JP2013219334A - Method for manufacturing substrate using film-like mold, and manufacturing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a device for manufacturing a substrate used for light diffraction and scattering and having heat resistance and weather resistance with high throughput.SOLUTION: A method for manufacturing a substrate comprises: a step S0 of preparing a long film-like mold; a step S1 of adjusting a sol gel material; a step S2 of forming a coating film composed of the sol gel material on the substrate; a step S3 of drying the coating film; a step S4 of pressing a pattern surface of the film-like mold to the dried coating film by a pressing roll while sending the film-like mold to the pressing roll; a step S5 of peeling the film-like mold from the coating film; and a step S6 of burning the coating film to which an even pattern is transferred.

Description

  The present invention relates to a manufacturing method for manufacturing a substrate having a fine pattern for light scattering and diffraction using a long film mold and an apparatus for carrying out the manufacturing method.

  Lithography is known as a method for forming a fine pattern such as a semiconductor integrated circuit. The resolution of the pattern formed by the lithography method depends on the wavelength of the light source and the numerical aperture of the optical system. In order to meet the recent demand for miniaturized devices, a light source having a shorter wavelength is desired. However, short wavelength light sources are expensive, and their development is not easy, and development of optical materials that transmit such short wavelength light is also necessary. In addition, manufacturing a large-area pattern by a conventional lithography method requires a large optical element, and is difficult both technically and economically. Therefore, a new method for forming a desired pattern having a large area has been studied.

  A nanoimprint method is known as a method for forming a fine pattern without using a conventional lithography apparatus. The nanoimprint method is a technique capable of transferring a nanometer order pattern by sandwiching a resin between a mold and a substrate, and thermal nanoimprint method, optical nanoimprint method, and the like have been studied depending on the material used. Among these, the optical nanoimprint method comprises four steps of i) application of a resin layer, ii) press with a mold, iii) photocuring, and iv) release, and can realize nano-size processing by such a simple process. Excellent in terms. In particular, since the resin layer uses a photocurable resin that is cured by light irradiation, the time required for the pattern transfer process is short, and high throughput can be expected. For this reason, practical application is expected not only in semiconductor devices but also in many fields such as optical members such as organic EL elements and LEDs, MEMS, and biochips.

  For example, in an organic EL element (organic light-emitting diode), holes that have entered from a hole injection layer and electrons that have entered from an electron injection layer are respectively carried to the light-emitting layer, and they are formed on organic molecules in the light-emitting layer. Recombine to excite organic molecules, thereby emitting light. Therefore, in order to use the organic EL element as a display device or a lighting device, it is necessary to efficiently extract light from the light emitting layer from the surface of the element. For this reason, the diffraction grating substrate is used as the light extraction surface of the organic EL element. It is known from Japanese Patent Application Laid-Open No. H10-228707.

JP 2006-236748 A WO2011 / 007878A1

  In addition, in Patent Document 2, the present applicant applied a solution in which a block copolymer satisfying a predetermined condition in a solvent is applied on a base material in order to produce a concavo-convex pattern of a diffraction grating substrate for an organic EL element. A method for obtaining a matrix (metal substrate) on which a fine irregular irregular pattern is formed by forming a microphase separation structure of the block copolymer using the phenomenon of self-organization of the block copolymer Is disclosed. A mixture of a silicone polymer and a curing agent is dropped onto the matrix and cured to obtain a transfer pattern as a mold, and then a glass substrate coated with a curable resin is pressed against the transfer pattern and cured with ultraviolet rays. By curing the functional resin, a diffraction grating in which the transfer pattern is duplicated is produced. An organic EL element is obtained by laminating a transparent electrode, an organic layer, and a metal electrode on the diffraction grating.

  However, in order to mass-produce a diffraction grating for an organic EL element as described above, it is necessary to efficiently transfer to a material such as a curable resin using a transfer pattern as a mold.

  Therefore, there has been a demand for a transfer process and a transfer apparatus suitable for mass-producing an optical substrate such as a diffraction grating substrate used for an organic EL element or the like with high throughput using the nanoimprint method.

  By the way, the photocurable resin as described above generally has low heat resistance, and decomposes or yellows at high temperatures. Therefore, if there is a high-temperature treatment in the subsequent process, the film having a fine pattern may be decomposed. In addition, the photo-curing resin has low adhesion to the glass substrate, and further, when the pattern-transferred resin layer is used for an element such as an organic EL element, impurities are eluted from the resin layer and the element is adversely affected. There is a fear. Therefore, in order to mass-produce an optical substrate such as a diffraction grating substrate for an organic EL element with high throughput using the nanoimprint method, it is necessary to optimize materials and mold materials for forming a concavo-convex pattern on the glass substrate. .

  Accordingly, an object of the present invention is to provide a novel manufacturing method and manufacturing apparatus capable of mass-producing a substrate having a fine unevenness pattern having high adhesion to the substrate and having heat resistance and weather resistance with high throughput. It is to provide.

According to a first aspect of the present invention, there is provided a method of manufacturing a substrate having a concavo-convex pattern,
Preparing a long film-shaped mold having an uneven pattern surface;
Forming a sol-gel material coating on the substrate;
A step of making the concavo-convex pattern surface of the film-shaped mold and the coating film face each other, pressing a pressing roll against a surface opposite to the concavo-convex pattern surface of the film-shaped mold, and transferring the concavo-convex pattern surface to the coating film; ,
Peeling the film mold from the coating film;
And a step of curing the coating film having the concavo-convex pattern transferred thereon. A method for producing a substrate is provided.

  In the method of manufacturing the optical substrate, the step of curing the coating film may include curing by baking the coating film.

  In the method for manufacturing the substrate, the substrate may be an optical substrate. The step of preparing the long film-shaped mold includes applying a concavo-convex forming material to a long film-like substrate and pressing the transfer roll having a concavo-convex pattern while rotating the applied concavo-convex forming material. Rolling the concavo-convex pattern onto the concavo-convex forming material, and curing the concavo-convex forming material onto which the concavo-convex pattern has been roll-transferred to obtain the long film mold in a roll form. . Moreover, the film-form base material which has the said uneven | corrugated formation material may be wound up with a film winding roll, and / or using the film winding roll which rolls out the said film-shaped base material, and the film winding roll which winds up The concavo-convex pattern of the transfer roll may be transferred while the film-like substrate is conveyed. In any case, the long film-shaped mold in the form of a roll wound up by the film winding roll can be fed out and moved with respect to the pressing roll. Furthermore, the peeled long film-shaped mold may be wound up by a mold winding roll.

  In the method of manufacturing the substrate, the pressing roll can be pressed against the surface opposite to the uneven pattern surface while heating the uneven forming material. By doing so, the sol material is temporarily fired at the same time, so that the formation of the concave / convex pattern can be ensured and peeling of the concave / convex pattern surface after pressing from the coating film can be facilitated. Further, the pressed unevenness forming material can be heated between the transfer step and the peeling step or in the peeling step to further facilitate peeling from the coating film on the pattern surface after pressing.

