JP4913925B2 - Method for producing imprint roll mold - Google Patents

Abstract

Disclosed is a method for producing a roll-shaped mold having a plurality of protuberances and recesses on the surface of same, in which a cylindrical aluminum base material, comprising aluminum immersed in an electrolysis solution in an anodizing tank, is anodized by electrification using an electrifying member. Furthermore, the method for producing a roll-shaped mold includes an anodizing step, in which, when the aforementioned aluminum base material is in contact with the aforementioned electrifying member, the aforementioned aluminum base material is electrified using the aforementioned electrifying member, while rotating the aforementioned aluminum base material with the central axis of the aforementioned aluminum base material as the axis of rotation.

Description

The present invention relates to an anodizing apparatus for producing an imprint roll mold in which an anodized alumina having a plurality of pores is formed on an outer peripheral surface of a roll aluminum substrate, and an imprint roll mold. The present invention relates to a production method and a method for producing an article having a plurality of convex portions on the surface using the imprint roll mold.
The present invention also relates to a treatment tank for electrolytically treating a cylindrical substrate in an electrolytic solution, and an electrolytic treatment apparatus for electrolytically treating a cylindrical substrate in an electrolytic solution.
The present application was filed on March 25, 2010, Japanese Patent Application No. 2010-070280, filed in Japan, June 15, 2010, Japanese Patent Application No. 2010-136227, filed in Japan, July 29, 2010. Japanese Patent Application No. 2010-170458 filed in Japan, Japanese Patent Application No. 2011-018226 filed in Japan on January 31, 2011, and Japanese Patent Application No. 2011 filed on March 4, 2011 in Japan Claims priority based on No. 047561, the contents of which are incorporated herein.

As a method for treating the surface of the substrate, there are a film treatment such as plating and a chemical conversion treatment such as anodization.
When processing the surface of the substrate, for example, as shown in FIGS. 7A and 7B, a treatment liquid 1L ′ such as an electrolytic solution is supplied to the treatment tank 170 from a supply pipe 171 installed at the lower part of the rectangular parallelepiped treatment tank 170. Then, while adjusting the flow of the treatment liquid 1L ′ in the treatment tank 170 by the perforated plate 172, the treatment liquid 1L ′ is overflowed from the upper part of the treatment tank 170, and the cylindrical substrate 1A is treated in the treatment tank 170. In general, the surface treatment is performed by dipping in the liquid 1L ′.

Further, Patent Document 1 includes a rectangular parallelepiped plating tank, an overflow part surrounding the four sides of the plating tank, a reserve tank communicating with the overflow part, and a pump for supplying a plating solution from the reserve tank to the plating tank. There is disclosed a plating apparatus comprising: In this plating apparatus, a U-shaped porous tube is provided in a liquid discharge portion of a pump, and a porous plate for vertically partitioning the inside of a plating tank is installed on the upper portion of the porous tube, and an object to be plated (base material) Is accommodated in the plating tank so as to be positioned above the perforated plate.
According to this plating processing apparatus, the plating solution is introduced into the plating tank by a pump, and discharged from the discharge port of the perforated pipe to the upper side of the plating tank. It is said that the flow of the plating solution can be made uniform by the upper porous plate.

However, when the surface of the base material is processed using the processing tank 170 as shown in FIGS. 7A and 7B or the plating tank described in Patent Document 1, the flow state of the processing liquid 1L ′ appears unevenly on the lower side of the porous plate 172. It was easy to occur. As a result, the flow of the treatment liquid 1L ′ that moves from the lower part to the upper part of the treatment tank 170 is disturbed, and the treatment liquid 1L ′ may partially stay (generation of a staying part). When the staying portion is generated, it becomes difficult to uniformly treat the surface of the base material 1A.
Such a tendency is likely to occur when the substrate 1A has a long shape as shown in FIGS. 7A and 7B, and becomes more prominent as the length in the longitudinal direction becomes longer. The reason for this is considered as follows.

  Usually, the supply pipe 171 extends from the end surface of the processing tank 170 to the back toward the end surface opposite to the end surface. Therefore, the longer the substrate 1A is, the longer the shape of the treatment tank 170 that accommodates the substrate 1A is, and the longer the supply pipe 171 is in accordance with the length of the treatment tank 170 in the longitudinal direction. Since the processing liquid 1L ′ is extruded from the supply pipe 171 to the processing tank 170 by the pump 173, the pressure received by the processing liquid 1L ′ is easily different depending on the distance from the pump 173. The longer the supply pipe 171 is, the farther away it is from the pump 173, so that a pressure difference is likely to occur between the near side near the pump 173 and the far side away from the pump 173. Therefore, it is considered that spots are more likely to occur in the flow state of the treatment liquid 1L ', and a staying portion is likely to occur.

  Further, when the base material 1A becomes longer, the processing tank 170 that accommodates the base material 1A also becomes larger, so that the apparatus becomes larger and the amount of the processing liquid 1L 'used also increases.

  By the way, in recent years, articles such as an optical film having a fine concavo-convex structure with a period equal to or less than the wavelength of visible light on the surface exhibit an antireflection effect, a lotus effect, and the like, and thus its usefulness has attracted attention. In particular, a fine uneven structure called a moth-eye structure is known to exhibit an effective antireflection function by continuously increasing the refractive index from the refractive index of air to the refractive index of the material of the article. .

  Examples of the method for producing an article having a fine concavo-convex structure on the surface include an imprint method in which the fine concavo-convex structure formed on the surface of the mold is transferred to the surface of a transfer target such as a base film. As the imprint method, for example, the following method is known (Patent Document 2).

  The ultraviolet curable resin is irradiated with ultraviolet rays in a state where the ultraviolet curable resin is interposed between the roll-shaped mold in which the anodized alumina having a plurality of pores is formed on the outer peripheral surface and the transparent base film. The light that cures the ultraviolet curable resin to form a cured resin layer having a plurality of convex portions whose pores of the anodized alumina are inverted on the surface, and peels the base film from the roll mold together with the cured resin layer Imprint method.

  As a method for producing a mold used in this imprint method, for example, a cylindrical (roll-shaped) aluminum substrate is anodized in an electrolytic solution, and a plurality of pores (concave portions) are provided on the peripheral surface of the aluminum substrate. Methods for forming anodized alumina are known (Patent Documents 2 and 3).

However, when a cylindrical aluminum substrate is anodized in an electrolytic solution using a treatment tank 170 as shown in FIGS. 7A and 7B, if a staying portion is generated in the treatment tank 170, particularly in the upper part of the porous plate 172. Temperature spots tend to occur in the treatment liquid (electrolyte) 1L ′. The surface temperature of the base material 1A is easily affected by the temperature spots of the treatment liquid 1L ′, and if the temperature spots are generated in the treatment liquid 1L ′, the surface of the base material 1A is likely to be spotted.
The depth of pores formed on the substrate surface by anodization is susceptible to the temperature during processing. Therefore, when temperature spots occur on the electrolyte solution or the substrate surface, a mold having a variation in the depth of pores depending on the location may be obtained. When such a mold is used and the fine concavo-convex structure formed on the surface of the mold is transferred by the imprint method, the height of the convex portion varies depending on the location, that is, the article has a variation in reflectance. .

  The cause of uneven anodic oxidation is affected by the temperature of the electrolyte, current density, electrolysis voltage, etc., and the temperature unevenness of the roll-shaped aluminum surface and the current-carrying member and aluminum for supplying a stable current It is conceivable that the substrate is not in close electrical contact, such as poor energization.

JP 2009-242878 A JP 2009-174007 A International Publication No. 2006/059686 Pamphlet

This invention is made | formed in view of the said situation, The 1st side surface of this invention provides the method of manufacturing the roll-shaped mold for imprint in which the variation in the depth of a pore was suppressed.
The second aspect of the present invention provides a method for producing an article having a plurality of convex portions on the surface, in which variations in the height of the convex portions are suppressed.

  According to a third aspect of the present invention, there is provided an anodizing apparatus capable of manufacturing a roll-shaped mold for imprinting in which variation in pore depth is suppressed.

According to a fourth aspect of the present invention, there is provided an electrolytic processing apparatus capable of preventing the stagnation of the electrolytic solution even when processing a long base material and further suppressing the amount of the electrolytic solution used.
The 5th side surface of this invention provides the processing tank used suitably for the said electrolytic treatment apparatus.

A first aspect of the present invention, a cylindrical aluminum substrate of aluminum immersed in the electrolyte of the anodic oxidation processing tank, subjected to anodic oxidation treatment is energized with a current-carrying member, a plurality of irregularities on the surface A method for producing a roll-shaped mold having
The anodizing bath contains an electrolytic solution, the processing bath main body in which the aluminum base material is immersed, an electrolytic solution supply unit that supplies the electrolytic solution to the processing bath main body, and an overflow unit that discharges the electrolytic solution from the processing bath main body With
With the current-carrying member in contact with the aluminum base material, the electrolytic solution supplied from the electrolytic solution supply part to the aluminum base is supplied to the overflow part with the central axis of the aluminum base as the center of rotation . The present invention relates to a roll mold manufacturing method including an anodizing step of energizing the aluminum substrate through the energizing member while rotating in a direction opposite to the flowing direction .
A 2nd aspect of this invention is related with the manufacturing method of the roll-shaped mold as described in a 1st aspect with which the said aluminum base material and the said electricity supply member rotate synchronously.
According to a third aspect of the present invention, the energizing member includes a conductive shaft member, and a contact that is fixed to the shaft member and is in contact with the aluminum base, and the contact is cylindrical. 1st aspect which is contact | abutted by the inner peripheral surface of the said aluminum base material, and is arrange | positioned in the position which at least one edge part of the said shaft member contacts with the electroconductive electric power supply member which supplies electric power to the said shaft member Or it is related with the manufacturing method of the roll-shaped mold as described in a 2nd aspect.
In a fourth aspect of the present invention, at least one end of the shaft member is located outside the aluminum base along the axial direction of the aluminum base, and the shape of the at least one end is conical. And at least one end of the shaft member relates to the method for manufacturing a roll-shaped mold according to the third aspect, wherein the shaft member rotates while sliding with the power feeding member.
According to a fifth aspect of the present invention, the aluminum substrate rotates about a central axis by rotating a rotating jig fixed to an axial end of the aluminum substrate, and the shaft member is It is related with the manufacturing method of the roll-shaped mold as described in a 3rd aspect fixed to the said rotation jig | tool and rotating in synchronization with the said aluminum base material.
A sixth aspect of the present invention relates to the method for manufacturing a roll-shaped mold according to the fifth aspect, wherein the rotating jig stops the end of the aluminum base material.
A seventh aspect of the present invention, the while discharging a part of the electrolyte from the anodizing bath, the anodizing bath, the electrolytic solution of the electrolyte solution in the same amount to be discharged is supplied, It is related with the manufacturing method of the roll-shaped mold as described in a 1st aspect.
In an eighth aspect of the present invention, the electrolytic solution is overflowed from the overflow portion above the aluminum base material of the anodizing treatment tank to discharge a part of the electrolytic solution, and the overflowed electrolytic solution is discharged to the aluminum. It is related with the manufacturing method of the roll-shaped mold as described in a 1st aspect which returns in the anodizing treatment tank from the said electrolyte solution supply part provided below the base material.
A ninth aspect of the present invention, the shape of the anodizing tank, a semi-cylindrical shape, and uniformly supplied to the electrolyte from one side, overflowing from the other side, to a seventh aspect of The present invention relates to a method for producing the described roll-shaped mold.
The tenth aspect of the present invention is the production of the roll-shaped mold according to the first aspect, wherein the bottom of the treatment tank main body is curved in an arc shape so as to follow the peripheral surface of the immersed aluminum base material. Regarding the method.
An eleventh aspect of the present invention, the processing tank body is a long shape before Symbol aluminum substrate is immersed, from the electrolytic solution supply portion provided along the longitudinal direction of the treatment Riso body The electrolyte is supplied from above one side of the treatment tank main body, and the electrolyte is discharged from the overflow portion provided on the other side upper portion of the treatment tank main body along the longitudinal direction of the treatment tank main body. It is related with the manufacturing method of the roll-shaped mold as described in a 1st aspect.
A twelfth aspect of the present invention is the method for producing a roll-shaped mold according to the first aspect or the second aspect, wherein the energizing member is an energizing member in surface contact with one end face or both end faces of the aluminum substrate. About.
In a thirteenth aspect of the present invention, the energization member is disposed so as to abut one end surface or both end surfaces of the aluminum base material, and the aluminum base material is sandwiched in the axial direction, and rotates the energization member. The roll-shaped mold manufacturing method according to the twelfth aspect, wherein the energizing member and the aluminum base material are rotated in contact with each other.
A fourteenth aspect of the present invention, the end of the previous SL aluminum substrate that has been stopping water, a method for manufacturing a roll-like mold according to the first aspect.
A fifteenth aspect of the present invention is the roll-shaped mold according to the twelfth aspect, wherein the energizing member is moved along the axial direction of the aluminum base material to bring the aluminum base material into contact with the energizing member. It relates to a manufacturing method.
In a sixteenth aspect of the present invention, a first tapered surface is included in one end surface or both end surfaces of the aluminum base material, and the energizing member has a second tapered surface in surface contact with the first tapered surface, The roll tape mold manufacturing method according to the twelfth aspect, wherein the first taper surface and the second taper surface are brought into contact with each other to bring the aluminum base material into contact with the current-carrying member.

  As another aspect of the present invention, there is provided a method for producing an imprint roll mold according to the present invention, wherein an anodized alumina having a plurality of pores is formed on an outer peripheral surface of a roll-shaped aluminum base material. A method for producing a mold, characterized in that when an aluminum substrate is anodized in an electrolytic solution in an anodizing tank, the aluminum substrate is rotated about the central axis of the aluminum substrate.

