WO2011126044A1 - Production method and production device for article having microrelief structure on surface thereof - Google Patents

Abstract

Provided is a method for producing an article having a microrelief structure on the surface thereof, wherein a microrelief structure on the surface of a roll-shaped mold, the surface of which has been treated by release agent, is transferred onto a surface of a film (article body), and wherein the method comprises transferring the finely rugged structure to the surface of the film, measuring the infrared spectroscopic spectrum of the surface of the roll-shaped mold from which the film has been removed, and assessing whether the status of the release agent is good or bad on the surface of the roll-shaped mold on the basis of the infrared spectroscopic spectrum. The production method and the production device for an article having a microrelief structure on the surface thereof enables the easy online monitoring of the status of the release agent on the surface of the mold, and can suppress reductions in productivity.

Description

Manufacturing method and manufacturing apparatus for article having fine uneven structure on surface

The present invention relates to a method and an apparatus for manufacturing an article having a fine concavo-convex structure on its surface by transferring the fine concavo-convex structure on the surface of a mold whose surface is treated with a release agent to the surface of the article main body.
This application claims priority based on Japanese Patent Application No. 2010-090456 for which it applied to Japan on April 9, 2010, and uses the content here.

In recent years, articles having a fine concavo-convex structure with a period of less than or equal to the wavelength of visible light on the surface exhibit an antireflection effect, a lotus effect, and the like, and thus have been attracting attention for their usefulness. In particular, it is known that a fine 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 for producing an article having a fine concavo-convex structure on its surface, for example, a method having the following steps (i) to (iii) is known (for example, Patent Document 1).
(I) An ultraviolet curable resin composition is sandwiched between a mold having an inverted structure of a fine concavo-convex structure on the surface and the surface treated with a release agent, and a base film serving as a main body of the article Process.
(Ii) A step of irradiating the ultraviolet curable resin composition with ultraviolet rays to cure the ultraviolet curable resin composition to form a cured resin layer having a fine uneven structure.
(Iii) A step of releasing the mold from the cured resin layer on the surface of the base film to obtain an article having a fine concavo-convex structure on the surface.

A mold treated with a mold release agent often deteriorates in performance due to repeated transfer of a fine concavo-convex structure, and finally the mold cannot be released from the cured resin layer. If it becomes the said state, cured resin will adhere to the surface of a mold, and washing | cleaning will become difficult, or a base film will fracture | rupture during manufacture. Therefore, the production is interrupted for a long time, and the productivity is significantly reduced. In order to solve the above-mentioned problem, a method capable of easily monitoring the state of the mold release agent on the mold surface online is required.

JP 2007-326367 A

The present invention provides a manufacturing method and a manufacturing apparatus for an article having a fine concavo-convex structure on the surface, which can easily monitor on-line the state of the mold release agent on the mold surface and suppress a decrease in productivity.

The method of manufacturing an article having a fine concavo-convex structure on the surface thereof according to the present invention transfers the fine concavo-convex structure on the surface of the mold whose surface has been treated with a release agent to the surface of the article main body, and the fine concavo-convex structure on the surface. A method for manufacturing an article having a structure in which a fine concavo-convex structure is transferred to a surface of an article body, an infrared spectrum of the surface of the mold after the article body is peeled from the mold is measured, and the infrared spectrum is obtained. The quality of the state of the mold release agent on the surface of the mold is determined based on this.

In the method for manufacturing an article having a fine concavo-convex structure on the surface of the present invention, when the state of the mold release agent on the surface of the mold is determined to be poor, the surface of the article main body of the fine concavo-convex structure on the mold surface The transfer onto the mold may be stopped, or a release agent may be supplied to the fine concavo-convex structure on the surface of the mold.
In the method for producing an article having a fine concavo-convex structure on the surface of the present invention, it is preferable to continuously or intermittently measure the infrared spectrum of the mold surface.

In the method for producing an article having a fine concavo-convex structure on the surface of the present invention, the absorbance area (A) of the peak near the wave number derived from the chemical structure of the release agent in the infrared spectroscopic spectrum and the surface of the mold When the area ratio ((A) / (B)) to the absorbance area (B) of the peak near the wave number derived from the chemical structure is equal to or higher than a preset threshold value, the state of the mold release agent on the mold surface is good. Is preferably determined.

The apparatus for manufacturing an article having a fine concavo-convex structure on the surface of the present invention transfers the fine concavo-convex structure on the surface of the mold whose surface is treated with a release agent to the surface of the article main body, and the fine concavo-convex structure on the surface. An apparatus for manufacturing an article having a fine concavo-convex structure on a surface, the mold having the surface treated with a release agent, and transferring the fine concavo-convex structure to the surface of the article main body. A reflection type infrared spectroscopic device for measuring an infrared spectrum of the surface of the mold after peeling, and a determination means for judging the quality of the release agent on the surface of the mold based on the infrared spectrum It is characterized by that.

