WO2011118591A1 - Method for producing molds and method for producing products with superfine concave-convex structures on surface - Google Patents

Abstract

Disclosed is a mold production method comprising, (I) a step for manufacturing a main body of a mold (16) with superfine concave-convex structures formed on the surface; (II) a step for treating the surface of the mold main body (16), on the side on which the superfine concave-convex structures are formed, with a release agent which comprises a functional group (B) that can react with a functional group (A) present on the aforementioned surface; (III) a step for heating and humidifying the mold main body (16) that has been treated with the release agent; and (IV) a step that repeats aforementioned steps (II) and (III) two or more times. Said production method produces molds that can maintain mold release properties for a long period even after repeated transfer of the surface superfine concave-convex structures. Also disclosed is a method for producing products with surfaces of superfine concave-convex structures productively.

Description

Method for producing mold and method for producing article having fine uneven structure on surface

The present invention relates to a method for producing a mold having a fine concavo-convex structure on the surface and a method for producing an article having a fine concavo-convex structure on the surface.
This application claims priority based on Japanese Patent Application No. 2010-070281 filed in Japan on March 25, 2010, the contents of which are incorporated herein by reference.

In recent years, it is known that an article having a fine concavo-convex structure on the surface with a period shorter than the wavelength of visible light exhibits an antireflection effect, a lotus effect, and the like. In particular, it is known that a concavo-convex structure called a moth-eye structure is an effective antireflection means by continuously increasing the refractive index from the refractive index of air to the refractive index of the material of the article.

As a method of forming a fine concavo-convex structure on the surface of an article, a method of transferring a fine concavo-convex structure of the mold to the surface of an article using a mold having an inverted structure of the fine concavo-convex structure formed on the surface is attracting attention . In the mold, the surface on the side where the fine relief structure is formed is usually treated with a release agent (Patent Document 1).

However, when the fine concavo-convex structure of the mold is repeatedly transferred onto the surface of the article, there is a problem that the releasability gradually decreases as the number of transfers increases. And since it becomes impossible to release at a relatively early stage, an article having a fine concavo-convex structure on the surface cannot be manufactured with high productivity.

JP 2007-326367 A

The present invention provides a method for producing a mold capable of maintaining releasability over a long period of time even if the fine concavo-convex structure on the surface is repeatedly transferred, and a method for producing an article having the fine concavo-convex structure on the surface with high productivity.

The mold manufacturing method of the present invention is characterized by having the following steps (I) to (IV).
(I) The process of producing the mold main body by which the fine uneven structure was formed on the surface.
(II) After step (I), the surface of the mold body on which the fine concavo-convex structure is formed has a functional group (B) that can react with the functional group (A) present on the surface. The process of processing with an agent.
(III) A step of placing the mold body under heating and humidification after step (II).
(IV) A step of repeating the steps (II) and (III) two or more times.

In the mold manufacturing method of the present invention, the functional group (B) is preferably a hydrolyzable silyl group. More preferably, the functional group (B) of the release agent of the present invention is a hydrolyzable silyl group and has a perfluoropolyether structure.
The mold in which the fine concavo-convex structure in the step (I) is formed is preferably an anodized aluminum substrate and a fine concavo-convex structure having two or more pores formed on the surface thereof.

The method for producing an article having a fine concavo-convex structure on the surface of the present invention is characterized in that the fine concavo-convex structure on the surface of the mold obtained by the mold production method of the present invention is transferred to the surface of the article main body.

That is, the present invention relates to the following.
(1) A method for producing a mold, comprising the following steps (I) to (IV):
(I) The process of producing the mold main body by which the fine uneven structure was formed on the surface.
(II) After step (I), the surface of the mold body on which the fine concavo-convex structure is formed has a functional group (B) that can react with the functional group (A) present on the surface. The process of processing with an agent.
(III) A step of placing the mold body under heating and humidification after step (II).
(IV) A step of repeating the steps (II) and (III) twice or more.
(2) The method for producing a mold according to (1), wherein the functional group (B) is a hydrolyzable silyl group.
(3) The mold production method according to (1) or (2), wherein the functional group (B) of the release agent is a hydrolyzable silyl group and a release agent having a perfluoropolyether structure. .
(4) The method for producing a mold according to any one of (1) to (3), wherein in the step (II), the concentration of the release agent is 0.06% by mass or more and 0.15% by mass or less. .
(5) The mold in which the fine concavo-convex structure in the step (I) is formed is obtained by anodizing an aluminum substrate and forming a fine concavo-convex structure having two or more pores on the surface thereof (1) The method for producing a mold according to any one of (4) to (4).
(6) The mold manufacturing method according to any one of (1) to (5), wherein an average interval between the pores is 400 nm or less.
(7) The mold production method according to (6), wherein an average interval between the pores is 20 nm or more and 400 nm or less.
(8) The step (I) includes the following steps (a) to (f):
The step (II) includes the following steps (g) to (j):
The step (III) has the following step (k) and / or (l):
The method for producing a mold according to any one of (1) to (7), wherein the step (IV) includes the following steps (m) and / or (n):
(A) A step of forming an oxide film on the surface of an aluminum substrate by anodizing the aluminum substrate in an electrolytic solution under a constant voltage.
(B) A step of removing the oxide film and forming anodic oxidation pore generation points on the surface of the aluminum substrate.
(C) After the step (b), the step of anodizing the aluminum base material again in the electrolytic solution to form an oxide film having pores at the pore generation points.
(D) A step of enlarging the diameter of the pores after the step (c).
(E) A step of anodizing again in the electrolytic solution after the step (d).
(F) The process of obtaining the mold main body by which the said process (d) and the said process (e) are repeated, and the anodic oxidation alumina which has a 2 or more pore is formed in the surface of the said aluminum base material.
(G) A step of washing the mold body after the step (f).
(H) After the step (g), air is blown onto the mold body to remove impurities adhering to the surface of the mold body.
(I) After the steps (f) to (h), a step of immersing the mold body having a hydroxyl group introduced into the surface thereof in a diluted solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a fluorine-based solvent.
(J) A step of drying the mold body after the step (i).
(K) A step of placing the mold body under heating and humidification after step (i).
(L) A step of washing the mold body immediately after the step (k) with a fluorinated solvent.
(M) A step in which the steps (i) to (l) are defined as one cycle and the cycle is repeated twice or more.
(N) A step of drying the mold body after the step (m).
(9) A fine concavo-convex structure comprising transferring the fine concavo-convex structure on the surface of the mold obtained by the method for producing a mold according to any one of (1) to (8) to the surface of the article body. A method for producing an article on a surface.

