KR20130009791A - Anodizing device, treatment tank, method for producing roll-shaped mold for imprinting, and method for producing article having plurality of protruding parts on surface - Google Patents

Abstract

The present invention is a method for producing a roll-shaped mold having a plurality of irregularities on the surface by energizing a cylindrical aluminum substrate made of aluminum immersed in an electrolytic solution of an anodizing tank using an energizing member to perform anodization.
A roll shape including an anodizing step of energizing the aluminum substrate through the conductive member while rotating the aluminum substrate with the center axis of the aluminum substrate as the rotation center in the state where the energizing member is in contact with the aluminum substrate. A method for producing a mold.

Description

Anodizing device, a processing tank, a manufacturing method of an imprint roll-shaped mold, and a manufacturing method of an article having a plurality of convex portions on the surface. ARTICLE HAVING PLURALITY OF PROTRUDING PARTS ON SURFACE}

The present invention provides a method for producing an anodizing apparatus and an imprint roll-shaped mold for producing an imprint roll-shaped mold having anodized alumina having a plurality of pores on an outer circumferential surface of a roll-shaped aluminum substrate, and the roll for imprint. It relates to a method of manufacturing an article having a plurality of convex portions on the surface by using a shape mold.

Moreover, this invention relates to the processing tank for electrolytically treating a columnar base material in electrolyte solution, and the electrolytic treatment apparatus which electrolytically processes a columnar base material in electrolyte solution.

This application is as follows: Patent application 2010-070280 for which it applied to Japan on March 25, 2010, Patent application 2010-136227 for which it applied in Japan on June 15, 2010, and Japan on July 29, 2010. Based on Patent Application No. 2010-170458, Patent Application No. 2011-018226, filed in Japan on January 31, 2011, and Patent Application No. 2011-047561, filed in Japan on March 4, 2011 Claim the priority and use the content here.

As a method of treating the surface of a base material, there exist coating processes, such as plating, and chemical conversion processes, such as anodization.

When treating the surface of a base material, for example, as shown to FIG. 7A and 7B, process liquid 170, such as electrolyte solution, is processed from the supply pipe 171 provided in the lower part of the rectangular parallelepiped process tank 170. While flowing the processing liquid 1L 'from the top of the processing tank 170 while adjusting the flow of the processing liquid 1L' in the processing tank 170 by the porous plate 172. It is common to perform surface treatment by immersing 1 A of columnar base materials in the processing liquid 1L 'in the processing tank 170. As shown in FIG.

Further, Patent Document 1 supplies a plating solution in a rectangular parallelepiped plating tank, an overflow portion surrounding all sides of the plating tank, a reservoir tank in communication with the overflow portion, and a plating bath from the reservoir tank. A plating treatment apparatus provided with a pump is disclosed. In this plating processing apparatus, a U-shaped porous tube is provided in the liquid discharge part of the pump, and a porous plate for partitioning the inside of the plating tank up and down is provided at the upper portion of the porous tube, and the plated object (substrate) is used. It is housed in a plating bath so as to be located above the stencil.

According to this plating treatment apparatus, the plating liquid is introduced into the plating tank by a pump, and the liquid is supplied to the plating liquid in the plating tank by discharging upward from the discharge port of the porous tube, and the plating liquid flows by the porous plate on the upper portion of the porous tube. Is said to be uniform.

However, when treating the surface of a base material using the processing tank 170 and the plating tank of patent document 1 as shown to FIG. 7A and 7B, the flow of the processing liquid 1L 'under the porous plate 172 is carried out. It was easy to produce nonuniformity in the state. As a result, the flow of the processing liquid 1L ', which flows from the lower portion of the processing tank 170 to the upper portion, may be disturbed, and the processing liquid 1L' may partially stay (occurrence of the retention portion). When the retention portion is generated, it is difficult to uniformly treat the surface of the substrate 1A.

As shown in Figs. 7A and 7B, such a tendency is more likely to occur in the case of a shape in which the substrate 1A is elongated, and the longer the length in the longitudinal direction is, the more remarkable it is. This reason is considered as follows.

Usually, the supply pipe 171 extends from the end surface of the processing tank 170 to the inside toward the end surface opposite to this. Therefore, the longer the base material 1A becomes, the longer the shape of the processing tank 170 accommodating the base material 1A becomes, and the supply pipe 171 also becomes longer in accordance with the length of the processing 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 that the processing liquid 1L' receives varies depending on the distance from the pump 173. The longer the supply pipe 171 is, the farther it is from the pump 173, so that a pressure difference tends to occur at the front near the pump 173 and the inner side away from the pump 173. Therefore, it is considered that the nonuniformity tends to be more likely to occur in the flow state of the processing liquid 1L ', and the retention portion is more likely to occur.

In addition, when the base 1A is lengthened, the treatment tank 170 accommodating the base 1A also becomes large, so that the apparatus is enlarged, and the usage amount of the processing liquid 1L 'also increases.

By the way, in recent years, the article, such as an optical film which has the fine concavo-convex structure of the period below a visible light wavelength on the surface, shows the usefulness in the expression of antireflection effect, a lotus effect, etc. In particular, it is known that a fine uneven structure called a moth eye structure exhibits 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.

As a manufacturing method of the article which has a fine uneven structure on the surface, the imprint method which transfers the fine uneven structure formed in the surface of a mold to the surface of the to-be-transferred bodies, such as a base film, is mentioned. As said imprinting method, the following method is known, for example (patent document 2).

An ultraviolet-ray curable resin is irradiated with an ultraviolet-ray curable resin in the state which an ultraviolet curable resin was interposed between the roll-shaped mold and transparent base film in which the anodized alumina which has a some pore was formed in the outer peripheral surface, and hardened | cured an ultraviolet curable resin and anodized alumina The optical imprint method of forming the cured resin layer which has a some convex part in which the pore of which was inverted on the surface, and peels a base film from a roll mold with the said cured resin layer.

As a method of manufacturing the mold used by this imprinting method, for example, a columnar (roll-shaped) aluminum substrate is anodized in an electrolyte solution to form anodized alumina having a plurality of pores (concave portions) on the main surface of the aluminum substrate. This is known (patent documents 2 and 3).

However, in the case where the columnar aluminum substrate is anodized in the electrolytic solution using the treatment tank 170 as shown in Figs. 7A and 7B, when the retention portion is generated in the treatment tank 170, the porous plate 172 is particularly The temperature nonuniformity tends to arise in 1 L 'of a process liquid (electrolyte liquid) in the upper part. The surface temperature of the base material 1A is easily affected by the temperature nonuniformity of the processing liquid 1L ', and when the temperature nonuniformity occurs in the processing liquid 1L', the surface of the base material 1A also tends to have temperature nonuniformity.

The depth of the pores formed on the surface of the substrate by anodization is likely to be affected by the temperature during processing. Therefore, when temperature nonuniformity arises in electrolyte solution or a base material surface, the mold with a deviation in the depth of a pore may be obtained in some places. Using such a mold, when the fine concavo-convex structure formed on the surface of the mold is transferred by an imprinting method, it becomes an article having a variation in the height of the convex portion, that is, a variation in reflectance, depending on the place.

As a cause of the anodic oxidation nonuniformity, the temperature of the electrolyte, the current density, the electrolytic voltage, etc. are influencing, and the electrical conduction member and the aluminum base material for supplying the temperature nonuniformity of the roll-shaped aluminum surface and the stable electric current are electrically Poor energization due to not being in close contact may be considered.

Japanese Patent Publication No. 2009-242878 Japanese Patent Publication No. 2009-174007 International Publication No. 2006/059686 Brochure

This invention is made | formed in view of the said situation, The 1st aspect of this invention provides the method of manufacturing the roll shape mold for imprints in which the dispersion | variation in the depth of a pore was suppressed.

A second aspect of the present invention provides a method for producing an article having a plurality of convex portions on the surface, in which variation in the height of the convex portions is suppressed.

The 3rd aspect of this invention provides the anodizing apparatus which can manufacture the roll shape mold for imprints in which the deviation of the pore depth was suppressed.

The fourth aspect of the present invention provides an electrolytic treatment apparatus which can prevent the retention of an electrolyte even when treating a long substrate, and can further suppress the amount of the electrolyte used.

The 5th side of this invention provides the processing tank used suitably for the said electrolytic treatment apparatus.

According to a first aspect of the present invention, an anodic oxidation treatment is performed by energizing a cylindrical aluminum substrate made of aluminum immersed in an electrolytic solution of an anodic oxidation tank using an energizing member, thereby producing a roll-shaped mold having a plurality of irregularities on its surface. As a way to,

A roll shape including an anodizing step of energizing the aluminum substrate through the conductive member while rotating the aluminum substrate with the center axis of the aluminum substrate as the rotation center in the state where the energizing member is in contact with the aluminum substrate. A method for producing a mold.

The 2nd aspect of this invention relates to the manufacturing method of the roll-shaped mold of 1st aspect with which the said aluminum base material and the said electricity supply member rotate in synchronization.

According to a third aspect of the present invention, the energizing member includes a conductive shaft member and a catalyst fixed to the shaft member and in contact with the aluminum substrate, wherein the catalyst is formed on an inner circumferential surface of the cylindrical aluminum substrate. The manufacturing method of the roll-shaped mold as described in the 1st aspect or 2nd aspect which abuts and is arrange | positioned in the position which contact | connects the electrically conductive feeding member which feeds at least one edge part of the said shaft member to the said shaft member. will be.

According to a fourth aspect of the present invention, at least one end of the shaft member is positioned outside the aluminum substrate along the axial direction of the aluminum substrate, and the shape of the at least one end portion is conical and at least one of the shaft members. One end part relates to the manufacturing method of the roll-shaped mold as described in the 3rd aspect which rotates, sliding with the said power feeding member.

According to a fifth aspect of the present invention, the aluminum substrate is rotated about a central axis by rotating a rotary jig fixed to an axial end of the aluminum substrate, and the shaft member is fixed to the rotary jig. The manufacturing method of the roll shape mold as described in a 3rd aspect which rotates in synchronization with an aluminum base material.

A sixth aspect of the present invention relates to a method for producing a roll-shaped mold according to the fifth aspect, wherein the rotating jig indexes an end portion of the aluminum substrate.

A seventh aspect of the present invention relates to a method for producing a roll-shaped mold according to the first aspect, wherein the same amount of electrolyte is supplied to the anodic oxidation tank while discharging a part of the electrolyte solution from the anodic oxidation tank.

According to an eighth aspect of the present invention, an electrolyte is overflowed above the aluminum substrate of the anodic oxidation tank to discharge a part of the electrolyte, and the overflowed electrolyte is supplied from the supply port provided below the aluminum substrate into the anodic oxidation tank. It relates to the manufacturing method of the roll-shaped mold of 7th aspect to convey.

In the ninth aspect of the present invention, in the method for producing a roll-shaped mold according to the seventh aspect, the anodic oxidation tank has a semi-circular shape, uniformly supplied with an electrolyte solution from one side, and overflowed from the other side. It is about.

According to a tenth aspect of the present invention, the anodic oxidation tank is an elongated shape in which an electrolyte solution is accommodated and the aluminum substrate is immersed, and the bottom portion is arcuate so as to follow the main surface of the substrate immersed in the treatment tank body. The treatment tank main body, the electrolyte supply unit for supplying the electrolyte solution to the treatment tank main body, and the overflow portion for discharging the electrolyte solution from the treatment tank main body, and are provided so as to follow the longitudinal direction of the treatment tank main body. 9th aspect which supplies electrolyte solution from one side upper side of a treatment tank main body, and discharges the said electrolyte solution from the said overflow part provided in the upper side of the other side of a treatment tank main body so that along the longitudinal direction of a treatment tank main body. It relates to a method for producing a roll-shaped mold described.

An eleventh aspect of the present invention relates to a method for producing a roll-shaped mold according to the tenth aspect, wherein the aluminum substrate is rotated in a direction opposite to a direction in which the electrolyte supplied from the electrolyte supply portion flows into the overflow portion.

A twelfth aspect of the present invention relates to a method for producing a roll-shaped mold according to the first aspect or the second aspect, wherein the conductive member is a conductive member which is in surface contact with one end face or both end faces of the aluminum substrate.

According to a thirteenth aspect of the present invention, the conduction member is disposed so as to contact one end surface or both end surfaces of the aluminum substrate, and the aluminum substrate is sandwiched in the axial direction, and the conduction member is rotated so that the conduction member and the It relates to the manufacturing method of the roll-shaped mold of the 12th aspect which rotates in the state which contacted the aluminum base material.

A fourteenth aspect of the present invention relates to a method for producing a roll-shaped mold according to the thirteenth aspect, wherein the rotary jig indexes an end portion of the aluminum substrate.

A fifteenth aspect of the present invention relates to a method for producing a roll-shaped mold according to the twelfth aspect, wherein the conductive member is moved along the axial direction of the aluminum substrate to bring the aluminum substrate into contact with the conductive member.

According to a sixteenth aspect of the present invention, a first tapered surface is included on one or both end surfaces of the aluminum substrate, and the energizing member has a second tapered surface in surface contact with the first tapered surface, and the first taper The manufacturing method of the roll-shaped mold of the 12th aspect which makes a surface and said 2nd taper surface contact and abuts the said aluminum base material and the said electricity supply member.

As another aspect of the present invention, the method for manufacturing an imprint roll-shaped mold of the present invention is a method for manufacturing an imprint roll-shaped mold having anodized alumina having a plurality of pores formed on an outer circumferential surface of a roll-shaped aluminum substrate, When the aluminum substrate is anodized in the electrolyte solution of the anodizing tank, the aluminum substrate is rotated using the central axis of the aluminum substrate as the rotation axis.

In the above aspect, it is preferable to supply the same amount of electrolyte solution to the anodic oxidation tank while discharging a part of the electrolyte solution from the anodic oxidation tank; It is more preferable that the electrolyte is overflowed from the anodic oxidation tank and the overflowed electrolyte is conveyed into the anodic oxidation tank from a supply port provided below the aluminum substrate.

