JP2009216875A - Method for processing outer surface of cylinder and method for manufacturing pattern sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for processing the outer surface of a cylinder, in which a preferable patterned shape is formed on the outer surface of a cylinder by controlling a film thickness of a photoresist to be substantially uniform, and to provide a method for manufacturing a pattern sheet. <P>SOLUTION: The method for processing the outer surface of a cylinder, in which an embossed pattern is formed on the cylindrical outer surface 3a of a workpiece 3 includes: a dipping step of dipping the workpiec 3 into a coating liquid 1 in a liquid tank 2; a taking out step of pulling up the workpiece 3 while rotating around a center axis CA; a drying step of drying a coating liquid 1 applied on the outer surface 3a of the workpiece 3 to form a photoresist layer 5; and a light irradiation step of irradiating the photoresist layer 5 with light to from a concave pattern. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for processing a cylindrical outer surface for forming a fine pattern on a cylindrical outer surface, and a method for manufacturing a pattern sheet using a stamper roll processed by this method.

  In general, as a method of seamlessly forming a fine pattern on the surface of a large area sheet having a width of 1 m or more, a stamper roll having a desired pattern shape formed on a cylindrical outer surface is manufactured, and the sheet is wound around the stamper roll. There is a method in which a pattern shape is continuously transferred to a traveling sheet by traveling while traveling. And, as a processing method of the outer surface of the stamper roll used in this method, conventionally, after applying a photoresist mixed with a light absorber on the outer surface of the stamper roll, the photoresist is applied by laser light from a YAG laser irradiation head. Is known, and a technique for forming a plating layer on the removed portion is known (see Patent Document 1).

  Specifically, in this technique, the stamper roll is rotated around an axis along the horizontal direction, and a resin solvent mixed with a light absorber is sprayed and applied to the outer surface of the rotated stamper roll by a spray gun. Yes.

  Patent Document 2 describes that fine irregularities are formed by irradiating a cylindrical processing object made of a heat-reactive base material with laser light. It is not described about applying.

JP-A-5-156492 JP 2007-216263 A

  However, in the prior art shown in Patent Document 1, since the resin solvent applied to the outer surface of the stamper roll is dried in the order sprayed with the spray gun, there is a problem that the film thickness of the photoresist is uneven. . When this problem occurs, there is a possibility that the pattern shape cannot be formed satisfactorily on the outer surface of the stamper roll. In particular, in order to form a concavo-convex pattern on the order of submicron with high accuracy, the film thickness of the photoresist must be made very thin. If unevenness occurs in the film thickness of such a thin photoresist, There was a risk that the disturbance would be noticeable.

  Therefore, the present invention provides a method for processing a cylindrical outer surface and a method for manufacturing a pattern sheet, which can form a good pattern shape on a cylindrical outer surface by forming a photoresist layer in a substantially uniform thickness. The purpose is to provide.

  The present invention that solves the above-described problems is a processing method of a cylindrical outer surface that forms a concavo-convex pattern on the outer surface of a work having a cylindrical outer surface, and constitutes a photoresist layer that can change the shape of a heat mode. In the liquid tank containing the compound-containing coating solution, the workpiece is placed so that the central axis is along the vertical direction and immersed in the coating solution, and after the immersion step, the workpiece is rotated around the central axis. A step of pulling up while forming, a drying step of drying the coating liquid applied to the outer surface of the workpiece to form the photoresist layer, and a light for forming a recess pattern by irradiating the photoresist layer with light An irradiation step.

  According to the present invention, the coating liquid is applied to the entire outer surface of the work by immersing the work in the coating liquid in the liquid tank in the dipping process. Therefore, after the work is taken out from the liquid tank in the take-out process, the coating liquid applied to the entire outer surface of the work can be dried almost simultaneously, so that the drying is sequentially performed partially in the conventional manner. Compared with the method, the photoresist layer can be formed in a substantially uniform thickness. Further, by pulling up the work while rotating it in the take-out process, a centrifugal force is applied to the coating liquid that is about to flow down along the outer surface of the work taken out from the liquid tank. It becomes difficult to flow downward. Therefore, it can suppress that the thickness of a coating liquid becomes thick gradually toward the lower part from the upper part of a workpiece | work by the influence of gravity.

  Moreover, in this invention, you may dry the coating liquid on a workpiece | work by rotating a workpiece | work following the said extraction process in the said drying process.

  According to this, since the coating liquid is dried by continuously rotating the workpiece after the take-out process, the uneven thickness of the coating liquid due to the influence of gravity described above can be further suppressed, and the coating liquid can be quickly discharged. Can be dried.

  In the present invention, the coating solution may be prepared by dissolving a compound constituting the photoresist layer in an organic solvent. According to this, since the coating liquid can be dried quickly, it is less susceptible to the influence of gravity, and the coating liquid can be prevented from dripping during drying. In addition, the viscosity of the said coating liquid can be set in the range of 0.5-20 mPa * s.

  In the present invention, in the light irradiation step, the photoresist layer may be removed by irradiating light until the outer surface of the workpiece is exposed.

  Further, in the present invention, a concavo-convex pattern made of the metal material is formed on the outer surface of the workpiece by removing the photoresist layer after forming a metal material on the outer surface of the workpiece and the outer surface of the photoresist layer. An irregularity forming step for forming the film may be further provided.

  According to this, a favorable uneven | corrugated pattern can be formed in a cylindrical outer surface with a metal.