According to the mold manufacturing method of the present invention, it is possible to manufacture a mold that can maintain releasability over a long period of time even if the fine concavo-convex structure on the surface is repeatedly transferred.
According to the method for producing an article having the fine uneven structure on the surface of the present invention, an article having the fine uneven structure on the surface can be produced with high productivity.

It is sectional drawing which shows the manufacturing process of the mold which has an anodized alumina on the surface. It is a block diagram which shows an example of the manufacturing apparatus of the articles | goods which have a fine concavo-convex structure on the surface. It is sectional drawing which shows an example of the article | item which has a fine concavo-convex structure on the surface.

In the present specification, (meth) acrylate means acrylate or methacrylate. Moreover, an active energy ray means visible light, an ultraviolet-ray, an electron beam, plasma, a heat ray (infrared rays etc.), etc.

<Mold manufacturing method>
The method for producing a mold of the present invention is a method having the following steps (I) to (IV).
(I) The process of producing the mold main body by which the fine uneven structure was formed on the surface.
(II) After step (I), the surface of the mold body on which the fine concavo-convex structure is formed has a functional group (B) that can react with the functional group (A) present on the surface. The process of processing with an agent.
(III) A step of placing the mold body under heating and humidification after step (II).
(IV) A step of repeating the steps (II) and (III) twice or more.

(Process (I))
In step (I), a mold body is produced by forming a fine relief structure on the surface of the substrate. Examples of the material for the substrate include metals (including those having an oxide film formed on the surface), quartz, glass, resin, and ceramics. Examples of the shape of the substrate include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.

Examples of the method for producing the mold main body include a method of forming anodized alumina having two or more pores (concave portions) on the surface of an aluminum base. The above method is a preferable production method from the viewpoint that the area can be increased and the production is simple.

As the above method, specifically, a method having the following steps (a) to (f) is preferable.
(A) A step of forming an oxide film on the surface of an aluminum substrate by anodizing the aluminum substrate in an electrolytic solution under a constant voltage.
(B) A step of removing the oxide film and forming anodic oxidation pore generation points on the surface of the aluminum substrate.
(C) After the step (b), the step of anodizing the aluminum substrate again in the electrolytic solution to form an oxide film having pores at the pore generation points.
(D) A step of expanding the diameter of the pores after the step (c).
(E) A step of anodizing again in the electrolytic solution after the step (d).
(F) A step of repeating steps (d) and (e) to obtain a mold body in which anodized alumina having two or more pores is formed on the surface of an aluminum substrate.

Step (a):
As shown in FIG. 1, when the aluminum substrate 10 is anodized, an oxide film 14 having pores 12 is formed. Here, examples of the shape of the aluminum substrate include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
Since the oil used when processing the aluminum base material into a predetermined shape may be adhered, it is preferable to degrease the aluminum base material in advance. The aluminum substrate is preferably subjected to electrolytic polishing (etching) in order to smooth the surface state.

The purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more. When the purity of aluminum is low, when anodized, an uneven structure having a size to scatter visible light may be formed due to segregation of impurities, or the regularity of pores obtained by anodization may be lowered.
Examples of the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.

When oxalic acid is used as the electrolytic solution: The concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid exceeds 0.7M, the current value becomes too high, and the surface of the oxide film may become rough. When the formation voltage is 30 to 60 V, anodized alumina having highly regular pores with an average interval of 100 nm can be obtained. Regardless of whether the formation voltage is higher or lower than this range, the regularity tends to decrease. The temperature of the electrolytic solution is preferably 60 ° C. or lower, and more preferably 45 ° C. or lower. When the temperature of the electrolytic solution exceeds 60 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.

When sulfuric acid is used as the electrolytic solution: the concentration of sulfuric acid is preferably 0.7 M or less. If the concentration of sulfuric acid exceeds 0.7M, the current value may become too high to maintain a constant voltage. When the formation voltage is 25 to 30 V, anodized alumina having highly regular pores with an average interval of 63 nm can be obtained. The regularity tends to decrease whether the formation voltage is higher or lower than this range. The temperature of the electrolytic solution is preferably 30 ° C. or lower, and more preferably 20 ° C. or lower. When the temperature of the electrolytic solution exceeds 30 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.

Step (b):
As shown in FIG. 1, the regularity of the pores can be improved by removing the oxide film 14 once and using it as the pore generation points 16 for anodic oxidation.

Examples of the method for removing the oxide film include a method in which aluminum is not dissolved but dissolved in a solution that selectively dissolves the oxide film and removed. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

Step (c):
As shown in FIG. 1, when the aluminum substrate 10 from which the oxide film has been removed is anodized again, an oxide film 14 having cylindrical pores 12 is formed.
Anodizing conditions are not particularly limited, but anodizing is performed in the same conditions as in step (a) or in a shorter time than in step (a).

Step (d):
As shown in FIG. 1, a process for expanding the diameter of the pores 12 (hereinafter referred to as a pore diameter expansion process) is performed. The pore diameter expansion treatment is a treatment for expanding the diameter of the pores obtained by anodic oxidation by immersing in a solution dissolving the oxide film. Examples of such a solution include a phosphoric acid aqueous solution of about 5% by mass. The longer the pore diameter expansion processing time, the larger the pore diameter.

Step (e):
As shown in FIG. 1, when anodized again, cylindrical pores 12 having a small diameter that extend downward from the bottom of the cylindrical pores 12 are further formed.
Anodization may be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.

Step (f):
As shown in FIG. 1, when the pore diameter enlargement process in the step (d) and the anodic oxidation in the step (e) are repeated, the pores 12 have a shape in which the diameter continuously decreases in the depth direction from the opening. An oxide film 14 is formed, and a mold body 18 having anodized alumina (aluminum porous oxide film (alumite)) on the surface of the aluminum substrate 10 is obtained. The end may be completed in either step (d) or step (e), but it is preferable to end in step (d).

The total number of repetitions is preferably 3 times or more, and more preferably 5 times or more. When the number of repetitions is 2 times or less, the diameter of the pores decreases discontinuously, so that the effect of reducing the reflectance of the moth-eye structure formed using anodized alumina having such pores is insufficient.

