KR101473069B1 - Method for producing molds and method for producing products with superfine concave-convex structures on surface - Google Patents

Abstract

The present invention relates to a process for producing a mold body 16 in which (I) a micro concavo-convex structure is formed on the surface, (II) a step of forming the surface of the mold body 16 on the side where the micro concavo-convex structure is formed, (III) a step of placing the mold body 16 treated with the mold release agent under heating and humidification, (IV) the step (II) and the step (III) ) Is repeated twice or more. The present invention can provide a method for producing a mold capable of retaining the releasing property for a long period of time even if the fine concave-convex structure of the surface is repeatedly transferred, and a method for producing an article having a fine concave-convex structure on its surface with good productivity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a mold, and a method of manufacturing an article having a fine concavo-

The present invention relates to a method for producing a mold having a fine concavo-convex structure on its surface and a method for producing an article having a fine concavo-convex structure on its surface.

The present application claims priority based on Japanese Patent Application No. 2010-070281 filed on March 25, 2010, the contents of which are incorporated herein by reference.

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

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

However, when the fine concavo-convex structure of the mold is repeatedly transferred to the surface of the article, there is a problem that the releasability gradually decreases with an increase in the number of transfer. In addition, since it can not be released at a relatively early stage, an article having a fine uneven structure on its surface can not be produced with good productivity.

Japanese Patent Application Laid-Open No. 2007-326367

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

The method for producing a mold of the present invention is characterized by having the following steps (I) to (IV).

(I) A process for producing a mold body having a fine uneven structure on its surface.

(II) A step of treating the surface of the mold main body on the side where the micro concavo-convex structure is formed with a mold releasing agent having a functional group (B) capable of reacting with the functional group (A) present on the surface after the step (I).

(III) A step of placing the mold body under heating and humidification after the step (II).

(IV) A step of repeating the step (II) and the step (III) two or more times.

In the process for producing a mold of the present invention, the functional group (B) is preferably a hydrolyzable silyl group. The functional group (B) of the release agent of the present invention is preferably a hydrolyzable silyl group and also has a perfluoropolyether structure.

The mold having the micro concavo-convex structure of the step (I) is preferably anodically oxidized to form a micro concavo-convex structure having two or more pores on its surface.

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

That is, the present invention relates to the following.

(1) A process for producing a mold having the following steps (I) to (IV).

(I) A process for producing a mold body having a fine uneven structure on its surface.

(II) A step of treating the surface of the mold main body on the side where the micro concavo-convex structure is formed with a mold releasing agent having a functional group (B) capable of reacting with the functional group (A) present on the surface after the step (I).

(III) A step of placing the mold body under heating and humidification after the step (II).

(IV) A step of repeating the step (II) and the step (III) two or more times.

(2) The process for producing a mold according to (1), wherein the functional group (B) is a hydrolyzable silyl group.

(3) The process for producing a mold according to (1) or (2), wherein the functional group (B) of the releasing agent is a hydrolyzable silyl group and a mold release agent having a perfluoropolyether structure.

(4) The process for producing a mold according to any one of (1) to (3), wherein the concentration of the releasing agent is 0.06 mass% or more and 0.15 mass% or less in the step (II).

(5) The method according to any one of (1) to (4), wherein the mold having the fine uneven structure of the step (I) is formed by anodic oxidation of the aluminum substrate to form a micro concavo-convex structure having two or more pores on the surface thereof. A method for producing a mold according to claim 1.

(6) The method for producing a mold according to any one of (1) to (5), wherein the average interval of the pores is 400 nm or less.

(7) The method for producing a mold according to (6), wherein the average interval of the pores is 20 nm or more and 400 nm or less.

(8) The process according to the above (1), wherein the step (I) has the following steps (a) to (f)

Wherein the step (II) has the following steps (g) to (j)

Wherein the step (III) has the following steps (k) and / or (1)

The process for producing a mold according to any one of (1) to (7), wherein the step (IV) comprises the following step (m) and / or (n).

(a) Anodizing an aluminum substrate in an electrolytic solution under a constant voltage to form an oxide film on the surface of the aluminum substrate.

(b) removing the oxide film to form pore generation points on the surface of the aluminum substrate.

(c) after the step (b), anodic oxidation of the aluminum base material in the electrolytic solution to form an oxide film having pores at the pore generation point.

(d) a step of expanding the diameter of the pores after the step (c).

(e) a step of re-anodizing the electrolyte solution after the step (d).

(f) Repeating the step (d) and the step (e) to obtain a mold main body on the surface of the aluminum base material having an anodic alumina having two or more pores.

(g) washing the mold body after the step (f).

(h) After the step (g), air is sprayed onto the mold body to remove impurities attached to the surface of the mold body.

(i) a step of immersing a mold body into which a hydroxyl group has been introduced into a dilute solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a fluorine-containing solvent, after the steps (f) to (h).

(j) a step of drying the mold body after the step (i).

(k) a step of placing the mold body under heating and humidifying after the step (i).

(1) A step of washing the mold main body immediately after the step (k) with a fluorine-based solvent.

(m) The step of repeating the above cycle (i) to (l) by one cycle, and repeating the cycle twice or more.

(n) After the step (m), the step of drying the mold body.

(9) A method for producing an article having a fine concavo-convex structure on its surface, which comprises 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) Way.

According to the method for producing a mold of the present invention, it is possible to manufacture a mold capable of retaining the releasability for a long time even if the fine concavo-convex structure on the surface is repeatedly transferred.

According to the method for producing an article having a fine concavo-convex structure on the surface of the present invention, an article having a fine concavo-convex structure on its surface can be produced with good productivity.

1 is a cross-sectional view showing a manufacturing process of a mold having an anodized alumina on its surface.
Fig. 2 is a configuration diagram showing an example of an apparatus for manufacturing an article having a fine concavo-convex structure on its surface.
3 is a cross-sectional view showing an example of an article having a fine concavo-convex structure on its surface.