In the above aspect, it is preferable to supply the same amount of the electrolytic solution to the anodizing tank while discharging a part of the electrolytic solution from the anodizing tank; More preferably, it is returned into the anodizing tank from a supply port provided below the aluminum base.
Said aspect WHEREIN: As for the supply amount of the electrolyte solution to an anodizing tank, the frequency | count of circulation is preferable once or more in 3 minutes with respect to the volume of an anodizing tank. By doing so, the anodizing tank can be renewed frequently, and heat removal and generated hydrogen can be efficiently removed. For example, when the tank capacity is 105 L, it is preferably 35 L / min to 60 L / min, more preferably 41 L / min to 55 L / min.
In the above aspect, at the time of anodizing, it is preferable that the aluminum base is an anode, and at least one cathode plate is disposed substantially parallel to the central axis of the aluminum base and facing the aluminum base. .
A seventeenth aspect of the present invention is a method of manufacturing an article having a plurality of irregularities on the surface, and is formed on the outer peripheral surface of the imprint roll-shaped mold obtained by the manufacturing method described in the first aspect. Transferring a plurality of fine pores of the anodized alumina to a transferred material by an imprint method, and obtaining an article having a plurality of convex portions on the surface in which the fine pores are inverted and transferred. And a method for manufacturing the article.

According to an eighteenth aspect of the present invention, there is provided a treatment tank for electrolytically treating a cylindrical substrate in an electrolytic solution, a long treatment tank main body, a treatment tank main body in which the electrolytic solution is accommodated and the substrate is immersed. An electrolytic solution supply unit that supplies the electrolytic solution to the liquid tank, and an overflow unit that discharges the electrolytic solution from the treatment tank body, and the inner surface of the bottom of the treatment tank body is formed on the peripheral surface of the substrate immersed in the treatment tank body The electrolyte supply part is provided above one side surface of the treatment tank body so as to be along the longitudinal direction of the treatment tank body, and the overflow part is the longitudinal length of the treatment tank body. It is related with the processing tank provided in the other side upper part of the processing tank main body so that a direction may be followed.
According to a nineteenth aspect of the present invention, there is provided an electrolytic treatment apparatus for electrolytically treating a cylindrical base material in an electrolytic solution. The long processing tank main body, in which the base material is immersed, An electrolytic solution supply unit that supplies an electrolytic solution, a processing bath that includes an overflow unit that discharges the electrolytic solution from the processing bath main body, and an electrode plate that is disposed so as to sandwich the substrate immersed in the processing bath main body And the inner surface of the bottom of the treatment tank body is curved in an arc shape so as to be along the peripheral surface of the substrate immersed in the treatment tank body, and the electrolyte supply part is in the longitudinal direction of the treatment tank body. And the overflow portion relates to an electrolytic treatment apparatus provided on the other side upper portion of the processing tank main body so as to be along the longitudinal direction of the processing tank main body. .

Here, it is preferable that the said electrode plate is curving so that the inner surface shape of the bottom part of the said processing tank main body may be followed.
Furthermore, it is preferable to provide a rotating means for rotating the base material around the central axis of the base material.
Moreover, it is preferable that the said rotation means rotates the said base material in the direction opposite to the direction where the electrolyte solution supplied from the electrolyte solution supply part flows into an overflow part.

According to a twentieth aspect of the present invention, there is provided an anodizing apparatus for anodizing a roll-shaped aluminum substrate made of aluminum with an electrolytic solution in an anodizing tank, wherein one end surface or both end surfaces of the aluminum substrate are used. The present invention relates to an anodizing apparatus that includes a current-carrying member that is in surface contact with the aluminum substrate and that energizes the aluminum substrate while rotating the current-carrying member in synchronization with the aluminum substrate that rotates about a central axis.
Moreover, the anodizing apparatus according to the twentieth aspect of the present invention is characterized by having a rotation driving means for rotating the aluminum substrate.
Moreover, the anodizing apparatus according to the twentieth aspect of the present invention has an axial direction drive means for moving the current-carrying member forward and backward in the axial direction of the aluminum base material, and the axial direction drive means includes the aluminum A base material and the said electricity supply member are contacted or separated, It is characterized by the above-mentioned.
In the anodizing apparatus according to the twentieth aspect of the present invention, a first tapered surface is included in one end surface or both end surfaces of the aluminum base material, and the energizing member is in surface contact with the first tapered surface. It has the 2nd taper surface, It is characterized by the above-mentioned.

According to a twenty-first aspect of the present invention, there is provided an anodizing apparatus for anodizing a roll-shaped aluminum base made of aluminum with an electrolytic solution in an anodizing tank, wherein the aluminum base is electrically conductive. Rotating the aluminum substrate around the center axis of the aluminum substrate and rotating the aluminum substrate in synchronization with the aluminum substrate in a state of contacting the aluminum substrate And an anodizing apparatus for energizing the aluminum substrate.
An anodizing apparatus according to a twenty-first aspect of the present invention is in contact with a conductive rotating shaft that fixes the contact and extends along the axial direction of the aluminum base, and an end of the rotating shaft. A conductive power supply plate member for supplying power to the rotating shaft, and rotating the rotating shaft in synchronization with the aluminum base, thereby rotating the contact in synchronization with the aluminum base. It is characterized by that.
The anodizing apparatus according to the twenty-first aspect of the present invention is characterized in that the portion of the rotating shaft that comes into contact with the power feeding plate member has a conical shape.
In the anodizing apparatus according to the present invention, the aluminum base is rotated about a central axis by a rotation jig fixed to an end, and the rotation axis is fixed to the rotation jig. Thus, it rotates in synchronization with the aluminum substrate.
Moreover, the anodizing apparatus according to the twenty-first aspect of the present invention is characterized in that it has a structure capable of stopping water so that an electrolytic solution does not enter the aluminum substrate.

According to the method for producing an imprint roll mold of the present invention, it is possible to produce an imprint roll mold in which variation in pore depth is suppressed.
According to the twentieth aspect of the present invention, the aluminum substrate and the energization member are brought into surface contact and energized to the aluminum substrate while being rotated in synchronization with each other, so that stable energization can be performed without energization failure. In addition, since the contact area is large, it is possible to suppress the touch of the current value caused by rotation such as rubbing due to the rotation of the contact portion of the aluminum base material and the current-carrying member, and it is possible to further improve the yield of the roll mold. it can.
According to the twenty-first aspect of the present invention, since the aluminum base material and the touch element are synchronized with each other while the aluminum base material and the touch element are in contact with each other, electricity is supplied from the touch element to the aluminum base material. Further, it is possible to eliminate the wear between the aluminum base material and the touch element and to suppress the failure of energization, and to further improve the yield of the roll-shaped mold.
According to the article manufacturing method of the present invention, it is possible to manufacture an article having a plurality of convex portions on the surface, in which variations in the height of the convex portions are suppressed.

The treatment tank of the present invention is suitable as a treatment tank of an electrolytic treatment apparatus that prevents the electrolytic solution from staying even when a long substrate is processed, and that can also suppress the amount of the electrolytic solution used.
In addition, the electrolytic treatment apparatus of the present invention can prevent stagnation of the electrolytic solution even when a long substrate is processed, and can also suppress the amount of electrolytic solution used.

It is a side view which shows an example of the processing tank of this invention. It is sectional drawing which follows the 1I-1I 'line of FIG. It is a side view which shows the other example of an overflow part. It is sectional drawing which shows an example of the electrolytic processing apparatus of this invention. FIG. 5A is a cross-sectional view taken along line 1II-1II 'of FIG. FIG. 5B is a perspective view of a treatment tank and an electrode plate provided in the electrolytic treatment apparatus shown in FIG. It is sectional drawing which shows the formation process of the pore of an anodized alumina. It is a figure which shows an example of the conventional processing apparatus, and FIG. 7A is the side view. It is a figure which shows an example of the conventional processing apparatus, FIG. 7B is sectional drawing which follows the 1III-1III 'line of FIG. 7A. It is a graph which compares the electrolyte solution temperature when carrying out the electrolysis process with the processing tank of this invention, and a rectangular parallelepiped processing tank, and is the graph which showed the maximum temperature which rose at several points near the processing tank wall surface. It is a graph which compares the electrolyte solution temperature when carrying out the electrolytic treatment with the processing tank of this invention, and a rectangular parallelepiped processing tank, and is the graph which showed the maximum temperature difference in the longitudinal direction several points of the base-material surface. It is sectional drawing of the anodizing apparatus which concerns on embodiment of this invention. It is sectional drawing which follows the 2A-2A line of FIG. It is the figure which showed the graph explaining the electricity supply state with respect to the aluminum base material in the anodizing apparatus which concerns on Example 2 of this invention. It is the figure which expanded and showed the specific range of the graph shown to FIG. 12A. It is sectional drawing which showed schematic structure of the anodizing apparatus based on the comparative example 3. It is the figure which showed the graph explaining the electricity supply state with respect to the aluminum base material in the anodizing apparatus which concerns on the comparative example 3. FIG. It is sectional drawing which shows an example of an anodizing apparatus. It is a schematic block diagram which shows an example of the manufacturing apparatus of articles | goods. It is sectional drawing which showed the position which divides the outer periphery of a roll-shaped mold into six equal circumferences. It is sectional drawing of the anodizing apparatus which concerns on embodiment of this invention. It is sectional drawing which follows the 4A-4A line | wire of FIG. It is principal part sectional drawing explaining the detail of the member shown by FIG. It is the figure which showed the graph explaining the electricity supply state with respect to the aluminum base material in an anodizing apparatus.

  The method for producing a roll-shaped mold according to the first to sixteenth aspects of the present invention is a treatment tank for electrolytically treating a cylindrical substrate in an electrolytic solution, which is the eighteenth aspect of the present invention; It is carried out by applying an electrolytic treatment apparatus for electrolytic treatment of a columnar base material in an electrolytic solution according to a nineteenth aspect; or an anodizing treatment apparatus according to the twentieth or twenty-first aspect of the present invention. Can do.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[Treatment tank]
The treatment tank of the present invention is for electrolytic treatment of a cylindrical substrate in an electrolytic solution.
FIG. 1 is a view showing an example of the treatment tank 110 according to the present embodiment, and is a side view seen from the electrolyte solution supply unit side described later. 2 is a cross-sectional view taken along line 1I-1I ′ of FIG.
In addition, the outer tank 140 which accommodates the processing tank 110 shown in FIG. 1 was added to FIG.
In the present invention, the shape of the base material to be subjected to the electrolytic treatment is a columnar shape, but may be a hollow shape (cylindrical shape) as shown in FIGS.

The processing tank 110 shown in FIGS. 1 and 2 contains an electrolytic solution 1L, a long processing tank body 111 in which a hollow cylindrical base material 1A is immersed, and an electrolytic solution that supplies the processing tank body 111 with the electrolytic solution 1L. A supply unit 112 and an overflow unit 113 for discharging the electrolytic solution 1L from the processing tank main body 111 are provided.
This processing tank 110 is accommodated in the outer tank 140 as shown in FIG.

<Treatment tank body>
The treatment tank main body 111 accommodates 1 L of the electrolytic solution, and the substrate 1A is immersed in the electrolytic solution 1L.
The inner surface 111a ′ of the bottom 111a of the processing tank body 111 is curved in an arc shape so as to be along the peripheral surface (outer peripheral surface) 1A ′ of the substrate 1A immersed in the processing tank body 111. Since the inner surface 111a ′ of the bottom portion 111a is curved in an arc shape, the electrolytic solution 1L supplied from the electrolytic solution supply unit 112 described later can smoothly flow to the overflow portion 113.
In the present invention, the “arc shape” is not limited to a perfect circle.

  The shape of the inner surface 111a 'of the bottom portion 111a is preferably a shape that is smoothly bent along one direction without a bending point, such as a semicircular shape and a semielliptical shape, and among them, a semicircular shape is more preferable. If the shape of the inner surface 111a 'of the bottom part 111a is semicircular, the electrolyte 1L supplied from the electrolyte supply part 112 flows to the overflow part 113 while maintaining a smoother flow on the inner surface 111a' of the bottom part 111a.

  The material of the treatment tank main body 111 is not particularly limited as long as it is not easily corroded by the electrolytic solution 1L, and examples thereof include stainless steel and polyvinyl chloride (PVC).

The size of the processing tank main body 111 is not particularly limited as long as it can accommodate the base material 1A. For example, when the base material 1A is disposed in the processing tank main body 111 as shown in FIG. The size of the gap S is formed between the outer peripheral surface 1A ′ of 1A and the inner surface 111a ′ of the bottom 111a. Specifically, the distance D from the central axis P of the substrate 1A to the inner surface 111a ′ of the bottom 111a is preferably 1.25 to 2 times the radius (r) of the substrate 1A.
When the shape of the inner surface 111a ′ of the bottom 111a is a semicircular shape, the base 1A is placed in the treatment tank main body 111 so that the center on the diameter of the semicircle and the central axis P of the base 1A overlap. It is preferable to arrange.

By the way, as described above, when forming the pores on the peripheral surface by anodizing the base material, the depth of the pores is easily affected by temperature spots on the electrolyte solution and the base material surface (outer peripheral surface). Need to reduce temperature spots.
The temperature spots on the surface of the electrolytic solution and the base material are mainly caused by the electrolytic solution staying in the processing tank. However, if the distance between the base material and the inner surface of the processing tank is narrow, the temperature spots may occur. This is presumably because when the anodization is performed, the treatment tank is easily heated by heat generation, and the surface of the base material in the vicinity of the treatment tank is directly and non-uniformly heated by the heat of the treatment tank, resulting in temperature spots. This tendency is considered to occur more easily as the distance between the base material and the inner surface of the treatment tank is shorter.