  In the method for manufacturing the substrate, the long film-shaped mold is continuously fed below the pressing roll, and a plurality of substrates are conveyed to the pressing roll while forming a sol-gel material coating film at predetermined time intervals. The concave and convex pattern surfaces of the film mold may be sequentially pressed against the coating films of the plurality of substrates with a pressing roll. Since a long film mold is used, such a substrate can be continuously processed, and the throughput of substrate manufacture can be improved. The length of the film mold can be adjusted to a length sufficient to produce one lot of substrates, for example, several hundred to several thousand substrates, for example, several hundred meters to several thousand meters.

  The concavo-convex pattern of the film mold used in the method for producing the substrate is, for example, an irregular concavo-convex pattern, the concavo-convex average pitch is in the range of 100 to 1500 nm, and the average value of the concavo-convex depth distribution. The (average height) can be in the range of 20 to 200 nm, and the substrate may be a glass substrate. Since the sol material is formed of an inorganic material, it is preferable because the refractive index is close to that of the glass substrate. The sol-gel material can include a silica precursor.

According to a second aspect of the present invention, an apparatus for manufacturing a substrate,
A coating film forming section for forming a sol-gel material coating film on the substrate;
A substrate transport unit for transporting the substrate on which the coating film is formed to a predetermined position;
A long film-shaped mold having a concavo-convex pattern surface is provided with a mold feeding roll and a mold winding roll for winding the long film-shaped mold, and the film shape is continuously from the feeding roll to the predetermined position. A mold transporting unit that transports the film-shaped mold to a predetermined position by unwinding the mold and winding the film-shaped mold with a mold winding roll;
A part of the concavo-convex pattern surface of the elongated film-shaped mold that is rotatably installed at the predetermined position and is fed to the predetermined position by the mold conveyance unit is conveyed to the predetermined position by the substrate conveyance unit. And a pressing roll for pressing against the coating film of the substrate.

  The substrate manufacturing apparatus may further include a peeling roll in order to promote peeling of a part of the concavo-convex pattern surface of the long film-shaped mold pressed by the pressing roll from the coating film of the substrate. . The substrate may be an optical substrate.

  The apparatus for manufacturing a substrate may further include a heating unit that heats a coating film on the substrate against which a part of the concavo-convex pattern surface of the film mold is pressed, and the heating unit is provided as a heater in the pressing roll. May be. The substrate manufacturing apparatus may further include a heating unit that heats the coating film when the film mold is peeled from the coating film.

  The substrate manufacturing apparatus may further include a support roll provided at a position facing the pressing roll to support the substrate from below, and the coating film forming unit moves the substrate while holding the substrate. May be provided.

  The concavo-convex pattern of the film mold used in the substrate manufacturing apparatus is, for example, an irregular concavo-convex pattern used for light diffraction or scattering, and the average pitch of the concavo-convex ranges from 100 to 1500 nm. The average value (average height) of the uneven depth distribution may be in the range of 20 to 200 nm. The substrate may be a glass substrate, and the sol-gel material may contain a silica precursor.

  The substrate manufacturing apparatus may further include a roll process device for forming the long film mold. The roll process device has a transport system for transporting the substrate film and unevenness on the substrate film being transported. It can have an applicator for applying the forming material, a transfer roll located on the downstream side of the applicator for transferring the pattern, and an irradiation light source for irradiating the substrate film with light. The transport system includes a film feeding roll for feeding out the substrate film, a nip roll for biasing the substrate film to the transfer roll, a peeling roll for promoting the peeling of the substrate film from the transfer roll, and the pattern being transferred. And a film take-up roll for taking up the substrate film. In this case, the film take-up roll obtained by taking up the substrate film can be used as a mold feeding roll for feeding out the film-like mold.

  According to the third aspect of the present invention, a diffraction grating substrate having an uneven surface as an optical substrate is produced using the method for manufacturing the substrate of the first aspect, and a transparent surface is formed on the uneven surface of the diffraction grating substrate. There is provided a method for producing an organic EL element, wherein an organic EL element is produced by sequentially laminating an electrode, an organic layer and a metal electrode.

  In the method for producing a substrate of the present invention, a sol-gel material is used as a concavo-convex pattern forming material, and pattern transfer is performed by using a roll process with a long film mold for forming a concavo-convex pattern using such a sol-gel material. The substrate can be manufactured with high throughput while performing accurately and reliably. Since the concavo-convex pattern of the substrate manufactured by the manufacturing method of the present invention is formed from a sol-gel material, it has excellent heat resistance, weather resistance (concept including light resistance) and corrosion resistance, and is also used in the manufacturing process of an element incorporating the substrate. There is resistance, and the lifetime of these elements can be extended. Therefore, the substrate obtained by the production method of the present invention is extremely effective for various devices such as organic EL elements and solar cells, and the thus obtained substrate is used as an optical substrate for heat resistance and weather resistance. And the organic EL element excellent in corrosion resistance can be manufactured. In carrying out the substrate manufacturing method of the present invention, the substrate manufacturing apparatus of the present invention is optimal.

  In the present invention, since a long film mold is used, the following advantages are obtained. Hard molds made of metal, quartz, etc. can be cleaned and repaired (defect repaired) when defects are found in the concavo-convex pattern, thereby transferring the defects to the sol-gel side. It is possible to prevent defects due to being performed. However, in the case of a film mold, such cleaning and repair is not easy. On the other hand, a mold made of metal, quartz or the like is in a roll shape, and when a defect occurs due to clogging or the like, the transfer device must be stopped immediately to replace the mold. On the other hand, since film-like molds are transferred while corresponding to a glass substrate with a single sheet, a portion with a defect such as clogging is marked at the inspection stage, and glass is used until the defective portion passes through the glass substrate. The conveyance on the substrate side can be waited. For this reason, the generation of defective products can be reduced as a whole, thereby improving the throughput. Furthermore, when the concave / convex pattern is transferred directly from a hard mold such as metal or quartz to the sol-gel side, various limitations occur as described below, and the desired performance may not be sufficiently obtained. For example, when a hard substrate such as glass is used for the sol-gel substrate, damage to the substrate may occur if the mold pressure is increased because it is hard, and conversely if it is weakened, the uneven pattern transfer becomes shallower. Is difficult to adjust. Therefore, it is forced to use a flexible material for the substrate or a flexible material for the mold. Even when a film-like mold (soft mold) is used, it is easy to release from the film-like mold, and a material with good adhesion to the substrate side and good uneven pattern transferability is required. The material selection will be limited. For this reason, the desired substrate can be obtained by selecting a material suitable for each process, which is divided into two processes, a process for producing a film mold from a metal mold and a process for transferring the film mold to the sol-gel side. In addition, a desired material can be used, and not only necessary characteristics but also pattern transfer can be performed with no pattern defect and good releasability.