In the present specification, (meth) acrylate means acrylate or methacrylate. In addition, the active energy ray means visible light, ultraviolet ray, electron ray, plasma, and heat ray (infrared ray, etc.).

≪ Manufacturing method of mold >

The method for producing a mold of the present invention is a method having the following steps (I) to (IV).

(I) A process for producing a mold body having a fine uneven structure on its surface.

(II) A step of treating the surface of the mold main body on the side where the micro concavo-convex structure is formed with a mold releasing agent having a functional group (B) capable of reacting with the functional group (A) present on the surface after the step (I).

(III) A step of placing the mold body under heating and humidification after the step (II).

(IV) A step of repeating the step (II) and the step (III) two or more times.

(Process (I))

In the step (I), a micro concavo-convex structure is formed on the surface of the substrate to prepare a mold main body. Examples of the material of the base material include metal (including an oxide film formed on its surface), quartz, glass, resin, and ceramics. Examples of the shape of the substrate include a roll, a tubular, a flat, and a sheet.

As a production method of the mold main body, for example, a method of forming anodic oxidized alumina having two or more pores (concave portions) on the surface of an aluminum base material can be mentioned. The above method is a preferable production method because it is possible to make a large area and is easy to manufacture.

As the above-mentioned method, specifically, a method having the following steps (a) to (f) is preferable.

(a) Anodizing an aluminum substrate in an electrolytic solution under a constant voltage to form an oxide film on the surface of the aluminum substrate.

(b) a step of removing the oxide film and forming pore generation points of anodic oxidation on the surface of the aluminum base material.

(c) After the step (b), the step of anodic oxidation of the aluminum base material in the electrolytic solution to form an oxide film having pores at the pore generation point.

(d) a step of expanding the diameter of the pores after the step (c).

(e) a step of re-anodizing the electrolyte solution after the step (d).

(f) repeating steps (d) and (e) to obtain a mold body having an alumina anodized with two or more pores formed on the surface of the aluminum substrate.

Step (a):

As shown in Fig. 1, when the aluminum substrate 10 is subjected to anodic oxidation, an oxide film 14 having pores 12 is formed. Examples of the shape of the aluminum base material include a roll, a circular tube, a flat plate, and a sheet.

Since the aluminum base may adhere to the oil used when the aluminum base material is processed into a predetermined shape, it is preferable that the aluminum base material is degreased in advance. It is preferable that the aluminum substrate is subjected to electrolytic polishing treatment (etching treatment) 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, there is a case where an irregular structure having a size to scatter visible light due to segregation of impurities is formed when the anodic oxidation is carried out, or the regularity of the pores obtained by anodic oxidation is 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. If the concentration of oxalic acid exceeds 0.7 M, the current value becomes excessively high and the surface of the oxide film may be roughened. When the conversion voltage is 30 to 60 V, anodic alumina having highly regular pores with an average interval of 100 nm can be obtained. If the ignition voltage is higher or lower than this range, the regularity tends to decrease. The temperature of the electrolytic solution is preferably 60 占 폚 or lower, more preferably 45 占 폚 or lower. If the temperature of the electrolytic solution exceeds 60 캜, a phenomenon called so-called "sieging" occurs and the pores are broken, or the surface melts and the regularity of the pores may be disturbed.

When sulfuric acid is used as an electrolytic solution: The concentration of sulfuric acid is preferably 0.7 M or less. If the concentration of sulfuric acid exceeds 0.7 M, the current value becomes excessively high and the constant voltage may not be maintained. When the conversion voltage is 25 to 30 V, anodic alumina having pores having high regularity with an average interval of 63 nm can be obtained. If the ignition voltage is higher or lower than this range, the regularity tends to decrease. The temperature of the electrolytic solution is preferably 30 占 폚 or lower, more preferably 20 占 폚 or lower. When the temperature of the electrolytic solution exceeds 30 占 폚, a phenomenon called so-called "sieging" occurs and the pores are broken, or the surface melts 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 making it the pore generation point 16 of the anodic oxidation.

As a method for removing the oxide film, a method of dissolving the oxide film in a solution for selectively dissolving the oxide film without dissolving aluminum is known. Examples of such a solution include a chromic acid / phosphoric acid mixture solution and the like.

Step (c):

As shown in Fig. 1, when the aluminum substrate 10 from which the oxide film has been removed is again subjected to anodic oxidation, the oxide film 14 having the peripheral pores 12 is formed.

The anodizing condition is not particularly limited, but anodizing is performed under the same conditions as in the step (a) or in a shorter time than the step (a).

Step (d):

As shown in Fig. 1, a process of enlarging the diameter of the pores 12 (hereinafter referred to as a pore diameter enlarging process) is performed. The pore diameter enlarging process is a process in which the diameter of the pores obtained by the anodic oxidation is increased by immersing the oxide film in a solution dissolving the oxide film. Such a solution includes, for example, a 5% by mass aqueous solution of phosphoric acid or the like. The larger the pore diameter enlarging process is, the larger the pore diameter becomes.

Step (e):

As shown in Fig. 1, when the anodic oxidation is performed again, circular pores 12 having a small diameter extending downward from the bottom of the circular pore 12 are additionally formed.

The anodic oxidation may be carried out under the same conditions as in the step (a). Deep pores can be obtained as the anodic oxidation time is lengthened.

Step (f):

As shown in Fig. 1, the pore diameter enlarging process of the step (d) and the anodic oxidation of the step (e) are repeated to form an oxide film having pores 12 of a shape in which the diameter continuously decreases from the opening to the depth 14 is formed on the surface of the aluminum base material 10 to obtain the mold main body 18 having the anodic alumina (anodic oxide porous (alumite) of aluminum) on the surface of the aluminum base material 10. At the end, the step (d) or the step (e) may be terminated, but the step (d) is preferably terminated.