Examples of the shape of the pore 12 include a substantially conical shape, a pyramid shape, a cylindrical shape, and the like, and a cross-sectional area of the pore perpendicular to the depth direction from the outermost surface, such as a conical shape and a pyramid shape, A shape that continuously decreases in the depth direction is preferable.
The average interval between the pores 12 is not more than the wavelength of visible light, that is, not more than 400 nm. The average interval between the pores 12 is preferably 20 nm or more.
The range of the average interval between the pores 12 is preferably 20 nm or more and 400 nm or less, more preferably 50 nm or more and 300 nm or less, and further preferably 90 nm or more and 250 nm or less.
The average interval between the pores 12 was measured by measuring the distance between adjacent pores 12 (distance from the center of the pore 12 to the center of the adjacent pore 12) by electron microscope observation, and averaging these values. It is a thing.

When the average interval is 100 nm, the depth of the pores 12 is preferably 80 to 500 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm.
The depth of the pore 12 is a value obtained by measuring the distance between the bottom of the pore 12 and the top of the convex portion existing between the pores 12 when observed with an electron microscope at a magnification of 30000 times. It is.
The aspect ratio of the pores 12 (depth of pores / average interval between pores) is preferably 0.8 to 5, more preferably 1.2 to 4, and particularly preferably 1.5 to 3.

(Process (II))
In the step (II), the surface of the mold body on which the fine concavo-convex structure is formed is treated with a release agent having a functional group (B) that can react with the functional group (A).

The functional group (A) means a group capable of forming a chemical bond by reacting with a reactive functional group (B) possessed by a release agent described later.
Examples of the functional group (A) include a hydroxyl group, an amino group, a carboxyl group, a mercapto group, an epoxy group, and an ester group, and a water release agent that is described later often has a reactive functional group (B). A hydroxyl group is particularly preferred from the viewpoint of good reactivity with the decomposable silyl group. When the surface treated with the release agent is anodized alumina, the functional group (A) is a hydroxyl group.

When the functional group (A) is not present on the surface of the mold body on which the fine concavo-convex structure is formed, for example, the functional group (A) by the following method (II-1) or method (II-2) May be introduced.
(II-1) A method in which the functional group (A) is introduced into the surface of the mold main body by performing plasma treatment on the surface on which the fine concavo-convex structure is formed.
(II-2) By treating the surface of the mold body on which the fine concavo-convex structure is formed with a functional group (A) or a compound having a precursor thereof (such as a silane coupling agent), a functional group is formed on the surface. A method of introducing (A).

The functional group (B) means a group that can react with the functional group (A) to form a chemical bond or a group that can be easily converted into the group.
Examples of the functional group (B) when the functional group (A) is a hydroxyl group include a hydrolyzable silyl group, a silanol group, a hydrolyzable group containing a titanium atom or an aluminum atom, and the reactivity with the hydroxyl group is good. From the viewpoint, a hydrolyzable silyl group or a silanol group is preferable, and a hydrolyzable silyl group is more preferable. The hydrolyzable silyl group is a group that generates a silanol group (Si—OH) by hydrolysis, Si—OR (R is an alkyl group), and Si—X (X is a halogen atom). ) And the like.

Examples of the release agent include a silicone resin having a functional group (B), a fluororesin having a functional group (B), a fluorine compound having a functional group (B), and the like, and a fluorine compound having a hydrolyzable silyl group Is more preferable. Commercially available fluorine compounds having hydrolyzable silyl groups include fluoroalkylsilanes, and those having a perfluoropolyether structure include “OPTOOL (registered trademark)” series manufactured by Daikin Industries.
Further, the release agent is particularly preferably a fluorine compound having a functional group (B), wherein the functional group (B) is a hydrolyzable silyl group and has a perfluoropolyether structure. When the functional group (B) is a hydrolyzable silyl group and has a perfluoropolyether structure, the functional group (A) is highly reactive and the releasability is particularly good.

Examples of the treatment method using a release agent include the following methods (II-3) to (II-4), and the surface of the mold body on which the fine concavo-convex structure is formed can be treated with the release agent without unevenness. Therefore, the method (II-3) is particularly preferable.
(II-3) A method of immersing the mold body in a dilute solution of a release agent.
(II-4) A method in which a release agent or a diluted solution thereof is applied to the surface of the mold body on the side where the fine relief structure is formed.

As the method (II-3), a method having the following steps (g) to (j) is preferable.
(G) A step of washing the mold body with water after the step (f) as necessary.
(H) After the step (g), if necessary, a step of blowing air to the mold body to remove impurities adhering to the surface of the mold body.
(I) A step of immersing the mold body having a hydroxyl group introduced on the surface thereof in a diluted solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a fluorine-based solvent after the steps (f) to (h).
(J) A step of drying the mold body after step (i), if necessary.

Step (g):
Since the chemicals used in forming the fine concavo-convex structure (phosphoric acid aqueous solution used in the pore size enlargement process) and impurities (dust etc.) are adhered to the mold body, they are removed by washing with water. .

Step (h):
If water droplets are attached to the surface of the mold main body, the efficiency of the treatment with the release agent in the step (i) is lowered, so that air is blown onto the mold main body and the visible water droplets are almost removed.

Step (i):
Examples of the fluorine-based solvent for dilution include hydrofluoropolyether, perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and dichloropentafluoropropane.
The concentration of the fluorine compound having a hydrolyzable silyl group is preferably from 0.01 to 0.2% by mass, more preferably from 0.06% by mass to 0.15% by mass in the diluted solution (100% by mass). When the concentration of the fluorine compound having a hydrolyzable silyl group is within the above range, it is possible to suppress deterioration of the release agent solution due to the self-condensation reaction of the release agent during storage or use, and sufficient release. Type characteristics are obtained.
The immersion time is preferably 1 to 30 minutes.
The immersion temperature is preferably 0 to 50 ° C.

Step (j):
The mold body may be air-dried or forcibly heated and dried with a dryer or the like.
The drying temperature is preferably 50 to 150 ° C.
The drying time is preferably 5 to 300 minutes.

(Process (III))
Step (III) includes, for example, the following step (k) and / or step (l).
(K) A step of placing the mold body under heating and humidification after step (i).
(L) A step of washing the mold main body immediately after the step (k) with a fluorine-based solvent as necessary.

Step (k):
By leaving the mold body under heating and humidification, the hydrolyzable silyl group of the fluorine compound (release agent) is hydrolyzed to form a silanol group, and the reaction between the silanol group and the hydroxyl group on the surface of the mold body It proceeds sufficiently and improves the fixability of the fluorine compound.
The heating temperature is preferably 40 to 100 ° C.
The humidification condition is preferably a relative humidity of 85% or more.
The standing time is preferably 10 minutes to 1 day.