That is, the present invention relates to the following.
(1) A method for producing an article having a fine concavo-convex structure on its surface by transferring the fine concavo-convex structure on the surface of the mold whose surface has been treated with a release agent to the surface of the article body. Appropriateness of production continuity by transferring to the surface of the article main body, measuring the infrared spectrum of the mold surface after peeling the article main body from the mold, and the state of the release agent on the mold surface. A method for manufacturing the article, comprising: determining.
(2) When it is determined that the state of the mold release agent on the surface of the mold is poor, the transfer of the fine uneven structure on the surface of the mold to the surface of the article body is stopped, and / or the surface of the mold is The manufacturing method of the article | item which has the fine concavo-convex structure as described in (1) further including processing with a mold release agent again.
(3) The method according to (1) or (2), wherein measuring the infrared spectral spectrum of the surface of the mold includes continuously or intermittently measuring the infrared spectral spectrum of the surface of the mold. A method for producing an article having a fine relief structure on its surface.
(4) In the infrared spectrum, the absorbance area (A) of the peak near the wave number derived from the chemical structure of the release agent, or the absorbance area (A) of the peak near the wave number derived from the chemical structure of the release agent When the area ratio ((A) / (B)) with the absorbance area (B) of the peak near the wave number derived from the chemical structure existing on the surface of the mold is equal to or higher than a preset threshold, the separation of the mold surface A method for producing an article having a fine concavo-convex structure on the surface thereof according to any one of (1) to (3), comprising determining that the state of the mold is good.
(5) The mold is made of alumina, the release agent is a fluorine compound, the absorbance area (A) has a threshold value of 0.13, and the absorbance area ratio ((A) / (B)) The manufacturing method of the article | item which has the fine concavo-convex structure as described in (4) whose surface is 0.047.
(6) The absorbance area (A) is 0.13 or more and 1 or less, and the area ratio ((A) / (B)) of the absorbance is 0.047 or more and 10 or less. A method for producing an article having a fine relief structure on its surface.
(7) An apparatus for manufacturing an article having a fine concavo-convex structure on the surface by transferring the fine concavo-convex structure on the surface of the mold whose surface is treated with a release agent to the surface of the article body, A mold having a structure, the surface of which is treated with a release agent, and a fine concavo-convex structure is transferred to the surface of the article body, and the infrared spectrum of the mold surface is measured after the article body is peeled from the mold. An apparatus for manufacturing an article having a fine concavo-convex structure on a surface thereof, comprising: a reflective infrared spectroscopic device for performing determination; and a determination means for determining the quality of a release agent on the surface of the mold based on the infrared spectroscopic spectrum.

According to the method for producing an article having a fine concavo-convex structure on the surface of the present invention, the state of the mold release agent on the mold surface can be easily monitored online, and the reduction in productivity can be suppressed.
According to the apparatus for manufacturing an article having a fine concavo-convex structure on the surface of the present invention, the state of the mold release agent on the mold surface can be easily monitored online, and a decrease in productivity can be suppressed.

It is a block diagram which shows an example of the manufacturing apparatus of the articles | goods which have the fine concavo-convex structure of this invention on the surface. It is sectional drawing which shows the manufacturing process of the mold which has an anodized alumina on the surface. It is sectional drawing which shows an example of the article | item which has the fine concavo-convex structure of this invention on the surface. It is a figure which shows an example of the infrared spectroscopy spectrum of the surface of the mold which the surface treated with the fluorine compound which has a hydrolyzable silyl group, and which has anodized alumina on the surface. It is a figure which shows an example of the baseline (dashed line which connects the start point and the end point of each absorption curve) at the time of extracting an absorbance area (A) and an absorbance area (B).

In the present specification, (meth) acrylate means acrylate or methacrylate. The term “transparent” means that light having a wavelength of 400 to 1170 nm is transmitted. Moreover, an active energy ray means visible light, an ultraviolet-ray, an electron beam, plasma, a heat ray (infrared rays etc.), etc.

<Production apparatus for articles having fine concavo-convex structure on the surface>
The apparatus for manufacturing an article having a fine concavo-convex structure on the surface thereof according to the present invention has a fine concavo-convex structure on the surface, the surface is treated with a release agent, and the fine concavo-convex structure is transferred to the surface of the article main body. A reflective infrared spectroscopic device for measuring the infrared spectral spectrum of the surface of the mold immediately after the article main body is peeled from the mold, and the state of the release agent on the mold surface based on the infrared spectral spectrum. Determination means for determining.

FIG. 1 is a schematic configuration diagram showing an example of an apparatus for manufacturing an article having a fine concavo-convex structure on the surface according to the present invention. The manufacturing apparatus has a roll-shaped mold 20 having a fine concavo-convex structure (not shown) on the surface, and the surface is treated with a release agent; and the surface of the roll-shaped mold 20 in synchronization with the rotation of the roll-shaped mold 20 A tank 22 for supplying an active energy ray-curable resin composition between the roll-shaped mold 20 and the belt-shaped film 42 (article main body) moving along the roll; and the film 42 and the active energy between the roll-shaped mold 20 A nip roll 26 that nips the linear curable resin composition; a pneumatic cylinder 24 that adjusts the nip pressure of the nip roll 26; an active energy that is installed under the roll-shaped mold 20 and passes through the film 42 to the active energy linear curable resin composition. An active energy ray irradiation device 28 for irradiating a line; and a film 42 having a cured resin layer 44 formed on the surface thereof A peeling roll 30 that peels from the mold 20; a reflective infrared spectrometer 50 that measures the infrared spectrum of the surface of the roll mold 20 immediately after the cured resin layer 44 is peeled together with the film 42; and infrared spectroscopy. It has the determination means 60 which determines the quality of the state of the mold release agent on the surface of a mold based on a spectrum, and the control apparatus 62 which controls operation | movement of a manufacturing apparatus. In the present invention, “immediately after being peeled” means from the time when the article main body having a fine concavo-convex structure on the surface is peeled off from the mold until the mold next contacts the article main body. Specifically, from when the cured resin layer 44 is peeled from the roll-shaped mold 20 together with the film 42 to when the active energy ray-curable resin composition is supplied between the film 42 and the roll-shaped mold 20. .