The number of repetitions is preferably 3 or more times in total, and more preferably 5 or more times. Since the diameter of the pores decreases discontinuously when the number of repetitions is two or less, the effect of reducing the reflectance of the mosse structure formed using the anodized alumina having such pores is insufficient.

The pore 12 has a substantially conical shape, a square shape, and a columnar shape. The pore cross-sectional area in a direction orthogonal to the depth direction, such as a conical shape and a pyramidal shape, A continuously decreasing shape is preferred.

The average distance between the pores 12 is equal to or smaller than the visible light wavelength, that is, 400 nm or less. The average distance between the pores 12 is preferably 20 nm or more.

The average distance 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 distance between the pores 12 was measured by an electron microscope at 50 points between the adjacent pores 12 (the distance from the center of the pores 12 to the center of the adjacent pores 12) .

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 lowest part of the pore 12 and the distance between the lowest part of the convex part existing between the pores 12 when the magnification is observed at a magnification of 30,000 times by an electron microscope observation.

The aspect ratio (pore depth / average spacing of three spaces) of the pores 12 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 mold releasing agent having a functional group (B) capable of reacting with the functional group (A).

The functional group (A) means a group capable of reacting with a reactive functional group (B) contained in the releasing agent to be described later to form a chemical bond.

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 the reactivity with a hydrolyzable silyl group, which is often used as a reactive functional group (B) , The hydroxyl group is particularly preferable. When the surface treated with the releasing agent is anodized alumina, the functional group (A) is a hydroxyl group.

When the functional group (A) does not exist on the surface of the mold main body on which the micro concavo-convex structure is formed, the functional group (A) is introduced by the method (II-1) or the method (II- You can.

(II-1) A method of introducing a functional group (A) onto the surface by plasma-treating the surface of the mold main body on which the fine concavo-convex structure is formed.

(II-2) A method of introducing a functional group (A) onto the surface of the mold body 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).

The functional group (B) means a group capable of forming a chemical bond by reacting with the functional group (A) or a group which can be easily converted into the above group.

Examples of the functional group (B) in the case where the functional group (A) is a hydroxyl group include a hydrolyzable group containing a hydrolyzable silyl group, a silanol group, a titanium atom or an aluminum atom and the like, and from the viewpoint of good reactivity with a hydroxyl group, A decomposable silyl group or a silanol group is preferable, and a hydrolyzable silyl group is more preferable. The hydrolyzable silyl group is a group capable of generating a silanol group (Si-OH) by hydrolysis, and includes Si-OR (R is an alkyl group) and Si-X (X is a halogen atom).

Examples of the release agent include a silicone resin having a functional group (B), a fluorine resin having a functional group (B), and a fluorine compound having a functional group (B), and a fluorine compound having a hydrolyzable silyl group is more preferable. As a commercially available product of a fluorine compound having a hydrolyzable silyl group, fluoroalkylsilane and an "OPTOL (registered trademark)" series manufactured by DAIKIN INDUSTRIES CO., LTD. Can be cited as those having a perfluoropolyether structure.

As the mold releasing agent, a fluorine compound having a functional group (B) is particularly preferred, wherein the functional group (B) is a hydrolyzable silyl group and further has a perfluoropolyether structure. When the functional group (B) is a hydrolyzable silyl group and also has a perfluoropolyether structure, it is excellent in reactivity with the functional group (A), and the releasability is particularly good.

Examples of the treatment method with the release agent include the following methods (II-3) to (II-4), and from the viewpoint that the surface of the mold main body on which the fine uneven structure is formed can be uniformly treated with mold release agent (II-3) is particularly preferable.

(II-3) A method of immersing a mold body in a diluting solution of a mold release agent.

(II-4) A method of applying a releasing agent or a diluting solution thereof to the surface of the mold main body on which the fine uneven structure is formed.

As the method (II-3), a method having the following steps (g) to (j) is preferred.

(g) A step of washing the mold body after the step (f), if necessary.

(h) A step of removing impurities adhering to the surface of the mold body for spraying air onto the mold body after the step (g), if necessary.

(i) a step of immersing a mold body into which a hydroxyl group has been introduced into a dilute solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a fluorine-containing solvent after the steps (f) to (h).

(j) If necessary, the step of drying the mold body after the step (i).

Process (g):

The mold main body is removed by washing with water because the medicament (such as a phosphoric acid aqueous solution used for enlarging the pore diameter) and impurities (dust, etc.) used for forming the micro concavo-convex structure are attached.

Step (h):

If water droplets are adhered to the surface of the mold main body, the efficiency of the mold releasing agent in step (i) deteriorates. Therefore, air is sprayed to the mold main body to remove almost visible water droplets.

Step (i):

Examples of the diluent fluorinated solvent include hydrofluoropolyether, perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and dichloropentafluoropropane.

The concentration of the fluorine compound having a hydrolyzable silyl group is preferably 0.01 to 0.2 mass%, more preferably 0.06 mass% or more and 0.15 mass% or less, in the diluting solution (100 mass%). When the concentration of the fluorine compound of the fluorine compound having a hydrolyzable silyl group is within the above range, deterioration of the solution of the release agent by the self-condensation reaction of the release agent during storage or use can be suppressed and sufficient releasability can be obtained.

The immersion time is preferably 1 to 30 minutes.

The immersion temperature is preferably 0 to 50 占 폚.

Process (j):

The mold main body may be air-dried or forcedly heated and dried by a dryer or the like.

The drying temperature is preferably 50 to 150 占 폚.

The drying time is preferably 5 to 300 minutes.

(Step (III))

Step (III) comprises, for example, the following step (k) and / or step (l).

(k) a step of placing the mold body under heating and humidification after the step (i).

(1) A step of washing the mold main body immediately after the step (k) with a fluorine-containing solvent, if necessary.