In the above aspect, the supply amount of the electrolyte solution to the anodic oxidation tank is preferably one or more times in three minutes with respect to the volume of the anodic oxidation tank. By doing so, the anodic oxidation tank can perform frequent liquid update, and can efficiently remove heat generated and hydrogen removal. For example, when a crude capacity is 105L, it is preferable that they are 35L / min-60L / min, and 41L / min-55L / min are more preferable.

In the above aspect, in the case of anodizing, it is preferable that the aluminum substrate is used as the anode, and the at least one negative electrode plate is disposed substantially parallel to the central axis of the aluminum substrate, and the aluminum substrate is disposed to face each other.

A seventeenth aspect of the present invention is a method of manufacturing an article having a plurality of irregularities on the surface, and imprints a plurality of pores of anodized alumina formed on the outer circumferential surface of the roll-shaped mold for imprint obtained by the manufacturing method according to the first aspect. It transfers to a to-be-transferred body by the method, It is related with the manufacturing method of the said article including obtaining the article which has the some convex part of the shape which the said pore reversed and transferred to the surface.

An eighteenth aspect of the present invention is a treatment tank for electrolytically treating a columnar substrate in an electrolyte solution, the treatment tank main body in which an electrolyte solution is accommodated and the substrate is immersed, and an electrolyte solution supply unit for supplying an electrolyte solution to the treatment tank body, And an overflow portion for discharging the electrolyte solution from the treatment tank main body, wherein an inner surface of the bottom of the treatment tank main body is curved in an arc shape so as to follow a main surface of the substrate immersed in the treatment tank main body, and the electrolyte supply portion is treated. It is provided above one side of the processing tank main body so as to follow the longitudinal direction of a tank main body, and the said overflow part is provided in the processing tank provided in the upper side of the other side of a processing tank main body so that it may follow the longitudinal direction of a processing tank main body. It is about.

A nineteenth aspect of the present invention is an electrolytic treatment device for electrolytically treating a columnar substrate in an electrolyte solution, the electrolyte supply portion configured to accommodate an electrolyte solution and supply the electrolyte solution to a treatment tank main body and a treatment tank main body in which the substrate is immersed. And a treatment tank including an overflow portion for discharging the electrolyte solution from the treatment tank main body, and an electrode plate arranged to sandwich the substrate immersed in the treatment tank main body, and an inner surface of the bottom of the treatment tank body includes the treatment tank. It is curved in circular arc shape so that the main surface of the base material immersed in the main body, The said electrolyte supply part is provided above one side surface of the processing tank main body so that it may follow the longitudinal direction of the processing tank main body, The said overflow part is a processing tank main body. It relates to the electrolytic treatment apparatus provided in the upper side of the other side of a process tank main body so that along the longitudinal direction of the process tank.

Here, it is preferable that the said electrode plate is curved so that it may follow the inner surface shape of the bottom part of the said process tank main body.

Moreover, it is preferable to provide rotation means which rotates the said base material with the central axis of the said base material as the rotation center.

Moreover, it is preferable that the said rotating means rotates the said base material in the direction opposite to the direction through which the electrolyte solution supplied from the electrolyte supply part flows to an overflow part.

A twentieth aspect of the present invention is an anodizing apparatus for performing anodizing treatment of a rolled aluminum substrate made of aluminum with an electrolyte of an anodizing tank, and has an energizing member that is in surface contact with one or both ends of the aluminum substrate. The present invention relates to an anodizing apparatus for conducting electricity to the aluminum substrate while rotating the conduction member in synchronization with the aluminum substrate rotating around a central axis.

Moreover, the anodic oxidation apparatus which concerns on 20th aspect of this invention is characterized by having rotation drive means which rotates the said aluminum base material.

Further, the anodizing apparatus according to the twentieth aspect of the present invention has axial driving means for moving the conducting member forward and backward in the axial direction of the aluminum substrate, and the axial driving means includes the aluminum substrate and the energization. It is characterized by contacting or separating the member.

Moreover, in the anodic oxidation apparatus which concerns on the 20th aspect of this invention, the 1st taper surface is included in the one end surface or both end surfaces of the said aluminum base material, and the said electricity supply member is the 2nd which surface-contacts to the said 1st taper surface. It is characterized by having a tapered surface.

A twenty-first aspect of the present invention is an anodizing apparatus for anodizing a rolled aluminum substrate made of aluminum with an electrolytic solution of an anodizing tank, having an electroconductive catalyst for energizing the aluminum substrate, and a central axis of the aluminum substrate. The present invention relates to an anodizing apparatus which rotates the aluminum substrate as a center of rotation, rotates in synchronization with the aluminum substrate in a state where the catalyst is brought into contact with the aluminum substrate, and conducts electricity to the aluminum substrate.

In addition, the anodizing apparatus according to the twenty-first aspect of the present invention includes a conductive rotary shaft that fixes the catalyst and extends along the axial direction of the aluminum substrate, and a conductive feed that feeds the rotary shaft in contact with an end of the rotary shaft. It has a plate member, It rotates in synchronization with the said aluminum base material by rotating the said rotating shaft to the said aluminum base material, It is characterized by the above-mentioned.

In addition, the anodizing apparatus according to the twenty-first aspect of the present invention is characterized in that the shape of a portion in contact with the feed plate member of the rotating shaft is conical.

In the anodizing apparatus according to the present invention, the aluminum substrate is rotated around the center axis by a rotation jig fixed to an end thereof, and the rotation axis is synchronized with the aluminum substrate by being fixed to the rotation jig. It is characterized by rotating.

 Moreover, the anodizing apparatus according to the twenty-first aspect of the present invention is characterized in that the structure can be indexed so that an electrolyte solution does not enter the inside of the aluminum substrate.

According to the manufacturing method of the roll shape mold for imprints of this invention, the roll shape mold for imprints in which the dispersion | variation in the depth of a pore was suppressed can be manufactured.

According to the twentieth aspect of the present invention, since the current is supplied to the aluminum substrate while the aluminum substrate is brought into surface contact with the conductive member and rotated in synchronism, stable energization can be performed without conduction failure. In addition, since the contact area is large, the vibration of the current value caused by the rotation of the aluminum substrate and the contact portion of the conducting member such as friction can also be suppressed, and the yield of the roll-shaped mold can be further improved. .

According to the twenty-first aspect of the present invention, since the energization is performed from the catalyst to the aluminum substrate while the aluminum substrate and the catalyst are in contact with each other while rotating the synchronously with the aluminum substrate, the current is prevented from being worn between the aluminum substrate and the catalyst. A defect can be suppressed and the improvement of the yield of a roll mold can further be aimed at.

According to the manufacturing method of the article of this invention, the article which has a some convex part on the surface by which the deviation of the height of the convex part was suppressed can be manufactured.

The treatment tank of this invention is suitable as a treatment tank of the electrolytic treatment apparatus which can prevent the retention of electrolyte solution, and can also suppress the usage-amount of electrolyte solution also when processing a elongate base material.

In addition, the electrolytic treatment apparatus of the present invention can prevent the retention of the electrolyte even when treating a long substrate, and can further suppress the amount of the electrolyte used.

1 is a side view illustrating an example of a treatment tank of the present invention.
FIG. 2 is a cross-sectional view taken along line 1I-1I 'of FIG. 1.
3 is a side view illustrating another example of the overflow unit.
It is sectional drawing which shows an example of the electrolytic treatment apparatus of this invention.
5A is a cross-sectional view taken along the line 1II-1II 'of FIG. 4.
It is a perspective view of the processing tank and electrode plate with which the electrolytic process apparatus shown in FIG. 4 is equipped.
6 is a cross-sectional view illustrating a process of forming pores of anodized alumina.
7A is a diagram illustrating an example of a conventional processing apparatus, and FIG. 7A is a side view thereof.
FIG. 7B is a view showing an example of a conventional processing apparatus, and FIG. 7B is a sectional view taken along the line 1III-1III 'of FIG. 7A.
8 is a graph comparing the temperature of the electrolyte solution when the electrolytic treatment is performed in the treatment tank of the present invention and a rectangular parallelepiped treatment tank, and is a graph showing the maximum temperature raised at several points near the treatment tank wall surface.
It is a graph which compares the electrolyte solution temperature at the time of electrolytic treatment in the processing tank of this invention and a rectangular parallelepiped processing tank, and is a graph which shows the maximum temperature difference in the several points of the longitudinal direction of the surface of a base material.
10 is a cross-sectional view of the anodizing apparatus according to the embodiment of the present invention.
FIG. 11 is a cross-sectional view taken along the line 2A-2A of FIG. 10.
It is a figure which shows the graph explaining the energized state with respect to the aluminum base material in the anodizing apparatus which concerns on Example 2 of this invention.
12B is an enlarged view of a specific range of the graph shown in FIG. 12A.
13 is a sectional view showing a schematic configuration of an anodizing apparatus according to Comparative Example 3. FIG.
It is a figure which shows the graph explaining the energized 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 the anodizing apparatus.
It is a schematic block diagram which shows an example of the manufacturing apparatus of an article.
It is sectional drawing which shows the position which divides the outer periphery of roll-shaped mold into six circumferences by number.
18 is a cross-sectional view of the anodizing apparatus according to the embodiment of the present invention.
19 is a cross-sectional view taken along the line 4A-4A of FIG.
20 is a sectional view showing the principal parts of the detail of the member shown in FIG. 19.
It is a figure which shows the graph explaining the energized state with respect to the aluminum base material in the anodizing apparatus.

The manufacturing method of the roll-shaped mold which is the 1st-16th aspect of this invention is the processing tank for electrolytically treating the columnar base material which is an 18th aspect of this invention in electrolyte solution; An electrolytic treatment apparatus for electrolytically treating a columnar base material which is a nineteenth aspect of the present invention in an electrolytic solution; Or it can implement by applying the anodizing apparatus which is a 20th or 21st aspect of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described concretely based on drawing.

[Treatment Tank]

The treatment tank of this invention is for electrolytically treating a columnar base material in electrolyte solution.

FIG. 1: is a figure which shows an example of the processing tank 110 which concerns on this embodiment, and is a side view seen from the electrolyte solution supply side mentioned later. FIG. 2 is a cross-sectional view taken along the line 1I-1I 'of FIG. 1.

On the other hand, the outer tank 140 which accommodates the processing tank 110 shown in FIG. 1 was added to FIG.

In addition, in this invention, although the shape of the base material used for an electrolytic process is cylindrical shape, it may be hollow shape (cylindrical shape) as shown to FIG. 1, 2, and may not be hollow shape.

The processing tank 110 shown to FIG. 1, 2 is the processing tank main body 111 which is a long elongate in which 1L of electrolyte is accommodated, and the hollow columnar base material 1A is immersed, and the processing tank main body 111 The electrolyte solution supply part 112 which supplies 1L of electrolyte solution to the inside, and the overflow part 113 which discharges the electrolyte solution 1L from the process tank main body 111 are comprised.

This processing tank 110 is accommodated in the outer tub 140 as shown in FIG.

<Processing tank body>

The treatment tank main body 111 accommodates the electrolyte solution 1L, and the substrate 1A is immersed in the electrolyte solution 1L.

The inner surface 111a 'of the bottom part 111a of the processing tank main body 111 is curved in circular arc shape along the main surface (outer peripheral surface) 1A' of the base material 1A immersed in the processing tank main body 111. . Since the inner surface 111a 'of the bottom portion 111a is curved in an arc shape, the electrolyte 1L supplied from the electrolyte supply unit 112 described later can naturally flow to the overflow portion 113.

In addition, in this invention, "a circular arc shape" is not limited to a perfect circular shape.

As the shape of the inner surface 111a 'of the bottom part 111a, the shape curved in the smooth direction without a bending point, such as a semicircle shape and a semi-elliptic shape, is preferable, but semicircle shape is more preferable especially. If the shape of the inner surface 111a 'of the bottom portion 111a is semi-circular, the electrolyte 1L supplied from the electrolyte supply portion 112 overflows while maintaining the more natural flow of the inner surface 111a' of the bottom portion 111a. It flows to the part 113.

The material of the treatment tank main body 111 is not particularly limited as long as it is difficult to corrode with the electrolyte 1L, and examples thereof include stainless steel and polyvinyl chloride (PVC).

The size of the treatment tank main body 111 is not particularly limited as long as it is a size that can accommodate the substrate 1A. For example, when the substrate 1A is disposed in the treatment tank main body 111 as shown in FIG. 2. The gap S is formed between the outer circumferential surface 1A 'of the base 1A and the inner surface 111a' of the bottom 111a. Specifically, the distance D from the central axis P of the base 1A to the inner surface 111a 'of the bottom 111a is preferably 1.25 to 2 times the radius r of the base 1A. .

On the other hand, when the shape of the inner surface 111a 'of the bottom part 111a is semi-circle shape, the base material 1A is made to process the main body 1A so that the center on the diameter of this semicircle and the center axis P of the base material 1A may overlap. 111).

By the way, when a pore is formed in the main surface by anodizing a base material as mentioned above, since the depth of pore is easy to be influenced by the temperature nonuniformity of electrolyte solution or the surface (outer peripheral surface) of a base material, it is necessary to reduce temperature nonuniformity.

The temperature nonuniformity of the electrolyte solution or the surface of the substrate is mainly caused by the electrolyte solution remaining in the treatment tank. However, when the interval between the substrate and the inner surface of the treatment tank is narrow, temperature nonuniformity may occur. This is considered to be easy to heat the treatment tank by the heat generation when anodizing, the surface of the substrate in the vicinity of the treatment tank is directly and non-uniformly warm by the heat of the treatment tank, it is considered that the temperature irregularity occurs. This tendency is thought to occur more easily as the distance between the base material and the inner surface of the treatment tank is closer.

However, if the distance D from the central axis P of the base 1A to the inner surface 111a 'of the bottom 111a is 1.25 times or more of the radius r of the base 1A, the base 1A. A sufficient gap is formed between the outer circumferential surface 1A 'and the inner surface 111a' of the bottom 111a of the treatment tank main body 111. Therefore, since the electrolyte 1L positioned between the substrate 1A and the treatment tank main body 111 can fully fulfill the role of the buffer material, even if the treatment tank main body 111 is heated by heat generation during anodization, It is possible to suppress that the substrate 1A is directly warmed by the treatment tank main body 111. Therefore, the temperature nonuniformity of the outer peripheral surface 1A 'of the base material 1A can be prevented more effectively, and the pore in which the dispersion | variation in depth was suppressed can be formed in the outer peripheral surface of a base material.