(Reflective infrared spectrometer)
The reflection type infrared spectroscopic device 50 includes a light source 52 that irradiates the surface of the roll-shaped mold 20 with infrared light; and receives and spectrally analyzes the infrared light reflected from the surface of the roll-shaped mold 20, and detects the dispersed infrared light. A detector 54 that obtains an outer spectral spectrum; and an operation control device 56 that controls the light source 52 and the detector 54 and transmits the infrared spectral spectrum obtained by the detector 54 to the determination means 60. In the reflective infrared spectrometer 50, the active energy ray-curable resin composition is supplied between the film 42 and the roll mold 20 after the cured resin layer 44 is peeled from the roll mold 20 together with the film 42. It is installed at a position where the infrared spectrum of the surface of the roll-shaped mold 20 can be measured.
Examples of the reflection infrared spectroscopic device 50 include a Fourier transform type and a dispersion type using a diffraction grating, and a Fourier transform type infrared spectroscopic device is preferable because the measurement time is short.

(Judgment means)
The determination means 60 includes, for example, an extraction unit (not shown) that extracts the intensity or area of a peak near a predetermined wave number derived from a specific chemical structure from an infrared spectrum; and the intensity of two types of peaks as necessary Or a calculation unit (not shown) for calculating the area ratio; the intensity of the peak, the area, or the ratio thereof is greater than or equal to a preset threshold value (or less than the threshold value in some cases). A determination unit (not shown) for determining that the state of the release agent is good; a storage unit (not shown) for storing a threshold value inputted from the outside; and a determination unit for the release agent on the surface of the roll mold 20 And a transmission unit that transmits the information to the control device 62 when the state is determined to be defective.

The determination unit has an absorbance area (A) of a peak near the wave number derived from the chemical structure of the release agent, or a peak near the wave number derived from the chemical structure existing on the surface of the roll mold 20 with the absorbance area (A). When the area ratio ((A) / (B)) to the absorbance area (B) is equal to or higher than a preset threshold value, the state of the mold release agent on the mold surface is preferably determined to be good. .

When using a fluorine compound having a hydrolyzable silyl group or silanol group as a release agent, and using a mold having an anodized alumina having two or more pores on the surface of an aluminum substrate as the roll-shaped mold 20, Specifically, each part of the determination means 60 is preferably as follows.

From the infrared spectroscopic spectrum, the extractor is based on the absorbance area (A) of the peak in the vicinity of wave number 1080 to 1290 cm ⁻¹ derived from the chemical structure of the fluorine compound having a hydrolyzable silyl group or silanol group, and the chemistry of the anodized alumina. It is preferable to extract the absorbance area (B) of the peak near the wave number 730 to 1080 cm ⁻¹ derived from the structure. The baseline in this case is a line connecting the start point and end point of the absorption curve having a peak at a predetermined wave number. In addition, these wave numbers may change with the state of a mold release agent or an anodized alumina, and can be suitably changed with the peak position which appears.
It is preferable that the calculation unit calculates an area (A) extracted by the extraction unit or an area ratio ((A) / (B)) between the area (A) and the area (B).
The determination unit determines that the state of the release agent on the surface of the roll-shaped mold 20 is good when the area (A) or the area ratio ((A) / (B)) is equal to or greater than a preset threshold value. It is preferable.
Here, as the value used for the determination, if the thickness of the anodized alumina is constant, the area ratio ((A) / (B)) is more stable because problems such as reproducibility and error between apparatuses are reduced. This is preferable because it can be expected to be measured. However, when the thickness of the anodized alumina is not constant, it can be judged only by the area of the peak (A).

The determination means 60 may be realized by dedicated hardware, and the determination means 60 is constituted by a memory and a central processing unit (CPU), and is a program for realizing the function of the determination means 60. The function may be realized by loading the program into a memory and executing it.
In addition, an input device, a display device, and the like are connected to the determination unit 60 as peripheral devices. Here, the input device refers to an input device such as a display touch panel, a switch panel, and a keyboard, and the display device refers to a CRT, a liquid crystal display device, and the like.

(Control device)
The control device 62 includes a processing unit (not shown), an interface unit (not shown), and a storage unit (not shown).
The interface unit is used to electrically connect each device or the like constituting the manufacturing apparatus and the processing unit.
The processing unit controls the operation of the devices and the like based on various settings stored in the storage unit, determination information from the determination unit 60, and the like. For example, when the determination means 60 determines that the state of the release agent on the surface of the roll-shaped mold 20 is poor, the film 42 moves, the roll-shaped mold 20 rotates, and the active energy ray curable from the tank 22. The supply of the resin composition or the like is stopped, and the transfer of the fine uneven structure on the surface of the roll-shaped mold 20 to the surface of the film 42 is stopped.

The processing unit may be realized by dedicated hardware, and the processing unit is constituted by a memory and a central processing unit (CPU), and a program for realizing the function of the processing unit is stored in the memory. The function may be realized by loading and executing.
In addition, an input device, a display device, and the like are connected to the control device 62 as peripheral devices. Here, the input device refers to an input device such as a display touch panel, a switch panel, and a keyboard, and the display device refers to a CRT, a liquid crystal display device, and the like.
Further, as the control device 62, a device having the function of the determination unit 60 may be used, and the determination unit 60 provided separately from the control device 62 may be omitted.