It is a flowchart which shows the manufacturing method of the board | substrate of this invention. It is a conceptual diagram of the roll process apparatus for manufacturing the film mold used for the manufacturing method of the optical board | substrate of this invention. It is a conceptual diagram for demonstrating the roll process using a film-form mold. It is a conceptual diagram of the optical board | substrate manufacturing apparatus for enforcing the manufacturing method of the optical board | substrate of this invention. It is a conceptual diagram which shows the deformation | transformation form of the manufacturing apparatus of the optical board | substrate which does not use a peeling roll. It is a conceptual diagram which shows the deformation | transformation form of the optical board | substrate manufacturing apparatus which uses a film-form mold as an endless belt. It is a conceptual diagram which shows the deformation | transformation form of the optical substrate manufacturing apparatus which provided the heat zone in the press part as a heating means of a sol-gel material layer. It is a figure which shows the cross-section of an organic EL element.

  Embodiments of a substrate manufacturing method and a manufacturing apparatus according to the present invention will be described below with reference to the drawings. As shown in FIG. 1, the method for producing a substrate having a concavo-convex pattern according to the present invention mainly includes a step S0 for preparing a film-shaped mold, a solution preparation step S1 for preparing a sol-gel material, and the prepared sol-gel material as a substrate. Applying step S2 for applying, drying step S3 for drying the coating film of the sol-gel material applied to the substrate, transferring step S4 for pressing the film-shaped mold on which the transfer pattern is formed on the dried coating film, and applying the mold It has peeling process S5 which peels from a film | membrane, and main baking process S6 which carries out main baking of the coating film. Hereinafter, each process is demonstrated in order. In the following description, an optical substrate will be described as an example of the substrate. However, as will be described later, the substrate of the present invention is not limited to the optical substrate and can be applied to substrates having various uses.

[Process for preparing film mold]
The film-like mold used for the production of the optical member of the present invention is a long and flexible film or sheet-like mold having a concavo-convex transfer pattern on the surface. For example, silicone resin, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), polystyrene (PS), polyimide (PI), polyarylate Formed of an organic material. Moreover, the uneven | corrugated pattern may be directly formed in the said material, and may be formed in the coating | coated material coat | covered on it by making the said material into a base material (board | substrate sheet | seat). As the coating material, a photocurable resin, a thermosetting resin, or a thermoplastic resin can be used.

  The film mold is, for example, a long mold having a length of 100 m or more, and can have a width of 50 to 3000 mm and a thickness of 1 to 500 μm. The dimensions, particularly the length, of the film-shaped mold can be appropriately set according to the dimensions of the optical substrate to be mass-produced and the number of optical substrates (number of lots) continuously manufactured in one manufacturing process. A surface treatment or an easy adhesion treatment may be performed between the base material and the coating material in order to improve the adhesion. Moreover, you may perform a mold release process on those uneven | corrugated pattern surfaces as needed. The concavo-convex pattern can be formed in an arbitrary shape by an arbitrary method.

  The concavo-convex pattern of the film-shaped mold varies depending on the use of the optical substrate finally obtained, but may be an irregular concavo-convex pattern in which the concavo-convex pitch is not uniform and the direction of the concavo-convex is not directional. For example, when the optical substrate is used for diffraction or scattering of visible light, the average pitch of the irregularities can be in the range of 100 to 1500 nm, and more preferably in the range of 200 to 1500 nm. If the average pitch of the unevenness is less than the lower limit, the pitch becomes too small with respect to the wavelength of visible light, so that light diffraction due to the unevenness tends to be insufficient. On the other hand, if the upper limit is exceeded, the diffraction angle decreases. The function as an optical element such as a diffraction grating tends to be lost. In a similar application, the average value (average height) of the uneven depth distribution is preferably in the range of 20 to 200 nm, and more preferably in the range of 50 to 150 nm.

  The light scattered and / or diffracted from such a concavo-convex pattern has a relatively broad wavelength band, not light of a single or narrow band wavelength, and the scattered light and / or diffracted light is directed. There is no sex and heads in all directions. However, in the “irregular irregularity pattern”, the Fourier transform image obtained by performing the two-dimensional fast Fourier transform processing on the irregularity analysis image obtained by analyzing the shape of the irregularity on the surface shows a circular or annular pattern. In other words, it includes such a quasi-periodic structure in which the distribution of the pitch of the projections and depressions has no directivity in the direction of the projections and depressions. Therefore, in a substrate having such a quasi-periodic structure, as long as the uneven pitch distribution diffracts visible light, the transparent conductive material of a diffraction substrate or solar cell used in a surface light emitting device such as an organic EL device is used. A suitable substrate is preferable.

  An example of a method for producing a long film mold used in the present invention will be described with reference to FIG. The roll process apparatus (first unit) 70 shown in FIG. 2 is an apparatus for producing a film-shaped mold by forming a concavo-convex pattern on a film coated with a long substrate film. Base material) 80 conveying system 86, die coater 82 for applying an unevenness forming material to substrate film 80 being conveyed, transfer roll (metal mold) 90 for transferring a pattern located downstream of die coater 82, and substrate An irradiation light source 85 is provided mainly for irradiating the substrate film 80 with UV light. The irradiation light source 85 is provided to face the transfer roll 90 with the film 80 interposed therebetween. The transport system 86 for the substrate film 80 includes a film feeding roll 72 for feeding the substrate film 80, a nip roll 74 and a peeling roll 76 that are arranged on the upstream and downstream sides of the transfer roll 90 and bias the substrate film to the transfer roll 90, respectively. The film take-up roll 87 for taking up the substrate film 80a (film-shaped mold) to which the pattern is transferred, and a plurality of carrying rolls 78 for carrying the substrate film 80.

Using the roll process device 70, the film mold is manufactured by the following manufacturing process. The substrate film 80 that has been wound around the film feeding roll 72 in advance is fed downstream by the rotation of the film feeding roll 72 and the film winding roll 87. When the substrate film 80 passes through the die coater 82, the unevenness forming material 84 is applied to one surface of the substrate film 80 by the die coater 82, and a coating film having a predetermined thickness is formed. Next, the coating film of the substrate film 80 is pressed against the outer peripheral surface of the transfer roll 90 by the nip roll 74, and the pattern on the outer peripheral surface of the transfer roll 90 is transferred to the coating film. At the same time or immediately thereafter, the coating film is irradiated with UV light from the irradiation light source 85 and the unevenness forming material 84 is cured. The wavelength of the UV light varies depending on the unevenness forming material 84, but is generally 200 to 450 nm, and the irradiation amount can be 10 mJ / cm ^{2 to 5} J / cm ² . The substrate film 80 with the unevenness forming material having a cured pattern is separated from the transfer roll 90 by the peeling roll 76 and then taken up by the film take-up roll 87. Thus, a long film mold 80a is obtained. Since such a long film-shaped mold 80a is obtained in a form wound in a roll shape, it is suitable for a mass production process of an optical substrate using a press roll described later, and the optical substrate using this press roll This shape is also suitable for conveyance to an apparatus for performing a mass production process. Moreover, storage and an aging process can be performed by producing a film-shaped mold and winding it once in a roll shape.