On the other hand, it is preferable that distance D is 2 times or less of radius r of base material 1A. Even if the distance 1D exceeds twice the radius r of the base material 1A, the effect of preventing the temperature unevenness becomes a limit point, or because the treatment tank main body 111 becomes large, the electrolytic solution 1L High usage

<Electrolyte solution supply part>

The electrolyte supply part 112 of the example of illustration is comprised from the supply pipe 112a and the elongate discharge part 112b connected to the said supply pipe 112a.

The electrolyte is sent into the supply pipe 112a by a pump (not shown) or the like, and the electrolyte filled in the supply pipe 112a is discharged from the discharge port 1121a to the discharge part 112b.

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

The tip of the discharge part 112b is immersed in the electrolyte solution 1L accommodated in the processing tank main body 111, and 1L of electrolyte solution is supplied to the processing tank main 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.

The electrolyte discharged from the discharge part 112b is uniform with respect to the width direction in order to maintain a constant pressure in the electrolyte supply part in order to maintain a uniform flow state with respect to the longitudinal direction of the processing tank 111 main body. One flow can be formed. In order to maintain a positive pressure, it is good to provide so that the area of the discharge port 1121a of the supply pipe 112a may become larger than the opening area of the discharge port 1121b of the discharge part 112b.

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

<Overflow part>

The overflow part 113 discharges the electrolyte 1L overflowing from the processing tank main body 111 out of the processing tank main body 111, and arranges the processing tank main body (so that it may follow the longitudinal direction of the processing tank main body 111). It is provided in the upper part of the other side 111c of 111.

The overflow part 113 of the example of illustration changes the height of the one side 111b of the processing tank main body 111, and the other side 111c, specifically, the other side 111c of one side. It is formed to be lower than the side surface 111b.

&Lt; Action >

The treatment tank 110 of the present invention described above supplies the electrolyte L from one side 111b above the treatment tank main body 111 and discharges it from the upper side of the other side 111c. At this time, since the inner surface 111a 'of the bottom portion 111a of the treatment tank main body 111 is curved in an arc shape, the electrolyte 1L can naturally move to the overflow portion 113 without remaining.

On the other hand, a pump (not shown) or the like is used when the electrolyte 1L is sent to the electrolyte supply unit 112, but the electrolyte 1L is sent from the electrolyte supply unit 112 according to gravity. Therefore, the treatment tank 110 of the present invention, like the conventional treatment tank 170 shown in FIG. 8, uses the pump 173 from the supply pipe 171 provided in the lower portion of the treatment tank 170 by the pump 173. 1L ') is less likely to be affected by the pressure of the pump as compared with the case of discharging above the treatment tank 170 (that is, against gravity). Therefore, even if the base material 1A to be electrolytically lengthened and the length in the longitudinal direction of the treatment tank main body 111 and the electrolyte solution supply part 112 are long, the electrolyte solution received from the pump is provided at both ends of the electrolyte solution supply part 112. Pressure difference is small.

Therefore, when the treatment tank 110 of the present invention is used, it is possible to prevent the electrolyte 1L from partially remaining in the treatment tank body 111, so that the outer peripheral surface 1A 'of the substrate 1A is uniform. Can be electrolytically treated.

In particular, when anodizing an aluminum substrate, it becomes important to suppress temperature unevenness of the electrolyte solution or the surface of the substrate. However, when the treatment tank 110 of the present invention is used, the electrolyte solution 1L in the treatment tank body 111 is used. Since the retention part of) hardly occurs, temperature nonuniformity hardly occurs. Therefore, the dispersion | variation in the depth of the pore formed in the outer peripheral surface 1A 'of the base material 1A is suppressed.

Moreover, in the processing tank 110 of this invention, since the inner surface 111a 'of the bottom part 111a of the processing tank main body 111 is curved in circular arc shape, the processing tank of rectangular parallelepiped shape as shown in FIG. 8 ( It is possible to reduce the volume compared to 170). Therefore, the usage-amount of electrolyte solution can also be suppressed.

On the other hand, when the treatment tank 110 of the present invention is used, since the electrolyte 1L naturally flows inside the treatment tank main body 111, it is not necessary to provide a member for adjusting the flow of the porous plate or the like.

<Other embodiment>

The treatment tank of the present invention is not limited to the treatment tank 110 shown in FIGS. 1 and 2. For example, as long as the electrolyte supply part 112 of the processing tank 110 shown to FIG. 1, 2 is a shape which can be supplied uniformly in a longitudinal direction, it is good also as a tubular structure.

In addition, although the overflow part 113 makes the other side 111c of the process main body 111 lower than the one side 111b, the processing tank 110 of FIGS. For example, as shown in FIG. 3, you may provide the hole 113 'extending in the longitudinal direction of the processing tank main body 111 in the other side surface 111c, and let this be the overflow part 113. FIG. . In this case, however, it is preferable to provide the hole 113 'at a position higher than the base material 1A immersed in the treatment tank main body 111.

The hole 113 'may be continuous as shown in FIG. 3, or may be intermittent.

3, only the process tank main body 111, the hole 113 ', and the base material 1A were shown, and the electrolyte supply part was abbreviate | omitted.

Electrolytic Processing Unit

The electrolytic treatment apparatus of this invention is an apparatus which electrolytically processes a columnar base material in electrolyte solution.

FIG. 4 is a side cross-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 1II-1II 'of FIG. 4, and FIG. 5B is provided in the electrolytic treatment apparatus shown in FIG. 4. It is a perspective view of the processing tank 110 and the electrode plate 120.

The electrolytic treatment apparatus 11 of this example has an electrode plate arranged to sandwich the treatment tank 110 filled with the electrolyte L and the substrate 1A immersed in the treatment tank body 111 of the treatment tank 110. 120, the rotation means 130 which rotates the base material 1A with the center axis of the base material 1A as the rotation center, and the electrolyte 1L which received the processing tank 110 and overflowed from the processing tank 110. ), A flow passage for flowing down the outer tank 140, the storage tank 150 for storing the electrolyte 1L once, and the electrolyte 1L received in the outer tank 140, down the storage tank 150. 141, the conveyance flow path 151 which conveys the electrolyte 1L of the storage tank 150 to the electrolyte supply part 112 of the processing tank 110, and the pump 152 provided in the middle of the conveyance flow path 151 is provided. Doing.

Hereinafter, the case where the electrolytic treatment apparatus 11 of the present invention is used as the anodic oxidation treatment apparatus will be described in detail.

The electrolytic treatment apparatus 11 is equipped with the processing tank 110 of this invention mentioned above, As shown to FIG. 5A, 5B, the electrode plate 120 is the processing tank main body of this processing tank 110 ( The shape is curved so as to follow the shape of the inner surface 111a 'of the bottom part 111a of 111. As shown in FIG. Since the electrode plate 120 is in a curved shape, the flow of the electrolyte 1L is less likely to be prevented, so that the electrolyte 1L does not stay and can move to the overflow portion 113 more naturally.

In FIG. 5A, the outer tub 140 is omitted. In addition, in FIG. 5B, only the processing tank main body 111 and the overflow part 113, the electrode plate 120, and the base material 1A of the processing tank 110 are shown, and the structure of other electrolytic processing apparatus 11 is shown. Absence was omitted.

End surfaces 111d and 111e of the treatment tank main body 111 are U-shaped, as shown in Fig. 5B. Therefore, the sealing material (not shown) according to the shape is affixed to end surface 111d, 111e so that electrolyte solution may not leak from end surface 111d, 111e.

Further, on the lower side of the end faces 111d and 111e, as shown in Figs. 4 and 5A, as the rotation means 130, a support shaft 131 for supporting the substrate 1A along the axial direction in the horizontal direction is provided. It is.

As shown to FIG. 4, FIG. 5A, the support shaft 131 is provided in pair in the horizontal direction at the end surface 111d, 111e of the treatment tank main body 111, respectively, and each support shaft 131 processes It penetrates through the end surface 111d, 111e of the tank main body 111, and is rotatably supported with respect to the end surface 111d, 111e of these treatment tank main body 111. As shown in FIG.

The cylindrical elastic member 132 which consists of resin materials is inserted in the edge part in the process tank main body 111 of each support shaft 131, and the base material 1A has the elasticity of the outer peripheral surface at both ends of each support shaft 131, respectively. It is supported on the support shaft 131 so that it may be mounted on the member 132. Each support shaft 131 is connected to, for example, a rotational drive unit (not shown) such as a motor, and the support shaft 131 is rotated in the same direction by the rotational drive unit. The base 1A in contact with 132 is made to rotate.

In particular, as shown in FIG. 5A, the rotation means 130 includes the electrolyte 1L supplied from the electrolyte supply unit 112 of the treatment tank 110 to the treatment tank main body 111 as the overflow portion 113. It is preferable to rotate the substrate 1A in the direction opposite to the flowing direction. When the flow direction of the electrolyte solution 1L and the rotation direction of the substrate 1A are reversed, the flow of the electrolyte solution 1L in the vicinity of the surface relative to the substrate 1A becomes relatively fast, and the substrate 1A at the time of the electrolytic treatment The generated heat can be moved efficiently. When the flow direction of the electrolyte solution 1L and the rotation direction of the base material 1A are the same, the flow of the electrolyte solution 1L in the vicinity of the surface of the base material 1A is relatively slow, and the movement of heat is poor in the absence of speed, so that the treatment It will lead to the temperature rise of the electrolyte solution in the tank 110 whole.

Above the support shaft 131, a shaft for power transmission 133 along the axial direction in the horizontal direction is provided through the sealing material 114 attached to the end faces 111d and 111e, and this shaft for power transmission 133 is provided. ) Penetrates the outer tub 140 and is exposed to the outside. The electricity transmission shaft 133 is made of a conductive material and is rotatably supported by each of the encapsulants attached to the end surfaces 111d and 111e. On the other hand, the entire shaft 133 does not have to be made of an electrically conductive material, and it is sufficient that the current can be applied to the base 110 through the conducting member 134 described later. Specifically, the structure in which the exterior of the electricity transmission shaft 133 is coated with the insulating material may be sufficient, and the coating which is excellent in abrasion resistance etc. may be given to the site | part which contacts the sealing material attached to end surfaces 111d and 111e.

At the end part of the processing tank main body 111 of each electricity transmission shaft 133, the disk shaped electricity supply member 134 is integrally provided. The energization member 134 is in surface contact with both end faces of the hollow cylindrical substrate 1A. Here, the power supply 121 is electrically connected with the electrode plate 120 arrange | positioned so that the base material 1A may be clamped, and the electric current can be applied.

The electricity supply member 134 is provided so that an advance movement can be performed by the drive part (not shown) which performs an advance movement of an air cylinder etc. in the axial direction of the electricity supply shaft 133 or the base material 1A. After the base 1A is provided on the support shaft 131, it is possible to conduct electricity by bringing the energizing member 134 into contact with both end faces of the base 1A on both sides in the axial direction of the base 1A. On the other hand, in the example shown in FIG. 4, although the electricity supply member 134 was provided in the both end surfaces of the base material 1A, the electricity supply member 134 is provided only in one end surface of the base material 1A, and the other is a suppression member. You may also do it. In addition, the electricity supply member 134 does not need to contact the base material 1A strictly at the cross section of the base material 1A, and may be the structure which contacts the base material 1A in another position, such as an inner peripheral surface of the base material 1A.

Since the energization shaft 133 moves forward and backward through the treatment tank 110 and the outer tub 140, the energization shaft 133 is disposed between the energization shaft 133, the treatment tank 110, and the outer tub 140. A sliding bearing 135 that is rotatable and movably supported toward the shaft is provided.

The inner diameter side corners of both ends of the base material 1A of the example of illustration are cut off at the edges, and the taper surface 1a is formed in a part of both end surfaces of the base material 1A, while the outer diameter side corners of the energization member 134 are cut out at the edges. It is preferable that the taper surface 134a which comes into surface contact with the taper surface 1a of the base material 1A is formed, and the inclination of both is set to the same gradient. By surface contacting the taper surface 1a of the base material 1A and the taper surface 134a of the electricity supply member 134, both can be in intimate contact with each other, and the base material 1A or the electricity supply member 134 When the) side rotates, rotation can be transmitted by the contacted resistance, and it can rotate in synchronization.

With such a structure, the contact area is large, and the influence of slipping and abrasion when rotating is also reduced, so that stable current supply is possible.

In addition, since the electricity supply shaft 133 to which the electricity supply member 134 was connected rotates in synchronization with the base material 1A, the electricity supply shaft 133 and the power supply 121 are electrically connected by the rotating power supply connector (not shown). It is in contact. Although a rotary connector, a slip ring, etc. are mentioned as a connector which can rotate-feed, a rotary connector is preferable because of the good current stability at the time of rotation. In addition, the energization member 134 may be brought into surface contact with only one end surface of the substrate 1A.

The outer tank 140 accommodates the treatment tank 110, and as shown in FIGS. 2 and 4, the electrolyte 1L in the treatment tank 110 is discharged from the overflow portion 113 to the outer tank 140. Flow. The electrolyte 1L received in the outer tank 140 flows down into the storage tank 150 via the flow path 141.

The storage tank 150 is provided with a temperature adjusting means 153 of the electrolyte 1L, and the electrolyte 1L temperature-controlled in the storage tank 150 is treated by the pump 152 through the transfer flow path 151. It is conveyed to the processing tank main body 111 from the electrolyte solution supply part 112 of (110). On the other hand, as the temperature control means 153 provided in the storage tank 150, the heat exchanger which used water, oil, etc. as a fruit, an electric heater, etc. are mentioned.

&Lt; Action >

The electrolytic treatment apparatus 11 of this invention demonstrated above is equipped with the processing tank 110 of this invention. Therefore, the electrolyte 1L hardly stays in the treatment tank main body 111 of the treatment tank 110.