(Active energy ray irradiation device)
Examples of the active energy ray irradiation device 28 include a high-pressure mercury lamp, a metal halide lamp, and a fusion lamp.

(mold)
The mold has a fine concavo-convex structure on the surface of a mold substrate, and the surface is treated with a release agent.
Examples of the material for the mold base include metals (including those having an oxide film formed on the surface), quartz, glass, resin, and ceramics.
Examples of the shape of the mold substrate include a tubular shape, a flat plate shape, and a sheet shape in addition to the roll shape.

Examples of the mold production method include the following method (I-1) and method (I-2), and the method (I--) is possible because the area can be increased and the production is simple. 1) is particularly preferred.
(I-1) A method of forming anodized alumina having two or more pores (recesses) on the surface of an aluminum substrate.
(I-2) A method of directly forming a fine concavo-convex structure on the surface of a mold substrate by lithography or the like.

As the method (I-1), 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) A 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 enlarging the diameter of the pores.
(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 in which anodized alumina having two or more pores is formed on the surface of an aluminum substrate.

Step (a):
As shown in FIG. 2, when the aluminum substrate 10 is anodized, an oxide film 14 having pores 12 is formed.
Examples of the shape of the aluminum substrate include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
The aluminum substrate is preferably polished by mechanical polishing, feather polishing, chemical polishing, electrolytic polishing (etching) or the like in order to smooth the surface state. Moreover, since the oil used when processing an aluminum base material in a defined shape may adhere, it is preferable to degrease in advance before anodizing.

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 that scatters visible light due to segregation of impurities may be formed, 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 using oxalic acid as electrolyte:
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 a period 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 using sulfuric acid as the electrolyte:
The concentration of sulfuric acid is preferably 0.7M 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 a period 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 less, and more preferably 20 ° C. or less. 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. 2, 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 is 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. 2, 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.
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 (d):
As shown in FIG. 2, 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. 2, 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. 2, when the pore diameter enlargement process in the step (d) and the anodization 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 18 having anodized alumina (aluminum porous oxide film (alumite)) on the surface of the aluminum substrate 10 is obtained. It is preferable that the last end is 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 (pore depth / average interval between pores) of the pores 12 is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3.0. Is particularly preferred.

(Release agent)
Next, the surface of the mold on which the fine uneven structure is formed is treated with a release agent.
As the release agent, those having a functional group capable of forming a chemical bond with the anodized alumina of the aluminum substrate are preferable.

Examples of the mold release agent include silicone resin, fluororesin, and fluorine compound, and may have a silanol group or a hydrolyzable silyl group from the viewpoint of excellent releasability and excellent adhesion to a mold. Among them, a fluorine compound having a hydrolyzable silyl group is particularly preferable. Commercially available fluorine compounds having hydrolyzable silyl groups include fluoroalkylsilane, KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), “OPTOOL (registered trademark)” series (manufactured by Daikin Industries, Ltd.), and Novec EGC-1720. (Manufactured by Sumitomo 3M).

Examples of the treatment method using a release agent include the following method (II-1) and method (II-2), and the surface of the mold on which the fine relief structure is formed can be treated with the release agent without unevenness. In view of this, method (II-1) is particularly preferred.
(II-1) A method of immersing a mold in a dilute solution of a release agent.
(II-2) A method in which a release agent or a diluted solution thereof is applied to the surface of the mold on which the fine concavo-convex structure is formed.

As the method (II-1), a method having the following steps (g) to (l) is preferable.
(G) A step of washing the mold with water.
(H) A step of blowing air to the mold to remove water droplets attached to the surface of the mold.
(I) A step of immersing the mold in a diluted solution obtained by diluting a fluorine compound having a hydrolyzable silyl group with a solvent.
(J) A step of slowly lifting the immersed mold from the solution.
(K) A step of heating and humidifying the mold after the step (j) as necessary.
(L) A step of drying the mold.

<Method for producing article having fine concavo-convex structure on surface>
The method of manufacturing an article having a fine concavo-convex structure on the surface thereof according to the present invention transfers the fine concavo-convex structure on the surface of the mold whose surface has been treated with a release agent to the surface of the article main body, and the fine concavo-convex structure on the surface. A method for manufacturing an article having a structure in which a fine concavo-convex structure is transferred to a surface of an article body, an infrared spectrum of the surface of the mold after the article body is peeled from the mold is measured, and the infrared spectrum is obtained. This is a method for determining the quality of the state of the mold release agent on the surface of the mold.

Examples of the method for transferring the fine concavo-convex structure on the surface of the mold to the surface of the article main body include a method having the following steps (i) to (iii).
(I) A step of sandwiching an active energy ray-curable resin composition between a mold having a fine concavo-convex structure on the surface and the surface treated with a release agent, and the article body.
(Ii) A step of irradiating the active energy ray-curable resin composition with active energy rays to cure the active energy ray-curable resin composition to form a cured resin layer having a fine concavo-convex structure.
(Iii) A step of releasing the mold from the cured resin layer on the surface of the article body to obtain an article having a fine concavo-convex structure on the surface.

(Article body)
The material of the article main body is preferably a highly transparent material because active energy rays are irradiated through the article main body, and examples thereof include acrylic resins, polyethylene terephthalate, polycarbonate, and triacetyl cellulose.
Examples of the shape of the article body include a film, a sheet, an injection molded product, and a press molded product.