However, if the distance D from the central axis P of the substrate 1A to the inner surface 111a ′ of the bottom 111a is 1.25 times or more the radius (r) of the substrate 1A, the outer peripheral surface 1A ′ of the substrate 1A and the treatment A sufficient gap is formed between the bottom 111a of the tank body 111 and the inner surface 111a ′. Therefore, since the electrolyte solution 1L positioned between the base material 1A and the processing tank body 111 can sufficiently serve as a buffer material, even if the processing tank body 111 is heated by heat generated during anodization, the base material It can suppress that 1A is warmed directly by the processing tank main body 111. Therefore, temperature spots on the outer peripheral surface 1A ′ of the substrate 1A can be more effectively prevented, and pores with reduced depth variation can be formed on the outer peripheral surface of the substrate.
The distance D is preferably not more than twice the radius (r) of the substrate 1A. Even if the distance 1D exceeds twice the radius (r) of the substrate 1A, the effect of preventing temperature spots is not only limited, but also the treatment tank body 111 becomes large, so that the amount of electrolyte 1L used is increased. .

<Electrolyte supply unit>
The electrolyte supply unit 112 in the illustrated example includes a supply pipe 112a and a long discharge part 112b connected to the supply pipe 112a.
The electrolytic solution is fed into the supply pipe 112a by a pump (not shown) or the like, and the electrolytic solution filled in the supply pipe 112a is discharged from the discharge port 1121a to the discharge unit 112b.

  The discharge port 1121a may be formed continuously (slit) along the longitudinal direction of the supply pipe 112a or may be formed intermittently.

The tip of the discharge part 112b is immersed in the electrolytic solution 1L accommodated in the treatment tank body 111, and the electrolytic solution 1L is supplied to the treatment tank body 111 from the discharge port 1121b of the discharge part 112b.
The discharge port 1121b may be formed continuously along the longitudinal direction of the discharge part 112b, or may be formed intermittently.

  In order to keep the electrolyte discharged from the discharge part 112b in a uniform flow state with respect to the longitudinal direction of the main body of the processing tank 111, the structure can maintain the positive pressure in the electrolyte supply part. On the other hand, a uniform flow can be formed. In order to maintain the positive pressure, the supply port 112a may be provided so that the area of the discharge port 1121a is larger than the opening area of the discharge port 1121b of the discharge unit 112b.

  The material of the supply pipe 112a and the discharge part 112b is not particularly limited as long as it is difficult to be corroded by the electrolyte 1L, and examples thereof include stainless steel and polyvinyl chloride (PVC).

<Overflow part>
The overflow part 113 is for discharging the electrolyte 1L overflowing from the processing tank body 111 to the outside of the processing tank body 111, and on the other side surface 111c of the processing tank body 111 along the longitudinal direction of the processing tank body 111. Is provided.
The overflow portion 113 in the illustrated example is formed by making the height of one side surface 111b and the other side surface 111c of the processing tank main body 111 different, specifically, by making the other side surface 111c lower than the one side surface 111b. ing.

<Effect>
The processing tank 110 of the present invention described above supplies the electrolytic solution L from above the one side surface 111b of the processing tank main body 111 and discharges it from the upper part of the other side surface 111c. At this time, since the inner surface 111a ′ of the bottom 111a of the treatment tank body 111 is curved in an arc shape, the electrolyte 1L can move smoothly to the overflow portion 113 without stagnation.
Note that a pump (not shown) or the like is used when feeding the electrolytic solution 1L into the electrolytic solution supply unit 112, but the electrolytic solution 1L is fed out from the electrolytic solution supply unit 112 according to gravity. Therefore, the treatment tank 110 of the present invention is configured such that the electrolytic solution 1L ′ is supplied to the treatment tank 170 from the supply pipe 171 provided at the lower portion of the treatment tank 170 as in the conventional treatment tank 170 shown in FIG. Compared with the case of discharging upward (that is, against gravity), it is less affected by the pressure of the pump. Therefore, even if the base material 1A to be subjected to electrolytic treatment becomes long and the length in the longitudinal direction of the treatment tank body 111 or the electrolytic solution supply unit 112 becomes long, the pressure difference between the electrolytic solutions received from the pumps at both ends of the electrolytic solution supply unit 112 Is small.

Therefore, if the processing tank 110 of the present invention is used, the electrolytic solution 1L can be prevented from partially staying in the processing tank main body 111, so that the outer peripheral surface 1A ′ of the substrate 1A can be uniformly electrolytically processed.
In particular, when anodizing an aluminum substrate, it is important to suppress temperature fluctuations on the electrolytic solution and the surface of the substrate, but if the treatment tank 110 of the present invention is used, the electrolysis in the treatment tank body 111 is performed. Since the 1 L liquid staying portion is less likely to occur, temperature spots are less likely to occur. Therefore, variation in the depth of the pores formed on the outer peripheral surface 1A ′ of the base material 1A is suppressed.

Further, since the inner surface 111a ′ of the bottom 111a of the processing tank main body 111 is curved in an arc shape, the processing tank 110 of the present invention can be reduced in volume as compared to a rectangular parallelepiped processing tank 170 as shown in FIG. . Therefore, the usage-amount of electrolyte solution can also be suppressed.
If the treatment tank 110 of the present invention is used, the electrolyte 1L smoothly flows in the treatment tank main body 111, so there is no need to provide a member for adjusting the flow such as a perforated plate.

<Other embodiments>
The treatment tank of the present invention is not limited to the treatment tank 110 shown in FIGS. For example, the electrolytic solution supply unit 112 of the treatment tank 110 shown in FIGS. 1 and 2 may have a tubular structure as long as it can be supplied uniformly in the longitudinal direction.

1 and 2, the overflow portion 113 is formed by making the other side surface 111c of the processing tank main body 111 lower than the one side surface 111b. For example, as shown in FIG. A hole 113 ′ extending in the longitudinal direction of the processing tank body 111 may be provided on the other side surface 111 c, and this may be used as the overflow portion 113. However, in this case, it is preferable to provide the hole 113 ′ at a position higher than the base material 1 </ b> A immersed in the treatment tank body 111.
The hole 113 ′ may be continuous as shown in FIG. 3 or intermittent.
In FIG. 3, only the treatment tank main body 111, the hole 113 ′, and the base material 1A are shown, and the electrolytic solution supply unit is omitted.

[Electrolytic treatment equipment]
The electrolytic treatment apparatus of the present invention is an apparatus that performs electrolytic treatment on a cylindrical substrate in an electrolytic solution.
4 is a side sectional view showing an example of the electrolytic treatment apparatus 1 according to the present embodiment, FIG. 5A is a sectional view taken along the line II-II-II ′ in FIG. 4, and FIG. 5B is an electrolytic treatment apparatus shown in FIG. It is a perspective view of the processing tank 110 and the electrode plate 120 with which it is equipped.

  The electrolytic treatment apparatus 11 in this example includes a treatment tank 110 filled with an electrolytic solution L, an electrode plate 120 disposed so as to sandwich a substrate 1A immersed in the treatment tank body 111 of the treatment tank 110, a base plate Rotating means 130 for rotating the substrate 1A around the central axis of the material 1A, a processing tank 110, an outer tank 140 for receiving the electrolytic solution 1L overflowing from the processing tank 110, and the electrolytic solution 1L The storage tank 150 once stored, the flow-down flow path 141 for flowing down the electrolytic solution 1L received in the outer tank 140 to the storage tank 150, and the electrolytic solution 1L in the storage tank 150 are returned to the electrolytic solution supply unit 112 of the processing tank 110. A return flow path 151 and a pump 152 provided in the middle of the return flow path 151 are provided.

Hereinafter, the case where the electrolytic processing apparatus 11 of the present invention is used as an anodizing apparatus will be specifically described.
The electrolytic treatment apparatus 11 includes the above-described treatment tank 110 of the present invention. As shown in FIGS. 5A and 5B, the electrode plate 120 has an inner surface 111 a of the bottom 111 a of the treatment tank body 111 of the treatment tank 110. 'It has a curved shape along the shape. Since the electrode plate 120 has a curved shape, the flow of the electrolytic solution 1L is less likely to be hindered, so that the electrolytic solution 1L can move to the overflow portion 113 more smoothly without stagnation.
In FIG. 5A, the outer tub 140 is omitted. Moreover, in FIG. 5B, only the processing tank main body 111 and the overflow part 113 of the processing tank 110, the electrode plate 120, and the base material 1A are shown, and the other structural members of the electrolytic processing apparatus 11 are omitted.

The end surfaces 111d and 111e of the processing tank main body 111 are U-shaped as shown in FIG. 5B. Therefore, a sealing material (not shown) matching the shape is attached to the end surfaces 111d and 111e so that the electrolyte does not leak from the end surfaces 111d and 111e.
Further, as shown in FIGS. 4 and 5A, a support shaft 131 that supports the substrate 1A along the axial direction in the horizontal direction is provided on the lower side of the end faces 111d and 111e as the rotating means 130. .
As shown in FIG. 4 and FIG. 5A, a pair of support shafts 131 are provided in parallel with the end surfaces 111 d and 111 e of the processing tank main body 111, and each support shaft 131 has the end surfaces 111 d and 111 e of the processing tank main body 111. It penetrates and is supported so that it can rotate with respect to end surfaces 111d and 111e of these processing tank main parts 111.

A cylindrical elastic member 132 made of a resin material is inserted through the end of each support shaft 131 in the treatment tank main body 111, and the base material 1 </ b> A has its outer peripheral surfaces at both ends on each elastic member 132. It is supported on the support shaft 131 so as to be placed. Each support shaft 131 is connected to a rotation drive unit (not shown) such as a motor, and the support shaft 131 is rotated in the same direction by the rotation drive unit, so that the electrolytic processing apparatus 11 has an elastic member. The base material 1A in contact with 132 rotates.
In particular, as shown in FIG. 5A, the rotating means 130 has a base in a direction opposite to the direction in which the electrolyte 1L supplied from the electrolyte supply part 112 of the treatment tank 110 to the treatment tank body 111 flows to the overflow part 113. It is preferable to rotate the material 1A. Since the flowing direction of the electrolytic solution 1L and the rotation direction of the base material 1A are reversed, the flow of the electrolytic solution 1L near the surface with respect to the base material 1A becomes relatively fast, and the heat generated from the base material 1A during the electrolytic treatment Can be moved efficiently. When the flowing direction of the electrolytic solution 1L and the rotation direction of the base material 1A are the same, the flow of the electrolytic solution 1L near the surface of the base material 1A is relatively slow. This leads to an increase in the temperature of the electrolytic solution in the entire tank 110.

  Above the support shaft 131, a current-carrying shaft 133 extending in the horizontal direction is provided through the sealing material 114 attached to the end surfaces 111d and 111e. 140 also penetrates and is exposed to the outside. The energization shaft 133 is made of a conductive material, and is rotatably supported by the sealing materials attached to the end faces 111d and 111e. The energization shaft 133 does not have to be made of a conductive material as a whole, and it is sufficient that a current can be applied to the substrate 110 via an energization member 134 described later. Specifically, the outside of the current-carrying shaft 133 may be coated with an insulating material, and a portion having contact with the sealing material attached to the end faces 111d and 111e is coated with excellent wear resistance. It doesn't matter.

  A disc-shaped energizing member 134 is integrally provided at the end of each energizing shaft 133 in the processing tank body 111. The energizing member 134 is in surface contact with both end faces of the hollow cylindrical base material 1A. Here, a power source 121 is electrically connected to the electrode plate 120 disposed so as to sandwich the substrate 1A and the shaft 133 for energization, so that a current can be applied.

  The energizing member 134 is installed so that it can be moved forward and backward by a drive unit (not shown) that moves forward and backward such as an air cylinder in the axial direction of the energizing shaft 133 or the substrate 1A. After the base material 1A is installed on the support shaft 131, the energization member 134 is brought into contact with both end surfaces of the base material 1A from both sides in the axial direction of the base material 1A. In the example shown in FIG. 4, the current-carrying members 134 are provided on both end surfaces of the substrate 1A. However, the current-carrying members 134 may be provided only on one end surface of the substrate 1A and the other may be used as a pressing member. Further, the energizing member 134 does not have to be in contact with the base material 1A strictly at the end surface of the base material 1A, and may be configured to contact the base material 1A at other positions such as the inner peripheral surface of the base material 1A. .

  Since the energizing shaft 133 moves forward and backward through the processing tank 110 and the outer tank 140, the energizing shaft 133 can be rotated and moved axially between the energizing shaft 133 and the processing tank 110 and the outer tank 140. A sliding bearing 135 is provided for support.

The inner diameter side corners of both end portions of the base material 1A in the illustrated example are chamfered, and the tapered surface 1a is formed on a part of both end surfaces of the base material 1A, while the outer diameter side corner portions of the energizing member 134 are chamfered. In addition, it is preferable that a tapered surface 134a that is in surface contact with the tapered surface 1a of the substrate 1A is formed, and the inclination of both is set to the same gradient. When the taper surface 1a of the substrate 1A and the taper surface 134a of the energization member 134 are brought into surface contact with each other, both can be brought into electrical close contact with each other, and the substrate 1A or the energization member 134 side is rotated. The rotation can be transmitted by the contacted resistance and can be rotated in synchronization.
With such a structure, the contact area is large, and the effects of slipping and wear when rotating are reduced, so that stable current supply is possible.

  In addition, since the energizing shaft 133 to which the energizing member 134 is connected rotates in synchronization with the base material 1A, the energizing shaft 133 and the power source 121 are electrically contacted (connected) with a connector (not shown) that can be rotationally fed. Has been. There are a rotary connector, a slip ring, and the like as a connector capable of rotating power supply. However, the rotary connector is preferable because of good current stability during rotation. Further, the energization member 134 may be energized by bringing it into surface contact with only one end surface of the substrate 1A.