Process (k):

The hydrolyzable silyl group of the fluorine compound (releasing agent) is hydrolyzed to generate a silanol group by allowing the mold body to stand under heating and humidification, and the reaction between the silanol group and the hydroxyl group on the surface of the mold main body proceeds sufficiently, .

The heating temperature is preferably 40 to 100 占 폚.

The humidification condition is preferably at least 85% relative humidity.

It is preferable that the incubation time is 10 minutes to 1 day.

Step (l):

Examples of the cleaning fluorine-based solvent include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and dichloropentafluoropropane.

The mold body cleaned with the fluorine-based solvent may be washed again with water, alcohols or the like.

(Step (IV))

Step (IV) comprises, for example, the following step (m) and / or step (n).

(m) The step of repeating the cycle at least twice with one cycle of the steps (i) to (1).

(n) A step of drying the mold body after the step (m), if necessary.

Process (m):

The number of repetitions of the cycles of the steps (i) to (1) is 2 or more, preferably 2 to 10, and more preferably 3 to 5. If the number of repetitions is two or more, the releasability of the mold can be maintained for a long time.

Process (n):

The mold main body may be air-dried or forcedly heated and dried by a dryer or the like.

The drying temperature is preferably 40 to 150 占 폚.

The drying time is preferably 5 to 300 minutes.

(Action effect)

In the above-described method of manufacturing a mold of the present invention, the step (II) of treating the surface of the mold main body on the side where the micro concavo-convex structure is formed with mold releasing treatment and the step (III) It is possible to manufacture a mold capable of retaining the releasability for a long time even if the fine concavo-convex structure on the surface is repeatedly transferred.

The process for producing a mold of the present invention is particularly effective as a process for producing a mold having an anodized alumina on its surface for the following reasons.

The surface of the anodized alumina is difficult to react with the hydrolyzable silyl group (silanol group), and only a single treatment with the releasing agent tends to form a gap in which the releasing agent does not exist. Therefore, the releasing agent tends to peel off from the gap, and the releasability of the mold tends to deteriorate. On the other hand, in the present invention, since the treatment with the releasing agent is repeated twice or more, the gap can be filled with the releasing agent as much as possible, and the releasability of the mold is hardly lowered.

≪ Method for producing article having fine concavo-convex structure on its surface >

An article having a fine concavo-convex structure on the surface thereof is manufactured, for example, by using the production apparatus shown in Fig. 2 as follows.

(Not shown) having a fine concavo-convex structure on its surface and a strip-shaped film 42 (article main body) moving along the surface of the roll-shaped mold 20 from the tank 22, Ray-curable resin composition.

The film 42 and the active energy ray curable resin composition are nipped between the rolled mold 20 and the nip roll 26 whose nip pressure is adjusted by the air pressure cylinder 24 and the active energy ray curable resin composition is applied to the film 42 and the roll-shaped mold 20, and is filled in the concave portion of the fine concavo-convex structure of the rolled mold 20.

The active energy ray curable resin composition is irradiated with the active energy ray curable resin composition through the film 42 from the active energy ray irradiating device 28 provided below the rolled mold 20 to cure the active energy ray curable resin composition, The cured resin layer 44 onto which the fine uneven structure on the surface of the mold 20 is transferred is formed.

The film 42 on which the cured resin layer 44 is formed on the surface by the peeling roll 30 is peeled from the rolled mold 20 to obtain the article 40 shown in Fig.

As the active energy ray irradiating device 28, a high-pressure mercury lamp or a metal halide lamp is preferably used, and in this case, the amount of irradiated energy is preferably 100 to 10,000 mJ / cm 2.

The film 42 is a light-transmissive film. Examples of the material of the film include acrylic resins, polycarbonates, styrene resins, polyesters, cellulose resins (such as triacetylcellulose), polyolefins, and alicyclic polyolefins.

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 concavo-convex structure on its surface.

The fine concavo-convex structure on the surface of the article 40 in the case of using an anodic alumina mold is formed by transferring the fine concavo-convex structure of the anodic alumina surface, and is composed of two or more convex portions made of a cured product of the active energy ray- 46).

The fine convex-concave structure is preferably a so-called moth eye structure in which two or more protrusions (convex portions) such as a conical shape or a square pyramid shape are arranged. It is known that the Mohse eye structure in which the interval of the period of the incidence is equal to or less than the visible light wavelength is effective reflection preventing means by increasing the refractive index continuously from the refractive index of air to the refractive index of the material.

The average distance between the convex portions is preferably equal to or less than the visible light wavelength, that is, 400 nm or less. When the convex portion is formed using an anodic alumina mold, the average distance between the convex portions is about 100 nm, more preferably 200 nm or less, and particularly preferably 150 nm or less.

The average distance between the convex portions is preferably 20 nm or more in terms of easy formation of convex portions.

The average distance between the convex portions is preferably 20 to 400 nm, more preferably 50 to 300 nm, and even more preferably 90 to 250 nm.

The average distance between the convex portions is obtained by measuring the distance between the adjacent convex portions (the distance from the center of the convex portion to the center of the adjacent convex portion) by an electron microscopic observation at 50 points, and averaging these values.

When the average interval is 100 nm, the height of the convex portion is preferably 80 to 500 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm. When the height of the convex portion is 80 nm or more, the reflectance is sufficiently low and the wavelength dependence of the reflectance is small. When the height of the convex portion is 500 nm or less, the scratch resistance of the convex portion is improved.

The height of the convex portion is a value obtained by measuring the distance between the highest portion of the convex portion and the lowest portion of the concave portion existing between the convex portion when observed at a magnification of 30,000 times by an electron microscope.

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

The shape of the convex portion is a shape in which the cross-sectional area of the convex portion in the direction perpendicular to the height direction continuously increases from the outermost surface to the depth direction, that is, the shape in cross section in the height direction of the convex portion is triangular, trapezoidal, Shape is preferable.