(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 / acrylic A tetra- or higher functional monomer such as an 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)
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; and 2,4,6-trimethylbenzoyldiphenylphosphine Kisaido, and benzo dichloride ethoxy phosphine 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; and methylbenzoylformate, 1,7-bisacridini Examples include luheptane and 9-phenylacridine. 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 antifouling properties; fine particles, and a small amount of a solvent, if necessary. .

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

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 and C ₂ H ₅ C (O) O.

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 —, —CH (CH ₃ ) CH (CH ₃ ) —, and the like.

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 set the water contact angle on the surface of the fine uneven structure of the cured resin layer to 25 ° or less, an active energy ray-curable resin composition capable of forming a hydrophilic material is a composition containing at least a hydrophilic monomer. It is preferable to use it. 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 the tetrafunctional or higher polyfunctional (meth) acrylate 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, EBECRYL8301 and KRM8200), polyether acrylates (manufactured by Daicel-Cytec Corp .: E ECRYL81), modified epoxy acrylates (manufactured by Daicel-Cytech: EBECRYL3416), and polyester acrylates (manufactured by Daicel-Cytech: EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL811, EBECRYL81L Is mentioned. 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 proportion 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.

As the bifunctional or more hydrophilic (meth) acrylate, Aronix (registered trademark) M-240, Aronix (registered trademark) M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E, NK ester ATM-35E (Shin Nakamura Chemical) And polyfunctional acrylates having a long-chain polyethylene glycol such as 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., Ltd.); hydroxyalkyl (meth) acrylates 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.

(Specific example of manufacturing method)
The specific example of the manufacturing method of the articles | goods which have the fine concavo-convex structure of this invention on the surface using the manufacturing apparatus shown in FIG. 1 is demonstrated.

Between the roll-shaped mold 20 having a fine concavo-convex structure (not shown) on the surface and a strip-shaped film 42 (article main body) that moves along the surface of the roll-shaped mold 20 in synchronization with the rotation of the roll-shaped mold 20. The active energy ray-curable resin composition is supplied from the tank 22.

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. At the same time, it is filled in the concave portions of the fine concavo-convex structure of the roll-shaped mold 20.

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. The amount of light irradiation energy from the active energy ray irradiation device 28 is preferably 100 to 10,000 mJ / cm ² .
An article 40 as shown in FIG. 3 is obtained by peeling the film 42 having the cured resin layer 44 formed on the surface from the roll-shaped mold 20 by the peeling roll 30.

Then, the infrared spectrum of the surface of the roll-shaped mold 20 immediately after the film 42 is peeled is measured by the reflection type infrared spectrometer 50. The measurement of the infrared spectrum of the surface of the mold is preferably performed continuously or intermittently at predetermined intervals from the viewpoint of constantly grasping the state of the mold release agent on the mold surface. The reflective infrared spectroscopic device 50 may be a fixed type or a scanning type.

Next, in the determination means 60, the extraction unit extracts the intensity or area of a peak near a predetermined wave number derived from a specific chemical structure from the infrared spectrum measured by the reflection type infrared spectroscopy device 50; If necessary, calculate the ratio of the intensity or area of the two peaks; if the peak intensity, area, or ratio of the peaks is greater than a preset threshold (or less than the threshold in some cases) Sometimes the state of the release agent on the surface of the roll-shaped mold 20 is determined as good; when the determination unit determines that the state of the release agent on the surface of the roll-shaped mold 20 is defective, the information is transmitted from the transmission unit. This is transmitted to the control device 62.

In the determination unit, the absorbance area (A) of the peak near the wave number derived from the chemical structure of the release agent or the absorbance of the peak near the wave number derived from the chemical structure of the release agent from the point of relatively high accuracy of determination. The area ratio ((A) / (B)) between the area (A) and the absorbance area (B) of the peak near the wave number derived from the chemical structure existing on the surface of the roll-shaped mold 20 is not less than a preset threshold value. In this case, it is preferable to determine that the state of the mold release agent on the surface of the mold is good.

Specifically, in the determination means 60, a fluorine compound having a hydrolyzable silyl group or silanol group is used as a release agent, and anodized alumina having two or more pores is used as the roll-shaped mold 20 with aluminum. When using the mold which has in the surface of a base material, it is preferable to perform the following processes.

In the extraction part, from the infrared spectroscopic spectrum, the absorbance area (A) of the peak in the vicinity of wave number 1080 to 1290 cm ⁻¹ derived from the chemical structure of the fluorine compound having a hydrolyzable silyl group or silanol group, and the anodized alumina The absorbance area (B) of the peak near the wave number 730 to 1080 cm ⁻¹ derived from the chemical structure is extracted. The baseline in this case is a broken line connecting the start point and end point of an absorption curve having a peak at a predetermined wave number. A specific example is shown in FIG.
The calculation unit calculates the area (A) and the area (B) extracted by the extraction unit, and the area ratio ((A) / (B)) between the two.
The determination unit determines that the state of the release agent on the surface of the roll-shaped mold 20 is good when the area (A) or the area ratio ((A) / (B)) is equal to or greater than a preset threshold value.