  In the present invention, the workpiece is placed in a plating tank, a plating film is grown on the exposed outer surface of the workpiece, and then the photoresist layer is removed, whereby the uneven pattern made of a plating material is formed on the outer surface of the workpiece. An irregularity forming step for forming the film may be further provided.

  According to this, a favorable uneven | corrugated pattern can be formed in a cylindrical outer surface with a plating film.

  Further, in the present invention, an unevenness forming step of forming an uneven pattern by etching on the outer surface of the work by removing the photoresist layer after performing etching using the photoresist layer remaining on the outer surface of the work as a mask. Further, it may be provided.

  According to this, a favorable uneven | corrugated pattern can be formed in a cylindrical outer surface by an etching.

  Further, in the present invention, the concave / convex formation for forming the concave / convex pattern made of the metal material on the outer surface of the workpiece by continuously forming a metal material on the outer surface of the workpiece and the outer surface of the photoresist layer. A process may be further provided.

  According to this, it is possible to satisfactorily form a concavo-convex pattern made of a metal material on a cylindrical outer surface only by depositing a metal material on the entire outer surface of the work with the photoresist layer left. Further, in this method, since it is not necessary to remove the photoresist layer after the metal material is formed, facilities for removing the photoresist layer and the like are not necessary, and the manufacturing cost can be reduced.

  Further, in the present invention, in the light irradiation step, the work or light is moved along the central axis while rotating the work or light around the central axis of the work, thereby forming a spiral on the outer surface of the work. A concave pattern may be formed. According to this, since the concave pattern can be continuously formed over the entire outer surface of the workpiece, compared to a method in which machining for one round of the roll diameter is repeatedly performed in the axial direction by intermittently moving the head in the axial direction. The processing time can be shortened by eliminating the waste of stopping the head and the like.

  In addition, this invention is especially effective when the width | variety of the said recessed part pattern is 1 micrometer or less. That is, by using a concave pattern formed by irradiating light to a photoresist layer capable of changing the shape of the heat mode, a concave pattern having a width of 1 μm or less, for example, a submicron order can be formed satisfactorily. it can.

  Moreover, you may use the stamper roll by which the uneven | corrugated pattern was formed in the cylindrical outer surface by each processing method mentioned above in the manufacturing method of a pattern sheet. That is, the concavo-convex pattern may be continuously formed on the traveling sheet by winding the traveling sheet around the stamper roll on which the concavo-convex pattern has been formed by the above-described processing methods. According to this, a concavo-convex pattern of, for example, submicron order formed on the surface of the stamper roll can be transferred to the sheet, and a pattern sheet having a concavo-convex pattern of submicron order can be manufactured easily and easily.

  According to the present invention, since the work is dipped in a liquid tank and then pulled up while being rotated, the coating liquid on the work is dried at substantially the same time and has a substantially uniform thickness by centrifugal force. Can be formed substantially uniformly on the cylindrical outer surface.

  Next, an embodiment of a processing method of a cylindrical outer surface and a manufacturing method of a pattern sheet according to the present invention will be described in detail with reference to the drawings as appropriate. In the drawings to be referred to, FIG. 1 is a cross-sectional view showing equipment used in a method for processing a cylindrical outer surface, and FIG. 2 is a cross-sectional view showing an immersion process (a), and a cross-sectional view showing a take-out process and a drying process (b). It is. FIG. 3 is a cross-sectional view (a) showing a state in which light is applied to the photoresist layer to start forming a concave pattern, and a cross-sectional view (b) showing a state in which the formation of the concave pattern has been completed. Further, FIG. 4 is a cross-sectional view (a) showing a state in which a concave pattern is formed in the photoresist layer, and a cross-sectional view showing a state in which chromium is formed on the outer surface of the photoresist layer and the outer surface of the workpiece ( It is sectional drawing (c) which shows the state which removed the photoresist layer from b) and the outer surface of a workpiece | work.

First, a method for processing the cylindrical outer surface will be described.
As shown in FIG. 1, first, a liquid tank 2 containing a coating liquid 1 is prepared, and a chuck device 4 that supports a cylindrical workpiece 3 (workpiece) so as to be rotatable around its central axis CA is prepared. To do.

  Here, the coating liquid 1 is produced | generated by the compound which comprises the photoresist layer 5 (refer FIG. 3) mentioned later being melt | dissolved in the organic solvent. For example, as the coating liquid 1, a material obtained by dissolving a dye material having the following chemical formula in a TFP (tetrafluoropropanol) solvent, which is an organic solvent, at 2% (weight ratio) can be used.

As the material of the workpiece 3, for example, a stainless steel material (or a metal material that can be easily processed), Al ₂ O ₃ or the like is preferable. The outer surface 3a of the work 3 may be chrome plated. When chromium plating is performed in this manner, the surface hardness and surface smoothness of the workpiece 3 can be increased. In addition, before apply | coating the coating liquid 1 to the outer surface 3a of the workpiece | work 3, the workpiece | work 3 is wash | cleaned.

  Further, as the chuck device 4, it is desirable to use a device that supports the inner peripheral surface of the workpiece 3 rather than a device that supports the outer surface of the workpiece 3 as shown in FIG. 1. In the apparatus that supports the outer surface of the work 3, the coating liquid 1 cannot be applied to the upper end of the work 3 (the part that is gripped by the chuck device 4). However, in the apparatus that supports the inner peripheral surface of the work 3, the work This is because the coating liquid 1 can be applied to the entire outer surface 3. Therefore, when a device that supports the inner peripheral surface of the workpiece 3 is used, it is not necessary to form the workpiece 3 unnecessarily long, and the yield of the material can be improved.