The outer tank 140 accommodates the processing tank 110, and as shown in FIGS. 2 and 4, the electrolyte 1 L in the processing tank 110 is discharged from the overflow portion 113 and flows to the outer tank 140. The electrolytic solution 1L received in the outer tank 140 flows down to the storage tank 150 through the flow-down channel 141.
The storage tank 150 is provided with temperature control means 153 for the electrolyte 1L. The electrolyte 1L adjusted in temperature in the storage tank 150 passes through the return flow channel 151 by the pump 152 and is supplied to the electrolyte supply unit 112 of the processing tank 110. To the processing tank main body 111. In addition, as the temperature control means 153 provided in the storage tank 150, a heat exchanger, an electric heater, etc. which used water, oil, etc. as the heat medium are mentioned.

<Effect>
The electrolytic treatment apparatus 11 of the present invention described above includes the treatment tank 110 of the present invention. Therefore, the electrolytic solution 1L is less likely to stay in the processing tank main body 111 of the processing tank 110.
Note that a pump (not shown) or the like is used when feeding the electrolytic solution 1L into the electrolytic solution supply unit 112, but the electrolytic solution 1L is fed out from the electrolytic solution supply unit 112 according to gravity. Accordingly, the treatment tank 110 of the present invention is configured such that the electrolytic solution 1L ′ is treated by the pump 173 from the supply pipe 171 provided at the lower part of the treatment tank 170 as in the conventional treatment tank 170 shown in FIGS. 7A and 7B. Compared with the case where the liquid is discharged above 170 (that is, against gravity), it is less susceptible to the pressure of the pump. Therefore, even if the base material 1A to be subjected to electrolytic treatment becomes long and the length in the longitudinal direction of the treatment tank body 111 or the electrolytic solution supply unit 112 becomes long, the pressure difference between the electrolytic solutions received from the pumps at both ends of the electrolytic solution supply unit 112 Is small.

Therefore, with the electrolytic treatment apparatus 11 of the present invention, it is possible to prevent the electrolytic solution L from partially staying in the treatment tank main body 111 of the treatment tank 110, so that the outer peripheral surface of the substrate 1A can be subjected to uniform electrolytic treatment. .
In particular, when anodizing an aluminum substrate, it is important to suppress temperature fluctuations on the electrolyte solution and the surface of the substrate, but in the electrolytic treatment apparatus 11 of the present invention, Since the retention part of 1 L of electrolyte solution is hard to generate | occur | produce, it is hard to produce a temperature spot. Therefore, variation in the depth of the pores formed on the outer peripheral surface of the substrate 1A is suppressed.

Moreover, since the bottom part of the processing tank main body 111 is curving in circular arc shape, the electrolytic processing apparatus 11 of this invention can reduce a volume compared with the rectangular parallelepiped processing tank 170 as shown to FIG. 7A, 7B. Therefore, the usage-amount of electrolyte solution can also be suppressed.
In the electrolytic treatment apparatus 11 of the present invention, the electrolytic solution 1L smoothly flows in the treatment tank main body 111, so that it is not necessary to provide a member for adjusting the flow such as a perforated plate in the treatment tank 110.

<Other embodiments>
The electrolytic treatment apparatus of the present invention is not limited to the electrolytic treatment apparatus 11 shown in FIGS. For example, the electrolytic treatment apparatus 11 shown in FIGS. 4, 5A, and 5B includes the support shaft 131 as the rotating means 130 for rotating the base material 1A, but the energizing shaft 133 connected to the energizing member 134 may be used as the rotating means. Good. In that case, the support shaft 131 does not need to be connected to the rotation drive unit described above, and may have a structure that can rotate in synchronization with the base material 1A.

Further, as described above, the energization member 134 does not have to be made of a conductive material as a whole, and it is sufficient that the base member A and the energization shaft 133 can be electrically connected. . Specifically, the configuration may be such that a portion other than the portion that electrically connects the tapered surface 134a of the energizing member 134 and the energizing shaft 133 is coated with an insulating material. As for the tapered portion 134a, as long as the base material 1A and the energizing member 134 can be stably electrically connected, a part of the surface thereof may be made of a material other than the conductive material.
In the embodiment described above, the inner diameter side corners of both ends of the substrate 1A are chamfered to form the tapered surface 1a, and the outer diameter side corner of the energizing member 134 is chamfered to form the tapered surface 134a. However, the outer diameter side corners of both ends of the substrate 1A may be chamfered, and the inner diameter side corners of the energizing member 134 may be chamfered to form a tapered surface.
Furthermore, the tapered surfaces 134a formed on the respective energizing members 134 need not have the same shape, and may have different shapes. In addition, the tapered surface 134 a may be configured to be formed on at least one of the energizing members 134.

<Application>
The electrolytic treatment apparatus of the present invention can be used as an apparatus for electrolytically treating the surface of a substrate such as chemical conversion treatment such as anodization or coating treatment such as plating. In particular, an anodization treatment for anodizing an aluminum substrate. It is suitable as a device.
Hereinafter, an example of a method for producing a mold by anodizing an aluminum substrate using the electrolytic treatment apparatus of the present invention will be described.

First, as shown in FIGS. 4, 5A, and 5B, an aluminum base material is installed on the support shaft 131 as the base material 1A. At this time, as shown in FIG. 2, the base 1 </ b> A is supported on the support shaft 131 so that a gap S is formed between the outer peripheral surface 1 </ b> A ′ of the base 1 </ b> A and the inner surface 111 a ′ of the bottom 111 a of the treatment tank body 111. Install on top. Specifically, the substrate 1A is installed so that the distance D from the central axis P of the substrate 1A to the inner surface 111a ′ of the bottom 111a is 1.5 times the radius (r) of the substrate 1A. Is preferred.
When the shape of the inner surface 111a ′ of the bottom 111a is a semicircular shape, it is preferable to install the base 1A so that the center on the diameter of the semicircle and the central axis P of the base 1A overlap.

Thereafter, the energizing shaft 133 is moved simultaneously from both sides by using the drive unit (not shown) that moves back and forth to bring the energizing member 134 into contact with the base material 1A. The electrolytic solution 1L may be supplied to the treatment tank main body 111 after the substrate 1A is brought into contact with the conductive member 134, or the conductive member 134 is used in a state where the electrolytic solution 1L is contained in the treatment tank main body 111. You may make it contact the material A. The rotation drive unit (not shown) is driven in a state where the energization member 134 and the substrate 1A are in contact with each other, and the support shaft 131 is rotated to rotate the substrate 1A.
While rotating the substrate 1A, a voltage is applied to the substrate 1A serving as the anode and the electrode plate 120 serving as the cathode through the energizing shaft 133 and the energizing member 134, thereby anodizing the substrate 1A.

  When the current-carrying member 134 is brought into contact with the substrate 1A, the pressing pressure for contact is preferably 0.2 MPa or more. Slip occurs on the tapered surface that is contacted during rotation, and there is an influence on stable current supply due to insufficient contact. However, if the pressing pressure is too large, it may cause distortion of the base material 1A, or the rotation cannot be transmitted and may stop, so it is necessary to make an appropriate selection depending on the workpiece shape and the specifications of the rotation drive source.

While the base material 1A is anodized, the same amount of electrolytic solution is supplied to the processing tank body 111 while discharging a part of the electrolytic solution 1L from the processing tank body 111 while rotating the base material 1A. Specifically, the electrolytic solution 1L is discharged from the processing tank main body 111 to the outer tank 140 in the overflow portion 113 of the processing tank 110, and the discharged electrolytic solution L is caused to flow down from the outer tank 140 to the storage tank 150. After the temperature of the storage tank 150 is adjusted, the electrolyte solution 1L is returned to the electrolyte solution supply unit 112 provided above one side surface along the longitudinal direction of the treatment tank body 111, and this electrolyte solution supply It supplies from the part 112 in the processing tank main body 111. FIG.
At this time, since the inner surface 111a ′ of the bottom 111a of the processing tank body 111 is curved in an arc shape, a substantially uniform flow of the electrolyte 1L is formed, and the electrolyte 1L does not stay and smoothly flows into the overflow portion 113. And move.
In addition, it is preferable to rotate the base material 1A in the direction opposite to the direction in which the electrolysis solution 1L flows.

  The supply amount of the electrolytic solution 1L from the electrolytic solution supply unit 112 to the processing tank main body 111 is preferably such that the number of circulations is at least once every three minutes with respect to the volume of the processing tank main body 111. By doing so, the processing tank main body 111 can perform frequent liquid renewal, and can efficiently remove heat and remove generated hydrogen.

  The peripheral speed of the substrate 1A is preferably 0.1 m / min or more. If the peripheral speed of the base material 1A is 0.1 m / min or more, unevenness in the concentration and temperature of the electrolyte 1L around the base material 1A can be more effectively suppressed. From the viewpoint of the capability of the driving device, the peripheral speed of the substrate 1A is preferably 25.1 m / min or less.

When the base material 1A is anodized as described above, an oxide film 162 having pores 161 is formed as shown in FIG. 6B from the state shown in FIG.
The purity of aluminum used as the substrate 1A is preferably 99% or more, more preferably 99.5% or more, and further 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 is formed, or the regularity of the pores 161 formed by anodization is lowered. Examples of the electrolytic solution include oxalic acid and sulfuric 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.
In order to obtain anodized alumina having fine pores with high regularity at a predetermined cycle, it is necessary to apply a conversion voltage suitable for the predetermined cycle. For example, in the case of anodized alumina having a period of 100 nm, the formation voltage is preferably 30 to 60V. When the formation voltage suitable for the predetermined cycle is not applied, the regularity tends to be lowered.
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.
In order to obtain anodized alumina having fine pores with high regularity at a predetermined cycle, it is necessary to apply a conversion voltage suitable for the predetermined cycle. For example, in the case of anodized alumina having a period of 63 nm, the formation voltage is preferably 25 to 30V. When the formation voltage suitable for the predetermined cycle is not applied, the regularity tends to be lowered.
The temperature of the electrolytic solution is preferably 30 ° C. or lower, and more preferably 20 ° C. or lower. When the temperature of the electrolytic solution exceeds 30 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.

  And after forming the oxide film 162 which has the pore 161 as shown in FIG.6 (b), the anodic oxidation alumina which has a several pore is carried out by anodizing using the electrolytic treatment apparatus 11 of this invention. A roll-shaped mold is manufactured by repeating the step of forming (anodizing treatment) and the step of expanding the pore diameter (pore diameter expanding treatment).

When repeating the anodizing process and the pore diameter expanding process, first, as shown in FIG. 6C, the oxide film 162 is once removed. Here, the regularity of the pores can be improved by using this as the pore generation point 163 for anodization.
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.

Then, when the base material 1A from which the oxide film has been removed is anodized again, an oxide film 162 having columnar pores 161 is formed as shown in FIG. 6 (d).
Anodization is performed using the above-described electrolytic treatment apparatus 11. The conditions may be the same as those when the oxide film 162 shown in FIG. 6B is formed. Deeper pores can be obtained as the anodic oxidation time is lengthened.

Then, as shown in FIG. 6 (e), a process for enlarging the diameter of the pore 161 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.

Then, when anodized again, as shown in FIG. 6 (f), cylindrical pores 161 having a small diameter and extending downward from the bottom of the cylindrical pores 161 are further formed.
Anodization is performed using the above-described electrolytic treatment apparatus 11. The conditions may be the same conditions as described above. Deeper pores can be obtained as the anodic oxidation time is lengthened.

Then, when the pore diameter enlargement process and the anodizing process as described above are repeated, the anodized alumina having the pores 161 whose diameter continuously decreases in the depth direction from the opening (the aluminum porous body). A roll-shaped mold 160 as shown in FIG. 6G on which an oxide film (alumite) is formed is obtained. It is preferable that the last end is a pore diameter expansion process.
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 or less, the diameter of the pores decreases discontinuously, and thus the effect of reducing the reflectance of the optical film produced by transferring such pores is insufficient.

  Examples of the shape of the pore 161 include a substantially conical shape and a pyramid shape. The average period between the pores 161 is not more than the wavelength of visible light, that is, not more than 400 nm. The average period between the pores 161 is preferably 25 nm or more.

  The aspect ratio (depth of the pore / width of the opening of the pore) of the pore 161 is preferably 1.5 or more, and more preferably 2.0 or more.

  The depth of the pore 161 is preferably 100 to 500 nm, and more preferably 150 to 400 nm. The surface of the optical film manufactured by transferring the pores 161 as shown in FIG. 6 has a so-called moth-eye structure.

  In the electrolytic treatment apparatus 11 according to the present embodiment described above, when the roll-shaped aluminum base material is anodized in the electrolytic solution 1L of the treatment tank body 111 as the base material 1A, the electrolytic solution 1L is treated with the treatment tank body 111. Is supplied from above one side and discharged from the upper part of the other side. At this time, since the inner surface of the bottom of the treatment tank main body 111 is curved in an arc shape, the electrolytic solution 1L can smoothly move to the overflow portion without stagnation. Accordingly, since temperature fluctuations on the electrolyte solution and the substrate surface are suppressed, anodization is performed almost uniformly over the entire outer peripheral surface of the substrate 1A, and as a result, a roll shape in which variation in the depth of the pores is suppressed. Can be manufactured.

In particular, if the base material 1A is rotated with the central axis of the base material 1A as a rotation axis, the unevenness of the concentration and temperature of the electrolyte around the base material can be suppressed, so that the base material 1A can be anodized more uniformly. It is possible to manufacture a roll-shaped mold in which the variation in the depth of the pores is further suppressed.
Furthermore, if the base material 1A is installed in the processing tank body 111 such that a gap of a specific size is formed between the outer peripheral surface of the base material 1A and the bottom inner surface of the processing tank body, The electrolyte solution 1L located between the processing tank main bodies 111 can fully fulfill the role of a buffer material. As a result, even if the treatment tank main body 111 is heated by the heat generated during the anodic oxidation, the substrate 1A can be prevented from being directly warmed by the treatment tank main body 111. Accordingly, temperature variations on the outer peripheral surface of the base material can be more effectively prevented, and a roll-shaped mold in which variation in depth is further suppressed can be manufactured.