  In the above manufacturing process, the substrate film 80 is made of, for example, silicone resin, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), polystyrene (PS). ), Polyimide (PI), and a substrate made of an organic material such as polyarylate. The thickness of the substrate film can be in the range of 1 to 500 μm.

  As the unevenness forming material 84, for example, epoxy, acrylic, methacrylic, vinyl ether, oxetane, urethane, melamine, urea, polyester, phenol, cross-linked liquid crystal, fluorine, silicone, etc. Curable resins such as various UV curable resins. The thickness of the curable resin is preferably in the range of 0.5 to 500 μm. If the thickness is less than the lower limit, the height of the irregularities formed on the surface of the cured resin layer tends to be insufficient, and if the thickness exceeds the upper limit, the influence of the volume change of the resin that occurs during curing increases and the irregular shape is well formed. It may not be possible.

In the above manufacturing process, a die coat method using a die coater was used to apply the unevenness forming material 84, but instead, a spin coat method, a spray coat method, a dip coat method, a dropping method, a gravure printing method, a screen printing. Various coating methods such as a printing method, a relief printing method, a curtain coating method, an ink jet method, and a sputtering method can be employed. Furthermore, conditions for curing the unevenness forming material 84 such as a curable resin vary depending on the type of resin used. For example, the curing temperature is in the range of room temperature to 250 ° C., and the UV irradiation amount is 10 mJ / cm ^2. It is preferably in the range of ˜5 J / cm ² . Moreover, it may be cured by irradiating energy rays such as an electron beam instead of UV light.

  The transfer roll 90 used in the manufacturing process may be, for example, a transfer roll in which a pattern is directly formed on the roll surface, a transfer roll in which a substrate such as a metal substrate having a pattern is wound and fixed on the roll, or Alternatively, a transfer substrate or the like in which a cylindrical substrate having a pattern is prepared and this is fitted into a roll and fixed may be used. The transfer roll 90 may be formed of a hard material other than metal.

  Here, a method for forming a concavo-convex pattern provided on the surface of the transfer roll 90 will be described. The concavo-convex pattern is, for example, a method using self-organization (microphase separation) of a block copolymer described in Japanese Patent Application No. 2011-006487 by the present applicants (hereinafter referred to as “BCP (Block Copolymer) method” as appropriate). And a method of forming irregularities due to wrinkles on the polymer surface by heating and cooling the polymer film on the deposited film disclosed in WO2011 / 007878A1 by the present applicants (hereinafter referred to as “BKL (Buckling) method” as appropriate). Is preferably used. Instead of the BCP method and the BKL method, a photolithography method may be used. In the case of forming a pattern by the BCP method, any material can be used for forming the pattern. However, a styrenic polymer such as polystyrene, a polyalkyl methacrylate such as polymethyl methacrylate, polyethylene oxide, polybutadiene, A block copolymer consisting of two combinations selected from the group consisting of isoprene, polyvinyl pyridine, and polylactic acid is preferred.

  The pitch and height of the unevenness of the pattern are arbitrary. For example, when the pattern is used for a diffraction grating that scatters or diffracts light in the visible region, the average pitch of the unevenness is in the range of 100 to 1500 nm. It is preferable that it is in the range of 200 to 1500 nm. If the average pitch of the irregularities is less than the lower limit, the pitch becomes too small with respect to the wavelength of visible light, so that there is a tendency that light diffraction due to the irregularities does not occur. The function as an optical element such as a grating tends to be lost. The average value of the uneven depth distribution is preferably in the range of 20 to 200 nm, and more preferably in the range of 50 to 150 nm. When the average value of the uneven depth distribution is less than the lower limit, the required diffraction tends not to occur because the height is too low with respect to the wavelength of visible light. On the other hand, when the upper limit is exceeded, the diffracted light intensity is uneven. As a result, for example, when this concavo-convex pattern is used as an optical element for extracting light from an organic EL element, the electric field distribution inside the EL layer becomes non-uniform and the electric field concentrates on a specific location. Leakage tends to occur and the lifetime tends to be shortened.

  After forming the matrix of the pattern by the BCP method or the BKL method, it is possible to form a mold further transferring the pattern by an electroforming method or the like as follows. First, a seed layer that becomes a conductive layer for electroforming can be formed on a matrix having a pattern formed by electroless plating, sputtering, vapor deposition, or the like. The seed layer is preferably 10 nm or more in order to make the current density uniform in the subsequent electroforming process and to make the thickness of the metal layer deposited by the subsequent electroforming process constant. Examples of seed layer materials include nickel, copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chromium, gold / cobalt alloy, gold / nickel alloy, boron / nickel alloy, solder, copper / nickel / chromium An alloy, a tin-nickel alloy, a nickel-palladium alloy, a nickel-cobalt-phosphorus alloy, or an alloy thereof can be used. Next, a metal layer is deposited on the seed layer by electroforming (electroplating). The thickness of the metal layer can be, for example, 10 to 3000 μm in total including the thickness of the seed layer. Any of the above metal species that can be used as a seed layer can be used as a material for the metal layer deposited by electroforming. From the viewpoints of wear resistance as a mold of the metal substrate, releasability and the like, nickel is preferable. In this case, it is preferable to use nickel also for the seed layer. The formed metal layer desirably has an appropriate hardness and thickness from the viewpoint of ease of processing such as pressing, peeling and cleaning of the resin layer for forming a subsequent mold.

  The metal layer including the seed layer obtained as described above is peeled off from the matrix having the concavo-convex structure to obtain a metal substrate. The peeling method may be physically peeled off, or the material forming the pattern may be removed by dissolving it using an organic solvent that dissolves them, for example, toluene, tetrahydrofuran (THF), chloroform or the like. When the metal substrate is peeled from the mother die, the remaining material components can be removed by washing. As a cleaning method, wet cleaning using a surfactant or the like, or dry cleaning using ultraviolet rays or plasma can be used. Further, for example, remaining material components may be adhered and removed using an adhesive or an adhesive. In this way, a metal substrate having a pattern transferred from the matrix is obtained. A transfer roll 90 having a concavo-convex pattern is obtained by winding the metal substrate thus obtained around the surface of the roll body. Using this transfer roll 90, a film mold can be formed by the manufacturing process as described above. Needless to say, the long film-shaped mold does not need to be manufactured by itself, and may be one produced by a manufacturer such as a film maker. Moreover, the process which prepares a film-shaped mold should just be before transfer process S4 mentioned later, and does not need to be performed before a sol-gel material adjustment process (S1).