The threshold of the area (A) or the area ratio ((A) / (B)) is preliminarily performed using the same manufacturing apparatus and the same material as those used in actual manufacturing, and the roll-shaped mold 20 is cured. The area (A) or the area ratio ((A) / (B)) may be confirmed and set immediately before it becomes impossible to release from the resin layer 44 or when a defect due to defective release occurs in part. Anodized alumina having two or more pores as a roll-shaped mold 20 using a fluorine compound having a hydrolyzable silyl group or silanol group (Optool (registered trademark) DSX, manufactured by Daikin Industries, Ltd.) as a release agent When the mold having the surface of the aluminum substrate is used, if the area (A) is 0.13, or the area ratio ((A) / (B)) is 0.047 or more, there will be no release defects. When the area (A) is 0.15 or the area ratio ((A) / (B)) is 0.070 or more, the present inventors repeatedly perform preliminary experiments that transfer can be performed more stably. By confirming that. The upper limit of the area (A) or the area ratio ((A) / (B)) is not particularly limited. However, when the amount of the release agent increases, there arises a problem that the fine uneven structure of the roll-shaped mold 20 cannot be accurately transferred. Therefore, the area (A) is preferably 1 or less, and more preferably 0.8 or less. Further, the area ratio ((A) / (B)) is preferably 10 or less, and more preferably 5 or less.

As the mold release agent, the fluorine compound (Optool (registered trademark) DSX, manufactured by Daikin Industries, Ltd.) is used, and as the roll-shaped mold 20, a mold having anodized alumina having two or more pores on the surface of an aluminum substrate Is preferably 0.13 or more and 1 or less, more preferably 0.15 or more and 0.8 or less.
When the fluorine compound is used as a release agent and the mold is used as the roll mold 20, the area ratio ((A) / (B)) is preferably 0.047 or more and 10 or less, and 0.070 or more and 5 or less. More preferred.

In the control device 62, for example, when the determination unit 60 determines that the state of the release agent on the surface of the roll mold 20 is defective, the movement of the film 42, the rotation of the roll mold 20, and the tank 22. The supply of the active energy ray-curable resin composition is stopped, and the transfer of the fine uneven structure on the surface of the roll-shaped mold 20 to the surface of the film 42 is stopped. After the stop, the mold may be removed and a release agent may be applied. Further, the control device 62 can be configured to apply a release agent to the surface of the roll-shaped mold 20 in accordance with the output from the determination means 60.

(Goods)
FIG. 3 is a cross-sectional view showing an example of an article 40 having a fine concavo-convex structure on the surface obtained by the production method of the present invention.
The film 42 is a light transmissive film. Examples of the film material include polycarbonate, polystyrene resin, polyester, polyurethane, acrylic resin, polyether sulfone, polysulfone, polyether ketone, cellulose resin (triacetyl cellulose, etc.), polyolefin, and alicyclic polyolefin. Can be mentioned.

The cured resin layer 44 is a film made of a cured product of the active energy ray curable resin composition, 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 not more than the wavelength of visible light, that is, not more than 400 nm. When the convex portions are formed using an anodized alumina mold, the average distance between the convex portions is about 100 to 200 nm, and is particularly preferably 250 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 convex part (height of convex part / average interval between convex parts) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3.0. Particularly preferred. If the aspect ratio of the convex portion is 1.0 or more, the reflectance is sufficiently low. If the aspect ratio of the convex portion is 5.0 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 25 ° or less, more preferably 23 ° or less, and particularly preferably 21 ° or less. If the water contact angle is 25 ° or less, the dirt attached to the surface is washed away with water, and 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 23 °, and more preferably 3 ° to 21 °. The following are particularly preferred:

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

(Function and effect)
In the manufacturing method and the manufacturing apparatus of the article having the fine concavo-convex structure on the surface according to the present invention described above, the fine concavo-convex structure is transferred to the surface of the article main body, and the mold immediately after the article main body is peeled off from the mold. Since the surface infrared spectrum is measured and the quality of the mold release agent state on the mold surface is judged based on the infrared spectrum, the mold surface release agent condition can be easily monitored online. As a result, a mold release failure can be grasped in advance, and a decrease in productivity of an article having a fine concavo-convex structure on the surface can be suppressed.

That is, according to the present invention, since the state of the mold release agent on the surface of the mold can be determined in a non-contact and non-destructive manner, it can be determined online during the manufacture of the article. Therefore, it is possible to predict a release failure in advance, and it is possible to stop the production of the article immediately before the release failure. As a result, since an article can be manufactured until just before the release failure, the mold can be used efficiently, and the cured resin can be prevented from adhering to the release failure, so that the mold can be easily cleaned. Moreover, since troubles due to mold release defects can be avoided, articles can be manufactured more safely.

In the present invention, the reason why the reflection infrared spectroscopy is employed is as follows.
As described above, when the fine concavo-convex structure on the surface of the mold is continuously transferred to the surface of the article main body, the releasability is eventually deteriorated. As the cause, dropping of the release agent from the mold, alteration of the release agent due to active energy rays (ultraviolet rays or the like), heat, or the like can be considered. Therefore, in order to determine the cause of mold release failure when a fluorine compound having a hydrolyzable silyl group is used as a mold release agent, the surface of the mold that had the initial mold and the mold release failure was analyzed, and the mold release agent We decided to estimate the amount of Usually, since the release agent is applied to the mold very thinly, it is necessary to use a method with excellent surface sensitivity. For example, it is conceivable to use TOF-SIMS, XPS, and IR methods. Therefore, as a result of analysis by XPS and TOF-SIMS, for example, the amount of release agent (atomic ratio F / Al) obtained from XPS has decreased from 8.3 at the initial stage to 2.1 at the time of release failure. It was. Moreover, the structural change of the mold release agent remaining on the mold was not recognized. From this result, it became clear that the cause of the release failure was the release of the release agent. Therefore, it becomes possible to predict a mold release failure in advance by grasping the amount of the mold release agent on the surface of the mold.