  The outer peripheral surface of the roll-shaped mold 160 may be treated with a release agent so that separation from the transfer target is facilitated. Examples of the release agent include silicone resins, fluororesins, fluorine compounds, and the like, and fluorine compounds having a hydrolyzable silyl group are preferable in terms of excellent releasability and excellent adhesion to the roll mold 160. . Commercially available fluorine compounds include fluoroalkylsilanes and “OPTOOL” series manufactured by Daikin Industries.

  FIG. 10 is a side sectional view of the anodizing apparatus 210 according to this embodiment. 11 is a cross-sectional view taken along line 2A-2A in FIG.

  As shown in FIG. 10, an anodizing apparatus 210 includes an anodizing tank 211 filled with an electrolytic solution, and an outer tank 212 that surrounds the anodizing tank 211 and receives the electrolyte that overflows from the anodizing tank 211. And a storage tank 225 that temporarily stores the electrolytic solution, and a flow-down channel 229 that causes the electrolytic solution received in the outer tank 212 to flow down to the storage tank 225. In the anodizing tank 211, a roll-shaped aluminum base material 220 is accommodated and immersed in an electrolytic solution.

  A supply port 218 is formed at the bottom of the anodizing tank 211 below the aluminum base material 220, and the anodizing apparatus 210 further returns a return channel 228 for returning the electrolyte in the storage tank 225 to the anodized layer 211. A pump 227 provided in the middle of the return flow path 228, and a rectifying plate 217 for adjusting the flow of the electrolyte discharged from the supply port 218.

  The storage tank 225 is provided with temperature control means 226 for the electrolytic solution, and the electrolytic solution adjusted in the storage tank 225 forms a flow toward the anodizing tank 211 through the return flow path 228 by the pump 227. At the same time, it is discharged from the supply port 218 with momentum. Thereby, a flow of the electrolyte rising from the bottom to the top of the anodizing tank 211 is formed. In addition, as the temperature control means 226 provided in the storage tank 225, the heat exchanger which used water, oil, etc. as the heat medium, an electric heater, etc. are mentioned.

  The rectifying plate 217 is a plate-like member having a plurality of through holes that adjust the flow of the electrolytic solution so that the electrolytic solution discharged from the supply port 218 rises almost uniformly from the entire bottom of the anodizing tank 211. is there. The current plate 217 is disposed between the aluminum base material 220 and the supply port 218 so that the surface (surface direction) is substantially horizontal. Further, the two cathode plates 221 shown in FIG. 11 are arranged in parallel to the central axis of the aluminum base material 220 and are spaced from the aluminum base material 220 so as to sandwich the aluminum base material 220 from the horizontal direction. The metal plates are arranged opposite to each other.

  Referring to FIG. 10, a support shaft 215 that supports the aluminum base material 220 along the axial direction in the horizontal direction is provided on the lower side of the side walls 211 </ b> A and 211 </ b> B that face each other in the anodizing tank 211. As shown in FIG. 11, a pair of support shafts 215 are provided in parallel in the horizontal direction on the side walls 211A and 211B, and each support shaft 215 penetrates the side walls 211A and 211B and is rotatable with respect to the side walls 211A and 211B. It is supported by.

  A cylindrical elastic member 216 made of a resin material such as an O-ring is inserted through the end of each support shaft 215 in the anodizing tank 211, and the aluminum base material 220 has outer peripheral surfaces at both ends thereof. It is supported on the support shaft 215 so as to be placed on the elastic member 216. Each support shaft 215 is connected to a rotation drive unit (not shown) such as a motor, for example, and the rotation drive unit rotates each support shaft 215 in the same direction, so that the anodizing apparatus 210 is elastic. The aluminum substrate 220 in contact with the member 216 is rotated.

  In the side walls 211A and 211B, an energizing shaft 214 extending in the axial direction in the horizontal direction is provided above the support shaft 215, and the energizing shaft 214 also passes through the outer tub 212 and is exposed to the outside. . The energization shaft 214 is made of a conductive material and is rotatably supported on the side walls 211A and 211B. The energization shaft 214 does not have to be made entirely of a conductive material, and it is sufficient that a current can be applied to the aluminum base member 220 via an energization member 213 described later. Specifically, the outside of the energizing shaft 214 may be coated with an insulating material, and a portion having contact with the side walls 211A and 211B may be coated with excellent wear resistance.

  A disc-shaped energizing member 213 is integrally provided at the end of each energizing shaft 214 in the anodizing tank 211. The current-carrying member 213 is in surface contact with both end faces of a hollow cylindrical aluminum base material 220 that serves as an anode. Here, a power source 224 is electrically connected to the two cathode plates 221 disposed opposite to each other with the aluminum base material 220 interposed therebetween and the energizing shaft 214 so that a current can be applied.

  The energizing member 213 is installed so that it can be moved forward and backward by a drive unit (not shown) that moves forward and backward such as an air cylinder in the axial direction of the energizing shaft 214 or the aluminum base material 220. After the aluminum base material 220 is installed on the support shaft 215, energization can be performed by bringing the energization member 213 into contact with both end faces of the aluminum base material 220 from both sides in the axial direction of the aluminum base material 220. In the example shown in FIG. 10, the current-carrying members 213 are provided on both end faces of the aluminum base material 220. However, the current-carrying members 213 may be provided only on one end face of the aluminum base material 220, and the other may be used as a pressing member. . In addition, the energizing member 213 does not need to be in contact with the aluminum base material strictly at the end surface of the aluminum base material 220, and is configured to contact the aluminum base material 220 at other positions such as the inner peripheral surface of the aluminum base material 220. It doesn't matter.

  Since the energizing shaft 214 moves forward and backward through the anodizing tank 211 and the outer tank 212, the energizing shaft 214 is rotatable and axially between the energizing shaft 214 and the anodizing tank 211 and the outer tank 212. A sliding bearing 219 that is movably supported is provided.

The inner diameter side corners of both ends of the aluminum base material 220 are chamfered, and a tapered surface 220A is formed on a part of both end faces of the aluminum base material 220, while the outer diameter side corners of the energizing member 213 are chamfered. In addition, it is preferable that a tapered surface 213A that is in surface contact with the tapered surface 220A is formed, and the inclination of both is set to the same gradient. By bringing the taper surface 220A of the aluminum base material 220 into contact with the taper surface 213A of the energization member 213, both can be brought into electrical close contact with each other, and the aluminum base material 220 or the energization member 213 side is rotated. In some cases, the rotation can be transmitted by the contacted resistance, and can be rotated in synchronization.
For this reason, since the contact area is large and there is no influence of sliding or wear when rotating, stable current supply is possible.

  About the taper angle of the aluminum base material 220 and the electricity supply member 213, 15-45 degrees are preferable with respect to an axial direction (0 degree), and 22.5-37.5 degrees are more preferable. When the taper angle is small, the resistance of the contact surface may be greatly restricted when the taper is brought into contact, and the aluminum base material 220 may be deformed. Also, if the taper angle is large, slippage tends to occur on the contact surface when rotating by contact.

  The surface roughness of the taper surfaces 220A and 213A of the aluminum base member 220 and the energizing member 213 is preferably a finished surface of Ra 3.2 or less, and more preferably a precise finished surface of Ra 1.6 or less. When the surface roughness of the taper surface is rough, when the aluminum base material 220 and the energizing member 213 are brought into contact with each other, floating occurs at a part of the contact portion, making it impossible to make a close contact, or the taper of the energizing member 213. This is because anodized alumina is formed at the location where the surface 213A is floating, which affects stable current supply.

  Further, since the energizing shaft 214 connected to the energizing member 213 rotates in synchronization with the aluminum base material 220, the energizing shaft 214 and the power source 224 are electrically contacted (connected) by a connector (not shown) capable of rotational power feeding. ) There are a rotary connector, a slip ring, and the like as a connector capable of rotating power supply. The rotary connector is preferable because it has good current stability during rotation. Alternatively, the energization member 213 may be brought into surface contact with only one end surface of the aluminum base material 220 for energization.

As a means for rotating the energizing member 213 and the aluminum base material 220 in synchronization, the energizing member 214 connected to the rotating member 213 may be a rotational drive source instead of the support shaft 215. In that case, the support shaft 215 is not connected to the rotation driving unit described above, and may be configured to be able to rotate in synchronization with the aluminum base material 220. In this embodiment, the inner diameter side corners of both ends of the aluminum base material 220 are chamfered to form a tapered surface 220A, and the outer diameter side corners of the energizing member 213 are chamfered to form the tapered surface 213A. However, the outer diameter side corners of both ends of the aluminum base material 220 may be chamfered, and the inner diameter side corners of the energization member 213 may be chamfered to form a tapered surface. In addition, the energization member 213 is not necessarily made of a conductive material as described above, but may be configured to be able to electrically connect the aluminum base material 220 and the energization shaft 214. . Specifically, the configuration may be such that a portion other than the portion that electrically connects the taper surface 220A of the energization member and the energization shaft 214 is coated with an insulating material. As for the tapered portion 213A, as long as the aluminum base member 220 and the energizing member 213 can be electrically connected stably, a part of the surface thereof may be made of a material other than the conductive material.
Further, the tapered surfaces 213A formed on the respective energizing members 213 do not need to have the same shape, and may have different shapes. Further, the tapered surface 213A may be formed by a configuration formed on at least one of the energization members 213.

Anodization of the aluminum substrate 220 using this anodizing apparatus 210 is performed as follows.
The aluminum base material 220 is installed on the support shaft 215. Thereafter, the energizing shaft 214 is moved simultaneously from both sides by using the drive unit (not shown) that moves back and forth to bring the energizing member 213 into contact with the aluminum base material 220. Note that the electrolytic solution may be added to the anodized layer 211 after the aluminum member 220 is brought into contact with the energizing member 213, and the energizing member 213 is placed in the aluminum substrate 220 in a state where the electrolytic solution is in the anodized layer 211. You may make it contact. The rotation drive unit (not shown) is driven in a state where the energization member 213 and the aluminum base material 220 are in contact with each other, and the support shaft 215 is rotated to rotate the aluminum base material 220.
A voltage is applied to the aluminum substrate 220 and the cathode plate 221 through the energizing shaft 214 and the energizing member 213 while rotating the aluminum substrate 220, and the aluminum substrate 220 is anodized.

  When the current-carrying member 213 is brought into contact with the aluminum base material 220, the pressing pressure for contact is preferably 0.2 MPa or more. Slip occurs on the tapered surface that is contacted during rotation, and the contact with the taper surface is not close enough, which affects stable current supply. However, if the pressing pressure is too large, it may cause distortion of the aluminum base material 220, or the rotation cannot be transmitted and may stop, so it is necessary to make an appropriate selection depending on the workpiece shape and the specification of the rotation drive source.

While the aluminum base material 220 is anodized, the same amount of electrolytic solution is supplied to the anodizing tank 211 while rotating the aluminum base material 220 and discharging a part of the electrolytic solution from the anodizing tank 211. Specifically, the electrolytic solution is overflowed from the anodizing tank 211, the overflowed electrolytic solution is caused to flow into the storage tank 225, and the temperature of the electrolytic solution is adjusted in the storage tank 225. It returns to the inside of the anodic oxidation tank 211 from the supply port 218 provided on the lower side.
At this time, the pump 227 generates momentum from the supply port 218 to discharge the electrolyte, and the electrolyte discharged from the supply port 218 by the rectifying plate 217 rises almost uniformly from the entire bottom of the anodizing tank 211. By adjusting the flow of the electrolytic solution, a substantially uniform flow of the electrolytic solution rising from the bottom to the top of the anodizing tank 211 is formed.

  The supply amount of the electrolyte solution to the anodizing tank 211 (the discharge amount of the electrolyte solution from the supply port 218) is preferably 1 or more times per 3 minutes with respect to the volume of the anodizing tank 211. By doing so, the anodic oxidation tank 211 can be frequently renewed, and heat can be removed and generated hydrogen can be removed efficiently. Specifically, when the tank capacity is 107 L, the supply flow rate is preferably about 36 L / min.

  The peripheral speed of the aluminum base material 220 is preferably 0.1 m / min or more. If the peripheral speed of the aluminum base material 220 is 0.1 m / min or more, unevenness in the concentration and temperature of the electrolyte solution around the aluminum base material 220 can be sufficiently suppressed. From the viewpoint of the capability of the driving device, the peripheral speed of the aluminum base material 220 is preferably 25.1 m / min or less.

  The step of forming the oxide film having a plurality of pores by anodizing the aluminum base material 220 as described above is performed by anodizing the base material 1A as shown in FIG. It is performed in the same manner as the forming step.

  In the anodizing apparatus 210 according to the present embodiment described above, when the roll-shaped aluminum base material 220 is anodized in the electrolytic solution in the anodizing tank 211, the central axis of the aluminum base material 220 is used as the rotation axis. Since the aluminum base material 220 is rotated, unevenness in the concentration and temperature of the electrolyte around the aluminum base material 220 is suppressed, and anodization is performed almost uniformly over the entire outer peripheral surface of the aluminum base material 220. As a result Thus, it is possible to manufacture a roll mold in which variation in the depth of the pores is suppressed.

  Since the aluminum base material 220 and the energization member 213 are in surface contact with each other while the aluminum base material 220 and the energization member 213 are rotated in synchronization with each other, power is supplied to the aluminum base material 220, so that the contact area is large. In addition, since there is no influence of slippage and wear when rotating, it is possible to suppress poor energization and further improve the yield of the roll mold.

A method for producing an imprint roll mold (also simply referred to as a roll mold in this specification) according to one embodiment of the present invention has a plurality of pores on the outer peripheral surface of a roll-shaped aluminum substrate. A method for producing a roll-shaped mold on which anodized alumina (aluminum porous oxide film (alumite)) is formed, wherein an aluminum substrate is anodized when an aluminum substrate is anodized in an electrolytic solution of an anodizing tank. The aluminum substrate is rotated with the central axis of the material as the rotation axis.
Hereinafter, an example of the manufacturing method of a roll-shaped mold is demonstrated in detail.