[Sol-gel material preparation process]
In the method for producing an optical substrate of the present invention, a sol-gel material (sol solution) used for forming a coating film to which a pattern is transferred by a sol-gel method is prepared (step S1 in FIG. 1). For example, when silica is synthesized on a substrate by a sol-gel method, a sol-gel material of a metal alkoxide (silica precursor) is prepared. As precursors of silica, tetramethoxysilane (MTES), tetraethoxysilane (TEOS), tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane, tetra- Tetraalkoxide monomers such as sec-butoxysilane and tetra-t-butoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane Ethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxy , Phenyl tripropoxy silane, methyl triisopropoxy silane, ethyl triisopropoxy silane, propyl triisopropoxy silane, isopropyl triisopropoxy silane, phenyl triisopropoxy silane, and other trialkoxide monomers, and polymers obtained by polymerizing these monomers in small amounts And metal alkoxides such as a composite material in which a functional group or a polymer is introduced into a part of the material. Furthermore, metal acetylacetonate, metal carboxylate, oxychloride, chloride, a mixture thereof and the like can be mentioned, but not limited thereto. Examples of the metal species include, but are not limited to, Ti, Sn, Al, Zn, Zr, In, and a mixture thereof in addition to Si. What mixed suitably the precursor of the said metal oxide can also be used.

When a mixture of TEOS and MTES is used, the mixing ratio can be 1: 1, for example, in a molar ratio. This sol-gel material produces amorphous silica by performing hydrolysis and polycondensation reactions. In order to adjust the pH of the solution as a synthesis condition, an acid such as hydrochloric acid or an alkali such as ammonia is added. The pH is preferably 4 or less or 10 or more. Moreover, you may add water in order to perform a hydrolysis. The amount of water to be added can be 1.5 times or more in molar ratio with respect to the metal alkoxide species. A material other than silica can be used as the sol-gel material. For example, a Ti-based material, an ITO (indium-tin-oxide) -based material, Al ₂ O ₃ , ZrO ₂ , ZnO, or the like can be used.

  Solvents for the sol-gel material include, for example, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), butanol, aliphatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene, mesitylene, etc. Aromatic hydrocarbons, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, isophorone and cyclohexanone, ethers such as butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol and benzyloxyethanol Alcohols, glycols such as ethylene glycol and propylene glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Glycol ethers such as glycol monomethyl ether acetate, esters such as ethyl acetate, ethyl lactate and γ-butyrolactone, phenols such as phenol and chlorophenol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Amides such as pyrrolidone, halogen-based solvents such as chloroform, methylene chloride, tetrachloroethane, monochlorobenzene and dichlorobenzene, hetero-containing compounds such as carbon disulfide, water, and mixed solvents thereof. In particular, ethanol and isopropyl alcohol are preferable, and those in which water is mixed are also preferable.

  Additives for sol-gel materials include polyethylene glycol, polyethylene oxide, hydroxypropyl cellulose, polyvinyl alcohol for viscosity adjustment, alkanolamines such as triethanolamine, which are solution stabilizers, β-diketones such as acetylacetone, and β-ketoesters. , Formamide, dimethylformamide, dioxane and the like can be used.

[Coating process]
The sol-gel material prepared as described above is applied onto the substrate (step S2 in FIG. 1). From the viewpoint of mass productivity, it is preferable to apply the sol-gel material to the substrate at a predetermined position while continuously transporting the plurality of substrates. As a coating method, any coating method such as a bar coating method, a spin coating method, a spray coating method, a dip coating method, a die coating method, and an ink jet method can be used. The die coating method, the bar coating method, and the spin coating method are preferable because the coating can be completed quickly before the sol-gel material is gelled.

  Substrates made of inorganic materials such as glass, quartz and silicon substrates, polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA), polystyrene Resin substrates such as (PS), polyimide (PI), and polyarylate can be used. The substrate may be transparent or opaque, but it is relatively hard if the sol-gel material layer is formed on this substrate, and further the functional layer is further formed on the optical substrate when it is incorporated into the device. A substrate is preferred. Moreover, if the uneven | corrugated pattern board | substrate obtained from this board | substrate is used for manufacture of the organic EL element mentioned later, a board | substrate provided with heat resistance, weather resistance with respect to UV light etc. is desirable. In these respects, a substrate made of an inorganic material such as glass, quartz, or silicon substrate is more preferable, and the substrate made of these inorganic materials can be divided into a substrate and a sol-gel material if the applied sol-gel material is an inorganic material. It is also preferable in that the difference in refractive index between the layers is small and unintended refraction and reflection in the optical substrate can be prevented. In order to improve adhesion, a surface treatment or an easy-adhesion layer may be provided on the substrate, or a gas barrier layer may be provided for the purpose of preventing the ingress of gases such as moisture and oxygen. . In addition, since a desired concavo-convex pattern is formed by a sol-gel material layer in a later step, the substrate surface (including surface treatment and an easily adhesive layer, if any) may be flat. Has no pattern. Each substrate coated with the sol-gel material is preferably transported as it is for the subsequent drying step and transfer step.

[Drying process]
After the coating process, the substrate is held in the air or under reduced pressure and dried in order to evaporate the solvent in the coated film (hereinafter also referred to as “sol-gel material layer” as appropriate) (step S3 in FIG. 1). If this holding time is short, the viscosity of the coating film is too low to transfer the pattern in the subsequent transfer step, and if the holding time is too long, the polymerization reaction of the precursor proceeds so much that transfer cannot be performed in the transfer step. In the case of mass production of an optical substrate, this holding time can be managed by the transport time of the substrate from the application of the sol-gel material to the subsequent transfer process using a film mold. The holding temperature of the substrate in this drying step is preferably a constant temperature in the range of 10 to 100 ° C, and more preferably in the range of 10 to 30 ° C. When the holding temperature is higher than this range, the gelation reaction of the coating film proceeds rapidly before the transfer process, which is not preferable. When the holding temperature is lower than this range, the gelation reaction of the coating film before the transfer process is slow. This is not preferable because productivity decreases. After application of the sol-gel material, the evaporation of the solvent proceeds and the polymerization reaction of the precursor also proceeds, and the physical properties such as the viscosity of the sol-gel material change in a short time. The amount of evaporation of the solvent also depends on the amount of solvent (concentration of the sol-gel material) used when preparing the sol-gel material. For example, when the sol-gel material is a silica precursor, a hydrolysis / condensation polymerization reaction of the silica precursor occurs as a gelation reaction, and alcohol is generated in the sol-gel material through a dealcoholization reaction. On the other hand, a volatile solvent such as alcohol is used as a solvent in the sol-gel material. That is, the sol-gel material contains alcohol generated in the hydrolysis process and alcohol present as a solvent, and the sol-gel reaction proceeds by removing them in the drying step. Therefore, it is desirable to adjust the holding time and holding temperature in consideration of the gelation reaction and the solvent used. In the drying process, since the solvent in the sol-gel material evaporates simply by holding the substrate as it is, it is not always necessary to perform an aggressive drying operation such as heating or blowing, and the substrate on which the coating film has been formed is left as it is for a predetermined time. It can be left alone or transported for a predetermined time for a subsequent process. In this respect, the drying process is not essential.