Step (l):
Examples of the fluorinated solvent for washing include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and dichloropentafluoropropane.
The mold main body washed with the fluorinated solvent may be further washed with water or alcohol.

(Process (IV))
Step (IV) includes, for example, the following step (m) and / or step (n).
(M) A step of repeating steps (i) to (l) as one cycle and repeating the cycle twice or more.
(N) A step of drying the mold body after the step (m) as necessary.

Step (m):
The number of repetitions of the cycle of step (i) to step (l) is 2 times or more, preferably 2 to 10 times, more preferably 3 to 5 times. If the number of repetitions is 2 or more, the mold releasability can be maintained for a long time.

Step (n):
The mold body may be air-dried or forcibly heated and dried with a dryer or the like.
The drying temperature is preferably 40 to 150 ° C.
The drying time is preferably 5 to 300 minutes.

(Function and effect)
In the mold manufacturing method of the present invention described above, the step (II) of treating the surface of the mold body on the side where the fine concavo-convex structure is formed with a release agent, and the mold body under heating and humidification Since the placing step (III) is repeated twice or more, it is possible to produce a mold capable of maintaining the releasability for a long time even if the fine concavo-convex structure on the surface is repeatedly transferred.

The mold manufacturing method of the present invention is particularly effective as a mold manufacturing method having an anodized alumina on the surface for the following reasons.
The surface of the anodized alumina hardly reacts with the hydrolyzable silyl group (silanol group), and a gap free from the release agent is easily formed only by treating with the release agent once. Therefore, the release agent is easily peeled from the gap, and the mold releasability is likely to be lowered. On the other hand, in the present invention, since the treatment with the release agent is repeated twice or more, the gap can be filled with the release agent as much as possible, and the mold releasability is unlikely to deteriorate.

<Method for producing article having fine concavo-convex structure on surface>
An article having a fine concavo-convex structure on its surface is manufactured as follows using, for example, a manufacturing apparatus shown in FIG.
An active energy ray curable resin from the tank 22 between a roll-shaped mold 20 having a fine concavo-convex structure (not shown) on the surface and a strip-shaped film 42 (article main body) moving along the surface of the roll-shaped mold 20. Supply the composition.

The film 42 and the active energy ray curable resin composition are nipped between the roll-shaped mold 20 and the nip roll 26 whose nip pressure is adjusted by the pneumatic cylinder 24, and the active energy ray curable resin composition is niped with the film 42. And the roll-shaped mold 20 are uniformly distributed, and at the same time, the concave portions of the fine concavo-convex structure of the roll-shaped mold 20 are filled.

By irradiating the active energy ray curable resin composition through the film 42 from the active energy ray irradiating device 28 installed below the roll-shaped mold 20, the active energy ray curable resin composition is cured. Then, the cured resin layer 44 to which the fine uneven structure on the surface of the roll-shaped mold 20 is transferred is formed.
By peeling the film 42 having the cured resin layer 44 formed on the surface from the roll-shaped mold 20 with the peeling roll 30, an article 40 as shown in FIG. 3 is obtained.

The active energy ray irradiation device 28 is preferably a high-pressure mercury lamp, a metal halide lamp, or the like. In this case, the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm ² .

The film 42 is a light transmissive film. Examples of the film material include acrylic resin, polycarbonate, styrene resin, polyester, cellulose resin (such as triacetyl cellulose), polyolefin, and alicyclic polyolefin.

The cured resin layer 44 is a film made of a cured product of an active energy ray-curable resin composition described later, and has a fine uneven structure on the surface.
When the anodized alumina mold is used, the fine uneven structure on the surface of the article 40 is formed by transferring the fine uneven structure on the surface of the anodized alumina, and the active energy ray-curable resin composition is cured. It has two or more convex parts 46 which consist of things.

The fine concavo-convex structure is preferably a so-called moth-eye structure in which two or more protrusions (convex portions) having a substantially conical shape or a pyramid shape are arranged. It is known that the moth-eye structure in which the distance between the protrusions is less than or equal to the wavelength of visible light is an effective anti-reflection measure by continuously increasing the refractive index from the refractive index of air to the refractive index of the material. It has been.

The average interval between the convex portions is preferably not more than the wavelength of visible light, that is, not more than 400 nm. In the case where the convex portions are formed using an anodized alumina mold, the average distance between the convex portions is about 100 nm, so that it is more preferably 200 nm or less, and particularly preferably 150 nm or less.

The average interval between the convex portions is preferably 20 nm or more from the viewpoint of easy formation of the convex portions.
The range of the average distance between the convex portions is preferably 20 to 400 nm, more preferably 50 to 300 nm, and further preferably 90 to 250 nm.
The average interval between the convex portions is obtained by measuring 50 intervals between adjacent convex portions (distance from the center of the convex portion to the center of the adjacent convex portion) by electron microscope observation, and averaging these values. .

The height of the protrusions is preferably 80 to 500 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm when the average interval is 100 nm. If the height of the convex portion is 80 nm or more, the reflectance is sufficiently low and the wavelength dependency of the reflectance is small. If the height of a convex part is 500 nm or less, the scratch resistance of a convex part will become favorable.
The height of the convex portion is a value obtained by measuring the distance between the topmost portion of the convex portion and the bottommost portion of the concave portion existing between the convex portions when observed with an electron microscope at a magnification of 30000 times.

The aspect ratio of the protrusions (the height of the protrusions / the average interval between the protrusions) is preferably 0.8 to 5, more preferably 1.2 to 4, and particularly preferably 1.5 to 3. If the aspect ratio of the convex portion is 0.8 or more, the reflectance is sufficiently low. When the aspect ratio of the convex portion is 5 or less, the scratch resistance of the convex portion is good.

The shape of the convex part is a shape in which the convex sectional area in the direction perpendicular to the height direction continuously increases in the depth direction from the outermost surface, that is, the sectional shape in the height direction of the convex part is a triangle, trapezoid, A shape such as a bell shape is preferred.

The difference between the refractive index of the cured resin layer 44 and the refractive index of the film 42 is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. When the refractive index difference is 0.2 or less, reflection at the interface between the cured resin layer 44 and the film 42 is suppressed.