As a manufacturing method of a roll-shaped mold, the method which has the following process (a)-(f) is mentioned, for example.
(A) A step of forming an oxide film on the outer peripheral surface by anodizing a hollow cylindrical aluminum base material in an electrolytic solution under a constant voltage.
(B) A step of removing the oxide film and forming pore generation points for anodic oxidation.
(C) A step of anodizing again in the electrolytic solution after the step (b) to form an oxide film having pores at the pore generation points.
(D) A step of enlarging the diameter of the pores after the step (c).
(E) A step of anodizing again in the electrolytic solution after the step (d).
(F) A step of repeatedly performing the step (d) and the step (e).

(Process (a))
FIG. 15 is a cross-sectional view showing an example of an anodizing apparatus.
The anodizing apparatus 310 has an anodizing tank 312 filled with an electrolytic solution, and a flange 314 for covering the upper part of the anodizing tank 312 and receiving the electrolytic solution overflowing from the anodizing tank 312 at the periphery. An upper cover 316, a storage tank 318 that temporarily stores the electrolytic solution, a flow-down flow path 320 that causes the electrolytic solution received by the collar 314 to flow down to the storage tank 318, and an electrolytic solution in the storage tank 318 are supplied from the aluminum base material 330. The return flow path 324 for returning to the supply port 322 formed near the bottom of the anodizing tank 312 on the lower side, the pump 326 provided in the middle of the return flow path 324, and the electrolysis discharged from the supply port 322 A rectifying plate 328 that adjusts the flow of the liquid, an axial center 334 that is inserted into a hollow cylindrical aluminum base material 330 that serves as an anode, and the central axis 332 is held horizontally; A driving device (not shown) for rotating the shaft center 334 and the aluminum base material 330 with the central shaft 332 (that is, the central axis of the aluminum base material 330) as a rotation axis, and two sheets disposed opposite to each other with the aluminum base material 330 interposed therebetween It has a cathode plate 336, a power source 338 electrically connected to the central axis 332 of the shaft center 334 and the two cathode plates 336, and temperature adjusting means 340 for adjusting the temperature of the electrolyte in the storage tank 318.

The pump 326 forms a flow of the electrolytic solution from the storage tank 318 through the return flow path 324 toward the anodizing tank 312 and discharges the electrolytic solution from the supply port 322 to discharge the electrolytic solution. The flow of the electrolyte rising from the bottom to the top is formed.
The rectifying plate 328 is a plate-like member having a plurality of through holes that adjust the flow of the electrolyte so that the electrolyte discharged from the supply port 322 rises almost uniformly from the entire bottom of the anodizing tank 312. And disposed between the aluminum base 330 and the supply port 322 so that the surface is substantially horizontal.

The drive device (not shown) is a ring-shaped chain or a motor connected to the central shaft 332 of the shaft center 334 by a member (not shown) such as a gear.
The two cathode plates 336 are arranged in parallel to the central axis of the aluminum base 330 and are opposed to each other with a gap from the aluminum base 330 so as to sandwich the aluminum base 330 from the horizontal direction. It is a board.
Examples of the temperature control means 340 include a heat exchanger using water, oil, or the like as a heat medium, an electric heater, or the like.

Anodization of the aluminum substrate 330 using the anodizing apparatus 310 is performed as follows, for example.
In a state where the aluminum base material 330 is immersed in the electrolytic solution of the anodizing tank 312, a driving device (not shown) is driven, and the central axis 332 of the axis 334 (that is, the central axis of the aluminum base material 330) is the rotation axis. The shaft center 334 and the aluminum base material 330 are rotated as follows.
While rotating the aluminum base material 330, a voltage is applied between the aluminum base material 330 and the cathode plate 336 to perform anodization of the aluminum base material 330.

  While the aluminum substrate 330 is anodized, the same amount of electrolyte is supplied to the anodizing bath 312 while rotating the aluminum substrate 330 and discharging a part of the electrolyte from the anodizing bath 312. Specifically, the electrolytic solution is overflowed from the anodizing tank 312, the overflowed electrolytic solution is caused to flow into the storage tank 318, and the temperature of the electrolytic solution is adjusted in the storage tank 318. It returns to the inside of the anodic oxidation tank 312 from the supply port 322 provided on the lower side. At this time, the pump 326 exerts momentum from the supply port 322 to discharge the electrolyte, and the electrolyte discharged from the supply port 322 by the rectifying plate 328 rises almost uniformly from the entire bottom of the anodizing tank 312. By adjusting the flow of the electrolyte, a substantially uniform flow of the electrolyte rising from the bottom to the top of the anodizing tank 312 is formed.

  The supply amount of the electrolyte solution to the anodizing tank 312 (the discharge amount of the electrolyte solution from the supply port 322) is preferably one or more circulations per 3 minutes with respect to the volume of the anodizing tank 312. By doing so, the anodic oxidation tank 312 can be frequently renewed, and heat can be removed and generated hydrogen can be removed efficiently. For example, when the tank capacity is 105 L, 35 L / min or more is preferable, and 41 L / min or more is more preferable. When the supply amount of the electrolytic solution is 41 L / min or more, a sufficient flow of the electrolytic solution is generated in the entire anodizing tank 312. In view of the capability of the pump 326, the supply amount of the electrolyte is preferably 60 L / min or less, and more preferably 55 L / min or less.

  The peripheral speed of the aluminum base 330 is preferably 0.1 m / min or more. If the peripheral speed of the aluminum base material 330 is 0.1 m / min or more, unevenness in the concentration and temperature of the electrolyte solution around the aluminum base material 330 can be sufficiently suppressed. The peripheral speed of the aluminum base 330 is preferably 25.1 m / min or less from the viewpoint of the capability of the driving device.

  The step of anodizing the aluminum substrate 330 as described above to form an oxide film having a plurality of pores is performed by anodizing the substrate 1A as shown in FIG. It is performed in the same manner as the forming step.

  In the method for manufacturing an imprint roll mold of the present invention described above, when the roll-shaped aluminum base material 330 is anodized in the electrolytic solution of the anodizing tank 312, the central axis of the aluminum base material 330 is used. Since the aluminum base 330 is rotated about the rotation axis, unevenness in the concentration and temperature of the electrolyte solution around the aluminum base 330 is suppressed, and the entire outer peripheral surface of the aluminum base 330 is anodized almost uniformly. Is called. As a result, it is possible to manufacture a roll mold in which variations in the depth of the pores are suppressed.

  Further, since the same amount of electrolyte is supplied to the anodizing tank 312 while discharging a part of the electrolyte from the anodizing tank 312, the electrolyte flows in the anodizing tank 312, and the aluminum base material The unevenness of the concentration and temperature of the electrolyte solution around 330 is further suppressed. As a result, it is possible to manufacture a roll mold in which the variation in the depth of the pores is further suppressed.

  Furthermore, if the electrolyte is overflowed from the anodizing tank 312 and the overflowed electrolyte is returned into the anodizing tank 312 from the supply port 322 provided below the aluminum base material 330, the bottom of the anodizing tank 312 is obtained. As a result, a flow of the electrolyte rising from the top to the top is generated, and the unevenness of the concentration and temperature of the electrolyte around the aluminum base material 330 is further suppressed. As a result, it is possible to manufacture a roll mold in which the variation in the depth of the pores is further suppressed.

  Further, the two cathode plates 336 are arranged so as to face each other with a gap from the aluminum base material 330 so as to be substantially parallel to the central axis of the aluminum base material 330 and sandwich the aluminum base material 330 from the horizontal direction. Therefore, the cathode plate 336 does not hinder the flow of the electrolytic solution generated in the anodizing tank 312. As a result, it is possible to manufacture a roll mold in which unevenness of the concentration and temperature of the electrolyte solution around the aluminum base material 330 is further suppressed, and variation in the depth of the pores is further suppressed.

<Production method>
The method for producing an article of the present invention comprises imprinting a plurality of pores of anodized alumina formed on the outer peripheral surface of an imprint roll mold obtained by the method for producing an imprint roll mold of the present invention. This is a method for obtaining an article having a plurality of convex portions with inverted pores on the surface, which are transferred to a transfer medium by a method.

As the imprint method, an optical imprint method, which will be described later, or heat that presses a heated roll-shaped mold onto a transfer object made of a thermoplastic resin to transfer a plurality of pores of anodized alumina to the transfer object. Examples of the imprint method include an optical imprint method from the viewpoint of equipment and productivity.
Hereinafter, a method for producing an article by the optical imprint method will be described in detail.

Examples of the method for producing an article by the photoimprint method include a method having the following steps (I) to (III).
(I) A step of sandwiching the active energy ray-curable resin composition between the surface of the base film and the surface of the roll mold while moving the base film along the surface of the rotating roll mold.
(II) The active energy ray curable resin composition sandwiched between the surface of the base film and the surface of the roll mold is irradiated with active energy rays to cure the active energy ray curable resin composition. The process of forming the cured resin layer which has the some convex part in which the pore of the anodic oxidation alumina was reversed on the surface.
(III) The process of peeling a base film from a roll-shaped mold with a cured resin layer.

Examples of the base film include a polyethylene terephthalate film, a polycarbonate film, an acrylic film, and a triacetyl cellulose film.
Examples of the active energy ray-curable resin composition include active energy ray-curable compositions described in paragraphs [0046] to [0055] of JP2009-174007A (Patent Document 1), and JP2009-241351A. Examples include active energy ray-curable resin compositions described in paragraphs [0052] to [0094] of the publication.

When an article is manufactured by the optical imprint method, for example, it is manufactured as follows using a manufacturing apparatus shown in FIG.
An active energy ray curable from a tank 354 between a roll-shaped mold in which anodized alumina having a plurality of pores is formed on the outer peripheral surface and a strip-shaped base film 352 that moves along the surface of the roll-shaped mold. A resin composition 356 is supplied.

  The base film 352 and the active energy ray curable resin composition 356 are nipped between the roll-shaped mold and the nip roll 360 whose nip pressure is adjusted by the pneumatic cylinder 358, and the active energy ray curable resin composition 356 is The base film 352 and the roll mold 350 are uniformly distributed, and at the same time, the pores on the outer peripheral surface of the roll mold are filled.

Using an active energy ray irradiation device 362 installed below the roll-shaped mold in a state where the active energy ray-curable resin composition 356 is sandwiched between the roll-shaped mold and the substrate film 352, the substrate film The active energy ray-curable resin composition 356 was irradiated with active energy rays from the 352 side to cure the active energy ray-curable resin composition 356, thereby transferring a plurality of pores on the outer peripheral surface of the roll-shaped mold. A cured resin layer 364 is formed.
The article 368 is obtained by peeling the base film 352 having the cured resin layer 364 formed on the surface thereof from the roll mold by the peeling roll 366.

As the active energy ray irradiation device 362, a high-pressure mercury lamp, a metal halide lamp, or the like is preferable. In this case, the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm ² .
Examples of the article 368 include an optical film (such as an antireflection film).

  In the manufacturing method of the article of the present invention described above, the imprinting roll mold obtained by the manufacturing method of the imprinting roll mold of the present invention with suppressed variation in the depth of the pores is obtained. Since it uses, the article | item which has the some convex part on the surface by which the variation in the height of a convex part was suppressed can be manufactured.

  FIG. 18 is a cross-sectional view of the anodizing apparatus 410 according to this embodiment. 19 is a cross-sectional view taken along line 4A-4A in FIG. FIG. 20 is a cross-sectional view of a main part for explaining details of the members shown in FIG.

  As shown in FIG. 18, an anodizing apparatus 410 includes an anodizing tank 412 filled with an electrolytic solution, and a flange 414 that covers the upper part of the anodizing tank 412 and receives the electrolytic solution overflowing from the anodizing tank 412. The upper cover 416 formed at the periphery, the storage tank 418 for temporarily storing the electrolyte, the flow-down flow path 420 for flowing the electrolyte received by the collar 414 to the storage tank 418, and the electrolyte in the storage tank 418 A return flow path 424 for returning to the supply port 422 formed near the bottom of the anodizing tank 412 below the aluminum base 430, a pump 426 provided in the middle of the return flow path 424, and a supply port Rectifying plate 428 for adjusting the flow of the electrolyte discharged from 422.

  Referring also to FIG. 19, an anodizing apparatus 410 includes a pair of disk-shaped rotating jigs 432A and 432B inserted into openings 431A and 431B at both ends of a hollow cylindrical aluminum base material 430 serving as an anode, A pair of holding plates 433A and 433B (see FIG. 19) that supports the rotation jigs 432A and 432B so that the rotation jigs 432A and 432B can rotate respectively, and support the aluminum base material 430 via the rotation jigs 432A and 432B, Two cathode plates 436 arranged opposite to each other with the 430 interposed therebetween, a power source 438 electrically connected to the aluminum base 430 and the two cathode plates 436, and a temperature adjustment of the electrolyte in the storage tank 418. And a temperature means 440.

  The pump 426 forms a flow of the electrolytic solution from the storage tank 418 through the return flow path 424 to the anodizing tank 412 and discharges the electrolytic solution from the supply port 422 to discharge the electrolytic solution. The flow of the electrolyte rising from the bottom to the top is formed.

  The rectifying plate 428 is a plate-like member having a plurality of through holes that adjust the flow of the electrolytic solution so that the electrolytic solution discharged from the supply port 422 rises almost uniformly from the entire bottom of the anodizing tank 412. And disposed between the aluminum base 430 and the supply port 422 so that the surface is substantially horizontal.