[Transfer process]
After the elapsed time set as described above, the film mold prepared in the above-described step S0 is pressed against the coating film by a pressing roll (laminating roll) to transfer the uneven pattern of the film mold to the coating film on the substrate. (Step S4 in FIG. 1). For example, as shown in FIG. 3, by feeding a film-shaped mold 80a between the pressing roll 22 and the substrate 40 conveyed immediately below, the concavo-convex pattern of the film-shaped mold 80a is formed on the coating film (sol-gel material) on the substrate 40. ) 42 can be transferred. That is, when the film-shaped mold 80a is pressed against the coating film (sol-gel material) 42 by the pressing roll 22, the film-shaped mold 80a is conveyed on the surface of the coating film 42 of the substrate 40 while the film-shaped mold 80a and the substrate 40 are conveyed synchronously. To coat. At this time, the film-shaped mold 80a and the coating film (sol-gel material) 42 are advanced by rotating the pressing roll 22 while pressing it against the back surface of the film-shaped mold 80a (the surface opposite to the surface on which the concavo-convex pattern is formed). Adhere while. In order to feed the long film-shaped mold 80a toward the pressing roll 22, the film-shaped roll 80 (see FIG. 2) on which the long film-shaped mold 80a is wound in step S0 is used as it is. It is advantageous to extend and use the mold 80a.

  The roll process using such a press roll has the following advantages compared with the press type. i) Since the time for contact between the mold and the coating film is short, it is possible to prevent the pattern from being damaged due to the difference in thermal expansion coefficient between the mold, the substrate and the stage on which the substrate is installed. ii) Since it is a roll process, the productivity is improved, and the productivity can be further improved by using a long film mold. iii) It is possible to prevent gas bubbles from being generated in the pattern or gas marks from remaining due to bumping of the solvent in the gel solution. iv) Since it is in line contact with the substrate (coating film), the transfer pressure and peeling force can be reduced, and it is easy to cope with an increase in area. v) No air bubbles are involved when pressed. Furthermore, in the manufacturing method of the present invention, since a flexible film mold is used as a mold, when the concave / convex pattern of the mold is transferred to the sol-gel material layer 42 formed on the relatively hard substrate 40. Further, the mold pattern can be uniformly pressed to the sol-gel material layer over the entire surface of the substrate. Thereby, the uneven | corrugated pattern of a mold is transcribe | transferred faithfully to a sol-gel material layer, and generation | occurrence | production of transcription | transfer leakage and a defect can be suppressed.

  In this transfer step, the film mold may be pressed against the coating film while heating the coating film. As a method of heating the coating film, for example, the heating may be performed through a pressing roll, or the coating film may be heated directly or from the substrate side. When heating is performed through a pressure roll, a heating means may be provided inside the pressure roll (transfer roll), and any heating means can be used. A heater provided with a heater inside the pressing roll is suitable, but a heater separate from the pressing roll may be provided. In any case, any pressing roll may be used as long as pressing is possible while heating the coating film. The pressure roll is preferably a roll having a coating of a resin material such as ethylene-propylene-diene rubber (EPDM), silicone rubber, nitrile rubber, fluorine rubber, acrylic rubber, or chloroprene rubber having heat resistance on the surface. Further, in order to resist the pressure applied by the pressing roll, a supporting roll may be provided so as to sandwich the substrate facing the pressing roll, or a supporting table for supporting the substrate may be installed.

  The heating temperature of the coating film during pressing can be 40 ° C. to 150 ° C. When heating is performed using a pressing roll, the heating temperature of the pressing roll can be similarly set to 40 ° C. to 150 ° C. it can. By heating the pressing roll in this way, the mold can be immediately peeled off from the coating film pressed by the mold, and productivity can be improved. If the heating temperature of the coating film or the pressure roll is less than 40 ° C, the mold cannot be promptly peeled off from the coating film. If the heating temperature exceeds 150 ° C, the solvent used evaporates rapidly and the uneven pattern transfer is insufficient. There is a risk of becoming. Moreover, the effect similar to the temporary baking of the sol-gel material layer mentioned later can be anticipated by pressing a coating film, heating.

  After pressing the mold against the coating film (sol-gel material layer), the coating film may be temporarily fired. In the case where the coating is pressed without heating, it is preferable to perform temporary baking. Pre-baking promotes gelation of the coating film, solidifies the pattern, and makes it difficult to collapse during peeling. When pre-baking is performed, it is preferable to heat in the atmosphere at a temperature of 40 to 150 ° C.

[Peeling process]
The mold is peeled off from the coating film (sol-gel material layer) after the transfer process or the temporary baking process (process S5). Since the roll process is used as described above, the peeling force may be smaller than that of the plate mold used in the press method, and the mold can be easily peeled off from the coating film without remaining in the mold. In particular, since the coating is pressed while being heated, the reaction easily proceeds, and the mold is easily peeled off from the coating immediately after pressing. Furthermore, you may use a peeling roll for the improvement of the peelability of a mold. As shown in FIG. 3, the peeling roll 23 is provided on the downstream side of the pressing roll 22, and the film-like mold 80 a is turned into the coating film by rotating and supporting the film-like mold 80 a against the coating film 42 by the peeling roll 23. The attached state can be maintained only for the distance between the pressing roll 22 and the peeling roll 23 (a fixed time). Then, the film-shaped mold 80 a is peeled off from the coating film 42 by changing the course of the film-shaped mold 80 a so that the film-shaped mold 80 a is pulled up above the peeling roll 23 on the downstream side of the peeling roll 23. In addition, you may perform temporary baking and heating of the above-mentioned coating film in the period when the film-shaped mold 80a is adhered to the coating film. In addition, when using the peeling roll 23, peeling of a coating film can be made still easier by peeling, for example, heating at 40-150 degreeC.