On the other hand, a pump (not shown) or the like is used when the electrolyte 1L is sent to the electrolyte supply unit 112, but the electrolyte 1L is sent from the electrolyte supply unit 112 by gravity. Therefore, the processing tank 110 of the present invention, like the conventional processing tank 170 shown in FIGS. 7A and 7B, is provided by a pump 173 from a supply pipe 171 provided in the lower portion of the processing tank 170. Compared to the case where the electrolyte 1L 'is discharged above the treatment tank 170 (that is, against gravity), the pressure of the pump is less likely to be affected. Therefore, even if the base material 1A to be electrolytically lengthened and the length in the longitudinal direction of the treatment tank main body 111 and the electrolyte solution supply part 112 are long, the pressure of the electrolyte solution received from the pump at both ends of the electrolyte solution supply part 112. The car is small

Therefore, in the electrolytic treatment apparatus 11 of the present invention, since the electrolyte L can be partially prevented from remaining in the treatment tank main body 111 of the treatment tank 110, the outer peripheral surface of the substrate 1A is removed. Electrolytic treatment can be performed uniformly.

In particular, when anodizing an aluminum substrate, it becomes important to suppress the temperature unevenness of the electrolyte solution or the substrate surface. However, if the electrolytic treatment apparatus 11 of the present invention is used, the electrolyte solution 1L in the treatment tank main body 111 is used. Since the retention portion of is hardly generated, temperature nonuniformity is unlikely to occur. Therefore, the dispersion | variation in the depth of the pore formed in the outer peripheral surface of 1A of base materials is suppressed.

Moreover, since the bottom part of the processing tank main body 111 is curved in circular arc shape, the electrolytic treatment apparatus 11 of this invention reduces volume compared with the rectangular parallelepiped processing tank 170 shown to FIG. 7A, 7B. can do. Therefore, the usage-amount of electrolyte solution can also be suppressed.

On the other hand, in the electrolytic treatment apparatus 11 of the present invention, since the electrolyte 1L naturally flows in the treatment tank main body 111, it is necessary to provide a member for adjusting the flow of the porous plate or the like in the treatment tank 110. none.

<Other embodiment>

The electrolytic treatment apparatus of this invention is not limited to the electrolytic treatment apparatus 11 shown to FIG. 4, 5A, 5B. For example, although the electrolytic treatment apparatus 11 shown to FIG. 4, 5A, 5B is equipped with the support shaft 131 as the rotation means 130 which rotates the base material 1A, the electricity supply connected to the electricity supply member 134 is provided. The shaft 133 may be used as the rotation means. In that case, the support shaft 131 may be configured such that the support shaft 131 can rotate in synchronization with the substrate 1A without being connected to the rotation driving unit described above.

In addition, the electricity supply member 134 does not need to be comprised by the material which has the electroconductivity as the whole mentioned above, and should just be a structure which can electrically connect the base material A and the shaft 133 for electricity supply. Specifically, a configuration in which the tapered surface 134a of the electricity supply member 134 and the portion for electrically connecting the shaft 133 for electricity delivery may be coated with an insulating material. Moreover, also regarding the taper part 134a, if the base material 1A and the electricity supply member 134 can be electrically connected stably, a part of the surface may consist of other than a conductive material.

In addition, in embodiment mentioned above, the inner diameter side corner | angular part of both ends of 1 A of base materials is cut off, and the taper surface 1a is formed, and the outer diameter side corner part of the electricity supply member 134 is corner-cut, and the tapered surface 134a is cut off. Although formed, the outer diameter side corner parts of the both ends of 1 A of base materials may be cut off, and the inner diameter side corner parts of the electricity supply member 134 may be cut off, and a taper surface may be formed.

In addition, the tapered surface 134a formed in each electricity supply member 134 does not need to be the same shape, and may be a different shape. In addition, the tapered surface 134a may be suitable for the structure formed in at least one side of the electricity supply member 134. FIG.

<Use>

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 treatment such as anodic oxidation or coating treatment such as plating, but is particularly suitable as an anodizing apparatus for anodizing an aluminum substrate. .

Hereinafter, an example of the method of manufacturing an mold by anodizing an aluminum base material using the electrolytic treatment apparatus of this invention is demonstrated.

First, as shown to FIG. 4, 5A, 5B, the aluminum base material is provided on the support shaft 131 as 1A base material. At this time, as shown in FIG. 2, the substrate 1A such that a void S is formed between the outer peripheral surface 1A 'of the substrate 1A and the inner surface 111a' of the bottom 111a of the treatment tank main body 111. Is installed on the support shaft 131. Specifically, the substrate 1A such 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. It is desirable to install it.

On the other hand, when the shape of the inner surface 111a 'of the bottom part 111a is semi-circular, it is preferable to provide the base material 1A so that the center on the diameter of this semicircle and the center axis P of the base material 1A may overlap. Do.

Thereafter, the energizing shaft 133 is simultaneously moved on both sides using the drive unit (not shown) that moves back and forth, thereby bringing the energizing member 134 into contact with the substrate 1A. On the other hand, 1L of electrolyte may be supplied to the processing tank main body 111 after contacting the base material 1A to the electricity supply member 134, and electricity supply is carried out in the state in which 1L of electrolyte enters the processing tank main body 111. The member 134 may be in contact with the substrate A. The rotary drive unit (not shown) is driven while the energizing member 134 is in contact with the substrate 1A to rotate the support shaft 131 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 conduction shaft 133 and the conducting member 134 to anodic oxidation of the substrate 1A. Is done.

When the energizing member 134 is brought into contact with the substrate 1A, the pressing pressure for making the contact is preferably 0.2 MPa or more. Since the slippage occurs in the tapered surface contacted during rotation or does not break due to intimate contact, there is an effect on stable current supply. However, if the pressing pressure is too large, it may cause deformation of the substrate 1A, or rotation may not be transmitted, so it may be stopped. Therefore, it is necessary to appropriately select by the shape of the workpiece and the means of the rotation drive source.

During the anodic oxidation of the substrate 1A, the same amount of electrolyte is supplied to the treatment tank body 111 while discharging a part of the electrolyte 1L from the treatment tank body 111 while rotating the substrate 1A. . Specifically, 1L of electrolyte is discharged | emitted from the processing tank main body 111 to the outer tank 140 by the overflow part 113 of the processing tank 110, and discharged electrolyte L is stored from the outer tank 140 in the storage tank. After flowing down to 150 and adjusting the temperature of electrolyte 1L in the storage tank 150, the electrolyte supply part provided above the side surface on one side so that the said electrolyte solution 1L may follow the longitudinal direction of the process tank main body 111 It returns to 112 and supplies it into the processing tank main body 111 from this electrolyte supply part 112.

At this time, since the inner surface 111a 'of the bottom portion 111a of the treatment tank main body 111 is curved in an arc shape, an almost uniform flow of the electrolyte solution 1L is formed, and the electrolyte solution 1L does not stay naturally. The overflow unit 113 may be moved.

On the other hand, it is preferable to rotate the base material 1A in the direction opposite to the flow direction of the electric field liquid 1L.

As for the supply amount of the electrolyte solution 1L from the electrolyte supply part 112 to the processing tank main body 111, the circulation | recovery frequency is 1 or more times every 3 minutes with respect to the volume of the processing tank main body 111. As shown in FIG. By doing so, the processing tank main body 111 can perform frequent liquid update, and can efficiently perform heat removal and generated hydrogen removal.

As for the circumferential speed of the base material 1A, 0.1 m / min or more is preferable. If the peripheral speed of the base material 1A is 0.1 m / min or more, the nonuniformity of the density | concentration of electrolyte solution 1L and temperature around 1 A of base materials is suppressed more effectively. In view of the capability of the drive device, the circumferential 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 from the state shown in Fig. 6A as shown in Fig. 6B.

The purity of aluminum used as the base material 1A is preferably 99% or more, more preferably 99.5% or more, and even more 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 reduced. Oxalic acid, sulfuric acid, etc. are mentioned as electrolyte solution.

When oxalic acid is used as an electrolytic solution:

The concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid exceeds 0.7 M, the current value increases, and the surface of the oxide film may become rough.

In order to obtain anodized alumina having highly regular pores at a predetermined cycle, it is necessary to apply a chemical conversion voltage at a predetermined cycle. For example, in the case of anodized alumina having a period of 100 nm, the conversion voltage is preferably 30 to 60V. If the harmonic voltage for a predetermined period is not applied, the regularity tends to be lowered.

60 degrees C or less is preferable, and, as for the temperature of electrolyte solution, 45 degrees C or less is more preferable. When the temperature of electrolyte solution exceeds 60 degreeC, what is called a "yake" may arise, a pore may collapse, or the surface may melt | dissolve and regularity of a pore may be disturbed.

When sulfuric acid is used as an electrolytic solution:

The concentration of sulfuric acid is preferably 0.7 M or less. When the concentration of sulfuric acid exceeds 0.7 M, the current value may be high and constant voltage may not be maintained.

In order to obtain anodized alumina having highly regular pores at a predetermined cycle, it is necessary to apply a chemical conversion voltage at a predetermined cycle. For example, in the case of anodized alumina having a period of 63 nm, the conversion voltage is preferably 25 to 30V. If the harmonic voltage for a predetermined period is not applied, the regularity tends to be lowered.

30 degrees C or less is preferable, and, as for the temperature of electrolyte solution, 20 degrees C or less is more preferable. When the temperature of electrolyte solution exceeds 30 degreeC, what is called a "yake" may arise, a pore may collapse, or the surface may melt | dissolve and regularity of a pore may be disturbed.

And after forming the oxide film 162 which has the pore 161 as shown to FIG. 6 (b), it has a some pore by carrying out anodization using the electrolytic treatment apparatus 11 of this invention. A roll-shaped mold is manufactured by repeating the process (anode oxidation process) of forming anodized alumina, and the process (pore diameter expansion process) which enlarges the diameter of the said pore.

In the case of repeating the anodic oxidation treatment step and the pore diameter expansion treatment, the oxide film 162 is first removed as shown in Fig. 6C. Here, the regularity of the pores can be improved by using this as the pore generating point 163 of anodization.

As a method of removing an oxide film, the method of melt | dissolving and removing in an solution which melt | dissolves an oxide film selectively is mentioned, without melt | dissolving aluminum. As such a solution, chromic acid / phosphate mixed liquid etc. are mentioned, for example.

When the substrate 1A from which the oxide film has been removed is anodized again, as shown in Fig. 6D, an oxide film 162 having columnar pores 161 is formed.

Anodic oxidation is performed using the electrolytic treatment apparatus 11 mentioned above. The conditions may be the same as those when the oxide film 162 shown in Fig. 6B is formed. Deep pores can be obtained as the anodic oxidation time is lengthened.

And as shown in FIG.6 (e), the process which enlarges the diameter of the pore 161 is performed. The pore diameter expansion treatment is a treatment in which the diameter of the pores obtained by anodization is enlarged by immersion in a solution in which the oxide film is dissolved. As such a solution, about 5 mass% phosphoric acid aqueous solution etc. are mentioned, for example.

The larger the pore diameter enlarging process is, the larger the pore diameter becomes.

Then, when anodized again, as shown in Fig. 6 (f), a columnar pores 161 having a small diameter, which extend downward from the bottom of the columnar pores 161, are further formed.

Anodic oxidation is performed using the electrolytic treatment apparatus 11 mentioned above. The conditions may be the same conditions as described above. Deep pores can be obtained as the anodic oxidation time is lengthened.

Then, when the pore diameter expanding process and the anodizing process as described above are repeated, anodized alumina (a porous oxide film of aluminum) having pores 161 having a shape in which the diameter continuously decreases in the depth direction at the opening portion. )), The roll-shaped mold 160 as shown to FIG. 6 (g) is obtained. It is preferable to end with a pore diameter expansion process last.

The number of repetitions is preferably three or more times in total, and more preferably five or more times. When the number of repetitions is twice or less, since the diameter of the pores decreases discontinuously, the effect of reducing the reflectance of the optical film is insufficient due to transfer of such pores.

As a shape of the pore 161, a substantially cone shape, a pyramidal shape, etc. are mentioned. The average period between the pores 161 is equal to or less than the wavelength of visible light, that is, 400 nm or less. The average period between the pores 161 is preferably 25 nm or more.

1.5 or more are preferable and, as for the aspect ratio (depth of a pore / width of the opening of a pore) of the pore 161, 2.0 or more are more preferable.

100-500 nm is preferable and, as for the depth of the pore 161, 150-400 nm is more preferable. 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 rolled aluminum substrate is anodized in the electrolyte solution 1L of the treatment tank body 111 as the substrate 1A, the electrolyte solution 1L is used. It is supplied from above one side of the processing tank main body 111, and is discharged | emitted from the upper part of the other side. At this time, since the inner surface of the bottom part of the processing tank main body 111 is curved in circular arc shape, 1L of electrolyte solution does not stay and can move to an overflow part naturally. Therefore, since temperature nonuniformity of electrolyte solution and the surface of a base material is suppressed, anodization is performed almost uniformly over the outer peripheral surface of the base material 1A, As a result, the roll-shaped mold by which the dispersion | variation of the pore depth was suppressed can be manufactured. have.

In particular, when the substrate 1A is rotated using the central axis of the substrate 1A as the rotation axis, the concentration of the electrolyte solution and the unevenness of the temperature are suppressed, so that the substrate 1A can be anodized more uniformly. The mold of the roll shape in which the deviation of the depth of a pore was suppressed more can be manufactured.

Moreover, when the base material 1A is provided in the processing tank main body 111 so that the space | gap of a specific magnitude | size may be formed between the outer peripheral surface of the base material 1A and the inner surface of the bottom part of the processing tank main body, the base material 1A and the processing tank main body 111 Electrolyte solution 1L positioned between) can fully fulfill the role of the buffer material. As a result, even if the processing tank main body 111 is heated by the heat generation at the time of anodizing, it can suppress that the base material 1A is directly warmed by the processing tank main body 111. Therefore, the temperature nonuniformity of the outer peripheral surface of a base material can be prevented more effectively, and the roll-shaped mold by which the dispersion | variation in depth was suppressed more can be manufactured.