When the surface has a fine concavo-convex structure, if the surface is made of a hydrophobic material, super water repellency can be obtained by the lotus effect, and if the surface is made of a hydrophilic material, super hydrophilicity can be obtained. It is known that

When the material of the cured resin layer 44 is hydrophobic, the water contact angle on the surface of the fine uneven structure is preferably 90 ° or more, more preferably 110 ° or more, and particularly preferably 120 ° or more. If the water contact angle is 90 ° or more, water stains are less likely to adhere, so that sufficient antifouling properties are exhibited. Moreover, since water does not adhere easily, anti-icing can be expected.
When the material of the cured resin layer 44 is hydrophobic, the range of the water contact angle on the surface of the fine relief structure is preferably 90 ° or more and 180 ° or less, more preferably 110 ° or more and 180 ° or less, and 120 ° or more and 180 ° or less. Is particularly preferred.

When the material of the cured resin layer 44 is hydrophilic, the water contact angle on the surface of the fine uneven structure is preferably 30 ° or less, more preferably 25 ° or less, further preferably 23 ° or less, and particularly preferably 21 ° or less. If the water contact angle is 30 ° or less, the dirt adhering to the surface is washed away with water and the oil dirt is less likely to adhere, so that sufficient antifouling properties are exhibited. The water contact angle is preferably 3 ° or more from the viewpoint of suppressing the deformation of the fine concavo-convex structure due to water absorption of the cured resin layer 44 and the accompanying increase in reflectance.
When the material of the cured resin layer 44 is hydrophilic, the range of the water contact angle on the surface of the fine concavo-convex structure is preferably 3 ° to 30 °, more preferably 3 ° to 25 °, more preferably 3 ° to 23 °. The following is more preferable, and 3 ° to 21 ° is particularly preferable.

(Active energy ray-curable resin composition)
The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.
Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
The active energy ray-curable resin composition may contain a non-reactive polymer and an active energy ray sol-gel reactive composition.

Examples of the monomer having a radical polymerizable bond include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl ( )) (Meth) acrylate derivatives such as hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate; (meth) acrylic acid, (meth) acrylonitrile; styrene, And styrene derivatives such as α-methylstyrene; and (meth) acrylamide derivatives such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide It is done.
These may be used alone or in combination of two or more.

Polyfunctional monomers include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (3- (Meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) ) Butane, dimethylol tricyclodecane di (meth) acrylate, ethylene oxide adduct di (meth) acrylate of bisphenol A, propylene oxide adduct di (meth) acrylate of bisphenol A, neopentyl glycol di (meth) hydroxypivalate Bifunctional monomers such as acrylate, divinylbenzene, and methylenebisacrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethyleneo Trifunctional monomers such as side-modified tri (meth) acrylate, trimethylolpropane propylene oxide-modified triacrylate, trimethylolpropane ethylene oxide-modified triacrylate, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate; succinic acid / trimethylolethane / Tetra- or higher functional monomers such as acrylic acid condensation reaction mixture, dipentaerystol hexa (meth) acrylate, dipentaerystol penta (meth) acrylate, ditrimethylolpropane tetraacrylate, and tetramethylolmethane tetra (meth) acrylate; Bifunctional or higher urethane acrylate, bifunctional or higher polyester acrylate, and the like can be given. These may be used alone or in combination of two or more.

Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.

Examples of the oligomer or reactive polymer include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) Examples thereof include acrylates, urethane (meth) acrylates, cationic polymerization type epoxy compounds, and single or copolymerized monomers of the above-mentioned monomers having radical polymerizable bonds in the side chains.

Examples of non-reactive polymers include acrylic resins, styrene resins, polyurethane, cellulose resins, polyvinyl butyral, polyester, and thermoplastic elastomers.
Examples of the active energy ray sol-gel reactive composition include alkoxysilane compounds and alkylsilicate compounds.

As an alkoxysilane compound, the compound of following formula (1) is mentioned.
R ¹¹ _x Si (OR ¹² ) _y (1)
However, R ¹¹ and R ¹² each represent an alkyl group having 1 to 10 carbon atoms, and x and y represent integers satisfying the relationship of x + y = 4.

Examples of the alkoxysilane compound include tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, methyltriethoxysilane, Examples include methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane.

Examples of the alkyl silicate compound include a compound of the following formula (2).
R ²¹ O [Si (OR ²³ ) (OR ²⁴ ) O] _z R ²² (2)
R ²¹ to R ²⁴ each represents an alkyl group having 1 to 5 carbon atoms, and z represents an integer of 3 to 20.

Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate, and the like.

When using a photocuring reaction, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxy. Acetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, and 2-hydroxy-2-methyl-1-phenylpropane Carbonyl compounds such as -1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide And benzoyldiethoxyphosphine oxide and the like.
These may be used alone or in combination of two or more.

When using an electron beam curing reaction, examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t- Thioxanthones such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- Acetophenones such as 4-morpholinophenyl) -butanone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6- Acylphosphine oxides such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate; 1,7-bisacridinyl Heptane; and 9-phenylacridine and the like. These may be used alone or in combination of two or more.

When using a thermosetting reaction, examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, organic peroxides such as t-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; and N, N-dimethylaniline and N, N-dimethyl as the organic peroxide Examples thereof include a redox polymerization initiator combined with an amine such as -p-toluidine.

The amount of the polymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. When the amount of the polymerization initiator is less than 0.1 parts by mass, the polymerization is difficult to proceed. When the amount of the polymerization initiator exceeds 10 parts by mass, the cured film may be colored or the mechanical strength may be lowered.

The active energy ray-curable resin composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving the antifouling property, fine particles, and a small amount of a solvent, if necessary. .

(Hydrophobic material)
In order to increase the water contact angle of the surface of the fine uneven structure of the cured resin layer 44 to 90 ° or more, a fluorine-containing compound or a silicone compound is used as an active energy ray-curable resin composition capable of forming a hydrophobic material. It is preferable to use the composition containing.

Fluorine-containing compounds:
As the fluorine-containing compound, a compound having a fluoroalkyl group represented by the following formula (3) is preferable.
-(CF ₂ ) _n -X (3)
However, X represents a fluorine atom or a hydrogen atom, n represents an integer of 1 or more, preferably 1 to 20, more preferably 3 to 10, and particularly preferably 4 to 8.

Examples of the fluorine-containing compound include a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant, and a fluorine-containing polymer.