However, TOF-SIMS and XPS cannot measure a mold of a certain size or more because of a problem in the apparatus configuration, so that it is difficult to measure during the manufacture of an article and cannot be monitored online. In addition, the ATR method, which is excellent in surface sensitivity among infrared spectroscopy, cannot be measured in a non-contact manner and damages the surface of the mold, and thus cannot be measured during the manufacture of the article. Furthermore, in these methods, since the surface of the mold has a fine concavo-convex structure, it is difficult to determine which part is being measured. Therefore, by performing measurement by reflection infrared spectroscopy, the above problem can be solved, and the amount of the release agent can be grasped in a non-contact manner regardless of the size of the mold.

Here, the reflection infrared spectroscopy will be described. When the mold is irradiated with infrared rays, most of the release agent made of a fluorine compound having a hydrolyzable silyl group and anodized alumina on the surface is transmitted and reflected by the metal surface of the aluminum substrate. By analyzing the reflected light, an infrared spectrum of the release agent can be obtained. In this case, information on all the mold release agents inside and outside the fine concavo-convex structure of the mold can be obtained. Further, according to this method, since measurement can be performed without contact with the mold, measurement can be performed during manufacturing of an article without damaging the mold. Moreover, there is no restriction on the size or shape of a large roll mold or the like. From these features, in-line measurement is also possible. As infrared rays, near infrared rays to far infrared rays can be used depending on purposes.

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

(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.

(Transcription test)
The active energy ray-curable resin composition was poured onto the side of the mold where the fine concavo-convex structure was formed, and the acrylic film was covered, followed by curing with a UV irradiation machine (high pressure mercury lamp, integrated light quantity: 400 mJ / cm ² ). . Subsequently, the fine concavo-convex structure was transferred to the surface of the acrylic film by releasing the cured resin layer from the mold together with the acrylic film. This operation was repeated, and the number of times until a release failure that could be clearly recognized visually occurred was defined as the number of transferable times. The defective mold release in this case is a state in which a resin residue is generated on the fine uneven surface of the mold due to adhesion of the cured resin to the mold and the mold and the cured resin layer are difficult to release.

(Active energy ray-curable resin composition)
45 parts by weight of a condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4,
45 parts by mass of 1,6-hexanediol diacrylate (produced by Osaka Organic Chemical Co., Ltd.)
10 parts by mass of radical-polymerizable silicone oil (Shin-Etsu Chemical Co., Ltd., X-22-1602) and 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) are mixed. An active energy ray-curable resin composition was prepared.

(Mold production method)
A 50 mm × 50 mm × 0.3 mm thick aluminum plate (purity 99.99%) prepared by electrolytic polishing in a perchloric acid / ethanol mixed solution (1/4 volume ratio) was prepared.
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 four times in total, and finally the step (d) is performed, and anodized alumina having substantially conical pores with an average interval of 100 nm and a depth of 240 nm is formed on the surface. A formed mold was obtained.

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

Step (i):
The mold was immersed for 10 minutes at room temperature in a solution obtained by diluting OPTOOL (registered trademark) DSX (manufactured by Daikin Chemicals Sales Co., Ltd.) to 0.1% by mass with a diluent HD-ZV (manufactured by Harves).
Step (j):
The mold was slowly pulled up from the diluted solution at 3 mm / sec.
Step (l):
The mold was air-dried for 15 minutes to obtain a mold treated with a release agent.

[Example 1]
The infrared spectrum of the surface of the mold was measured using a Fourier transform infrared spectrometer (manufactured by ThermoFisher Scientific, Nicolet 380 / Continum). The results are shown in FIG. A peak A observed at 1080 to 1290 cm ⁻¹ is derived from a release agent, and a peak B observed at 730 to 1080 cm ⁻¹ is derived from anodized alumina. The absorbance area (A) of peak A is 0.43, the area ratio of absorbance ((A) / (B)) of the peak is 0.18, and the transfer test is performed once using the mold. The releasability was good.

[Example 2]
Subsequent to Example 1, the transfer test was performed 100 times, and the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.21, the area ratio of absorbance ((A) / (B)) of the peak was 0.089, and the transfer test was performed once using the mold. As a result, the releasability was good.

Example 3
The infrared spectrum of another mold surface produced by the same method as in Example 1 was measured. As a result, the absorbance area (A) of peak A was 0.35, and the area ratio of absorbance ((A) / (B)) of the peak was 0.14. Further, when the transfer test was performed once using the mold, the releasability was good.

Example 4
After repeating the transfer from Example 3 19 times (the release property was good during this time), the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.29, and the area ratio of absorbance ((A) / (B)) of the peak was 0.12. Further, when the transfer test was further performed once using the mold, the releasability was good.

Example 5
The transfer was repeated 19 times from Example 4 (the release property was good during this time), and the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.22, and the peak absorbance area ratio ((A) / (B)) was 0.085. Further, when the transfer test was further performed once using the mold, the releasability was good.

Example 6
After the transfer was repeated 19 times from Example 5 (the release property was good during this period), the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.18, and the peak absorbance area ratio ((A) / (B)) was 0.074. Further, when the transfer test was further performed once using the mold, the releasability was good.