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, the reflection at the interface between the cured resin layer 44 and the film 42 is suppressed.

It is known that, in the case of having a micro concavo-convex structure on its surface, superfluidity can be obtained by the Lotus effect if its surface is formed of a hydrophobic material, and superfine hydrophilicity can be obtained if its surface is formed of a hydrophilic material.

When the material of the cured resin layer 44 is hydrophobic, the water contact angle of the surface of the fine uneven structure is preferably 90 DEG or more, more preferably 110 DEG or more, and particularly preferably 120 DEG or more. When the water contact angle is 90 DEG or more, sufficient water repellency is exhibited because the water mist is not adhered well. In addition, since water is not adhered well, it is expected to prevent icing.

When the material of the cured resin layer 44 is hydrophobic, the range of the water contact angle of the surface of the micro concavo-convex structure is preferably 90 ° or more and 180 ° or less, more preferably 110 ° or more and 180 ° or less, Deg.] Is particularly preferable.

When the material of the cured resin layer 44 is hydrophilic, the water contact angle of the surface of the micro concavo-convex structure is preferably 30 째 or less, more preferably 25 째, more preferably 23 째, Particularly preferred. If the water contact angle is 30 DEG or less, the dirt adhering to the surface is washed out in the water and the oil mist is not adhered well, so that sufficient antifouling property is exhibited. The water contact angle is preferably not less than 3 degrees in view of suppressing the deformation of the fine concavo-convex structure due to the absorption of the cured resin layer 44 and consequently the rise of the reflectance.

When the material of the cured resin layer 44 is hydrophilic, the range of the water contact angle of the surface of the micro concavo-convex structure is preferably not less than 3 degrees and not more than 30 degrees, more preferably not less than 3 degrees and not more than 25 degrees, Deg.] Or less, more preferably 3 deg. Or more and 21 deg. Or less.

(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 radically polymerizable bonds and / or cationic polymerizable bonds in the molecule.

The active energy ray curable resin composition may contain a non-reactive polymer and an active energy precursor gel reactive composition.

Monomers having a radical polymerizable bond include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylates such as acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate and stearyl (Meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylate such as (meth) acrylate, Derivatives such as (meth) acrylic acid, (meth) acrylonitrile, styrene, and styrene derivatives such as? -Methylstyrene and (meth) acrylamide, N, (Meth) acrylamide, and (meth) acrylamide derivatives such as dimethylaminopropyl (meth) acrylamide.

These may be used singly or in combination of two or more.

Examples of the polyfunctional monomer 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 Acrylates such as di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Di (meth) acrylate, polybutylene di glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, Bis (3- (meth) acryloxy-2-hydroxypropyl) propane, 1,2-bis Hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) butane, dimethyloltricyclodecanedi (meth) Di (meth) acrylate of bisphenol A, di (meth) acrylate of bisphenol A, di (meth) acrylate of hydroxypivalic neopentyl glycol di (meth) acrylate, divinylbenzene, and methylene Bifunctional monomers such as trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri Trifunctional monomers such as acrylate, trimethylolpropane ethylene oxide modified triacrylate, and isocyanuric acid ethylene oxide modified tri (meth) acrylate; condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, And the like can be given two or more functional urethane acrylate, and the bifunctional or more polyester acrylate;, ditrimethylolpropane tetraacrylate, and tetramethylolmethane tetra (meth) acrylate of tetrafunctional or more monomers. These may be used singly or in combination of two or more.

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

(Meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) acrylate, Acrylate, urethane (meth) acrylate, cationic polymerization type epoxy compounds, and single or copolymerized polymers of the above-mentioned monomers having radically polymerizable bonds in the side chain.

Examples of the non-reactive polymer include an acrylic resin, a styrene resin, a polyurethane, a cellulose resin, polyvinyl butyral, a polyester, and a thermoplastic elastomer.

Examples of the active energy sol-gel reactive composition include an alkoxysilane compound and an alkyl silicate compound.

Examples of the alkoxysilane compound include compounds represented by the following formula (1).

R ¹¹ _x Si (OR ¹² ) _y ... (One)

R ¹¹ and R ¹² each represent an alkyl group having 1 to 10 carbon atoms, and x and y each represent an integer 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, Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, and the like. .

Examples of the alkyl silicate compounds include compounds represented by the following formula (2).

R ²¹ O [Si (OR ²³ ) (OR ²⁴ ) O] _z R ²² (2)

R ²¹ to R ²⁴ each represent an alkyl group of 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, and acetyl silicate.

When a photo-curing reaction is used, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzo Phenol, 2,2-diethoxyacetophenone,?,? -Dimethoxy-? -Phenylacetophenone, methylpentylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylamino) benzophenone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide; And benzoyl diethoxyphosphine oxide. These may be used singly or in combination of two or more kinds.

When the electron beam curing reaction is used, examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4- Thioxanthones such as phenyl benzophenone, t-butyl anthraquinone, 2-ethyl anthraquinone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, and 2,4-dichlorothioxanthone; diethoxyacetone Phenanone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethylketal, 1-hydroxycyclohexyl- Acetophenone such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isopropyl ether, and 2-benzyl-2-dimethylamino-1- Benzoin isobutyl ether; benzoin ethers such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Acylphosphine oxide such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 1,7-bisacrylidinyl heptane, and 9-phenylacridine .

These may be used singly or in combination of two or more kinds.

In the case of using the thermosetting reaction, examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, organic peroxides such as t-butyl peroxybenzoate and lauroyl peroxide, azo compounds such as azobisisobutyronitrile, and organic peroxides such as N, N-dimethylaniline, and N, N-dimethyl- - redox polymerization initiators in which amines such as toluidine are combined.