  The two cathode plates 436 are arranged in parallel to the central axis of the aluminum base 430, and are disposed opposite to each other with a gap from the aluminum base 430 so as to sandwich the aluminum base 430 from the horizontal direction. It is a board. Moreover, as the temperature control means 440 provided in the storage tank 418, the heat exchanger which used water, oil, etc. as the heat medium, an electric heater, etc. are mentioned.

  Referring to FIG. 19, holding plates 433A and 433B are metal plates arranged to face each other with a gap so as to sandwich the aluminum base 430 from the axial direction 4C1, and respectively on the extension of the aluminum base 430 in the axial direction 4C1. , Bearing parts 434A and 434B which are openings into which the rotating jigs 432A and 432B are rotatably inserted. Dry bearings 435A and 435B made of a resin material or a metal material are provided on the inner peripheral surfaces of the bearing portions 434A and 434B. With these dry bearings 435A and 435B, the rotating jigs 432A and 432B are attached to the holding plates 433A and 433B. It is rotatably supported.

  A plurality of bar members 441 penetrating over the holding plates 433A and 433B spaced apart from each other are provided (see also FIG. 18). The holding plates 433A and 433B are connected by the bar members 441 in a state of being parallel to each other so as to hang from the bar members 441.

  Referring to FIG. 20, rotating jigs 432A and 432B are fitted in openings 431A and 431B of aluminum base material 430 or inserted in a light press-fit state. At the same time, a waterproofing packing 470 is attached to both end faces of the opening of the aluminum base material 430. The rotary jigs 432A and 432B are brought into contact with the waterproofing packing 470 by flanges 471A and 471B protruding in the outer diameter direction. The aluminum base material 430 is fixed so as to be sandwiched from both ends. As a result, the aluminum base 430 has a structure in which the inside is sealed by the waterproofing packing 470 and the rotating jigs 432A and 432B. In addition to the packing, a sealing member such as an O-ring may be used as a water-stop method for sealing, and packing is provided on the peripheral surfaces of the inserted rotary jigs 432A and 432B in addition to both end surfaces of the opening of the aluminum base material 430. Etc. may be provided.

  By fixing the aluminum base 430 so as to be sandwiched between the rotary jigs 432A and 432B, the aluminum base 430 is restricted from rotating in the circumferential direction with respect to the rotary jigs 432A and 432B. More specifically, the aluminum base material 430 is supported by the rotary jigs 432A and 432B so that the axial direction 4C1 (FIG. 19) is in a horizontal state. That is, the aluminum base 430 is supported by the rotary jigs 432A and 432B so as to be in a state parallel to the bottom of the anodizing tank 412.

  In FIG. 19, a through hole 442 that penetrates in the axial direction 4C1 of the aluminum base 430 is formed in the rotation center region of the rotating jig 432A located on the left side of the paper surface. The through hole 442 is a rod-shaped body made of a conductive material. The energization main bar 443 is inserted and held so as not to rotate relative to the through-hole 442 in a state where the energization main bar 443 has penetrated. The energizing main bar 443 is integrally fixed to the rotating jig 432A, and rotates in conjunction with the rotation of the rotating jig 432A. Referring to FIG. 20, when the energizing main bar 443 is fixed to the rotating jig 432 </ b> A, an O-ring 472 is provided to stop water so that the electrolyte does not flow from the through hole 442. The inflow of the electrolytic solution from the through hole is eliminated, and the inside of the aluminum base material 430 becomes a completely sealed structure together with the water-stop packing 470 described above. The O-ring 472 is fitted in a groove 473 formed around the through hole 442 of the rotating jig 432A and is provided so as to be covered by a flange 474 formed on the energizing main bar 443. As a method of fixing the energizing main bar 443 to the rotating jig 432A, a mode in which a flange portion is formed on the energizing main bar 443 and bolt fastening is conceivable, but other modes may be used.

The reason why the aluminum base 430 has a hermetically sealed structure is that when a current-carrying member such as a contact 448 described later is brought into contact with the aluminum base 430 in the presence of the electrolyte solution and the current is supplied, the contact 448 This is because an oxide film having poor conductivity is also formed on the contact surface of the aluminum base 430 that comes into contact with the aluminum substrate 430, which may affect the state of conduction and affect the formation of the oxide film.
In addition, according to the sealed structure, the electrolyte does not enter the aluminum base 430, and the electrolyte remaining inside the aluminum base 430 is generated when passing through a plurality of treatment tanks. There is no carry-in to other processing tanks. Thereby, the change of the component and density | concentration of the process liquid of a processing tank is lost. Moreover, by using a sealed structure, the amount of electrolyte used in the anodizing tank 412 is reduced, leading to a reduction in waste liquid and electrolyte costs.

  One end of the energizing main bar 443 is formed in a conical shape, and the conical end portion 444 is in contact with a rotation receiving portion 446 formed on the lower end side of the power feeding flat bar 445 suspended from the bar member 441. The rotation receiving portion 446 has a conical concave portion 447. The tip of the conical end portion 444 is brought into contact with the lowermost surface of the concave portion 447 and the conical end portion 444 is surrounded by the side surface region of the concave portion 447. The position is restricted. The energizing main bar 443 is electrically connected to the power source 438 (FIG. 18) via the power feeding flat bar 445 and the rotation receiving portion 446, and is supplied with current from the power source 438. Note that the conical end portion 444 may be integrated with the energizing main bar 443 or may be a separate member that is detachably attached.

  A contact 448, which is a current-carrying member made of a pair of conductive materials projecting in the radial direction, is fixed to the other end side of the current-carrying main bar 443 so as to be able to be supplied with electricity integrally. Dimension setting and shape setting are made so as to contact the inner peripheral surface to such an extent that energization is possible. As a result, the contact 448 contacts the aluminum base material 430 and can supply a current to the aluminum base material 430. More specifically, the contact 448 is bent at the tip side located on the aluminum base 430 side, and the bent portion has a flat contact surface 448A that contacts the inner peripheral surface of the aluminum base 430. From here, the aluminum substrate 430 is energized.

  In the anodizing apparatus 410 configured as described above, the rotation jig 432A on the opening 431A side is rotated by the rotation jig 432B when the driving force of a motor (not shown) is transmitted to rotate the aluminum base material 430. It rotates in conjunction with the rotated aluminum substrate 430. For this reason, the energization main bar 443 fixed to the rotating jig 432A is in contact with a predetermined region on the inner peripheral surface of the aluminum base 430 and is in a state where it can be energized, and is synchronized (that is, interlocked) with the aluminum base 430. To rotate.

Anodization of the aluminum substrate 430 using this anodizing apparatus 410 is performed as follows.
In a state where the aluminum base 430 is immersed in the electrolytic solution of the anodizing tank 412, a motor (not shown) is driven to rotate the rotating jig 432B, and the aluminum base 430 is rotated about its axial direction 4C1. Rotate.
While rotating the aluminum substrate 430, a voltage is applied between the aluminum substrate 430 and the cathode plate 436 via the power feeding flat bar 445, the rotation receiving portion 446, and the contact 448, and the anodization of the aluminum substrate 430 is performed. I do.

While the aluminum base 430 is anodized, the same amount of electrolytic solution is supplied to the anodizing tank 412 while discharging a part of the electrolytic solution from the anodizing tank 412 while rotating the aluminum base 430. Specifically, the electrolytic solution is overflowed from the anodizing tank 412, the overflowed electrolytic solution is caused to flow into the storage tank 418, the temperature of the electrolytic solution is adjusted in the storage tank 418, and then the electrolytic solution is added to the aluminum base material 430. It is returned into the anodizing tank 412 from the supply port 422 provided on the lower side.
At this time, the pump 426 generates momentum from the supply port 422 to discharge the electrolyte, and the electrolyte discharged from the supply port 422 by the rectifying plate 428 rises almost uniformly from the entire bottom of the anodizing tank 412. By adjusting the flow of the electrolytic solution, a substantially uniform flow of the electrolytic solution rising from the bottom to the top of the anodizing tank 412 is formed.

  The supply amount of the electrolyte solution to the anodizing tank 412 (the discharge amount of the electrolyte solution from the supply port 422) is preferably one or more circulations per 3 minutes with respect to the volume of the anodizing tank 412. By doing so, the anodizing tank 411 can be renewed frequently, and heat removal and generated hydrogen can be efficiently removed. Specifically, when the tank capacity is 107 L, the supply flow rate is preferably about 36 L / min.

  The peripheral speed of the aluminum base 430 is preferably 0.1 m / min or more. If the peripheral speed of the aluminum base material 430 is 0.1 m / min or more, the concentration of the electrolytic solution and the temperature unevenness around the aluminum base material 430 are sufficiently suppressed. From the viewpoint of the capability of the driving device, the peripheral speed of the aluminum base material 430 is preferably 25.1 m / min or less.

  The step of anodizing the aluminum substrate 430 as described above to form an oxide film having a plurality of pores is performed by anodizing the substrate 1A as shown in FIG. It is performed in the same manner as the forming step.

  In the anodizing apparatus 410 according to the present embodiment described above, when the roll-shaped aluminum base material 430 is anodized in the electrolytic solution in the anodizing tank 412, the central axis of the aluminum base material 430 is used as the rotation axis. Since the aluminum base material 430 is rotated, unevenness in the concentration and temperature of the electrolyte around the aluminum base material 430 is suppressed, and anodization is performed almost uniformly over the entire outer peripheral surface of the aluminum base material 430. As a result Thus, it is possible to manufacture a roll mold in which variation in the depth of the pores is suppressed.

  Then, while the aluminum base 430 and the contact 448 are in contact with each other, the aluminum base 430 and the touch 448 are rotated in synchronization with each other, and the aluminum base 430 is energized from the touch 448. As a result, the wear between the aluminum base 430 and the contact 448 can be eliminated to prevent energization failure, and the yield of the roll mold can be further improved.

  That is, a mode in which only the aluminum base 430 is rotated without synchronizing the contact 448 with the aluminum base 430 (the touch 448 is fixed in a state in contact with the inner peripheral surface of the aluminum base 430, and only the aluminum equipment 430 is fixed. If the contactor 448 slides on the inner peripheral surface of the aluminum base material 430, contact wear occurs between the contactor 448 and the aluminum base material 430. There is a possibility that an energization failure may occur between the touch element 448 and the aluminum base material 430. However, in the present invention, the aluminum base material 430 and the touch element 448 are brought into contact with the aluminum base material 430 and the touch element 448. Are synchronized with each other to prevent the occurrence of such energization failure. The contact 448 and the aluminum base material 430 do not need to rotate completely in synchronization. For example, when the contact 448 and the aluminum base 430 are rotated by different power sources, it is difficult to rotate these members in complete synchronization. Accordingly, in the present invention, the state in which the contactor 448 and the aluminum base material 430 are rotated in conjunction with each other while being relatively fixed is also included in the fact that they are rotating in synchronization.

  Here, FIG. 21 shows an experimental example in which an energization state with respect to the aluminum base material 430 in the anodizing apparatus 410 is actually measured. In FIG. 21, the horizontal axis indicates the time axis (seconds), and the current value (A) energized to the aluminum base 430. As is clear from the figure, it was confirmed that the aluminum substrate 430 was energized in a state where the constant current value was stable over a long period after the initial applied current value was stable. Also from this experimental example, the effect of suppressing energization failure according to the present invention was confirmed.

  In this embodiment, the end portion of the energizing main bar 443 is conical (conical end portion 444). According to this, the contact area with the rotation receiving portion 446 is reduced and contact wear is generated. The powder can be minimized and the surface can be renewed. For this reason, an energized state can be maintained without forming an alumina layer having high electrical insulation.

  Hereinafter, the present invention will be specifically described by way of examples.

(Pores of anodized alumina)
Part of the anodized alumina is shaved, platinum is deposited on the cross section for 1 minute, and the cross section is subjected to acceleration voltage: 3.00 kV using a field emission scanning electron microscope (JSM-7400F, manufactured by JEOL Ltd.). Observe and measure the depth of the pores.
If the aluminum substrate is not rotated during anodization:
After the final anodic oxidation, for each of positions 1 to 6 where the outer periphery of the roll-shaped mold 350 shown in FIG. .
When rotating an aluminum substrate during anodization:
Immediately after finishing the last anodization, 10 positions of pores are respectively obtained at positions 1 to 6 that divide the outer periphery of the roll-shaped mold 350 shown in FIG. The depth was measured and the average value was determined.

(Reflectance)
Using a spectrophotometer (manufactured by Hitachi, Ltd., U-4000), the relative reflectance of the surface of the cured resin layer was measured in the range of incident angle: 5 ° and wavelength of 380 to 780 nm.
If the aluminum substrate is not rotated during anodization:
After finishing the final anodization, one end in the width direction of the film for each surface of the cured resin layer corresponding to positions 1 to 6 that divide the outer periphery of the roll-shaped mold 350 shown in FIG. The reflectance at three locations at the center and the other end was measured.
When rotating an aluminum substrate during anodization:
About the surface of the cured resin layer corresponding to positions 1 to 6 that divide the outer periphery of the roll-shaped mold 350 shown in FIG. The reflectances at three locations, one end, the center, and the other end in the width direction of the film, were measured.

(Active energy ray-curable resin composition A)
45 parts by mass of a condensation reaction mixture having a molar ratio of succinic acid / trimethylolethane / acrylic acid of 1: 2: 4, 45 parts by mass of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), radical polymerizability 10 parts by mass of silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-1602), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure (registered trademark) 184, wavelength range of 340 nm or more 3 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals, Irgacure (registered trademark) 819, having an absorption wavelength range of 340 nm or more. ) Of 0.2 parts by mass to obtain an active energy ray-curable resin composition A .

[Example 1]
A hollow cylindrical aluminum substrate (purity: 99.99%, length: 280 mm, outer diameter: 200 mm, inner diameter: 155 mm) was subjected to a feather polishing treatment, and then this was mixed in a perchloric acid / ethanol mixed solution ( Electropolishing was performed at a volume ratio = 1/4).