  Then, as shown in FIG. 2 (a), the cylindrical workpiece 3 gripped by the chuck device 4 is placed in the liquid tank 2 in such a posture that the central axis CA is along the vertical direction. In the coating solution 1 (immersion step). Thereafter, as shown in FIG. 2B, the workpiece 3 is pulled up to a predetermined position while being rotated around the central axis CA (an extraction step).

  By rotating the workpiece 3 in this way, a centrifugal force is applied to the coating liquid 1 that is about to flow down along the outer surface 3a of the workpiece 3 taken out from the liquid tank 2, so that it is difficult for the coating liquid 1 to flow downward. Therefore, it is possible to suppress the coating liquid 1 from gradually increasing from the top to the bottom of the workpiece 3 due to the influence of gravity. Moreover, since the workpiece | work 3 is immersed in the coating liquid 1 of the liquid tank 2, the coating liquid 1 apply | coated to the whole outer surface 3a of the workpiece | work 3 taken out from the liquid tank 2 is dried substantially simultaneously.

  And after pulling up the workpiece | work 3 to a predetermined position, the coating liquid 1 apply | coated to the outer surface 3a of the workpiece | work 3 is dried by continuing the rotation of the workpiece | work 3 (drying process). Thereby, the outer surface 3a of the workpiece 3 is quickly dried while the suppression of the unevenness of the thickness of the coating liquid 1 due to the influence of gravity is maintained. When the drying of the coating liquid 1 is completed, the photoresist layer 5 capable of changing the shape of the heat mode is formed on the outer surface 3a of the work 3 with a predetermined film thickness.

  Here, the photoresist layer 5 capable of changing the shape of the heat mode is a layer in which light is converted into heat by irradiation of strong light, and the shape of the material can be changed by this heat to form a recess. A layer of a so-called heat mode type photoresist material. The upper limit of the film thickness of the photoresist layer 5 is desirably 1 μm or less, more desirably 0.5 μm or less, and particularly desirably 0.3 μm or less. Further, the lower limit of the film thickness of the photoresist layer 5 is desirably 0.01 μm or more, more desirably 0.03 μm or more, and particularly desirably 0.05 μm or more.

  In addition, in order to control the film thickness of the photoresist layer 5 satisfactorily, the viscosity of the coating solution 1 is 0.5 to 20 mPa · s, preferably 0.5 to 15 mPa · s (CBC Corporation: laboratory vibration viscometer). VM-10A measured at room temperature), the peripheral speed of the workpiece 3 can be set from 0.1 to 10 m / s, and the lifting speed can be set from 0.02 to 2 m / s. desirable. Here, the viscosity of the coating liquid 1 is adjusted by adjusting the amount of the solvent.

For example, the coating material 1 has a pigment material concentration of 60 mg / cc, a viscosity of 12 mPa · s, and the workpiece 3 is rotated at a peripheral speed of 0.5 m / s while being pulled up at a speed of 0.2 m / s. When the peripheral speed is increased to 1 m / s by drying by gradually increasing the rotational speed of No. 3, the thickness of the photoresist layer 5 can be made substantially uniform (1.5 μm). More specifically, the peripheral speed is maintained at 0.5 m / s until the workpiece 3 is completely lifted from the liquid tank 2, and the peripheral speed is maintained at 0.5 m / s for 5 to 20 seconds after the lifting. Next, the peripheral speed is increased to 1 m / s over 5 to 20 seconds. Further, the peripheral speed is increased to 1.5 m / s over 5 to 10 seconds. Thereby, when the coating liquid 1 is not sufficiently dried on the workpiece 3, the scattering of the coating fluid 1 from the workpiece 3 is suppressed by rotating the workpiece 3 at a low speed, and the coating fluid 1 is dried to some extent. By gradually rotating the workpiece 3 at a high speed, drying of the coating liquid 1 can be accelerated. The acceleration in the circumferential direction of the work 3 is preferably 0.05 to 0.2 m / s ² , more preferably 0.05 to 0.1 m / s ² . Further, the film thickness of the photoresist layer 5 is affected not only by the peripheral speed and pulling speed of the work 3 but also by the physical properties of the coating liquid 1 and the wettability between the coating liquid 1 and the outer surface 3a of the work 3 It is desirable to adjust the film thickness while appropriately changing the conditions as necessary.

  After that, as shown in FIG. 3A, the chuck device 4 holding the workpiece 3 is moved to the front of the laser irradiation device 6. Then, as shown in FIGS. 3A and 3B, the chuck device 4 moves the workpiece 3 along the central axis CA while rotating it, and emits the condensed laser light from the laser irradiation device 6. Thus, a spiral concave pattern 51 is formed in the photoresist layer 5 (light irradiation step).

  Specifically, when the photoresist layer 5 is irradiated with laser light having a wavelength (wavelength absorbed by the material) that falls within the light absorption wavelength range of the material, the laser light is absorbed by the photoresist layer 5 and absorbed. The light is converted into heat, and the temperature of the light irradiated part rises. As a result, the photoresist layer 5 undergoes chemical or / and physical changes such as softening, liquefaction, vaporization, sublimation, and decomposition. Then, the material having such a change moves or / and disappears, and is removed from the outer surface 3a of the workpiece 3, whereby the concave pattern 51 is formed.