The amount of the polymerization initiator is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the polymerizable compound. When the amount of the polymerization initiator is less than 0.1 part by mass, polymerization hardly proceeds. If the amount of the polymerization initiator is more than 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 releasing agent, additives 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 make the water contact angle of the surface of the fine concavo-convex structure of the cured resin layer 44 90 degrees or more, a composition containing a fluorine-containing compound or a silicone compound as an active energy ray curable resin composition capable of forming a hydrophobic material Is preferably used.

Fluorine-containing compound:

As the fluorine-containing compound, a compound having a fluoroalkyl group represented by the following formula (3) is preferable.

- (CF _{2) n} -X ... (3)

X represents a fluorine atom or a hydrogen atom, and n represents an integer of 1 or more, preferably from 1 to 20, more preferably from 3 to 10, and particularly preferably from 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 a fluoroalkyl group-substituted (meth) acrylate, a fluoroalkyl group-substituted (meth) acrylamide, a fluoroalkyl group-substituted vinyl ether, and a fluoroalkyl group-substituted styrene.

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

As the fluorine-containing monomer, a fluoroalkyl group-substituted (meth) acrylate is preferable, and a compound represented by the following formula (4) is particularly preferable.

CH ₂ ═C (R ⁴¹ ) C (O) O- (CH ₂ ) _m - (CF ₂ ) _n -X (4)

However, R ⁴¹ is a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, m is an integer of 1-6, 1-3 is preferred, and is 1 or 2. More preferably n is 1 Represents an integer of 1 to 20, preferably 3 to 10, more preferably 4 to 8.

As the fluorine-containing silane coupling agent, a fluoroalkyl group-substituted silane coupling agent is preferable, and a compound represented by 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 at least one ether bond or an ester bond. R ^f is preferably a 3,3,3-trifluoropropyl group, a tridecafluoro-1,1,2,2-tetrahydrooctyl group, a 3-trifluoromethoxypropyl group, and 3-trifluoroacetoxy Propyl group and the like.

R ⁵¹ represents an alkyl group having 1 to 10 carbon atoms. R ⁵¹ includes 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 a methoxy group, an ethoxy group, a propyloxy group, an i-propyloxy group, a butoxy group, an i-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, 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 and C ₂ H ₅ C (O) O.

 a, b, and c each represent an integer satisfying a + b + c = 4, and also a? 1 and c? 1, and a = 1, b = 0, and c = 3 are preferable.

Examples of the fluorine-containing silane coupling agent include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethyl And tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, and the like.

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

Examples of the anionic surfactant containing a fluoroalkyl group 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 ) sulfonic acid, sodium 3- [omega-fluoroalkanoyl (C ₆ -C ₈ ) -N- ethylamino] -1 -propanesulfonic acid, fluoroalkyl ₁₁ ~ C ₂₀₎ carboxylic acid or its metal salt, perfluoroalkyl carboxylic acids (C ₇ ~ C _13), or their metal salts, perfluoroalkyl (C ₄ ~ C ₁₂₎ sulfonic acid or its metal salts, perfluoro octane acid diethanolamide, N- propyl -N- (2- hydroxyethyl) perfluoro octane sulfonamide, perfluoroalkyl (C ₆ ~ C ₁₀₎ sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl (C ₆ ~ C ₁₀ ) -N-ethylsulfonylglycine salt, and monoperfluoroalkyl (C ₆ -C ₁₆ ) ethylphosphoric acid ester.

Examples of the cationic surfactant containing a fluoroalkyl group include aliphatic quaternary ammonium salts such as a fluoroalkyl group-containing aliphatic primary, secondary or tertiary amine acid and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamide propyltrimethylammonium salt; Quaternary ammonium salts, chromium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

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 copolymer of a fluoroalkyl group-containing monomer and a crosslinking reactive group- . 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.

The poly (oxyalkylene) group is preferably a group represented by the following formula (6).

- (OR < ⁶ _> ) _p - (6)

Provided that 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 compound:

Examples of the silicone compound include (meth) acrylic acid modified silicone, silicone resin, and silicon-based silane coupling agent.

(Meth) acrylic acid modified silicone includes silicone (di) (meth) acrylate.

(Hydrophilic material)

It is preferable to use a composition containing at least a hydrophilic monomer as the active energy ray curable resin composition capable of forming a hydrophilic material so that the water contact angle of the surface of the micro concavo-convex structure of the cured resin layer 44 is 25 DEG or less Do. From the viewpoint of scratch resistance and water resistance, it is more preferable to contain a crosslinkable polyfunctional monomer. In addition, the hydrophilic monomer and the crosslinkable multifunctional monomer may be the same (i.e., hydrophilic multifunctional monomer). Further, 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 to 50% by mass of the tetrafunctional or higher polyfunctional (meth) acrylate,

30 to 80% by mass of a hydrophilic (meth) acrylate having two or more functional groups, and

And 0 to 20% by mass of a monofunctional monomer in a total of 100% by mass.

Examples of the tetrafunctional or higher polyfunctional (meth) acrylate include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol A condensation reaction mixture of 1: 2: 4 mol ratio of succinic acid / trimethylolethane / acrylic acid, urethane acrylates (manufactured by Daicel-Cotech Co., Ltd.) (EBECRYL220, EBECRYL1290, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL8301 and KRM8200), polyether acrylates (EBECRYL81 manufactured by Daicel Cytec Inc.), modified epoxy acrylates (EBECRYL3416 manufactured by Daicel Cytec) (EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL845, EBECRYL846, EBECRYL1870) The can. These may be used singly or in combination of two or more kinds.

As the polyfunctional (meth) acrylate having four or more functionalities, a polyfunctional (meth) acrylate having five or more functionalities is more preferable.

The ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is preferably from 10 to 50 mass%, more preferably from 20 to 50 mass%, and particularly preferably from 30 to 50 mass%, from the viewpoints of water resistance and chemical resistance. When the proportion of the tetrafunctional or higher polyfunctional (meth) acrylate is 10 mass% or more, the elastic modulus is increased and the scratch resistance is improved. When the proportion of the tetrafunctional or higher polyfunctional (meth) acrylate is 50 mass% or less, small cracks are not easily generated on the surface, and appearance defects are unlikely to occur.

Examples of hydrophilic (meth) acrylates having two or more functional groups include long chain polyethylene glycols such as Aronix M-240, Aronix M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E and NK ester ATM-35E (Shin Nakamura Chemical Co., And polyethyleneglycol dimethacrylate, and the like. These may be used singly or in combination of two or more kinds.

In the polyethylene glycol dimethacrylate, the total of the average repeating units of the polyethylene glycol chain present in one molecule is preferably from 6 to 40, more preferably from 9 to 30, and particularly preferably from 12 to 20. When the average repeating unit of the polyethylene glycol chain is 6 or more, 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 the polyfunctional (meth) acrylate having four or more functional groups is improved, and the active energy ray curable resin composition is not well separated.

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

The monofunctional monomer is preferably a hydrophilic monofunctional monomer.

Examples of the hydrophilic monofunctional monomer include monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-20G, M-90G and M-230G (Shin-Nakamura Chemical Co., Ltd.), hydroxyalkyl (meth) Monofunctional (meth) acrylates having a hydroxyl group in the ester group, monofunctional acrylamides, and cationic monomers such as methacrylamidopropyltrimethylammonium methylsulfate and methacryloyloxyethyltrimethylammonium methylsulfate. have.

As the monofunctional monomer, a viscosity adjuster such as acryloylmorpholine and vinylpyrrolidone, and an adhesion improver such as acryloyl isocyanate which improves the adhesion to the article main 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 the monofunctional monomer, adhesion between the article main body and the cured resin is improved. When the proportion of the monofunctional monomer is 20 mass% or less, the polyfunctional (meth) acrylate having a tetrafunctional or more functionality or the hydrophilic (meth) acrylate having a bifunctional or higher functionality is not deficient and the antifouling property or scratch resistance is sufficiently expressed.

The monofunctional monomer may be blended in an amount of 0 to 35 parts by mass with respect to the active energy ray-curable resin composition as a polymer (co) polymerized with one or more species. Examples of the polymer having a low degree of polymerization include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group such as M-230G (manufactured by Shin Nakamura Chemical Co., Ltd.) and 40/60 copolymerized oligomers of methacrylamide propyltrimethylammonium methyl sulfate Ltd., MG polymer).

(Usage)

Examples of the use of the article 40 include an antireflection article, an antifogging article, an antifouling article, and a water repellent article, more specifically, an antireflection film for display, an automobile meter cover, an automobile mirror, an automobile window, an organic or inorganic electroluminescence A light-extraction efficiency improving member of a solar cell, and a solar cell member.

(Action effect)

In the method of manufacturing an article having the fine concavo-convex structure of the present invention as described above on the surface thereof, since the mold obtained by the method for producing a mold of the present invention is used, the fine concave-convex structure of the mold is repeatedly transferred The releasability is less likely to deteriorate, and as a result, an article having a fine uneven structure on its surface can be produced with good productivity.

The article having the fine concavo-convex structure on its surface is not limited to the article 40 of the illustrated example. For example, the fine concavo-convex structure may be formed directly on the surface of the film 42 without forming 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 because the fine uneven structure can be efficiently formed by using the roll-shaped mold 20.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited thereto.

(Pores of anodic alumina)

A part of the anodic alumina was cut and platinum was vapor-deposited on the cross section for one minute. The cross section was observed under a condition of an acceleration voltage of 3.00 kV by using a field emission scanning electron microscope (JSM-7400F, , Pore spacing, and pore depth were measured. Each measurement was carried out at 50 points each, and an average value was obtained.

(Transfer test, peel strength)

1 [micro] l of the active energy ray-curable resin composition (A) was poured onto the surface of the mold where the micro concavo-convex structure was formed, covered with a polyethylene terephthalate (PET) film, and then irradiated with UV light (high pressure mercury lamp: Cm < 2 >). Subsequently, the cured resin was peeled off from the mold for each PET film.

This operation was repeated without changing the mold, and the 90 degree peel test was carried out at the time of 400th release to determine the peel strength.

(Active energy ray curable resin composition A)

45 parts by mass of condensation reaction mixture of TAS: succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4,

C6DA: 45 parts by weight of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

X-22-1602: 10 parts by mass of radically polymerizable silicone oil (Shin-Etsu Chemical Co., Ltd.)

Irg 184: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.); 3 parts by mass.

[Example 1]

An aluminum plate (purity: 99.99%) of 50 mm x 50 mm x 0.3 mm thick was electrolytically polished in a perchloric acid / ethanol mixed solution (1/4 volume ratio).

Step (a):

The above aluminum plate was subjected to anodic oxidation in a 0.3 M oxalic acid aqueous solution under the conditions of a direct current of 40 V and a temperature of 16 캜 for 6 hours.

Step (b):

The aluminum plate on which the oxide film was formed was immersed in a 6 mass% phosphoric acid / 1.8 mass% chromic acid mixed aqueous solution for 3 hours to remove the oxide film.

Step (c):

The aluminum plate was subjected to anodic oxidation in 0.3 M aqueous oxalic acid solution under the conditions of a direct current of 40 V and a temperature of 16 캜 for 30 seconds.

Step (d):

The aluminum plate on which the oxide film was formed was immersed in a 5 mass% aqueous phosphoric acid solution at 32 占 폚 for 8 minutes to carry out enlargement of the pore diameter.

Step (e):

The aluminum plate was subjected to anodic oxidation in 0.3 M aqueous oxalic acid solution under the conditions of a direct current of 40 V and a temperature of 16 캜 for 30 seconds.