The outer circumferential surface of the roll-shaped mold 160 may be treated with a release agent so that separation from the transfer target body is easy. As a mold release agent, a silicone resin, a fluororesin, a fluorine compound, etc. are mentioned, A fluorine compound which has a hydrolyzable silyl group is preferable at the point which is excellent in mold release property and excellent in adhesiveness with the roll-shaped mold 160. As a commercial item of a fluorine compound, the fluoroalkyl silane and the "off-through" series by Daikin Industries are mentioned.

10 is a side cross-sectional view of the anodic oxidation apparatus 210 according to the present embodiment. FIG. 11 is a cross-sectional view taken along the line 2A-2A of FIG. 10.

As shown in FIG. 10, the anodic oxidation apparatus 210 is configured to receive an electrolyte that has overflowed from the anodic oxidation tank 211 surrounded by the anodic oxidation tank 211 filled with the electrolyte and the anodic oxidation tank 211. The outer tank 212, the storage tank 225 which stores an electrolyte solution once, and the flow path 229 which flows the electrolyte solution received by the outer tank 212 to the storage tank 225 are provided. The roll-shaped aluminum base material 220 is accommodated in the anodic oxidation tank 211 and immersed in electrolyte solution.

The supply port 218 is formed in the bottom part of the anodizing tank 211 lower than the aluminum base material 220, and the anodizing apparatus 210 conveys the electrolyte solution of the storage tank 225 to the anodizing layer 211 further. The conveyance flow path 228, the pump 227 provided in the middle of the conveyance flow path 228, and the rectifying plate 217 which adjusts the flow of the electrolyte solution discharged from the supply port 218 are provided.

The storage tank 225 is provided with a temperature control means 226 of the electrolyte solution, and the electrolyte solution heated in the storage tank 225 flows toward the anodic oxidation tank 211 through the transfer flow path 228 by the pump 227. While being formed, a force is discharged from the supply port 218. As a result, a flow of the electrolyte solution rising from the bottom of the anodic oxidation tank 211 to the top is formed. On the other hand, as the temperature control means 226 provided in the storage tank 225, the heat exchanger, the electric heater, etc. which made water, oil, etc. a fruit are mentioned.

The rectifying plate 217 is a plate-shaped member having a plurality of through holes for adjusting the flow of the electrolyte so that the electrolyte discharged from the supply port 218 rises almost uniformly from the entire bottom of the anodic oxidation tank 211. The rectifying plate 217 is disposed between the aluminum base material 220 and the supply port 218 so that the surface (surface direction) is substantially horizontal. In addition, the two negative electrode plates 221 shown in FIG. 11 are arrange | positioned in parallel with respect to the central axis of the aluminum base material 220, and have a space | interval from the aluminum base material 220 so that the aluminum base material 220 may be pinched | interposed from a horizontal direction. It is a metal plate opposingly arranged.

Referring to FIG. 10, on the lower side of the side walls 211A and 211B facing each other in the anodic oxidation tank 211, a support shaft 215 supporting the aluminum substrate 220 in the axial direction in the horizontal direction is provided. . As shown in FIG. 11, a pair of support shafts 215 are provided on the side walls 211A and 211B in parallel to each other in the horizontal direction. Each support shaft 215 penetrates the side walls 211A and 211B. It is rotatably supported with respect to 211A and 211B.

The cylindrical elastic member 216 which consists of resin materials, such as an O-ring, is inserted in the edge part of the anodic oxidation tank 211 of each support shaft 215, and the aluminum base material 220 has the outer peripheral surface at both ends. It is mounted on each elastic member 216 and is supported on the support shaft 215. Each support shaft 215 is connected to a rotational drive unit (not shown) such as a motor, for example, and the support shafts 215 are rotated in the same direction by the rotational drive unit. In this case, the aluminum substrate 220 in contact with the elastic member 216 is rotated.

Above the support shaft 215 on the side walls 211A and 211B, a shaft 214 is provided to pass along the axial direction in the horizontal direction, and the shaft 214 penetrates the outer tub 212 as well. Is exposed to the outside. The electricity transmission shaft 214 is made of a conductive material and is rotatably supported by the side walls 211A and 211B, respectively. On the other hand, the entire shaft 214 does not have to be made of a material having electrical conductivity, and the electric current may be applied to the aluminum base material 220 through the electric conduction member 213 described later. Specifically, the structure in which the exterior of the electricity transmission shaft 214 is coated with the insulating material may be sufficient, and the coating etc. which are excellent in abrasion resistance may be given to the site | part which contacts the side walls 211A and 211B.

At the end portion of the anodic oxidation tank 211 of each of the shafts 214, a disk shaped energizing member 213 is integrally provided. The energization member 213 is in surface contact with both end faces of the hollow columnar aluminum base material 220 serving as an anode. Here, the power source 224 is electrically connected to the two negative electrode plates 221 which face the aluminum base material 220, and the shaft 214 for electricity supply, and the electric current can be applied.

The energization member 213 is provided so that an advancing / removing motion can be performed by the drive part (not shown) which performs an advancing / removing motion of an air cylinder etc. in the axial direction of the energization shaft 214 or the aluminum base material 220. As shown in FIG. After providing the aluminum base material 220 to the support shaft 215, it can supply electricity by making the electricity supply member 213 contact both end surfaces of the aluminum base material 220 from the both sides of the axial direction of the aluminum base material 220. As shown in FIG. On the other hand, in the example shown in FIG. 10, although the electricity supply member 213 was provided in the both end surfaces of the aluminum base material 220, the electricity supply member 213 is provided only in one end surface of the aluminum base material 220, and the other is suppressed. It may be a member. In addition, the electricity supply member 213 does not need to contact an aluminum base material exactly in the cross section of the aluminum base material 220, and may be the structure which contacts the aluminum base material 220 in another position, such as an inner peripheral surface of the aluminum base material 220, and it does not matter. none.

Since the energizing shaft 214 moves forward and backward through the anodic oxidation tank 211 and the outer tank 212, the energizing shaft (214) is provided between the energizing shaft 214, the anodic oxidation tank 211, and the outer tank 212. A sliding bearing 219 is provided for supporting the 214 so as to be rotatable and movable in the axial direction.

The inner diameter side corners of both ends of the aluminum substrate 220 are cut off at the corners, and a tapered surface 220A is formed at a part of both end surfaces of the aluminum substrate 220, while the outer diameter side corner portions of the conducting member 213 are edged. It is preferable that the taper surface 213A which cuts and cuts surface contact with 220 A of taper surfaces is formed, and the inclination of both is set to the same gradient. By bringing the tapered surface 220A of the aluminum base material 220 into contact with the tapered surface 213A of the energization member 213, both of them can be in intimate contact with each other. When the member 213 side rotates, rotation can be transmitted by the contacted resistance, and it can rotate in synchronization.

For this reason, since a contact area is large and there is also no influence of a slip and abrasion when it rotates, stable current supply is attained.

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. If the taper angle is small, the resistance of the contact surface may be largely constrained upon contact, and the aluminum base material 220 may be deformed. This is because, if the taper angle is large, slippage is likely to occur at the contact surface when contacting and rotating.

Moreover, as for the surface roughness of the taper surface 220A, 213A of the aluminum base material 220 and the electricity supply member 213, the finishing surface of Ra 3.2 or less is preferable, and the precise finishing surface of Ra 1.6 or less is more preferable. When the surface roughness of the tapered surface is rough, when the aluminum substrate 220 and the conductive member 213 are brought into contact with each other, lifting occurs in a part of the contact portion, so that intimate contact is not possible, or the tapered surface of the conductive member 213 is This is because anodized alumina is formed at the place where 213A is excited, which affects stable current supply.

In addition, since the electricity supply shaft 214 to which the electricity supply member 213 is connected rotates in synchronization with the aluminum base material 220, the electricity supply shaft 214 and the power supply 224 are electrically connected by the rotating power supply connector (not shown). Is contacted (connected). Although a rotary connector, a slip ring, etc. can be mentioned as a connector which can rotate-feed, a rotary connector is preferable because of the good current stability at the time of rotation. In addition, the energization member 213 may be in surface contact with only one end surface of the aluminum base material 220 to perform energization.

On the other hand, 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 rotation drive source instead of the support shaft 215. In that case, the support shaft 215 may be configured to be capable of rotating in synchronization with the aluminum base material 220 without being connected to the above-described rotation drive unit. In addition, in this embodiment, the inner diameter side corner parts of the both ends of the aluminum base material 220 are cut off to form taper surface 220A, and the outer diameter side corner parts of the electricity supply member 213 are cut off to the taper surface 213A. Although formed, the outer diameter side corner parts of the both ends of the aluminum base material 220 may be sharpened, and the inner diameter side corner parts of the electricity supply member 213 may be sharpened, and a taper surface may be formed. In addition, although the electricity supply member 213 mentioned above, it does not need to be comprised with the material which has the whole electroconductivity, What is necessary is just the structure which can electrically connect the aluminum base material 220 and the electricity transmission shaft 214. Specifically, the structure coated with insulating material may be sufficient as the part which electrically connects 220 A of taper surfaces of an electricity supply member, and the shaft 214 for electricity transmissions. Moreover, also regarding the taper part 213A, if the aluminum base material 220 and the electricity supply member 213 can be electrically connected stably, a part of the surface may consist of other than a conductive material.

In addition, the taper surface 213A formed in each electricity supply member 213 does not need to be the same shape, and may be a different shape. In addition, the taper surface 213A may be suitable for the structure formed in at least one side of the electricity supply member 213.

Anodization of the aluminum base material 220 using this anodic oxidation apparatus 210 is performed as follows.

The aluminum base material 220 is installed on the support shaft 215. Thereafter, the energization shaft 214 is simultaneously moved from both sides using the drive unit (not shown) that moves back and forth, so that the energization member 213 is brought into contact with the aluminum substrate 220. On the other hand, the electrolytic solution may be added to the anodizing layer 211 after the aluminum base member 220 is brought into contact with the energizing member 213, and the electroconductive member 213 is made of the aluminum base in a state in which the electrolytic solution enters the anodic oxide layer 211. You may contact 220. The rotary drive unit (not shown) is driven while the energizing member 213 and the aluminum substrate 220 are in contact with each other to rotate the support shaft 215 to rotate the aluminum substrate 220.

While rotating the aluminum base material 220, a voltage is applied to the aluminum base material 220 and the negative electrode plate 221 through the energization shaft 214 and the power supply member 213 to perform anodization of the aluminum base material 220.

When the electricity supply member 213 is brought into contact with the aluminum base material 220, the pressing pressure for making the contact is preferably 0.2 MPa or more. Since the slippage occurs in the tapered surface contacted during rotation or does not break due to intimate contact, there is an effect on stable current supply. However, if the pressing pressure is too large, it may cause deformation of the aluminum base material 220, or rotation may not be transmitted, so that it may be stopped. Therefore, it is necessary to select appropriately by means of the work shape and the rotation drive source.

During the anodic oxidation of the aluminum substrate 220, the same amount of electrolyte is supplied to the anodic oxidation tank 211 while discharging a part of the electrolyte solution from the anodic oxidation tank 211 while rotating the aluminum substrate 220. Specifically, the electrolyte is overflowed from the anodic oxidation tank 211, the overflowed electrolyte is flowed into the storage tank 225, and the temperature of the electrolyte is adjusted in the storage tank 225, and then the electrolyte is controlled by an aluminum substrate ( It feeds into the anodic oxidation tank 211 from the supply port 218 provided below 220.

At this time, the electrolyte is discharged from the supply port 218 by the pump 227 by the pump 227, and the electrolyte discharged from the supply port 218 by the rectifying plate 217 is the entire bottom of the anodic oxidation tank 211. By adjusting the flow of the electrolyte solution so as to rise almost uniformly from the bottom, an almost uniform flow of the electrolyte solution rising from the bottom of the anodic oxidation tank 211 to the top is formed.

As for the supply amount of the electrolyte solution to the anodic oxidation tank 211 (discharge amount of the electrolyte solution from the supply port 218), circulation number of times with respect to the volume of the anodic oxidation tank 211 is preferable at least once every 3 minutes. By doing so, the anodic oxidation tank 211 can perform frequent liquid update, and can efficiently perform heat removal and generated hydrogen removal. Specifically, when the bath capacity is 107L, the supply flow rate is preferably about 36L / min.

As for the peripheral speed of the aluminum base material 220, 0.1 m / min or more is preferable. If the circumferential speed of the aluminum base material 220 is 0.1 m / min or more, the nonuniformity of the density | concentration of electrolyte solution and temperature around the aluminum base material 220 will be fully suppressed. In view of the capability of the drive device, the circumferential speed of the aluminum base material 220 is preferably 25.1 m / min or less.

As described above, in the step of anodizing the aluminum base material 220 to form an oxide film having a plurality of pores, as shown in FIG. 6, the base material 1A is anodized to form a roll mold 160. It is performed similarly to the process of doing it.

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

Since the aluminum substrate 220 and the electricity supply member 213 are in surface contact with each other, the aluminum substrate 220 is supplied with power while the aluminum substrate 220 and the electricity supply member 213 are rotated in synchronization. Since the area is large and there is no influence of slipping and abrasion when rotated, poor energization can be suppressed, and the yield of the roll-shaped mold can be further improved.

The manufacturing method of the roll shape mold for imprint which is one aspect of this invention (it is only described as a roll shape mold in this specification.) Is anodic-oxidized alumina (aluminum of aluminum) which has a some pore in the outer peripheral surface of a roll-shaped aluminum base material. A method for producing a roll-shaped mold having a porous oxide film (Alumite), characterized in that when the aluminum substrate is anodized in the electrolytic solution of the anodic oxidation bath, the aluminum substrate is rotated using the central axis of the aluminum substrate as the rotation axis.

Hereinafter, an example of the manufacturing method of a roll-shaped mold is demonstrated concretely.

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 anodizing an aluminum substrate having a hollow columnar shape under a constant voltage in an electrolyte solution to form an oxide film on an outer circumferential surface thereof.

(b) A step of removing the oxide film to form pore generation points of anodic oxidation.

(c) A step of anodizing again in the electrolyte after the step (b) to form an oxide film having pores at the pore generation point.