  The output value of the laser light emitted from the laser irradiation device 6 is appropriately set to such a value that the outer surface 3a of the work 3 is exposed by the laser light irradiation for a relatively short time. The spot diameter of the laser beam is appropriately set so that the width (half width) of the concave pattern 51 is 1 μm or less. Here, the half width means a width at a depth position that is half the depth of the concave pattern 51.

  Moreover, as the laser irradiation apparatus 6, NE500 (wavelength 405nm, NA0.85) by the pulse tech industry company is employable, for example. Further, as a method of forming the concave pattern 51, for example, a pit forming method known for a write-once optical disc or a write-once optical disc can be applied. Specifically, for example, by detecting the intensity of the reflected light of the laser that changes depending on the pit size, and correcting the output of the laser so that the intensity of the reflected light is constant, a uniform pit is formed. A known running OPC technique (for example, paragraph [0012] of Japanese Patent No. 3096239) can be applied.

  And after forming the helical recessed part pattern 51 in the photoresist layer 5, as shown to Fig.4 (a), (b), the workpiece | work 3 is put into the vacuum chamber which is not shown in figure, and the outer surface of the workpiece | work 3 is shown. A chromium 7 as an example of a metal material is deposited on the outer surface 5a of the photoresist layer 5 by vapor deposition or sputtering. Thereafter, as shown in FIG. 4C, when the photoresist layer 5 is washed away with a cleaning solution such as ethanol, a pattern (convex portion) made of chromium 7 is formed on the outer surface 3a of the work 3 (unevenness forming step). ). And the cylindrical stamper roll 30 which has an uneven | corrugated pattern on the outer surface is manufactured by fitting a cylindrical member inside the cylindrical workpiece | work 3 comprised as mentioned above.

  Next, a method for manufacturing a pattern sheet using the stamper roll 30 will be described. In the drawings to be referred to, FIG. 5 is a conceptual diagram showing a pattern sheet manufacturing method using a stamper roll.

  As shown in FIG. 5, the stamper roll 30 is incorporated into a known pattern sheet manufacturing apparatus 10 (for example, see Japanese Patent Application Laid-Open No. 2007-83447), thereby continuously forming a fine pattern on the traveling sheet W. Contribute to. Specifically, in the pattern sheet manufacturing apparatus 10, the sheet W is sent from the sheet supply unit 11 at a constant speed. The sheet W is fed into the application unit 12 and the resin liquid is applied to the surface of the sheet W.

  Here, the coating means 12 is a device that applies a radiation curable resin liquid to the surface of the sheet W, a liquid supply source 12A that supplies the radiation curable resin liquid, a liquid supply device (liquid feed pump) 12B, and a coating head. 12C, a support roller 12D that wraps and supports the sheet W at the time of application, a pipe for supplying a radiation curable resin liquid from the liquid supply source 12A to the application head 12C, and the like.

  Then, after the resin liquid is applied by the applying means 12, the resin liquid applied to the sheet W is dried by the drying means 19, and the solvent component is evaporated. Next, the sheet W is fed into a forming unit including the stamper roll 30 and the nip roller 14. As a result, the continuously running sheet W is pressed between the rotating stamper roll 30 and the nip roller 14. That is, when the traveling sheet W is wound around the stamper roll 30 and molded, the uneven pattern on the outer surface of the stamper roll 30 is continuously transferred to the resin layer of the sheet W.

  Next, in a state where the sheet W is wound around the stamper roll 30, the resin curing means 15 transmits the sheet W and irradiates the resin liquid layer with radiation, thereby curing the resin liquid layer. Then, the sheet W is peeled from the stamper roll 30 by winding the sheet W around the peeling roller 16.

  The peeled sheet W is conveyed to the sheet take-up means 18 and the protective film H supplied from the protective film supply means 17 is supplied to the surface of the sheet W. It is wound up and stored by a winding roll. Thus, a pattern sheet on which a fine pattern is formed is manufactured.

According to the above, the following effects can be obtained in the present embodiment.
Since the work 3 is immersed in the liquid tank 2 and then pulled up while being rotated, the coating liquid 1 on the work 3 has a substantially uniform thickness and is dried substantially simultaneously by centrifugal force. Thus, a good pattern shape can be formed on the cylindrical outer surface of the stamper roll 30.

  Since the coating liquid 1 is dried by continuously rotating the workpiece 3 after the take-out step, the coating liquid 1 can be quickly dried while maintaining the suppression of uneven thickness of the coating liquid 1 due to the influence of gravity. .

  By passing through the extraction step and the drying step as in the present embodiment, a very thin photoresist layer 5 can be formed on the outer surface 3a of the workpiece 3 with a substantially uniform film thickness. The pattern of chromium 7 to be formed can be formed on the submicron order, for example. Therefore, a pattern sheet (an antireflection film, a polarizing plate, a wavelength plate, an electronic material, etc.) having a fine pattern on a submicron order is manufactured by using the stamper roll 30 on which such a fine pattern is formed. Can be produced efficiently in a large area. In addition, since the stamper roll 30 can be manufactured at low cost, a plurality of stamper rolls 30 can be manufactured as spare rolls, and the cost required for reproduction of the stamper rolls can be suppressed.

  Since the coating liquid 1 is produced by dissolving the compound constituting the photoresist layer 5 in an organic solvent, the coating liquid 1 can be dried quickly to make it less susceptible to the influence of gravity. Can be prevented from dripping.