[Main firing process]
After the mold is peeled off from the coating film (sol-gel material layer) 42 of the substrate 40, the coating film is baked (step S6 in FIG. 1). By the main baking, the hydroxyl group contained in the sol-gel material layer such as silica constituting the coating film is detached and the coating film becomes stronger. The main baking is preferably performed at a temperature of 200 to 1200 ° C. for about 5 minutes to 6 hours. Thus, the coating film is cured to obtain a substrate having an uneven pattern film corresponding to the uneven pattern of the mold, that is, a substrate in which a sol-gel material layer having an uneven pattern is directly formed on a flat substrate. At this time, when the sol-gel material layer is silica, it becomes amorphous or crystalline, or a mixed state of amorphous and crystalline depending on the firing temperature and firing time.

  In the optical substrate manufacturing method of the above embodiment, a sol-gel material that is cured by heating is used, but a photo-curable sol-gel material may be used instead. In this case, for example, by using a photoacid generator such as phosphorus hexafluoride aromatic sulfonium salt that generates an acid by light, or by adding a β-diketone typified by acetylacetone to the sol solution, the chemical modification (chelation And chemical modification can be removed by light irradiation. When a photocurable sol-gel material is used for the sol-gel material layer, after the mold is pressed against the coating film (sol-gel material layer) in the transfer step, gelation is performed by irradiating light instead of pre-baking the coating film ( Curing) may proceed. In the main baking step, after the mold is peeled from the coating film on the substrate, the coating film can be cured by irradiating with light instead of main baking the coating film.

[Optical substrate manufacturing equipment]
In order to carry out the optical substrate manufacturing method of the present invention, for example, an optical substrate manufacturing apparatus (second unit) 100 for manufacturing an optical substrate as shown in FIG. 4 can be used. The optical substrate manufacturing apparatus 100 mainly includes an application unit (coating film forming unit) 120 that applies a sol-gel material onto the substrate 40, a substrate transfer unit 130 that transfers the substrate, and a mold transfer unit that transfers the film-shaped mold 80a. 140, the mold transport unit 140 includes a pressing unit 150 that presses and transfers the film mold 80a to the substrate 40, and a peeling unit 160 that peels the film mold 80a from the substrate 40.

  The application unit 120 includes a substrate stage 34 that is movable while holding the substrate 40, and a die coater 30 that is positioned above the substrate stage and applies the sol-gel material 41 to the substrate 40. The substrate transport unit 130 includes a plurality of rotary rolls 36 arranged along the transport direction (from the left to the right in the drawing), and transports the substrate 40 placed thereon in the transport direction by the rotational drive of the rotary roll. Further, the substrate transport unit 130 includes a heating unit 27 for drying the substrate 40 to which the sol-gel material being transported is applied.

  The mold transport unit 140 is mainly provided at a predetermined position on the transport path of the substrate, and a coating film (not shown) of the substrate 40 on which the coating film (not shown) is formed. The pressure roll 22 that presses the film-shaped mold 80a from the side, and the film-shaped mold 80a that is provided downstream of the pressure roll 22 and is kept pressed against the coating film of the substrate 40 after a predetermined distance is peeled off A peeling roll 23 that is provided, a mold take-up roll 24 that is provided downstream of the peeling roll and winds up the film mold, and a conveyance roll 29 for conveying the film mold 80a in the traveling direction. The mold feeding roll 21 and the mold take-up roll 24 are rotatably attached to a support base (not shown) that enables them to be attached and detached. In addition, the mold supply roll 21 uses the film winding roll 87 (refer FIG. 2) by which the film-shaped mold 80a manufactured previously with the roll process apparatus 70 was wound up suitably to this apparatus 100, and uses it as it is. Is advantageous.

  The pressing unit 150 is provided with a support roll 26 facing the pressing roll 22, and the support roll 26 sandwiches the film mold 80 a and the substrate 40 together with the pressing roll 22 to press the substrate 40 from the lower side of the substrate and rotationally drive it. Then, the substrate 40 is sent out downstream in the substrate transport direction. A heater 22 a is provided inside the pressing roll 22. The support roll 26 may also be provided with a heater. The peeling unit 160 is provided with a peeling roll 23 on the conveyance path of the film-shaped mold 80a, and the film-shaped mold 80a is lifted upward by the conveyance roll 29 on the downstream side, thereby peeling the film-shaped mold 80a from the substrate 40. Facilitate. A heating furnace (heater) 28 is provided between the pressing unit 150 and the peeling unit 160. For the heating furnace 28, for example, an infrared heater, hot air heating, or a hot plate can be used. The optical substrate manufacturing apparatus 100 further includes charge removers 142 and 144 for discharging the film mold 80a fed from the mold feed roll 21 and the film mold 80a before being taken up by the mold take-up roll 24, respectively. A static eliminator 146 is provided for neutralizing the substrate 40 from which the film mold 80a has been peeled off.

  The optical substrate manufacturing apparatus 100 includes a mold transport unit 140 including a coating unit 120, a pressing unit 150, and a peeling unit 160, and a control unit (not shown) that summarizes the operations of the substrate transport unit 130 and the overall operation of the apparatus. In particular, the control unit includes the substrate transport unit 130 so that the substrate 40 transported by the substrate transport unit 130 and the film mold 80a transported by the mold transport unit 140 are transported in synchronization by the pressing unit 150. The drive speed of the mold conveyance unit 140 and the pressing roll 22 is controlled. The optical substrate manufacturing apparatus 100 further includes an inspection apparatus for observing the thickness and state of the coating film formed by the application unit 120, an inspection apparatus for observing the uneven pattern of the coating film after the film-shaped mold 80a is peeled off, and the like. Can be provided.

  An operation of processing the substrate 40 by the optical substrate manufacturing apparatus 100 will be described. In the application unit 120, the die coater 30 applies the sol-gel material 41 onto the substrate while the substrate stage 34 holding the substrate 40 moves in the transport direction, so that the sol-gel material is uniformly applied onto the substrate. Next, the substrate 40 on which the coating film of the sol-gel material is formed is transferred onto the rotating roll 36 on the upstream side of the mold conveying unit 140 and conveyed toward the pressing unit 150, particularly the pressing roll 22 provided at a predetermined position. The During this transport, the sol-gel material is dried. On the other hand, in the mold conveyance unit 140, the film-shaped mold 80 a is fed from the mold feeding roll 21, passed through a static eliminator 142 installed between the conveyance rolls 29, and then neutralized, and then pressed by the pressing unit 150 via the conveyance roll 29. To. In the pressing unit 150, the pressing roll 22 heated to 40 ° C. to 150 ° C. presses the substrate 80 with the film-shaped mold 80 a conveyed below. Thereby, the uneven | corrugated pattern of the film-shaped mold 80a is pressed against the coating film (sol-gel material) of the board | substrate 40, and transcription | transfer is performed. Moreover, the gelation of the coating film proceeds by heating the pressing roll 22. Next, the substrate 40 having the concavo-convex pattern transferred thereon by the pressing roll 22 passes through the heating furnace 28 with the film mold 80a being pressed and is conveyed to the peeling unit 160. In the heating furnace 28, the substrate 40 is heated to 40 to 150 ° C. in order to promote peeling from the coating film of the film mold 80a. In the peeling unit 160, when the film-shaped mold 80 a passes through the peeling roll 23, the film-shaped mold 80 a is peeled off from the coating film 42 by being pulled up by the mold winding roll 24 via the transport roll 29. Thereafter, the film-shaped mold 80 a is neutralized by the static eliminator 144 and wound on the mold winding roll 24. The substrate 40 from which the film mold 80a has been peeled is discharged by the charge eliminator 146 and exits the optical substrate manufacturing apparatus 100. In this way, the board | substrate 40 with which the uneven | corrugated pattern of the film-form mold 80a was transcribe | transferred to the coating film is obtained. Thereafter, the substrate 40 on which the pattern is formed is baked in an oven or the like (not shown). The main baking oven may be provided in the apparatus 100.