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

(e) A step of anodizing again in the electrolyte after the step (d).

(f) The process of repeating the said process (d) and a process (e).

(Step (a))

15 is a cross-sectional view showing an example of the anodizing apparatus.

The anodic oxidation treatment apparatus 310 covers the upper portion of the anodic oxidation tank 312 and the anodic oxidation tank 312 filled with the electrolyte solution, and the trough portion 314 for receiving the electrolyte solution overflowed from the anodic oxidation tank 312. The upper cover 316 formed on the periphery, the storage tank 318 for storing the electrolyte solution once, the flow passage 320 for flowing the electrolyte solution received from the trough portion 314 into the storage tank 318, and the storage tank ( The pump provided in the middle of the conveyance flow path 324 and the conveyance flow path 324 which conveys the electrolyte solution of 318 to the supply port 322 formed in the vicinity of the bottom part of the anodic oxidation tank 312 below the aluminum base material 330. 326, a rectifying plate 328 for adjusting the flow of the electrolyte discharged from the supply port 322, and a hollow columnar aluminum substrate 330 serving as an anode, thereby keeping the central axis 332 horizontal. The shaft center 334 and the central shaft 332 of the shaft core 334 (that is, the central shaft in the aluminum base material 330) as the rotating shaft. A driving device (not shown) for rotating the shim 334 and the aluminum base 330, two negative electrode plates 336 arranged to face each other by sandwiching the aluminum base 330, a central axis 332 of the shaft center 334, and The power supply 338 electrically connected to the two negative electrode plates 336, and the temperature control means 340 which adjusts the temperature of the electrolyte solution of the storage tank 318.

The pump 326 forms a flow of the electrolyte solution from the storage tank 318 to the anodic oxidation tank 312 through the conveyance flow path 324, and discharges the electrolyte solution with a force from the supply port 322. This is to form a flow of the electrolyte solution rising from the bottom of the oxidation tank 312 to the top.

The rectifying plate 328 is a plate-shaped member having a plurality of through holes for adjusting the flow of the electrolyte so that the electrolyte discharged from the supply port 322 rises almost uniformly from the entire bottom of the anodic oxidation tank 312. It is disposed between the aluminum substrate 330 and the supply port 322 so that the surface is approximately horizontal.

The drive device (not shown) is a motor or the like connected to the central axis 332 of the shaft core 334 by a member (not shown) such as a ring-shaped chain or gear.

The two negative plate 336 is a metal plate which is disposed in parallel with the central axis of the aluminum base 330, and is disposed to face the gap from the aluminum base 330 so as to sandwich the aluminum base 330 in the horizontal direction. .

As the temperature control means 340, a heat exchanger, an electric heater, etc. which made water, oil, etc. a fruit are mentioned.

Anodization of the aluminum base material 330 using the anodizing apparatus 310 is performed as follows, for example.

In the state where the aluminum base material 330 is immersed in the electrolyte solution of the anodic oxidation tank 312, a drive device (not shown) is driven and centered on the central axis 332 of the shaft center 334 (that is, centered on the aluminum base material 330). The shaft core 334 and the aluminum base material 330 are rotated using the axis) as a rotation axis.

While rotating the aluminum substrate 330, a voltage is applied between the aluminum substrate 330 and the negative electrode plate 336 to perform anodization of the aluminum substrate 330.

While anodizing the aluminum substrate 330, the same amount of electrolyte is supplied to the anodic oxidation tank 312 while discharging a part of the electrolyte solution from the anodic oxidation tank 312 while rotating the aluminum substrate 330. Specifically, the electrolyte is overflowed from the anodic oxidation tank 312, the overflowed electrolyte is flowed into the storage tank 318, and the temperature of the electrolyte is adjusted in the storage tank 318. It feeds into the anodic oxidation tank 312 from the supply port 322 provided below 330. At this time, the electrolyte is discharged from the supply port 322 by the pump 326 with force, and the electrolyte discharged from the supply port 322 by the rectifying plate 328 is the entire bottom of the anodic oxidation tank 312. By adjusting the flow of the electrolyte solution to rise almost uniformly from the bottom, an almost uniform flow of the electrolyte solution rising from the bottom of the anodic oxidation tank 312 to the top is formed.

As for the supply amount of the electrolyte solution to the anodic oxidation tank 312 (discharge amount of the electrolyte solution from the supply port 322), it is preferable that circulation number is 1 or more times every 3 minutes with respect to the volume of the anodic oxidation tank 312. By doing so, the anodic oxidation tank 312 can perform frequent liquid update, and can efficiently perform heat removal and generated hydrogen removal. For example, when the crude capacity is 105L, 35 L / min or more is preferable, and 41 L / min or more is more preferable. When the supply amount of the electrolyte is 41 L / min or more, a sufficient flow of the electrolyte occurs in the entire anodization tank 312. In terms of the capacity 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.

As for the peripheral speed of the aluminum base material 330, 0.1 m / min or more is preferable. If the peripheral speed of the aluminum base material 330 is 0.1 m / min or more, the density | concentration of electrolyte solution and the temperature nonuniformity around the aluminum base material 330 will be fully suppressed. In view of the capability of the drive device, the circumferential speed of the aluminum base material 330 is preferably 25.1 m / min or less.

As described above, in the step of anodizing the aluminum substrate 330 to form an oxide film having a plurality of pores, as shown in FIG. 6, the substrate 1A is anodized to form the roll-shaped mold 160. It is performed similarly to the process of forming.

In the manufacturing method of the roll-shaped mold for imprints of this invention demonstrated above, when the roll-shaped aluminum base material 330 is anodized in the electrolyte solution of the anodic oxidation tank 312, the aluminum axis 330 is made into the rotation axis, and aluminum is rotated. Since the base material 330 is being rotated, variations in the concentration and temperature of the electrolyte solution around the aluminum base material 330 are suppressed, and anodization is performed almost uniformly over the entire outer peripheral surface of the aluminum base material 330. As a result, the roll mold with which the dispersion | variation in the depth of a pore was suppressed can be manufactured.

Moreover, since the same amount of electrolyte is supplied to the anodic oxidation tank 312 while discharging a part of the electrolyte solution from the anodic oxidation tank 312, a flow of the electrolyte occurs in the anodic oxidation tank 312, and the aluminum base material 330 The nonuniformity of the concentration and temperature of the electrolyte solution in the vicinity of is further suppressed. As a result, the roll-shaped mold by which the dispersion | variation in the depth of a pore was further suppressed can be manufactured.

In addition, when the electrolyte overflows from the anodic oxidation tank 312 and the overflowed electrolyte is conveyed into the anodic oxidation tank 312 from the supply port 322 provided below the aluminum base material 330, the anodic oxidation tank 312 is provided. The flow of the electrolyte solution rising from the bottom of the panel to the upper part is generated, and the nonuniformity of the concentration and temperature of the electrolyte solution around the aluminum substrate 330 is further suppressed. As a result, the roll-shaped mold by which the dispersion | variation in the depth of a pore was further suppressed can be manufactured.

In addition, the two negative electrode plates 336 are disposed 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 to sandwich the aluminum base material 330 in the horizontal direction. Therefore, the negative electrode plate 336 does not disturb the flow of the electrolyte solution generated in the anodic oxidation tank 312. As a result, the nonuniformity of the density | concentration of electrolyte solution and temperature around the aluminum base material 330 can be suppressed further, and the roll shape mold by which the fluctuation | variation of the pore depth was further suppressed can be manufactured.

<Production method of the article>

In the method for producing an article of the present invention, a plurality of pores of anodized alumina formed on the outer circumferential surface of the roll-shaped mold for imprint obtained by the method for producing the roll-shaped mold for imprint of the present invention is transferred to the transfer member by an imprint method. It is a method of obtaining the article which has a some convex part in which the said pore was reversed on the surface.

As an imprinting method, the optical imprinting method mentioned later, or the thermal imprinting method which transfers the several pore of anodized alumina to a to-be-transferred body by making the roll-form mold heated to the to-be-transferred body made of a thermoplastic resin close to it, are mentioned In light of productivity and the like, a photoimprint method is preferable.

Hereinafter, the manufacturing method of the article by the optical imprint method is demonstrated concretely.

As a manufacturing method of the article by the optical imprint method, the method which has the following process (I)-(III) is mentioned, for example.

(I) The process of clamping an active energy ray curable resin composition between the surface of a base film and the surface of a roll shape mold, moving a base film along the surface of a rotating roll shape mold.

(II) The active energy ray curable resin composition is irradiated to the active energy ray curable resin composition sandwiched between the surface of a base film and the surface of a roll-shaped mold, hardening the said active energy ray curable resin composition, and the pore of anodizing alumina was reversed. Process of forming the cured resin layer which has several convex part on the surface.

(III) The process of peeling a base film from a roll mold with a cured resin layer.

As a base film, a polyethylene terephthalate film, a polycarbonate film, an acryl film, a triacetyl cellulose film, etc. are mentioned.

As an active energy ray curable resin composition, the active energy ray curable composition of Unexamined-Japanese-Patent No. 2009-174007 (patent document 1)-paragraphs [0046]-[0055] of Unexamined-Japanese-Patent No. 2009-241351, for example. And the active energy ray-curable resin compositions described in paragraphs [0052] to [0094].

When manufacturing an article by the optical imprint method, it manufactures as follows using the manufacturing apparatus shown in FIG. 16, for example.

The active energy ray curable resin composition 356 from the tank 354 between the roll-shaped mold in which anodized alumina having a plurality of pores is formed on the outer circumferential surface and the band-shaped base film 352 moving along the surface of the roll-shaped mold. ).

Between the roll-shaped mold and the nip roll 360 whose nip pressure is adjusted by the pneumatic cylinder 358, nip the base film 352 and the active energy ray curable resin composition 356, The active energy ray-curable resin composition 356 is uniformly evenly spread between the base film 352 and the roll-shaped mold 350, and filled in the pores of the outer peripheral surface of the roll-shaped mold.

The base film 352 using the active energy ray irradiation apparatus 362 provided below the roll mold in a state where the active energy ray curable resin composition 356 is sandwiched between the roll mold and the base film 352. Cured resin layer 364 in which a plurality of pores on the outer circumferential surface of the roll-shaped mold are transferred by irradiating an active energy ray to the active energy ray curable resin composition 356 on the side and curing the active energy ray curable resin composition 356. To form.

By the peeling roll 366, the article 368 is obtained by peeling the base film 352 in which the cured resin layer 364 was formed in the surface from the roll-shaped mold.

As the active energy ray irradiation device 362, a high pressure mercury lamp, a metal halide lamp, or the like is preferable, and the amount of light irradiation energy in this case is preferably 100 to 10000 mJ / cm ² .

As the article 368, an optical film (antireflection film etc.) etc. are mentioned.

In the manufacturing method of the article of this invention demonstrated above, since the roll-shaped mold for imprint in which the dispersion | variation in the depth of a pore obtained by the manufacturing method of the roll-shaped mold for imprint of this invention was used is used, The article which has a some convex part in which the dispersion | variation was suppressed on the surface can be manufactured.

18 is a cross-sectional view of the anodic oxidation apparatus 410 according to the present embodiment. 19 is a cross-sectional view taken along the line 4A-4A of FIG. 20 is a sectional view showing the principal parts of the detail of the member shown in FIG. 19.

As shown in FIG. 18, the anodic oxidation apparatus 410 covers the upper portion of the anodic oxidation tank 412 and the anodic oxidation tank 412 filled with the electrolyte solution, and receives the electrolyte solution overflowed from the anodic oxidation tank 412. The upper cover 416 formed at the periphery of the trough portion 414, a storage tank 418 for storing the electrolyte solution once, and a dripping passage 420 for flowing the electrolyte solution received through the trough portion 414 into the storage tank 418; In the middle of the conveyance flow path 424 and the conveyance flow path 424 which convey the electrolyte solution of the storage tank 418 to the supply port 422 formed in the vicinity of the bottom part of the anodic oxidation tank 412 below the aluminum base material 430. A pump 426 provided and a rectifying plate 428 for adjusting the flow of the electrolyte discharged from the supply port 422 are provided.

19, the anodizing apparatus 410 is a pair of disk-shaped rotary jig 432A respectively inserted into the openings 431A and 431B of both ends of the hollow columnar aluminum base material 430 serving as an anode. , 432B, and a pair of retaining plates 433A, 433B for rotatably supporting the rotary jigs 432A, 432B, and supporting the aluminum base material 430 through these rotary jigs 432A, 432B. (Refer to FIG. 19), two negative electrode plates 436 arranged to face each other with the aluminum base material 430 interposed therebetween, a power source 438 electrically connected to the aluminum base material 430 and the two negative electrode plates 436, and a storage tank. The temperature control means 440 which adjusts the temperature of the electrolyte solution of 418 is provided.

The pump 426 forms a flow of the electrolyte solution from the storage tank 418 to the anodic oxidation tank 412 through the conveyance flow path 424, and discharges the electrolyte solution with a force from the supply port 422. It is to form a flow of the electrolyte solution rising from the bottom of the oxidizing tank 412 to the top.

The rectifying plate 428 is a plate-shaped member having a plurality of through holes for adjusting the flow of the electrolyte so that the electrolyte discharged from the supply port 422 rises almost uniformly from the entire bottom of the anodic oxidation tank 412. It is arrange | positioned between the aluminum base material 430 and the supply port 422 so that the surface may be substantially horizontal.

The two negative electrode plates 436 are arranged in parallel to the central axis of the aluminum base material 430, and are metal plates facing each other with a gap from the aluminum base material 430 so as to sandwich the aluminum base material 430 from the horizontal direction. . Moreover, as the temperature control means 440 provided in the storage tank 418, the heat exchanger which used the water, oil, etc. as a fruit, an electric heater, etc. are mentioned.

Referring to FIG. 19, the holding plates 433A and 433B are metal plates that are disposed to face each other with a gap therebetween so as to sandwich the aluminum base material 430 from the axial direction 4C1, respectively, and the axial direction 4C1 of the aluminum base material 430, respectively. On the extension, it has bearing parts 434A, 434B, which are openings for rotatably inserting the rotary jigs 432A, 432B. On the inner circumferential surfaces of the bearing portions 434A and 434B, dry bearings 435A and 435B made of a resin material or a metal material are provided, and the rotary jig 432A and 432B is formed by the holding plate () by these dry bearings 435A and 435B. 433A and 433B are rotatably supported.