  Processing is performed without stopping the rotation of the workpiece 3 and the relative movement of the head in the axial direction with respect to the workpiece 3 by forming the concave pattern 51 in a spiral on the photoresist layer 5 formed on the outer surface of the workpiece 3. Therefore, compared to a method in which machining for one round of the roll diameter is repeated in the axial direction by intermittently moving the head in the axial direction, waste of stopping the head and the like can be eliminated, and machining time can be shortened.

In addition, this invention is not limited to the said embodiment, It can utilize with various forms so that it may illustrate below.
In the embodiment, after forming the concave pattern 51 in the photoresist layer 5, chromium 7 is deposited and the photoresist layer 5 is removed, thereby forming a fine concave / convex pattern on the outer surface 3 a of the workpiece 3. However, the present invention is not limited to this. For example, as shown in FIGS. 6A to 6C, a fine uneven pattern may be formed on the outer surface 3a of the workpiece 3 by plating.

  Specifically, in this method, as shown in FIG. 6 (a), after forming a concave pattern 51 in the photoresist layer 5, the work 3 is put in a plating tank (not shown) and shown in FIG. 6 (b). As described above, a plating film made of the plating material M is grown on the exposed outer surface 3a of the work 3. Thereafter, the photoresist layer 5 is removed with the cleaning liquid as in the above embodiment, thereby forming a pattern of the plating material M on the outer surface 3a of the workpiece 3 as shown in FIG. 6C (plating pattern forming step). ). Even with this method, a fine uneven pattern can be satisfactorily formed on the outer surface 3a of the workpiece 3. As the plating material M, a metal such as nickel, chromium, cobalt, molybdenum, aluminum, titanium, copper, or a metal-containing material can be employed.

  Further, as shown in FIGS. 7A to 7C, a fine uneven pattern may be formed on the outer surface 3a of the work 3 by etching.

  Specifically, in this method, as shown in FIG. 7A, after forming a concave pattern 51 in the photoresist layer 5, etching is performed using the photoresist layer 5 remaining on the outer surface 3a of the workpiece 3 as a mask. Thereby, as shown in FIG. 7B, the recess 3 b is formed on the outer surface 3 a of the work 3. Here, various etching methods such as wet etching, dry etching, and RIE (reactive ion etching) can be employed as the etching.

  Then, after the recess 3b is formed, the photoresist layer 5 is removed with the cleaning liquid as in the above-described embodiment, whereby an etching pattern (recess 3b) is formed on the outer surface 3a of the work 3 (etching pattern formation). Process). Even with this method, a fine uneven pattern can be satisfactorily formed on the outer surface 3a of the workpiece 3.

  Further, as shown in FIGS. 8A and 8B, the metal material MM is deposited or deposited so as to be continuous with the outer surface 5a of the photoresist layer 5 on which the concave pattern 51 is formed and the outer surface 3a of the workpiece 3. You may form a fine uneven | corrugated pattern in the outer surface 3a of the workpiece | work 3 by forming into a film by sputtering. According to this, since the concavo-convex pattern can be formed without removing the photoresist layer 5 remaining on the outer surface 3a of the workpiece 3 after the vapor deposition or sputtering process as in the above embodiment, the photoresist layer 5 Equipment for removal is not necessary, and the manufacturing cost can be reduced. In order to form the metal material MM so as to be continuous with the outer surface 5a of the photoresist layer 5 and the outer surface 3a of the work 3 as shown in FIG. 8, it is desirable to employ sputtering, as shown in FIG. In order to intermittently form a metal material (chromium 7), it is desirable to employ vacuum deposition. In the embodiment of FIG. 8, it is not necessary to form the concave pattern 51 until the outer surface 3a of the work 3 is exposed. That is, even if the outer surface 3a of the workpiece 3 is covered with the bottom surface of the concave pattern 51, the concave / convex pattern made of the metal material MM can be formed.

  In the above embodiment, after the workpiece 3 is taken out while being rotated, the workpiece 3 is dried by continuing the rotation, but the present invention is not limited to this, and after the workpiece 3 is taken out while being rotated, The rotation may be stopped and the work 3 may be dried. However, when the workpiece 3 is dried while being rotated as in the above-described embodiment, unevenness of the film thickness of the photoresist layer 5 due to the influence of gravity can be suppressed even during the drying step, so even during the drying step. It is desirable to rotate the workpiece 3.

  In the embodiment, the spiral concave pattern 51 is employed as the concave pattern, but the present invention is not limited to this, and any pattern may be used.

  In the above-described embodiment, the workpiece 3 is moved in the direction of the central axis CA while rotating the workpiece 3 by the chuck device 4, but the present invention is not limited to this, and light may be moved relative to the workpiece. For example, a method of moving a laser irradiation device along a central axis of a workpiece while rotating the laser irradiation device with respect to a stationary workpiece, or a laser along a central axis of a workpiece while rotating the workpiece You may employ | adopt the method etc. which move an irradiation apparatus.

  In the above-described embodiment, the cylindrical workpiece 3 is a processing target. However, the present invention is not limited to this, and for example, a bottomed cylindrical shape or a columnar workpiece may be the processing target. That is, the present invention may be any work such as a hollow roll or a solid roll as long as it has a cylindrical outer surface.

  In the above embodiment, chromium is used as the metal material to be deposited on the outer surface of the exposed workpiece 3, but the present invention is not limited to this, and for example, nickel, chromium, cobalt, molybdenum, or the like may be used.