Step (f):

The process (d) and the process (e) are repeated four times in total, and finally the process (d) is carried out to obtain anodic oxidation alumina having pores of substantially conical shape with an average interval of 100 nm and a depth of 240 nm To obtain a mold main body (a) formed on the surface.

Process (g):

The phosphoric acid aqueous solution on the surface of the mold main body (a) was lightly rinsed off using a shower, and the mold main body (a) was immersed in the water for 10 minutes.

Step (h):

Air was sprayed from the air gun onto the mold main body (a) to remove water droplets adhering to the surface of the mold main body (a).

Step (i):

The mold main body (a) was immersed in a solution obtained by diluting Optol DSX (manufactured by Daikin Chemicals Co., Ltd.) with 0.1% by mass of a diluent HD-ZV (manufactured by Harvesa) at room temperature for 10 minutes. The mold main body (a) was slowly pulled up from the diluted solution to 3 mm / sec.

Process (j):

The mold main body (a) was air-dried for 15 minutes.

Process (k):

The molded body (a) treated with the releasing agent was subjected to a heating and humidifying treatment at a temperature of 60 ° C and a relative humidity of 85% for 1 hour by using a thermostat and a humidity controller (manufactured by Kusumoto Chemical Co., Ltd.).

Process (m):

The steps (i) to (k) were repeated four times.

Process (n):

The mold main body (a) was air-dried overnight to obtain a mold.

A transfer test was conducted using the mold. The 400th peel strength obtained from the 90th degree peel test was extrapolated by exponential approximation to obtain the peel strength at the 800th peel, and the number of times the peel strength reached 35 N / m was calculated, Respectively. The results are shown in Table 1.

In Comparative Example 1, which will be described later, the peel strength reached 35 N / m at the number of transferable times of 240, and a region which could not be released due to adhesion of the cured resin to the mold side occurred.

[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 2 circuits.

A transfer test was carried out 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 carried out 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 carried out.

A transfer test was carried out 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 carried out.

A transfer test was carried out 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 carried out.

A transfer test was carried out 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 diluting solution of the Optol DSX was changed to 0.3 mass%.

A transfer test was carried out 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 diluting solution of the optool DSX was changed to 0.3 mass%.

A transfer test was carried out 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, it was found from the above Examples and Comparative Examples that a mold capable of retaining releasability for a long period of time by repeatedly transferring the fine concavo-convex structure of the surface by repeating the heating and humidifying treatment on the mold body treated with the releasing agent under an appropriate releasing agent concentration .

In particular, it can be seen that the releasability can be maintained for a very long time by repeating the heating and humidifying treatment twice or more at a concentration of 0.1 mass% of the releasing agent.

Industrial availability

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

10: Aluminum substrate
12: Handwork
14: oxide film (anodic alumina)
18: Mold body
20: roll mold
40: Goods
42: Film (article body)

Claims (9)

A process for producing a mold having the following steps (I) to (IV)
(I) a step of producing a mold body having a fine uneven structure on its surface;
(II) a step of treating the surface of the mold main body with a releasing agent by reacting the functional group (A) present on the surface of the mold main body on the side where the micro concavo-convex structure is formed with the functional group (B)
(III) a step of placing the mold body under heating and humidification after the step (II);
(IV) A step of repeating the step (II) and the step (III) two or more times. The method according to claim 1,
Wherein the functional group (B) is a hydrolyzable silyl group. 3. The method according to claim 1 or 2,
Wherein the functional group (B) of the releasing agent is a hydrolyzable silyl group and is a mold release agent having a perfluoropolyether structure. 3. The method according to claim 1 or 2,
Wherein in the step (II), the concentration of the releasing agent is 0.06 mass% or more and 0.15 mass% or less. 3. The method according to claim 1 or 2,
Wherein the mold body having the micro concavo-convex structure of the step (I) is anodically oxidized to form a micro concavo-convex structure having two or more pores on its surface. 6. The method of claim 5,
Wherein the average interval of the pores is 400 nm or less. 6. The method of claim 5,
Wherein an average interval of the pores is 20 nm or more and 400 nm or less. 3. The method according to claim 1 or 2,
Wherein the step (I) has the following steps (a) to (f)
Wherein the step (II) has the following steps (g) to (j)
Wherein the step (III) has at least one of the following steps (k) and (l)
Wherein the step (IV) comprises at least one of the following steps (m) and (n):
(a) anodizing an aluminum substrate in an electrolytic solution under a constant voltage to form an oxide film on the surface of the aluminum substrate;
(b) removing the oxide film to form pore generation points on the surface of the aluminum substrate;
(c) after the step (b), anodic oxidation of the aluminum base material in the electrolytic solution to form an oxide film having pores at the pore generation point;
(d) after the step (c), enlarging the diameter of the pores;
(e) anodizing the electrolytic solution after the step (d);
(f) repeating the step (d) and the step (e) to obtain a mold main body in which an anodized alumina having two or more pores is formed on the surface of the aluminum base;
(g) washing the mold body after the step (f);
(h) injecting air into the mold body after the step (g) to remove impurities attached to the surface of the mold body;
(i) a step of immersing a mold body into which a hydroxyl group has been introduced into a dilute solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a fluorine-containing solvent after the steps (f) to (h);
(j) drying the mold body after the step (i);
(k) after the step (i), placing the mold body under heating and humidification;
(1) washing the mold body immediately after the step (k) with a fluorinated solvent;
(m) repeating the cycle at least twice with the process (i) to the process (1) as one cycle;
(n) After the step (m), the step of drying the mold body. A method for producing an article having a fine concavo-convex structure on its surface, the method comprising: transferring the fine concavo-convex structure on the surface of the mold main body obtained by the method for producing a mold according to claim 1 or 2 onto a surface of the article main body.

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