Example 7
After repeating the transfer from Example 6 19 times (the release property was good during this period), the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.13, and the peak absorbance area ratio ((A) / (B)) was 0.056. Furthermore, when the transfer test was further performed once using the mold, it was possible to release the mold although a little force was required.

[Comparative Example 1]
The transfer was repeated 9 times from Example 7. During this time, the force required for peeling increased, and cracks occurred in the produced film having a fine concavo-convex structure when transferred for the 10th time from Example 7 (poor mold releasability). As a result of measuring the infrared spectrum of the mold surface at this time, the absorbance area (A) of peak A is 0.12, and the area ratio ((A) / (B)) of peak absorbance is 0.045. there were.

Example 8
The mold used in Comparative Example 1 was again treated with a release agent in the same manner as the above-described production method. The infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.26, and the area ratio of absorbance ((A) / (B)) of the peak was 0.11. Further, when the transfer test was performed once using the mold, the releasability was good.

Example 9
The transfer was repeated 19 times from Example 8 (the release property was good during this time), and the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.22, and the peak absorbance area ratio ((A) / (B)) was 0.090. Further, when the transfer test was further performed once using the mold, the releasability was good.

Example 10
The transfer from Example 9 was repeated 19 times (the release property was good during this time), and the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.18, and the area ratio of absorbance ((A) / (B)) of the peak was 0.078. Further, when the transfer test was further performed once using the mold, the releasability was good.

Example 11
After repeating the transfer from Example 10 19 times (the release property was good during this period), the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.14, and the area ratio of absorbance ((A) / (B)) of the peak was 0.062. Furthermore, when the transfer test was further performed once using the mold, it was possible to release the mold although a little force was required.

Example 12
After the transfer was repeated nine times from Example 11 (the release property was good during this period), the infrared spectrum of the mold surface was measured. As a result, the absorbance area (A) of peak A was 0.13, and the area ratio ((A) / (B)) of peak absorbance was 0.055. Furthermore, when the transfer test was further performed once using the mold, it was possible to release the mold although a little force was required.

[Comparative Example 2]
The transfer was repeated 8 times from Example 12. During this time, the force required for peeling increased, and when the transfer was performed for the ninth time from Example 11, cracks occurred in the produced film having a fine concavo-convex structure (poor mold releasability). As a result of measuring the infrared spectrum of the mold surface at this time, the absorbance area (A) of peak A is 0.11, and the area ratio ((A) / (B)) of the absorbance of the peak is 0.041. there were.

The method and apparatus for producing an article having a fine concavo-convex structure on the surface of the present invention are useful for efficient mass production of antireflection articles, antifogging articles, antifouling articles, and water repellent articles.

12 pores (fine relief structure)
18 mold 20 roll-shaped mold 40 article 42 film (article body)
46 Convex (fine concavo-convex structure)
50 Reflective Infrared Spectrometer 60 Determination Means

Claims (7)

1. A method of producing an article having a fine concavo-convex structure on the surface by transferring the fine concavo-convex structure on the surface of the mold whose surface is treated with a release agent to the surface of the article body,
   Transferring the micro uneven structure to the surface of the article body,
   Measuring the infrared spectroscopic spectrum of the surface of the mold after the article body is peeled from the mold, and determining whether or not the production is continued according to the state of the mold release agent on the surface of the mold. Production method.
2. When it is determined that the state of the mold release agent on the mold surface is poor, the transfer of the fine uneven structure on the mold surface to the surface of the article body is stopped, and / or the mold surface is released again. The manufacturing method of the articles | goods which have the fine concavo-convex structure of Claim 1 on the surface further including processing with an agent.
3. Measuring an infrared spectrum of the surface of the mold,
   The manufacturing method of the articles | goods which have the fine concavo-convex structure on the surface of Claim 1 or 2 including measuring the infrared spectroscopy spectrum of the surface of the said mold continuously or intermittently.
4. Absorbance area (A) of the peak near the wave number derived from the chemical structure of the release agent in the infrared spectrum, or the absorbance area (A) of the peak near the wave number derived from the chemical structure of the release agent and the mold surface When the area ratio ((A) / (B)) to the absorbance area (B) of the peak near the wave number derived from the chemical structure existing in the mold is equal to or higher than a preset threshold value, The method for producing an article having the fine concavo-convex structure according to any one of claims 1 to 3, comprising determining that the state is good.
5. The mold is made of alumina;
   The release agent is a fluorine compound;
   The threshold value of the absorbance area (A) is 0.13, or the threshold value of the area ratio of absorbance ((A) / (B)) is 0.047, and the surface has the fine uneven structure according to claim 4. Article manufacturing method.
6. 6. The fine concavo-convex structure according to claim 5, wherein the absorbance area (A) is 0.13 or more and 1 or less, or the absorbance area ratio ((A) / (B)) is 0.047 or more and 10 or less. A method for manufacturing an article.
7. An apparatus for producing an article having a fine concavo-convex structure on the surface by transferring the fine concavo-convex structure on the surface of the mold whose surface is treated with a release agent to the surface of the article body,
   A mold having a fine concavo-convex structure on the surface, and wherein the surface is treated with a release agent;
   A reflective infrared spectroscopic device for measuring the infrared spectrum of the surface of the mold after transferring the fine concavo-convex structure to the surface of the article body and peeling the article body from the mold;
   An apparatus for manufacturing an article having a fine concavo-convex structure on a surface thereof, comprising: a determination unit that determines whether the state of the release agent on the surface of the mold is good based on the infrared spectrum.

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