Examples of the fluorine-containing monomer include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer.
Examples of the fluoroalkyl group-substituted vinyl monomer include fluoroalkyl group-substituted (meth) acrylates, fluoroalkyl group-substituted (meth) acrylamides, fluoroalkyl group-substituted vinyl ethers, and fluoroalkyl group-substituted styrenes.

Examples of the fluoroalkyl group-substituted ring-opening polymerizable monomer include fluoroalkyl group-substituted epoxy compounds, fluoroalkyl group-substituted oxetane compounds, and fluoroalkyl group-substituted oxazoline compounds.

As the fluorine-containing monomer, a fluoroalkyl group-substituted (meth) acrylate is preferable, and a compound of the following formula (4) is particularly preferable.
CH ₂ = C (R ⁴¹ ) C (O) O— (CH ₂ ) _m — (CF ₂ ) _n —X (4)
R ⁴¹ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, preferably 1 to 3, more preferably 1 or 2, and n Represents an integer of 1 to 20, preferably 3 to 10, and more preferably 4 to 8.

As the fluorine-containing silane coupling agent, a fluoroalkyl group-substituted silane coupling agent is preferable, and a compound of the following formula (5) is particularly preferable.
(R ^f ) _a R ⁵¹ _b SiY _c (5)

R ^f represents a fluorine-substituted alkyl group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ^f includes a 3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctyl group, a 3-trifluoromethoxypropyl group, a 3-trifluoroacetoxypropyl group, and the like. Can be mentioned.

R ⁵¹ represents an alkyl group having 1 to 10 carbon atoms. Examples of R ⁵¹ include a methyl group, an ethyl group, and a cyclohexyl group.

Y represents a hydroxyl group or a hydrolyzable group.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, and R ⁵² C (O) O (wherein R ⁵² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Examples include octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, and lauryloxy group.
Examples of the halogen atom include Cl, Br, and I.
Examples of R ⁵² C (O) O include CH ₃ C (O) O, C ₂ H ₅ C (O) O, and the like.

A, b, and c are integers satisfying a + b + c = 4 and satisfying a ≧ 1 and c ≧ 1, and preferably a = 1, b = 0, and c = 3.

Fluorine-containing silane coupling agents include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, and Examples include tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane.

Examples of the fluorine-containing surfactant include a fluoroalkyl group-containing anionic surfactant and a fluoroalkyl group-containing cationic surfactant.

Examples of the fluoroalkyl group-containing anionic surfactant include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C ₆ -C ₁₁ ) oxy. ] -1-alkyl _(C 3 ~ C ₄₎ sulfonate, sodium 3- [omega - fluoroalkanoyl _{(C 6} ~ C 8) -N- ethylamino] -1-sodium sulfonic acid, fluoroalkyl _{(C 11} ~ C ₂₀ ) carboxylic acid or a metal salt thereof, perfluoroalkyl carboxylic acid (C ₇ to C ₁₃ ) or a metal salt thereof, perfluoroalkyl (C ₄ to C ₁₂ ) sulfonic acid or a metal salt thereof, perfluorooctanesulfonic acid diethanolamine N-propyl-N- (2-hydroxy Chill) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _~ C ₁₀₎ sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _{(C 6 ~} C 10) -N- ethylsulfonyl glycine salts and monoperfluoroalkyl, (C ₆ -C ₁₆ ) ethyl phosphate and the like.

Examples of the fluoroalkyl group-containing cationic surfactant include aliphatic quaternary compounds such as fluoroalkyl group-containing aliphatic primary, secondary or tertiary amine acids, and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salts. Examples thereof include ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

Examples of the fluorine-containing polymer include a polymer of a fluoroalkyl group-containing monomer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer, and a fluoroalkyl group-containing monomer and a crosslinking reactive group-containing monomer. A copolymer etc. are mentioned. The fluorine-containing polymer may be a copolymer with another copolymerizable monomer.

As the fluorine-containing polymer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer is preferable.
As the poly (oxyalkylene) group, a group represented by the following formula (6) is preferable.
-(OR ⁶¹ ) _p- (6)
R ⁶¹ represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 2 or more.
Examples of R ⁶¹ include —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, and —CH (CH ₃ ) CH (CH ₃ ) —.

The poly (oxyalkylene) group may be composed of the same oxyalkylene unit (OR ⁶¹ ) or may be composed of two or more oxyalkylene units (OR ⁶¹ ). The arrangement of two or more oxyalkylene units (OR ⁶¹ ) may be a block or random.

Silicone compounds:
Examples of the silicone compound include (meth) acrylic acid-modified silicone, silicone resin, silicone silane coupling agent, and the like.
Examples of the (meth) acrylic acid-modified silicone include silicone (di) (meth) acrylate.

(Hydrophilic material)
In order to make the water contact angle of the surface of the fine concavo-convex structure of the cured resin layer 44 25 ° or less, the active energy ray-curable resin composition capable of forming a hydrophilic material is a composition containing at least a hydrophilic monomer. Is preferably used. From the viewpoint of scratch resistance and imparting water resistance, those containing a cross-linkable polyfunctional monomer are more preferable. In addition, the same (namely, hydrophilic polyfunctional monomer) may be sufficient as the polyfunctional monomer which can be bridge | crosslinked with a hydrophilic monomer. Furthermore, the active energy ray-curable resin composition may contain other monomers.

As the active energy ray-curable resin composition capable of forming a hydrophilic material, it is more preferable to use a composition containing the following polymerizable compound.
10-50% by mass of tetrafunctional or higher polyfunctional (meth) acrylate,
A polymerizable compound comprising a total of 100% by mass of 30 to 80% by mass of a bifunctional or higher functional hydrophilic (meth) acrylate and 0 to 20% by mass of a monofunctional monomer.

Examples of tetrafunctional or higher polyfunctional (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / acrylic acid molar mixture 1: 2: 4 condensation reaction mixture, urethane acrylates (manufactured by Daicel-Cytec: EBECRYL220, EBECRYL1290K, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL 8301, KRM 8200), polyether acrylates (manufactured by Daicel-Cytec: EBEC) YL81), modified epoxy acrylates (manufactured by Daicel-Cytec: EBECRYL3416), polyester acrylates (manufactured by Daicel-Cytech: EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL8111, EBECRYL81L, EBECRYL81L It is done. These may be used alone or in combination of two or more.
The polyfunctional (meth) acrylate having 4 or more functional groups is more preferably a polyfunctional (meth) acrylate having 5 or more functional groups.

The ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is preferably 10 to 50% by mass, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass from the viewpoint of water resistance and chemical resistance. If the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is 10% by mass or more, the elastic modulus is increased and the scratch resistance is improved. If the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is 50% by mass or less, small cracks are hardly formed on the surface, and the appearance is hardly deteriorated.

Long-chains such as Aronix M-240, Aronix M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E, and NK ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) And polyfunctional acrylates having polyethylene glycol; and polyethylene glycol dimethacrylate. These may be used alone or in combination of two or more.
In polyethylene glycol dimethacrylate, the total of the average repeating units of polyethylene glycol chains present in one molecule is preferably 6 to 40, more preferably 9 to 30, and particularly preferably 12 to 20. If the average repeating unit of the polyethylene glycol chain is 6 or more, the hydrophilicity is sufficient and the antifouling property is improved. When the average repeating unit of the polyethylene glycol chain is 40 or less, the compatibility with a polyfunctional (meth) acrylate having 4 or more functionalities is improved, and the active energy ray-curable resin composition is hardly separated.

The ratio of the bifunctional or higher functional hydrophilic (meth) acrylate is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass. When the ratio of the bifunctional or higher hydrophilic (meth) acrylate is 30% by mass or more, the hydrophilicity is sufficient and the antifouling property is improved. When the proportion of the bifunctional or higher hydrophilic (meth) acrylate is 80% by mass or less, the elastic modulus is increased and the scratch resistance is improved.

As the monofunctional monomer, a hydrophilic monofunctional monomer is preferable.
Examples of hydrophilic monofunctional monomers include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group such as M-20G, M-90G, and M-230G (manufactured by Shin-Nakamura Chemical Co.); hydroxyalkyl (meth) acrylates, etc. And monofunctional (meth) acrylates having a hydroxyl group in the ester group; monofunctional acrylamides; and cationic monomers such as methacrylamidopropyltrimethylammonium methylsulfate and methacryloyloxyethyltrimethylammonium methylsulfate.
In addition, as a monofunctional monomer, viscosity modifiers such as acryloylmorpholine and vinylpyrrolidone; and adhesion improvers such as acryloyl isocyanates that improve adhesion to the article body may be used.

The proportion of the monofunctional monomer is preferably 0 to 20% by mass, and more preferably 5 to 15% by mass. By using a monofunctional monomer, the adhesion between the article body and the cured resin is improved. When the proportion of the monofunctional monomer is 20% by mass or less, antifouling property or scratch resistance is sufficient without a shortage of tetrafunctional or higher polyfunctional (meth) acrylate or bifunctional or higher hydrophilic (meth) acrylate. Expressed in

The monofunctional monomer may be blended in an active energy ray-curable resin composition in an amount of 0 to 35 parts by mass as a low-polymerization polymer obtained by (co) polymerizing one or more types. As a polymer having a low degree of polymerization, 40/60 of monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and methacrylamide propyltrimethylammonium methyl sulfate. Copolymer oligomer (MRC Unitech Co., Ltd., MG polymer) and the like can be mentioned.

(Use)
Applications of the article 40 include antireflection articles, antifogging articles, antifouling articles, and water repellent articles, more specifically antireflection for displays, automobile meter covers, automobile mirrors, automobile windows, organic or inorganic electro Examples include a light extraction efficiency improving member for luminescence, a solar cell member, and the like.

(Function and effect)
In the method for producing an article having the fine concavo-convex structure of the present invention described above on the surface, since the mold obtained by the mold production method of the present invention is used, the fine concavo-convex structure of the mold is formed on the surface of the article. Even when it is repeatedly transferred, the releasability is hardly lowered, and as a result, an article having a fine concavo-convex structure on the surface can be manufactured with high productivity.

Note that the article having the fine concavo-convex structure on the surface is not limited to the article 40 in the illustrated example. For example, the fine uneven structure may be directly formed on the surface of the film 42 without providing the cured resin layer 44. However, it is preferable that the fine uneven structure is formed on the surface of the cured resin layer 44 from the viewpoint that the fine uneven structure can be efficiently formed using the roll-shaped mold 20.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

(Pores of anodized alumina)
Part of the anodized alumina is shaved, platinum is deposited on the cross section for 1 minute, and the cross section is subjected to an acceleration voltage of 3.00 kV using a field emission scanning electron microscope (JSM-7400F, manufactured by JEOL Ltd.). Observed and measured pore spacing and pore depth. Each measurement was performed for 50 points, and the average value was obtained.

(Transfer test, peel strength)
1 μL of the active energy ray-curable resin composition A is poured onto the surface of the mold on which the fine concavo-convex structure is formed, and after covering with a polyethylene terephthalate (PET) film, a UV irradiator (high pressure mercury lamp: integrated light quantity 1100 mJ / Curing was performed by cm ² ). Next, the cured resin was peeled off (released) from the mold together with the PET film.
This operation was repeated without changing the mold, and a 90 ° peel test was performed at the 400th release to determine the peel strength.

(Active energy ray-curable resin composition A)
TAS: Succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4 condensation reaction mixture; 45 parts by mass
C6DA: 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Co., Ltd.); 45 parts by mass
X-22-1602: radical polymerizable silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.); 10 parts by mass
Irg184: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, Irgacure 184); 3 parts by mass.

[Example 1]
A 50 mm × 50 mm × 0.3 mm thick aluminum plate (purity 99.99%) electropolished in a perchloric acid / ethanol mixed solution (1/4 volume ratio) was used.
Step (a):
The aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution for 6 hours under conditions of a direct current of 40 V and a temperature of 16 ° C.
Step (b):
The aluminum plate on which the oxide film was formed was immersed in a 6% by mass phosphoric acid / 1.8% by mass chromic acid mixed aqueous solution for 3 hours to remove the oxide film.
Step (c):
The aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution for 30 seconds under conditions of a direct current of 40 V and a temperature of 16 ° C.

Step (d):
The aluminum plate on which the oxide film was formed was immersed in a 5% by mass phosphoric acid aqueous solution at 32 ° C. for 8 minutes to perform pore diameter expansion treatment.
Step (e):
The aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution for 30 seconds under conditions of a direct current of 40 V and a temperature of 16 ° C.

Step (f):
The step (d) and the step (e) are repeated a total of four times, and finally the step (d) is performed. The formed mold body a was obtained.

