact angle of water in the extension direction of the linear protrusions in the linear fine concavo-convex structure 2 is It was 18 degrees, and it was confirmed that the hydrophilicity was emphasized more than the contact angle on the flat cured film surface.

<Fingerprint wiping test>
The surface of the linear fine concavo-convex layer 1 and 2 obtained in Examples 1 and 2 was attached to a black acrylic plate with an adhesive layer with the surface on the side of the linear fine concavo-convex layer, and then the finger was pressed to attach the fingerprint I let you. Thereafter, the fingerprint was wiped dry with Zavina Minimax (Fuji Chemical). Dry wiping was performed 10 times with a force of about 3 kg / cm ² , and the appearance after wiping was evaluated.
In both of the linear fine concavo-convex structures 1 and 2, the linear convex portion was excellent in flexibility and restorability, excellent in wiping property in the linear concavo-convex direction, and fingerprint stains could not be visually recognized. Moreover, when wiping off, a linear convex part was not crushed or adhesion of tips was not produced.

DESCRIPTION OF SYMBOLS 1 Linear fine uneven | corrugated layer 1 'Receptive layer 2 Linear convex part 3 Linear fine uneven | corrugated shape 4 Base material 5, 5' End part 5a, 5'a of convex part One edge part 5b, 5'b of convex part The other end portion 6 of the convex portion Transparent substrate 10 Linear fine concavo-convex structure 11 Die 12 Press roller 13 Peeling roller 20 Molding roll die 30 Cylindrical base material 31 Byte X, Y, Z XYZ coordinate axes when the extension direction is Y

Claims (4)

A linear fine concavo-convex structure which is a dew condensation suppressing member,
A plurality of linear convex portions parallel to each other has a linear fine concavo-convex shape extending linearly or openly on the surface, and includes 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,
A linear fine concavo-convex structure having a contact angle of water of 60 degrees or less on a flat surface of a cured product of the resin composition. A linear fine concavo-convex structure which is a water repellent member,
A plurality of linear convex portions parallel to each other has a linear fine concavo-convex shape extending linearly or openly on the surface, and includes 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,
A linear fine concavo-convex structure having a contact angle of water exceeding 90 degrees on a flat surface of a cured product of the resin composition. A linear fine concavo-convex structure which is a powder adhesion suppressing member,
A plurality of linear convex portions parallel to each other has a linear fine concavo-convex shape extending linearly or openly on the surface, and includes a linear fine concavo-convex layer made of a cured product of the resin composition,
In the linear fine concavo-convex shape, a linear fine concavo-convex structure (excluding a linear fine concavo-convex structure applied to an antireflection article) having an average value p _{AVG of} adjacent linear convex portion intervals p of 500 nm or less. .) A linear fine concavo-convex structure which is a transparent conductive film,
A plurality of linear convex portions parallel to each other has a linear fine concavo-convex shape extending linearly or openly on the surface, and includes 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,
A linear fine concavo-convex structure comprising a transparent conductive layer on the surface of the linear fine concavo-convex layer, or the linear fine concavo-convex layer itself being a transparent conductive layer.