  Next, using the anodizing apparatus shown in FIG. 15, the aluminum base material is supplied in a 107 L electrolytic solution composed of a 0.3 M oxalic acid aqueous solution, bath temperature: 15.7 ° C., direct current: 40 V, and supply of the electrolytic solution. Anodization was performed for 30 minutes under the conditions of an amount of 41 L / min and a peripheral speed of the aluminum substrate of 3.8 m / min to form an oxide film (step (a)).

  The formed oxide film was once dissolved and removed in a 6% by mass phosphoric acid and 1.8% by mass chromic acid mixed aqueous solution (step (b)), and then again under the same conditions as in step (a). Anodized for 2 seconds to form an oxide film (step (c)).

Thereafter, the substrate was immersed in a 5% by mass phosphoric acid aqueous solution (31.7 ° C.) for 8 minutes, and subjected to a pore diameter expansion treatment (step (d)) for expanding the pores of the oxide film.
Further, anodization was performed for 45 seconds under the same conditions as in step (a) to form an oxide film (step (e)).
Further, the step (d) and the step (e) were repeated, the step (d) was performed 5 times in total, and the step (e) was performed 4 times in total (step (f)). A roll mold A in which anodized alumina having substantially conical pores was formed on the outer peripheral surface of the aluminum base material was obtained. The pore depth of the anodized alumina was measured. The results are shown in Table 1.
Subsequently, the roll mold A was dipped in a 0.1% by mass solution of a mold release agent (manufactured by Daikin Industries, Ltd., OPTOOL DSX (trade name)) for 10 minutes and air-dried for 24 hours to perform a mold release treatment.

An article having a plurality of convex portions on the surface was produced using the production apparatus shown in FIG.
As the roll mold 350, the roll mold A was used.
As the active energy ray curable resin composition 356, the active energy ray curable resin composition 3A was used.
As the base film 352, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: A4300, thickness: 75 μm) was used.
The active energy ray-curable resin composition A was cured by irradiating the active energy ray-curable resin composition A with ultraviolet rays having an integrated light amount of 1100 mJ / cm ² from the base film 352 side.
The relative reflectance of the surface of the cured resin layer of the obtained article was measured. The results are shown in Table 2.

[Comparative Example 1]
A roll-shaped mold B in which anodized alumina having substantially conical tapered pores is formed on the outer peripheral surface of the aluminum base material in the same manner as in Example 1 except that the aluminum base material is not rotated in the electrolytic solution. Got. The pore depth of the anodized alumina was measured. The results are shown in Table 1.
Next, in the same manner as in Example 1, the mold release process of the roll mold B was performed.
Next, an article having a plurality of convex portions on the surface was produced in the same manner as in Example 1 except that the roll mold B was used as the roll mold 350. The relative reflectance of the surface of the cured resin layer of the obtained article was measured. The results are shown in Table 3.

The roll-shaped mold A of Example 1 manufactured by anodizing while rotating the aluminum substrate in the electrolytic solution had little variation in the pore depth. As a result, even in an article having a plurality of convex portions on the surface, there was little variation in the height of the convex portions, that is, variation in reflectance.
On the other hand, the roll-shaped mold B of Comparative Example 1 manufactured by anodizing without rotating the aluminum substrate in the electrolytic solution had a large variation in pore depth. As a result, even in an article having a plurality of convex portions on the surface, the variation in the height of the convex portions, that is, the variation in the reflectance increased.

[Example 2]
In Example 2, the specific conditions were set in the anodizing apparatus 210 shown in FIG. Both end surfaces of the hollow cylindrical aluminum base material 220 (purity: 99.99%, length: 280 mm, outer diameter: 200 mm, inner diameter: 155 mm) and the end surface of the current-carrying member 213 have a taper angle of 30 ° with respect to the axial direction. The surface roughness of each of the tapered surfaces 220A and 213A was Ra 1.6.

  In 106 L electrolyte solution made of 0.3 mol / L aqueous solution of aluminum substrate 220, bath temperature: 15.7 ° C., supply amount of electrolyte solution: 36 L / min, pressing force of both current-carrying members 213: 0.2 MPa The aluminum substrate 220 was anodized for 60 minutes under the condition of the peripheral speed of 3.8 m / min and the voltage of 40 V to form an oxide film.

FIG. 12A shows an experimental example (graph) in which the state of the current value when the current is applied for 60 minutes in the anodizing apparatus 210 is actually measured. In FIG. 12A, the horizontal axis represents the integration time (seconds), and the vertical axis represents the fluctuation width (A) of the current value. FIG. 12B shows the measurement result of the amplitude of the current value up to 1800 seconds in the measurement result shown in FIG. 12A (In FIG. 12B, the scale of the amplitude (A) of the current value is shown in detail. Is shown).
In Example 2, as is clear from these figures, it was confirmed that the aluminum base material 220 was energized without a large fluctuation in a constant current value that was stable over a long period of time. Also from Example 2, the effect of suppressing energization failure according to the present invention was confirmed.

(Comparative Example 2)
Hereinafter, the example which compared the temperature when performing the electrolytic treatment with the processing apparatus of this invention and a rectangular parallelepiped processing tank is demonstrated.

  A hollow cylindrical aluminum substrate (purity: 99.99%, length: 1000 mm, outer diameter: 200 mm, inner diameter: 155 mm) is used as the substrate, and the anode is used in the treatment tank of the present invention and the rectangular parallelepiped treatment tank. Oxidation treatment was performed. In FIG. 2, the processing tank of the present invention has a distance D of 400 mm from the central axis P to the inner surface 111a 'of the bottom 111a, and the rectangular parallelepiped processing tank has the same shape as in FIGS. 7A and 7B. Each treatment tank is circulated at a flow rate of one circulation every 3 minutes, and an electrolytic solution whose temperature is adjusted to 16 ° C. is supplied to each treatment tank.

8 and 9 are graphs comparing the electrolyte temperature when anodizing is performed in each treatment tank. FIG. 8 is a graph when the electrolyte temperature at a location 50 mm away from the wall of the treatment tank is measured at several points throughout the treatment tank. By performing the anodizing treatment, the temperature in the treatment tank rises due to the effects of heat generated by energization, the heat of the oxidation reaction, etc. As can be seen from FIG. 8, the treatment tank of the present invention has a small increase in temperature. . This is because in a rectangular parallelepiped processing tank, a staying portion with poor circulation efficiency is generated, and the staying portion accumulates heat when heat is generated, and the temperature becomes higher than a portion other than the staying portion.
FIG. 9 is a graph showing the maximum temperature difference at several longitudinal points on the substrate surface. The temperature difference on the surface of the base material is temperature spots generated on the surface of the base material, and affects the variation in the depth of the pores when anodizing is performed. As can be seen from FIG. 9, the treatment tank of the present invention has a small temperature difference. This is also due to the staying portion that occurs in the rectangular parallelepiped treatment tank, and the electrolyte temperature on the surface of the base material near the staying portion is also increased.

  Moreover, although it is the processing tank which processed the base material this time, the volume of the rectangular parallelepiped processing tank was 250L, the processing tank of this invention was 130L.

  From the above comparison, it was confirmed that the retention of the electrolytic solution could be prevented and the amount of the electrolytic solution used could be suppressed in the treatment tank of the present invention.

(Comparative Example 3)
Hereinafter, as Comparative Example 3, the measured value of the current value when the energizing member is brought into contact with the aluminum base material with a point will be described. Referring to FIG. 13, in the anodizing apparatus used in Comparative Example 3, slide bearings 241 that are in contact with the inner surfaces of both ends of aluminum base material 220 are provided, and annular housing 240 is formed on the outer peripheral surface of slide bearing 241 with aluminum. It is connected so as to be fixed to the base material 220. The aluminum substrate 220 is rotated by an external rotation mechanism (not shown).
A contact 242 extending from the energizing member 243 is brought into contact with the inner surface of the aluminum base material 220 so that energization can be performed.

And the result of having actually measured the state which made the aluminum base material 220 energize on the conditions similar to the said Example 2 in the state of FIG. 13 is shown by FIG. In FIG. 14, the horizontal axis represents the integration time (seconds), and the vertical axis represents the fluctuation width (A) of the current value. In FIG. 14, the measurement results up to an integration time of 1200 seconds (20 minutes) are shown.
As can be seen from a comparison between the experimental example of the anodizing apparatus of the present invention shown in FIGS. 12A and 12B and FIG. 14, it can be seen that in Comparative Example 3, there is always a slight fluctuation in the current value. Further, there are places where the current value greatly fluctuates in some places. The reason is that the contact area is small because the aluminum base material 220 and the contact 242 are in contact with each other, and when the aluminum base material 220 is rotated, the contact surface varies greatly depending on the rotation period, so that the contact cannot be made stably. In addition, there is a state in which the aluminum base material 220 and the contact 242 are worn or slipped on the contact surface and are not in contact instantaneously, and the current value is considered to fluctuate greatly.

  The roll-shaped mold obtained by the production method according to the present invention is useful for producing an optical film having a fine concavo-convex structure called a moth-eye structure on the surface.

DESCRIPTION OF SYMBOLS 11 Electrolytic processing apparatus 110 Processing tank 111 Processing tank main body 111a Bottom part 111a 'Inner surface 111b, 111c Side surface 112 Electric field liquid supply part 113 Overflow part 120 Electrode plate 130 Rotating means 1A Base material 1A' Peripheral surface (outer peripheral surface)
1L Electrolyte 210 Anodizing device 211 Anodizing tank 213 Current-carrying member 213A Tapered surface 215 Support shaft (rotation drive means)
220 Aluminum substrate 220A Tapered surface 312 Anodizing tank 322 Supply port 330 Aluminum substrate 336 Cathode plate 342 Pore 344 Oxide film (anodized alumina)
350 Roll mold 352 Base film (transfer object)
368 Article 410 Anodizing device 412 Anodizing tank 430 Aluminum base 432A, 432B Rotating jig 443 Energizing main bar (rotating shaft)
446 Rotation receiving part (Rotation receiving part)
448 Toucher (electrical member)

Claims (13)

A method for producing a roll-shaped mold having a plurality of projections and depressions on a surface by conducting anodization by applying current to a cylindrical aluminum substrate made of aluminum immersed in an electrolytic solution of an anodizing treatment tank using a current-carrying member Because
The anodizing bath contains an electrolytic solution, the processing bath main body in which the aluminum base material is immersed, an electrolytic solution supply unit that supplies the electrolytic solution to the processing bath main body, and an overflow unit that discharges the electrolytic solution from the processing bath main body With
With the current-carrying member in contact with the aluminum base material, the electrolytic solution supplied from the electrolytic solution supply part to the aluminum base is supplied to the overflow part with the central axis of the aluminum base as the center of rotation. A method for producing a roll-shaped mold, comprising an anodizing step of energizing the aluminum substrate through the energization member while rotating in a direction opposite to the flowing direction.   The roll-shaped mold according to claim 1, wherein the same amount of the electrolytic solution as the discharged electrolytic solution is supplied to the anodizing bath while discharging a part of the electrolytic solution from the anodizing bath. Manufacturing method.   The manufacturing method of the roll-shaped mold of Claim 1 or 2 with which the bottom part curved in circular arc shape so that the said processing tank main body might follow the surrounding surface of the said immersed aluminum base material. The treatment tank body has a long shape in which the aluminum base material is immersed,
From the electrolyte supply part provided along the longitudinal direction of the treatment tank body, supply the electrolyte solution from above one side surface of the treatment tank body,
The roll as described in any one of Claims 1-3 which discharges | emits the said electrolyte solution from the said overflow part provided in the other side surface upper part of the said processing tank main body along the longitudinal direction of the said processing tank main body. Method for manufacturing a mold. The manufacturing method of the roll-shaped mold as described in any one of Claims 1-4 with which the said aluminum base material and the said electricity supply member rotate synchronizingly. The current-carrying member includes a conductive shaft member, and a contact that is fixed to the shaft member and is in contact with the aluminum base material.
The tentacle is brought into contact with the inner peripheral surface of the cylindrical aluminum substrate;
The roll-shaped mold according to any one of claims 1 to 5 , wherein at least one end of the shaft member is disposed at a position in contact with a conductive power supply member that supplies power to the shaft member. Production method. At least one end of the shaft member is located outside the aluminum substrate along the axial direction of the aluminum substrate;
The shape of the at least one end is conical,
The roll-shaped mold manufacturing method according to claim 6 , wherein at least one end portion of the shaft member rotates while sliding with the power supply member. The aluminum substrate rotates around a central axis by rotating a rotating jig fixed to the axial end of the aluminum substrate,
The roll shaft mold manufacturing method according to claim 6 or 7 , wherein the shaft member is fixed to the rotating jig and rotates in synchronization with the aluminum base material. The method for producing a roll-shaped mold according to any one of claims 1 to 5 , wherein the energizing member is an energizing member in surface contact with one end surface or both end surfaces of the aluminum base material. The current-carrying member is in contact with one end surface or both end surfaces of the aluminum base, and the aluminum base is disposed so as to be sandwiched in the axial direction.
The manufacturing method of the roll-shaped mold of Claim 9 which rotates the said electricity supply member and rotates the said electricity supply member and the said aluminum base material in contact. The manufacturing method of the roll-shaped mold as described in any one of Claims 1-10 with which the edge part of the said aluminum base material is water-stopped. The manufacturing method of the roll-shaped mold of Claim 9 which moves the said electricity supply member along the axial direction of the said aluminum base material, and makes the said aluminum base material and the said electricity supply member contact. A first tapered surface is included in one end surface or both end surfaces of the aluminum base material, and the energizing member has a second tapered surface in surface contact with the first tapered surface, and the first tapered surface and the first tapered surface The manufacturing method of the roll-shaped mold of Claim 9 which contacts the taper surface of 2 and contact | abuts the said aluminum base material and the said electricity supply member.

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