Step (g):
The phosphoric acid aqueous solution on the surface of the mold main body a was lightly washed off using a shower, and then the mold main body a was immersed in running water for 10 minutes.
Step (h):
Air was blown from the air gun onto the mold body a to remove water droplets adhering to the surface of the mold body a.

Step (i):
The mold main body a was immersed in a solution obtained by diluting OPTOOL DSX (manufactured by Daikin Chemicals Sales Co., Ltd.) to 0.1% by mass with a diluent HD-ZV (manufactured by Harves) at room temperature for 10 minutes. The mold body a was slowly pulled up from the diluted solution at 3 mm / sec.
Step (j):
The mold body a was air-dried for 15 minutes.
Step (k):
The mold main body a treated with the release agent was left to stand at a temperature of 60 ° C. and a relative humidity of 85% for 1 hour using a thermo-hygrostat (manufactured by Enomoto Kasei Co., Ltd.) and subjected to heating and humidification treatment.
Step (m):
Steps (i) to (k) were repeated four more times.
Step (n):
The mold body a was air-dried overnight to obtain a mold.
A transfer test was performed using the mold. The first to 400th peel strength obtained from the 90-degree peel test was extrapolated by exponential approximation to obtain the 800th peel strength, and the number of transfer times at which the peel strength reached 35 N / m was estimated to be the number of transferable times. The results are shown in Table 1.
In Comparative Example 1 described later, the peel strength reached 35 N / m after 240 transferable times, and a region that could not be released due to adhesion of the cured resin on the mold side was generated.

[Example 2]
A mold was obtained in the same manner as in Example 1 except that the number of repetitions in the step (m) was two.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

Example 3
A mold was obtained in the same manner as in Example 1 except that the number of repetitions in the step (m) was one.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

[Comparative Example 1]
A mold was obtained in the same manner as in Example 1 except that the step (k) and the step (m) were not performed.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

[Comparative Example 2]
A mold was obtained in the same manner as in Example 1 except that the step (m) was not performed.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

[Comparative Example 3]
A mold was obtained in the same manner as in Example 2 except that the step (k) was not performed.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

[Comparative Example 4]
A mold was obtained in the same manner as in Comparative Example 1 except that the concentration of the diluted OPTOOL DSX solution was changed to 0.3% by mass.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

[Comparative Example 5]
A mold was obtained in the same manner as in Comparative Example 2 except that the concentration of the diluted OPTOOL DSX solution was changed to 0.3% by mass.
A transfer test was conducted in the same manner as in Example 1 using the mold. The results are shown in Table 1.

From the above examples and comparative examples, by repeating the heating and humidification treatment on the mold body treated with the release agent under an appropriate release agent concentration, the mold release property can be extended for a long time even if the fine concavo-convex structure on the surface is repeatedly transferred. It can be seen that a mold that can be maintained over time can be produced.
In particular, it can be seen that the releasability can be maintained for a very long time by repeating the heat and humidification treatment at a concentration of about 0.1% by weight of the release agent twice or more.

The mold obtained by the production method of the present invention is useful as a mold for producing an antireflection film and a water repellent film by an imprint method.

10 Aluminum substrate 12 Pore 14 Oxide film (anodized alumina)
18 Mold body 20 Roll-shaped mold 40 Article 42 Film (article body)

Claims (9)

1. A method for producing a mold, comprising the following steps (I) to (IV):
   (I) The process of producing the mold main body by which the fine uneven structure was formed on the surface.
   (II) After step (I), the surface of the mold body on which the fine concavo-convex structure is formed has a functional group (B) that can react with the functional group (A) present on the surface. The process of processing with an agent.
   (III) A step of placing the mold body under heating and humidification after step (II).
   (IV) A step of repeating the steps (II) and (III) twice or more.
2. The method for producing a mold according to claim 1, wherein the functional group (B) is a hydrolyzable silyl group.
3. The method for producing a mold according to claim 1 or 2, wherein the functional group (B) of the release agent is a hydrolyzable silyl group and a release agent having a perfluoropolyether structure.
4. The method for producing a mold according to any one of claims 1 to 3, wherein in the step (II), the concentration of the release agent is 0.06 mass% or more and 0.15 mass% or less.
5. 5. The mold having the fine concavo-convex structure formed in the step (I) is obtained by anodizing an aluminum base material to form a fine concavo-convex structure having two or more pores on the surface thereof. The manufacturing method of the mold of any one of Claims 1.
6. The method for producing a mold according to any one of claims 1 to 5, wherein an average interval between the pores is 400 nm or less.
7. The method for producing a mold according to claim 6, wherein an average interval between the pores is 20 nm or more and 400 nm or less.
8. The step (I) includes the following steps (a) to (f):
   The step (II) includes the following steps (g) to (j):
   The step (III) has the following step (k) and / or (l):
   The method for producing a mold according to any one of claims 1 to 7, wherein the step (IV) includes the following steps (m) and / or (n).
   (A) A step of forming an oxide film on the surface of an aluminum substrate by anodizing the aluminum substrate in an electrolytic solution under a constant voltage.
   (B) A step of removing the oxide film and forming anodic oxidation pore generation points on the surface of the aluminum substrate.
   (C) After the step (b), the step of anodizing the aluminum base material again in the electrolytic solution to form an oxide film having pores at the pore generation points.
   (D) A step of enlarging the diameter of the pores after the step (c).
   (E) A step of anodizing again in the electrolytic solution after the step (d).
   (F) The process of obtaining the mold main body by which the said process (d) and the said process (e) are repeated, and the anodic oxidation alumina which has a 2 or more pore is formed in the surface of the said aluminum base material.
   (G) A step of washing the mold body after the step (f).
   (H) After the step (g), air is blown onto the mold body to remove impurities adhering to the surface of the mold body.
   (I) After the steps (f) to (h), a step of immersing the mold body having a hydroxyl group introduced into the surface thereof in a diluted solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a fluorine-based solvent.
   (J) A step of drying the mold body after the step (i).
   (K) A step of placing the mold body under heating and humidification after step (i).
   (L) A step of washing the mold body immediately after the step (k) with a fluorinated solvent.
   (M) A step in which the steps (i) to (l) are defined as one cycle and the cycle is repeated twice or more.
   (N) A step of drying the mold body after the step (m).
9. An article having a fine concavo-convex structure on its surface, comprising transferring the fine concavo-convex structure on the surface of the mold obtained by the method for producing a mold according to any one of claims 1 to 8 to the surface of the article main body. Production method.

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