  In the said embodiment, although the material which is shown by Chemical formula 1 was illustrated as a pigment | dye material put into the coating liquid 1, this invention is not limited to this. For example, preferable examples of the photoresist layer 5 having a dye material include methine dyes (cyanine dyes, hemicyanine dyes, styryl dyes, oxonol dyes, merocyanine dyes), macrocyclic dyes (phthalocyanine dyes, naphthalocyanine dyes, porphyrin dyes). Azo dyes (including azo metal chelate dyes), arylidene dyes, complex dyes, coumarin dyes, azole derivatives, triazine derivatives, 1-aminobutadiene derivatives, cinnamic acid derivatives, quinophthalone dyes, and the like. Of these, methine dyes, oxonol dyes, macrocyclic dyes, and azo dyes are preferable.

  Among these, the dye-type photoresist layer 5 preferably contains a dye having absorption in the exposure wavelength region. In particular, the upper limit of the extinction coefficient k indicating the amount of light absorption is preferably 10 or less, more preferably 5 or less, further preferably 3 or less, and 1 or less. Most preferred. The reason is that if the extinction coefficient k is too high, light does not reach from the light incident side of the photoresist layer 5 to the opposite side, and uneven holes are formed. Further, the lower limit value of the extinction coefficient k is preferably 0.0001 or more, more preferably 0.001 or more, and further preferably 0.1 or more. The reason is that if the extinction coefficient k is too low, the amount of light absorption is reduced, so that a larger laser power is required and the processing speed is reduced.

  Note that the photoresist layer 5 needs to absorb light at the exposure wavelength as described above. From such a viewpoint, a dye can be appropriately selected or the structure can be modified according to the wavelength of the laser light source. it can.

  For example, when the oscillation wavelength of the laser light source is around 780 nm, it is advantageous to select from pentamethine cyanine dye, heptamethine oxonol dye, pentamethine oxonol dye, phthalocyanine dye, naphthalocyanine dye, and the like. Among these, it is preferable to use a phthalocyanine dye or a pentamethine cyanine dye.

  When the oscillation wavelength of the laser light source is around 660 nm, it is advantageous to select from a trimethine cyanine dye, a pentamethine oxonol dye, an azo dye, an azo metal complex dye, a pyromethene complex dye, and the like.

  Further, when the oscillation wavelength of the laser light source is around 405 nm, a monomethine cyanine dye, monomethine oxonol dye, zero methine merocyanine dye, phthalocyanine dye, azo dye, azo metal complex dye, porphyrin dye, arylidene dye, complex It is advantageous to select from dyes, coumarin dyes, azole derivatives, triazine derivatives, benzotriazole derivatives, 1-aminobutadiene derivatives, quinophthalone dyes, and the like.

  Hereinafter, examples of preferable compounds as the photoresist layer 5 (photoresist material) are given for the case where the oscillation wavelength of the laser light source is around 780 nm, around 660 nm, and around 405 nm, respectively. Here, the compounds (I-1 to I-10) represented by the following chemical formulas 2 and 3 are compounds when the oscillation wavelength of the laser light source is around 780 nm. Further, the compounds (II-1 to II-8) represented by the chemical formulas 4 and 5 are compounds in the case of around 660 nm. Furthermore, the compounds (III-1 to III-14) represented by the chemical formulas 6 and 7 are compounds in the case of around 405 nm. In addition, this invention is not limited to the case where these are used for a photoresist material.

<Example of photoresist material when the oscillation wavelength of the laser light source is around 780 nm>

<Example of photoresist material when the oscillation wavelength of the laser light source is around 780 nm>

<Example of photoresist material when the oscillation wavelength of the laser light source is around 660 nm>

<Example of photoresist material when the oscillation wavelength of the laser light source is around 660 nm>

<Example of photoresist material when the oscillation wavelength of the laser light source is around 405 nm>

<Example of photoresist material when the oscillation wavelength of the laser light source is around 405 nm>

  JP-A-4-74690, JP-A-8-127174, 11-53758, 11-334204, 11-334205, 11-334206, 11-334207 The dyes described in JP-A No. 2000-43423, JP-A No. 2000-108513, JP-A No. 2000-158818, and the like are also preferably used.

Such a dye-type photoresist layer 5 is prepared by dissolving a dye in a suitable solvent together with a binder or the like to prepare a coating liquid 1, and then coating the coating liquid 1 on a workpiece 3 to form a coating film. Can be formed by drying. In that case, it is preferable that the temperature of the surface which apply | coats the coating liquid 1 is the range of 10-40 degreeC. More preferably, the lower limit is 15 ° C. or higher, more preferably 20 ° C. or higher, and particularly preferably 23 ° C. or higher. Moreover, as an upper limit, it is more preferable that it is 35 degrees C or less, It is still more preferable that it is 30 degrees C or less, It is especially preferable that it is 27 degrees C or less. As described above, when the surface temperature to be applied is in the above range, it is possible to prevent the occurrence of coating unevenness and coating failure and make the thickness of the coating film uniform.
Each of the upper limit value and the lower limit value can be arbitrarily combined.
Here, the photoresist layer 5 may be a single layer or a multilayer. In the case of a multilayer structure, the photoresist layer 5 is formed by performing the coating process a plurality of times.
The concentration of the pigment in the coating solution 1 is generally in the range of 0.01 to 15% by mass, preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, and most preferably. Is in the range of 0.5-3 mass%.