A plurality of bar members 441 penetrating through them are provided on the upper portions of the holding plates 433A and 433B which are separated from each other (see also FIG. 18). The holding plates 433A and 433B are connected by these bar members 441 in a state where they are dropped from these bar members 441 and are in parallel with each other.

Referring to FIG. 20, the rotary jigs 432A and 432B fit snugly to the openings 431A and 431B of the aluminum base material 430 or are inserted in a light press-fit state. At the same time, the water packing 470 is attached to both end faces of the opening of the aluminum base 430, and the rotary jig 432A, 432B has the water packing 470 at the flange portions 471A, 471B protruding in the outer diameter direction. ), And the aluminum base material 430 is fixed at both ends. As a result, the aluminum base material 430 has a structure in which the inside of the aluminum base material 430 is sealed by the water packing 470 and the rotary jigs 432A and 432B. As an index method for sealing, a sealing member such as an O-ring may be used in addition to the packing, and in addition to the opposite end surfaces of the opening of the aluminum base 430, a packing or the like is provided on the main surfaces of the inserted rotary jig 432A, 432B. May be used.

By fixing the aluminum substrate 430 to be fitted to the rotary jigs 432A and 432B, the aluminum substrate 430 is rotated in the circumferential direction with respect to the rotary jigs 432A and 432B, and the rotary jigs 432A and 432B. ), And in more detail, the aluminum base material 430 is supported by the rotation jig 432A, 432B so that the axial direction 4C1 (FIG. 19) may be in a horizontal state. That is, the aluminum base material 430 is supported by the rotation jig 432A, 432B so that it may be in parallel with the bottom part of the anodic oxidation tank 412. As shown in FIG.

In FIG. 19, a through hole 442 penetrating through the axial direction 4C1 of the aluminum base material 430 is formed in the rotation center region of the rotary jig 432A located on the left side of the page, and the conductive material is formed in the through hole 442. In the state where the electricity supply main bar 443 of the rod-shaped body which penetrated was penetrated, it is inserted and held with respect to the through-hole 442 so that relative rotation is impossible. The energization main bar 443 is fixed to the rotation jig 432A integrally, and rotates in association with the rotation of the rotation jig 432A. Referring to Fig. 20, when fixing the energized main bar 443 to the rotary jig 432A, an O-ring 472 is provided so that the electrolyte does not flow from the through hole 442, and the water is discharged. The inflow of the electrolyte solution from the through hole is eliminated, and the inside of the aluminum base material 430 together with the above-described water packing 470 is completely sealed. The O-ring 472 is fitted into the groove 473 formed around the through hole 442 of the rotating jig 432A and is covered by the flange 474 formed in the energizing main bar 443. As a fixing method of the rotating jig 432A of the electricity supply main bar 443, an aspect, such as forming a flange part in the electricity supply main bar 443 and fastening a bolt, is considered, but other aspects may be sufficient.

On the other hand, the reason why the aluminum substrate 430 is a sealed structure is that when the conductive member such as the catalyst 448 to be described later is brought into contact with the aluminum substrate 430 while the electrolyte is interposed, the aluminum substrate 462 is in contact with the aluminum substrate 430. This is because an oxide film having poor conductivity is also formed on the contact surface of the base material 430, which may affect the energized state and affect the oxide film formation.

In addition, the sealed structure prevents the electrolyte solution from entering the inside of the aluminum base material 430, and it is possible that the electrolyte remaining inside the aluminum base material 430, which occurs when passing through a plurality of process tanks, enters another process bath. Disappear. Thereby, the change of the component and density | concentration of the process liquid of a processing tank disappears. In addition, by using the sealed structure, the amount of electrolyte solution used in the anodic oxidation treatment tank 412 is also reduced, which leads to a reduction in waste solution and electrolyte solution cost.

One end of the energized main bar 443 is formed in a conical shape, and the conical end portion 444 is a rotation support portion 446 formed on the lower end side of the feed flat bar 445 received from the bar member 441. Abuts on The rotary receiving portion 446 has a conical recess 447, and the bottom surface of the recess 447 abuts the tip of the conical end portion 444, and the side surface of the recess 447. The area is regulated so as to surround the periphery of the conical end portion 444. The electricity supply main bar 443 is electrically connected to the power supply 438 (FIG. 18) via the power supply flat bar 445 and the rotation support part 446, and electric current is supplied from the power supply 438. In addition, the conical end part 444 may be integral with the electricity supply main bar 443, or may be a separate thing detachably attached.

On the other end side of the energized main bar 443, a catalyst 448 having a conducting member made of a pair of conductive materials projecting in the radial direction is fixed to be energized integrally, and the catalyst 448 is an aluminum substrate 430. The dimension setting and the shape setting are made so that the inner peripheral surface of the c) may be in contact with the electrical power. As a result, the catalyst 448 can be brought into contact with the aluminum base material 430, thereby supplying a current to the aluminum base material 430. More specifically, the catalyst 448 is bent the tip side positioned on the aluminum substrate 430 side, and the curved portion has a flat contact surface 448A which abuts against the inner circumferential surface of the aluminum substrate 430, The electric current is made to flow through the aluminum base material 430 from here.

In the anodic oxidation treatment apparatus 410 configured as described above, when the aluminum substrate 430 is rotated by transmitting the driving force of a motor (not shown), the rotation jig 432A on the opening 431A side is rotated by the rotation jig 432B. It rotates in conjunction with the aluminum substrate 430 rotated by). For this reason, the energization main bar 443 fixed to the rotating jig 432A is synchronized with the aluminum substrate 430 (i.e., interlocked) in a state in which the electricity supply main bar 443 is always in contact with a predetermined area of the inner circumferential surface of the aluminum substrate 430. To rotate.

Anodization of the aluminum base material 430 using this anodization apparatus 410 is performed as follows.

In the state where the aluminum base material 430 was immersed in the electrolyte solution of the anodic oxidation tank 412, a motor (not shown) is driven, the rotation jig 432B is rotated, and the aluminum base material 430 is axial direction 4C1. Rotate to the center of rotation.

While rotating the aluminum substrate 430, a voltage is applied between the aluminum substrate 430 and the negative electrode plate 436 through the feed flat bar 445, the rotation support portion 446, and the stator 448 to provide an aluminum substrate ( Anodization of 430 is performed.

During the anodic oxidation of the aluminum substrate 430, the same amount of electrolyte is supplied to the anodic oxidation tank 412 while discharging a part of the electrolyte solution from the anodic oxidation tank 412 while rotating the aluminum substrate 430. Specifically, the electrolyte is overflowed from the anodic oxidation tank 412, the overflowed electrolyte is flowed into the storage tank 418, and the temperature of the electrolyte is adjusted in the storage tank 418. It feeds into the anodic oxidation tank 412 from the supply port 422 provided below 430. As shown to FIG.

At this time, the electrolyte is discharged from the supply port 422 by the pump 426 and the electrolyte discharged from the supply port 422 by the rectifying plate 428 is the entire bottom of the anodic oxidation tank 412. By adjusting the flow of the electrolyte solution to rise almost uniformly from the top, an almost uniform flow of electrolyte solution rising from the bottom of the anodic oxidation tank 412 to the top is formed.

As for the supply amount of electrolyte solution (discharge amount of electrolyte solution from the supply port 422) to the anodic oxidation tank 412, it is preferable that circulation frequency is 1 or more times every 3 minutes with respect to the volume of the anodic oxidation tank 412. By doing so, the anodic oxidation tank 411 can perform frequent liquid update, and can efficiently perform heat removal and generated hydrogen removal. Specifically, when the bath capacity is 107L, the supply flow rate is preferably about 36L / min.

As for the peripheral speed of the aluminum base material 430, 0.1 m / min or more is preferable. If the peripheral speed of the aluminum base material 430 is 0.1 m / min or more, the density | concentration of electrolyte solution and temperature nonuniformity around the aluminum base material 430 will be fully suppressed. In view of the capability of the drive device, the circumferential speed of the aluminum base material 430 is preferably 25.1 m / min or less.

As described above, in the step of anodizing the aluminum substrate 430 to form an oxide film having a plurality of pores, as shown in FIG. 6, the substrate 1A is anodized to form the roll-shaped mold 160. It is performed similarly to the process of forming.

In the anodizing apparatus 410 according to the present embodiment described above, when the roll-shaped aluminum substrate 430 is anodized in the electrolyte solution of the anodic oxidation tank 412, the central axis of the aluminum substrate 430 is rotated. Since the aluminum base material 430 is rotated, variation in the concentration and temperature of the electrolyte solution 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, the roll mold with which the dispersion | variation in the depth of a pore was suppressed can be manufactured.

Then, while the aluminum substrate 430 and the catalyst 448 are in contact with each other, the aluminum substrate 430 and the catalyst 448 are rotated in synchronization with each other so that the electricity is supplied from the catalyst 448 to the aluminum substrate 430. As a result, the abrasion between the aluminum base material 430 and the catalyst 448 can be eliminated, so that a poor current supply can be suppressed, and the yield of the roll-shaped mold can be further improved.

That is, the aspect which rotates only the aluminum base material 430 without synchronizing the catalyst 448 with the aluminum base material 430 (fixing the catalyst 448 in the state which contacted the inner peripheral surface of the aluminum base material 430, the aluminum base material 430) In the case of rotating the bay only, the energizer 448 conducts electricity while sliding to the inner circumferential surface of the aluminum base material 430, and contact wear occurs between the catalyst 448 and the aluminum base material 430, and the tip 448. Although there is a possibility that a poor conduction may occur between the aluminum substrate 430 and the aluminum substrate 430, the present invention may rotate in synchronization with the aluminum substrate 430 and the catalyst 448 in a state where the aluminum substrate 430 is brought into contact with the catalyst 448. This prevents the occurrence of such poor energization. On the other hand, the catalyst 448 and the aluminum substrate 430 need not rotate completely in synchronization. For example, when the catalyst 448 and the aluminum substrate 430 seem to be rotated by separate power sources, it is difficult to rotate these members completely in synchronization. Therefore, in the present invention, the state in which the catalyst 448 and the aluminum base material 430 rotate in conjunction with each other in a relatively fixed state is also included in the rotation in synchronization.

Here, in FIG. 21, the experiment example which measured the energized state with respect to the aluminum base material 430 in the anodizing apparatus 410 is shown. In FIG. 21, the horizontal axis | shaft has shown the time axis (second) and the electric current value A which energized the aluminum base material 430 is shown. As apparent from the figure, it was confirmed that after the initially applied current value was in a stable state, the aluminum substrate 430 was energized in a stable state over a long period of time. Also from this experimental example, the effect of suppression of the electricity supply failure by this invention was confirmed.

In addition, in this embodiment, although the edge part of the electricity supply main bar 443 is made into the cone shape (conical end part 444), by this, the contact area with the rotation support part 446 is made small, and the contact | wear-out in contact wear is carried out. Occurrence can be suppressed to a minimum, and the surface can be updated. For this reason, the alumina layer with high electrical insulation is not formed, and it becomes possible to maintain an energized state.

Example

Hereinafter, the present invention will be described in detail with reference to examples.

(Pores of anodized alumina)

A portion of the anodized alumina was cut, and platinum was deposited on the cross section for 1 minute, and the cross section was observed under a condition of an acceleration voltage of 3.00 kV using a field emission scanning electron microscope (JSM-7400F manufactured by Nippon Electronics Co., Ltd.) The depth of the was measured.

If the aluminum substrate is not rotated during anodization:

After completion of the last anodization, the depths of the ten pores were measured for each of positions 1 to 6 where the outer circumference of the roll-shaped mold 350 shown in FIG. 17 was divided into six circumferences, and the average value was obtained.

When rotating an aluminum substrate during anodization:

Immediately after the end of the last anodization, in the state where the rotation of the aluminum base is stopped, the depths of the ten pores, respectively, to positions 1 to 6 that divide the outer circumference of the roll-shaped mold 350 shown in FIG. 17 into six circumferences. Was measured and the average value was calculated | required.

(reflectivity)

The relative reflectance of the surface of the cured resin layer was measured using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.) at an incident angle of 5 ° and a wavelength of 380 to 780 nm.

If the aluminum substrate is not rotated during anodization:

One end of the width direction of the film, respectively, to the surface of the cured resin layer corresponding to the positions 1 to 6 that divide the outer periphery of the roll-shaped mold 350 shown in FIG. The reflectance of three places in the center and the other end was measured.

When rotating an aluminum substrate during anodization:

With respect to the surface of the cured resin layer corresponding to positions 1 to 6 that circumferentially divides the outer circumference of the roll-shaped mold 350 shown in FIG. 17 in the state where the rotation of the aluminum substrate is stopped immediately after the end of the last anodization. The reflectances of three places of one end, the center, and the other end of the width direction of the film were respectively measured.

(Active energy ray curable resin composition (A))

45 parts by mass of the condensation reaction mixture having a molar ratio of succinic acid / trimethylolethane / acrylic acid 1: 2: 4, 45 parts by mass of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), radically polymerizable 10 parts by mass of silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-1602), 1-hydroxycyclohexylphenyl ketone (manufactured by Chiba Specialty Chemical Co., Irgacure (registered trademark) 184, wavelength 340 nm or more, and an absorption wavelength range). 3 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Chiba Specialty Chemicals Co., Ltd., Irgacure® 819, having an absorption wavelength range at a wavelength of 340 nm or more.) 0.2 A mass part was mixed and the active energy ray curable resin composition (A) was obtained.

[Example 1]

After carrying out polishing of the hollow columnar aluminum substrate (purity: 99.99%, length: 280 mm, outer diameter: 200 mm, inner diameter: 155 mm) with cloth, it was added to a perchloric acid / ethanol mixed solution (volume ratio of 1/4). Polished electrolytically.