Examples of the solvent for the coating solution 1 include esters such as butyl acetate, ethyl lactate, and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and chloroform; dimethylformamide and the like Amides; hydrocarbons such as methylcyclohexane; ethers such as tetrahydrofuran, ethyl ether, dioxane; alcohols such as ethanol, n-propanol, isopropanol, n-butanol diacetone alcohol; 2,2,3,3-tetrafluoropropanol, etc. Fluorine-based solvents; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether; Kill. Fluorine solvents, glycol ethers, and ketones are preferred. Particularly preferred are fluorine type solvents and glycol ethers. More preferred are 2,2,3,3-tetrafluoropropanol and propylene glycol monomethyl ether.
The said solvent can be used individually or in combination of 2 or more types in consideration of the solubility of the pigment | dye to be used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution 1 depending on the purpose.

  Further, at the time of coating, the temperature of the coating solution 1 is preferably in the range of 23 to 50 ° C, more preferably in the range of 24 to 40 ° C, and particularly in the range of 25 to 30 ° C. Particularly preferred.

  When the coating liquid 1 contains a binder, examples of the binder include natural organic polymer substances such as gelatin, cellulose derivatives, dextran, rosin and rubber; hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene. , Polyvinyl chloride, polyvinylidene chloride, vinyl resins such as polyvinyl chloride / polyvinyl acetate copolymer, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral And synthetic organic polymers such as resins, rubber derivatives, and initial condensates of thermosetting resins such as phenol / formaldehyde resins. When a binder is used in combination as a material for the photoresist layer 5, the amount of the binder used is generally in the range of 0.01 to 50 times (mass ratio) with respect to the dye, preferably 0.1. It exists in the range of double amount-5 times amount (mass ratio).

The photoresist layer 5 can contain various anti-fading agents in order to improve the light resistance of the photoresist layer 5.
As the antifading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used.
Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19587, and 60-35054. 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, JP-A-60-47069, 63-29995, JP-A-4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent 350399, and Japan Examples include those described in Chemical Society Journal, October 1992, page 1141. The use amount of the antifading agent such as the singlet oxygen quencher is usually in the range of 0.1 to 50% by weight, preferably in the range of 0.5 to 45% by weight, based on the amount of the dye. Preferably, it is the range of 3-40 mass%, Most preferably, it is the range of 5-25 mass%.

  The wavelength of the absorption peak of the dye is not necessarily limited to that in the visible light wavelength range, and may be in the ultraviolet range or the infrared range.

  The wavelength λw for forming the concave pattern 51 with the laser is preferably in the relationship of λa <λw in relation to the dye absorption wavelength λa. With such a relationship, the light absorption amount of the dye is appropriate, the formation efficiency is increased, and a clean uneven shape can be formed.

  The wavelength λw of the laser light for forming the concave pattern 51 may be any wavelength that can obtain a large laser power. For example, 193 nm, 210 nm, 266 nm, 365 nm, 405 nm, 488 nm, 532 nm, 633 nm, 650 nm, 680 nm , 780 nm, 830 nm and the like are preferably 1000 nm or less.

  The laser beam may be any laser such as a gas laser, a solid laser, or a semiconductor laser. However, in order to simplify the optical system, it is preferable to employ a solid-state laser or a semiconductor laser. The laser light may be continuous light or pulsed light, but it is preferable to employ laser light whose emission interval can be freely changed. For example, it is preferable to employ a semiconductor laser. When the laser cannot be directly on / off modulated, it is preferable to modulate with an external modulation element.

  Further, the laser power is preferably higher in order to increase the processing speed. However, as the laser power is increased, the scanning speed (speed at which the photoresist layer 5 is scanned with laser light) must be increased. Therefore, the upper limit value of the laser power is preferably 100 W in consideration of the upper limit value of the scanning speed, more preferably 10 W, still more preferably 5 W, and most preferably 1 W. The lower limit of the laser power is preferably 0.1 mW, more preferably 0.5 mW, and even more preferably 1 mW.

  Further, the laser light is preferably light that has excellent transmission wavelength width and coherency and can be narrowed down to a spot size that is comparable to the wavelength. As the exposure strategy (light pulse irradiation conditions for properly forming the concave pattern 51), it is preferable to adopt a strategy used in an optical disc. That is, it is preferable to adopt conditions such as the exposure speed, the peak value of the laser beam to be irradiated, and the pulse width as used in optical disks.

  Further, the vaporization, sublimation or decomposition of the photoresist layer 5 is preferably steep with a high rate of change. Specifically, the weight reduction rate by differential thermal balance (TG-DTA) during vaporization, sublimation or decomposition of the photoresist layer 5 is preferably 5% or more, more preferably 10% or more, and still more preferably 20 % Or more. Further, the slope of weight reduction (weight reduction rate per 1 ° C. temperature increase) by the differential thermal balance (TG-DTA) at the time of vaporization, sublimation or decomposition of the photoresist layer 5 is 0.1% / ° C. or more. Preferably, it is 0.2% / ° C. or more, more preferably 0.4% / ° C. or more.

  Further, the transition temperature of chemical or / and physical change such as softening, liquefaction, vaporization, sublimation, decomposition, etc., the upper limit is preferably 2000 ° C. or less, more preferably 1000 ° C. or less, more preferably 500 ° C. More preferably, it is as follows. The reason is that if the transition temperature is too high, a large laser power is required. The lower limit of the transition temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 150 ° C. or higher. The reason is that if the transition temperature is too low, the temperature gradient from the surroundings is small, and a clear hole edge shape cannot be formed.

It is sectional drawing which shows the equipment used for the processing method of a cylindrical outer surface. It is sectional drawing (a) which shows an immersion process, and sectional drawing (b) which shows an extraction process and a drying process. FIG. 4 is a cross-sectional view (a) showing a state in which the photoresist layer is irradiated with light and starting to form a concave pattern, and a cross-sectional view (b) showing a state in which the formation of the concave pattern has been completed. A cross-sectional view (a) showing a state in which a concave pattern is formed on the photoresist layer, a cross-sectional view (b) showing a state in which chromium is formed on the outer surface of the photoresist layer and the outer surface of the workpiece, It is sectional drawing (c) which shows the state which removed the photoresist layer from the outer surface. It is a conceptual diagram which shows the manufacturing method of the pattern sheet using a stamper roll. It is sectional drawing which shows the form which forms an uneven | corrugated pattern in the outer surface of a workpiece | work by plating, and is sectional drawing (a) which shows the state in which the recessed part pattern was formed in the photoresist layer, and made plating material grow on the outer surface of a workpiece | work FIG. 6 is a cross-sectional view (b) showing a state where the photoresist layer is removed, and a cross-sectional view (c) showing a state where the photoresist layer is removed from the outer surface of the workpiece. It is sectional drawing which shows the form which forms an uneven | corrugated pattern in the outer surface of a workpiece | work by etching, sectional drawing (a) which shows the state in which the recessed part pattern was formed in the photoresist layer, and the state which etched the outer surface of the workpiece | work It is sectional drawing (b) and sectional drawing (c) which shows the state which removed the photoresist layer from the outer surface of a workpiece | work. It is sectional drawing which shows the form which forms an uneven | corrugated pattern by forming a metal material into a film so that it may continue to the outer surface of a photoresist layer, and the outer surface of a workpiece | work, and shows the state by which the recessed part pattern was formed in the photoresist layer. It is sectional drawing (a) shown, and the sectional view (b) which shows the state which formed the metal material into a film so that the outer surface of a photoresist layer and the outer surface of a workpiece | work may be followed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Coating liquid 2 Liquid tank 3 Work 3a Outer surface 3b Recessed part 5 Photoresist layer 5a Outer surface 6 Laser irradiation apparatus 7 Chrome 10 Pattern sheet manufacturing apparatus 30 Stamper roll 51 Recessed pattern CA Central axis M Plating material MM Metallic material W Sheet

Claims (12)

A cylindrical outer surface processing method for forming a concavo-convex pattern on the outer surface of a workpiece having a cylindrical outer surface,
A dipping process in which the workpiece is placed in a liquid bath containing a compound having a compound constituting a photoresist layer capable of changing the shape of the heat mode so that the central axis is along the vertical direction and immersed in the coating liquid; ,
After the immersion step, an extraction step of pulling up while rotating the work around the central axis,
A drying step of drying the coating solution applied to the outer surface of the workpiece to form the photoresist layer;
A light irradiation step of forming a recess pattern by irradiating the photoresist layer with light;
A method for processing an outer surface of a cylinder, comprising: In the drying step,
2. The cylindrical outer surface processing method according to claim 1, wherein the coating liquid on the workpiece is dried by rotating the workpiece following the extraction step.   The method for processing an outer surface of a cylinder according to claim 1 or 2, wherein the coating solution is obtained by dissolving a compound constituting the photoresist layer in an organic solvent.   The method for processing an outer surface of a cylinder according to claim 3, wherein the coating solution has a viscosity of 0.5 to 20 mPa · s.   5. The cylindrical outer surface according to claim 1, wherein in the light irradiation step, the photoresist layer is removed by irradiating light until the outer surface of the workpiece is exposed. Processing method.   A concavo-convex forming step of forming a concavo-convex pattern made of the metal material on the outer surface of the work by removing the photoresist layer after forming a metal material on the outer surface of the work and the outer surface of the photoresist layer. The cylindrical outer surface processing method according to claim 5, further comprising:   An unevenness forming step for forming an uneven pattern made of a plating material on the outer surface of the work by removing the photoresist layer after putting the work in a plating tank and growing a plating film on the exposed outer surface of the work The cylindrical outer surface processing method according to claim 5, further comprising:   Etching using the photoresist layer remaining on the outer surface of the workpiece as a mask and then removing the photoresist layer, thereby further comprising an irregularity forming step for forming an irregular pattern by etching on the outer surface of the workpiece. The processing method of the cylindrical outer surface according to claim 5.   A concavo-convex forming step of forming a concavo-convex pattern made of the metal material on the outer surface of the work by continuously forming a metal material on the outer surface of the work and the outer surface of the photoresist layer. The processing method of the cylinder outer surface in any one of Claims 1-5 characterized by these. In the light irradiation step,
The spiral concave pattern is formed on the outer surface of the workpiece by moving the workpiece or light along the central axis while rotating the workpiece or light around the central axis of the workpiece. The processing method of the cylindrical outer surface of any one of Claims 1-9.   The method for processing an outer surface of a cylinder according to any one of claims 1 to 10, wherein the width of the concave pattern is 1 µm or less. A pattern sheet manufacturing method for continuously forming a pattern on a traveling sheet by winding a traveling sheet on a stamper roll and molding it.
A method for producing a pattern sheet, wherein a stamper roll having a concavo-convex pattern formed on a cylindrical outer surface by the processing method according to any one of claims 1 to 11 is used as the stamper roll.

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