Subsequently, using the anodizing apparatus shown in FIG. 15, in an 107 L electrolyte solution consisting of 0.3 M aqueous oxalic acid solution, the bath temperature was 15.7 ° C., the direct current was 40 V, and the supply amount of the electrolyte solution was 41 L / min. Circumferential speed: Anodizing was performed for 30 minutes under the conditions of 3.8 m / min, and the oxide film was formed (process (a)).

The formed oxide film was once dissolved and removed in a 6 mass% phosphoric acid and 1.8 mass% chromic acid mixed aqueous solution (step (b)), and then anodized for 45 seconds again under the same conditions as in step (a). Was formed (step (c)).

Then, it immersed in 5 mass% phosphoric acid aqueous solution (31.7 degreeC) for 8 minutes, and performed the hole diameter expansion process (process (d)) which enlarges the diameter of the pore of an oxide film.

Further, under the same conditions as in step (a), anodization was performed for 45 seconds to form an oxide film (step (e)).

Furthermore, process (d) and process (e) were repeated, and process (d) was performed 5 times in total and process (e) was performed 4 times in total (process (f)). The roll-shaped mold A in which the anodized alumina which has a substantially conical pore on the outer peripheral surface of the aluminum base material was formed. The depth of the pores of the anodized alumina was measured. The results are shown in Table 1.

Subsequently, the roll-shaped mold (A) was dipped in 0.1 mass% solution of a mold release agent (made by Daikin Industries, Ltd., off-through DSX (brand name)) for 10 minutes, dried in air for 24 hours, and the mold release process was performed.

The article which has a some convex part on the surface was manufactured using the manufacturing apparatus shown in FIG.

As the roll mold 350, the roll mold (A) was used.

As active energy ray curable resin composition 356, active energy ray curable resin composition (3A) was used.

As a base film 352, the polyethylene terephthalate film (The Toyo Spinning agent, brand name: A4300, thickness: 75 micrometers) was used.

From the base film 352 side, the ultraviolet-ray of integrated light quantity 1100mJ / cm <^2> was irradiated to active energy ray curable resin composition (A), and hardening of active energy ray curable resin composition (A) was performed.

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]

Except not rotating the aluminum base material in electrolyte solution, it carried out similarly to Example 1, and obtained the roll-shaped mold B in which the anodized alumina which has the taper-shaped pore of substantially conical shape was formed in the outer peripheral surface of the aluminum base material. The depth of the pores of the anodized alumina was measured. The results are shown in Table 1.

Subsequently, similarly to Example 1, the mold release process of the roll mold B was performed.

Next, except having used the roll mold (B) as the roll mold 350, it carried out similarly to Example 1, and manufactured the article which has a some convex part on the surface. 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 an aluminum base material in electrolyte solution had small deviation of the 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 portion, that is, the variation in reflectance was small.

On the other hand, the roll-shaped mold (B) of Comparative Example 1 produced by anodizing without rotating the aluminum substrate in the electrolyte solution had a large variation in the depth of the pores. As a result, even in the article which has a some convex part on the surface, the deviation of the height of the convex part, ie, the deviation of a reflectance, became large.

EXAMPLE 2

In the present Example 2, specific conditions were set to the anodic oxidation apparatus 210 shown in FIG. 10, and operation was performed. Both end surfaces of the hollow columnar aluminum substrate 220 (purity: 99.99%, length: 280 mm, outer diameter: 200 mm, inner diameter: 155 mm) and the cross section of the conducting member 213 are set to a taper angle of 30 ° with respect to the axial direction, The surface roughness of each tapered surface 220A, 213A was set to Ra 1.6.

In 106 L of electrolyte solution which consists of 0.3 mol / L aqueous solution, the aluminum base material 220 is bath temperature: 15.7 degreeC, electrolyte supply amount: 36 L / min, pressurization pressure of the both parts electricity supply member 213: 0.2 Mpa, aluminum base material 220 Anodic oxidation was performed for 60 minutes under conditions of a voltage of 40V under conditions of a circumferential speed of 3.8 m / min.) To form an oxide film.

12A shows an experimental example (graph) in which the state of the current value when the current was energized in the anodizing apparatus 210 for 60 minutes was measured. In Fig. 12A, the horizontal axis represents integration time (seconds), and the vertical axis represents amplitude (A) of the current value. 12B shows a measurement result of the amplitude of the current value up to 1800 seconds in the measurement result shown in FIG. 12A (in contrast, in FIG. 12B, the scale of the amplitude A of the current value is shown in detail). .

In the second embodiment, as evident from these figures, it was confirmed that the constant current value stable over a long period of time did not fluctuate greatly and was energized by the aluminum substrate 220. Also from this Example 2, the effect of suppression of poor energization according to the present invention could be confirmed.

(Comparative Example 2)

Hereinafter, the example which compared the temperature at the time of performing electrolytic treatment in the processing apparatus of this invention and a rectangular parallelepiped processing tank is demonstrated.

Anodizing treatment was performed in the treatment tank and the rectangular parallelepiped treatment tank of the present invention using a hollow columnar aluminum substrate (purity: 99.99%, length: 1000 mm, outer diameter: 200 mm, inner diameter: 155 mm). In FIG. 2, the treatment tank of the present invention has a distance D from the central axis P to the inner surface 111a ′ of the bottom portion 111a as 400 mm, and the rectangular parallelepiped treatment tank has the same shape as FIGS. 7A and 7B. Each treatment tank circulates at a flow rate at which the circulation number is once every three minutes, and supplies an electrolytic solution temperature-controlled at 16 ° C to each treatment tank.

8 and 9 are graphs comparing the electrolyte solution temperatures when the anodic oxidation treatment was performed in each treatment tank. FIG. 8 is a graph when several points of the electrolyte solution temperature of 50 mm from the treatment tank wall surface are measured throughout the treatment tank. FIG. Although the temperature rises under the influence of the heat generation of electricity supply, the heat of an oxidation reaction, etc. by performing an anodizing process, as can be seen from FIG. 8, it turns out that the process tank of this invention has a small temperature rise. This is because, in the rectangular parallelepiped processing tank, a retention portion having poor circulation efficiency is generated, and heat when the heat generation portion generates heat is left, and the temperature becomes higher compared with a portion other than the retention portion.

9 is a graph when the maximum temperature difference is shown at several points of the length of the substrate on the surface of the substrate. The temperature difference on the surface of the base material is a temperature nonuniformity occurring on the surface of the base material, and affects the nonuniformity of the depth of the pores when anodizing is performed. As can be seen from FIG. 9, it can be seen that the treatment tank of the present invention has a small temperature difference. This is also because the retention portion that occurs in the rectangular parallelepiped processing tank is caused, and the electrolyte temperature on the surface of the substrate close to the retention portion also increases.

In addition, in the processing tank which processed this base material, the volume of a rectangular parallelepiped processing tank was 130L compared with 250L.

From the above comparison, it was confirmed that in the treatment tank of the present invention, the retention of the electrolyte solution can be prevented, and the amount of the electrolyte solution can be further suppressed.

(Comparative Example 3)

Hereinafter, as a comparative example 3, the measured value of the electric current value at the time of making the aluminum base material contact the electricity supply member at the point is demonstrated. Referring to FIG. 13, in the anodic oxidation apparatus used in Comparative Example 3, sliding bearings 241 are provided in contact with inner surfaces of both ends of the aluminum base material 220, and an annular shape is formed on the outer circumferential surface of the sliding bearings 241. The housing 240 is connected to be fixed to the aluminum base material 220. The aluminum base material 220 is made to rotate by an external rotating mechanism (not shown).

The contactor 242 extended from the electricity supply member 243 contacts the inner surface of the aluminum base material 220 so that electricity can be supplied.

And the result of having measured the state which energized the aluminum base material 220 on the conditions similar to Example 2 in the state of FIG. 13 is shown in FIG. In Fig. 14, the horizontal axis represents integration time (seconds), and the vertical axis represents amplitude (A) of the current value. In addition, the measurement result to integration time 1200 second (20 minutes) is shown in FIG.

As can be seen by comparing the experimental example in the anodic oxidation treatment apparatus of the present invention shown in Figs. 12A and 12B with Fig. 14, it can be seen that in Comparative Example 3, there is always a slight vibration in the current value. Moreover, the place where the electric current value fluctuated here and there generate | occur | produces everywhere. As the cause, since the aluminum base material 220 and the contactor 242 are in contact with each other, the contact area is small, and when the aluminum base material 220 rotates, the contact surface due to the rotation cycle is large, so that the aluminum base material 220 can be stably contacted. It is considered that the aluminum substrate 220 and the contactor 242 are not in contact with the contact surface due to abrasion or slippage, and the contact with the aluminum substrate 220 and the contactor 242 is not instantaneously brought about.

The roll-shaped mold obtained by the manufacturing method which concerns on this invention is useful for manufacture of the optical film which has a fine concavo-convex structure called a MOS eye structure on the surface.

11: electrolytic treatment device
110: treatment tank
111: treatment tank body
111a: bottom
111a ': inside
111b, 111c: side
112: field liquid supply unit
113: overflow portion
120: electrode plate
130: rotating means
1A: substrate
1A ': Main surface (outer surface)
1L: electrolyte
210: anodic oxidation device
211: anodic oxidation tank
213: energized member
213A: tapered side
215: support shaft (rotary drive means)
220: aluminum substrate
220A: tapered side
312: anodic oxidation tank
322: supply port
330: aluminum base
336: negative electrode plate
342: handwork
344: oxide film (anode alumina)
350: roll shape mold
352: base film (transfer object)
368: Goods
410: anodic oxidation device
412: anodizing tank
430: aluminum base
432A, 432B: rotary jig
443: energized main bar (rotary shaft)
446: rotation support (rotation support)
448: tactile (without electricity)

Claims (17)

As a method for producing a roll-shaped mold having a plurality of irregularities on the surface by energizing a cylindrical aluminum substrate made of aluminum immersed in an electrolytic solution of an anodic oxidation tank using an energizing member to perform anodization.
A roll shape including an anodizing step of energizing the aluminum substrate through the conductive member while rotating the aluminum substrate with the center axis of the aluminum substrate as the rotation center in the state where the energizing member is in contact with the aluminum substrate. Method of making a mold. The method of claim 1,
The said aluminum base material and said electricity supply member are synchronized, and are rotated and the manufacturing method of the roll-shaped mold. 3. The method according to claim 1 or 2,
The energizing member includes a conductive shaft member and a chuck fixed to the shaft member and in contact with the aluminum substrate,
The catalyst is in contact with the inner peripheral surface of the cylindrical aluminum substrate,
The manufacturing method of the roll mold which is arrange | positioned at the position which the at least one edge part of the said shaft member contacts with the electrically conductive feeding member which supplies electric power to the said shaft member. The method of claim 3, wherein
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 portion is a cone shape,
At least one end of the shaft member rotates while sliding with the power feeding member. The method of claim 3, wherein
The aluminum substrate is rotated about a central axis by rotating a rotation jig fixed to the axial end of the aluminum substrate,
The shaft member is fixed to the rotary jig, and rotates in synchronization with the aluminum substrate, the manufacturing method of the roll-shaped mold. The method of claim 5, wherein
The said rotating jig makes the edge part of the said aluminum base material index the manufacturing method of the roll shape mold. The method of claim 1,
A method of producing a roll-shaped mold, wherein an equivalent amount of electrolyte is supplied to the anodic oxidation tank while discharging a part of the electrolyte solution from the anodic oxidation tank. The method of claim 7, wherein
Production of the roll-shaped mold which overflows electrolyte solution from the aluminum base of the said anodizing tank, discharges a part of said electrolyte solution, and conveys the overflowed electrolyte solution into the anodizing tank from the supply port provided below the said aluminum base material. Way. The method of claim 7, wherein
The shape of the said anodic oxidation tank is semi-cylindrical shape, The electrolyte solution is supplied uniformly from one side surface, and is overflowed from the other side surface. The method of claim 9,
The anodic oxidation tank has a long shape in which an electrolyte solution is accommodated and the aluminum substrate is immersed, and a bottom portion is curved in an arc shape so as to follow the main surface of the substrate immersed in the treatment tank body, and the treatment tank. An electrolyte solution supply part for supplying an electrolyte solution to the main body, and an overflow part for discharging the electrolyte solution from the treatment tank main body,
From the said electrolyte supply part provided so that it may follow the longitudinal direction of a treatment tank main body, electrolyte solution will be supplied from one side surface upper side of a treatment tank main body,
The manufacturing method of the roll-shaped mold which discharges the said electrolyte solution from the said overflow part provided in the upper side of the other side of a processing tank main body so that the process tank main body may be longitudinally followed. 11. The method of claim 10,
The said aluminum base material rotates in the direction opposite to the direction in which the said electrolyte solution supplied from the said electrolyte supply part flows to the said overflow part, The manufacturing method of the roll-shaped mold. 3. The method according to claim 1 or 2,
A method for producing a roll-shaped mold, wherein the conductive member is a conductive member which is in surface contact with one end face or both end faces of the aluminum substrate. 13. The method of claim 12,
The energizing member is disposed so as to abut one end surface or both end surfaces of the aluminum substrate, and the aluminum substrate is sandwiched in the axial direction,
The manufacturing method of the roll-shaped mold which rotates the said electricity supply member and rotates in the state which contacted the electricity supply member and the said aluminum base material. The method of claim 13,
And the rotating jig indexes an end of the aluminum substrate. 13. The method of claim 12,
A method for producing a roll-shaped mold, wherein the conductive member is moved along the axial direction of the aluminum substrate to bring the aluminum substrate into contact with the conductive member. 13. The method of claim 12,
One or both end surfaces of the aluminum substrate includes a first tapered surface, and the energizing member has a second tapered surface in surface contact with the first tapered surface, and the first tapered surface and the second tapered surface are separated from each other. A method for producing a roll-shaped mold, wherein the aluminum substrate and the conductive member are brought into contact with each other by contact. A method of manufacturing an article having a plurality of irregularities on its surface, wherein a plurality of pores of anodized alumina formed on the outer circumferential surface of the roll-shaped mold for imprint obtained by the manufacturing method according to claim 1 is transferred to a transfer member by an imprint method. And obtaining an article having a plurality of convex portions of a shape in which the pores are reversed and transferred to the surface.

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