  In the optical substrate manufacturing apparatus 100, the peeling angle can be adjusted by appropriately adjusting the installation position of the peeling roll 23 and the position of the mold winding roll 24 that winds the mold through the peeling roll 23. Instead of the support roll 26, other driving means such as a moving table that supports and moves the substrate can be used. Moreover, although the peeling roll 23 was used in order to maintain the state with the uneven | corrugated pattern of the film-form mold 80a pressed with the coating film 42 with the press roll 22, it replaced with the peeling roll 23 in order to maintain such a state. In addition, other support members such as a plate-like member having a smooth surface and curved corners can be used. The optical substrate manufacturing apparatus 100 as the second unit may include the roll process apparatus 70 as the first unit shown in FIG. For example, the roll process apparatus 70 as the first unit is integrated into the optical substrate manufacturing apparatus 100 as the second unit, and the film take-up roll 87 of the roll process apparatus 70 is used as the mold feeding roll 21 of the optical substrate manufacturing apparatus 100 as it is. It may be used. In this case, the rotation mechanism that drives the film take-up roll 87 can be controlled by the control device of the optical substrate manufacturing apparatus 100 to switch the rotation direction. Or the optical substrate manufacturing apparatus 100 as a 2nd unit may be equipped with the roll process apparatus 70 as a 1st unit as a different body. In this case, the film take-up roll 87 on which the film mold 80a is taken up by the roll process device 70 is transported to the position where the mold feed roll 21 of the optical substrate manufacturing apparatus 100 is provided and used as the mold feed roll 21. can do. If necessary, the optical substrate manufacturing apparatus 100 and the roll process apparatus 70 can be separated and one or both can be used in place.

Below, the deformation | transformation form of the optical board | substrate manufacturing apparatus of the said embodiment is demonstrated.
<Modification 1>
Although the peeling roll is provided in the optical substrate manufacturing apparatus 100 of the above embodiment, the peeling roll may be omitted as shown in FIG. In the apparatus shown in FIG. 5, the film-shaped mold 80 a fed from the mold feed roll 21 (see FIG. 4) is pressed against the coating film 42 by the heating press roll 22, and then the mold is wound above the substrate 40. It is wound up by a roll 24 (see FIG. 4). By heating the pressing roll 22 or using other heating means, peeling from the coating film of the mold immediately after pressing can be promoted and the coating film can be pre-baked.

<Modification 2>
In the optical substrate manufacturing apparatus 100 of the above-described embodiment, the end portions of the film-shaped mold 80a are wound around the mold feeding roll 21 and the mold winding roll 24, respectively, but the film-shaped mold 80a is formed as an endless belt as shown in FIG. Also good. By doing so, it is not necessary to replace the mold feeding roll 121 and the mold winding roll 124 when the film-shaped mold 80a is completely unwound from the mold feeding roll 121 and all of the film-shaped mold 80a is wound up by the mold winding roll 124. .

<Modification 3>
In the optical substrate manufacturing apparatus 100 of the above embodiment, the heater 22a is provided inside the pressing roll 22. However, a configuration as shown in FIG. . As shown in FIG. 7, the heater 22 b can be provided not in the pressing roll 22 but in the heat zone 35 provided in the peripheral portion of the pressing roll 22 of the pressing portion 150. Since the heater is provided inside the heat zone 35, the inside of the heat zone is maintained at the heating temperature. In this case, the coating film 42 is temporarily baked inside the heat zone 35. In addition to the heat zone 35, a heater may be provided inside the pressing roll 22 and the support roll 26. Further, as another modification of the installation of the heater, the heater 22a may be provided inside the support roll 26 instead of being provided inside the pressing roll 22. In this case, the coating film 42 is temporarily baked by the heat generated from the heater 22 a inside the support roll 26. Alternatively, the heater 22a may be provided inside both the pressing roll 22 and the support roll 26.

  The substrate on which the pattern composed of the sol-gel material layer is formed through the roll process as described above is, for example, a diffraction grating substrate for an organic EL element, a wire grid polarizer, an antireflection film, or a photoelectric conversion surface side of a solar cell. It can be used as an optical element for providing a light confinement effect inside the solar cell. Or you may transcribe | transfer the said pattern to another resin using the board | substrate which has the said pattern as a mold (mother). In this case, since the transferred resin pattern is a reverse pattern of the pattern on the substrate, a mold as a replica of the substrate may be manufactured by further transferring the transferred reverse pattern to another resin. These molds can be electroformed with Ni or the like to form metal molds. By using these molds, optical parts such as a diffraction grating substrate for an organic EL element can be mass-produced more efficiently. In the optical substrate manufacturing apparatus of the above embodiment, the sol-gel material is cured by heat, but curing by light irradiation may be performed using a photo-curable sol-gel material. In this case, the heater 22a may not be used. A light irradiator may be installed in place of the heating furnace 28.

<Method for producing organic EL element>
An example of a manufacturing method for manufacturing an organic EL element using a substrate on which a pattern composed of a sol-gel material layer is formed through a roll process as described above will be described with reference to FIG. First, in order to remove foreign substances and the like attached to a substrate on which a pattern composed of a sol-gel material layer is formed, washing is performed with a brush, and then organic substances are removed with an alkaline cleaning agent and an organic solvent. Next, as shown in FIG. 8, the transparent electrode 92 is laminated on the sol-gel material layer 42 of the substrate 40 so that the uneven structure formed on the surface of the sol-gel material layer 42 is maintained. As the material of the transparent electrode 92, for example, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) that is a composite thereof, gold, platinum, silver, and copper are used. Among these, ITO is preferable from the viewpoints of transparency and conductivity. The thickness of the transparent electrode 92 is preferably in the range of 20 to 500 nm. If the thickness is less than the lower limit, the conductivity tends to be insufficient, and if it exceeds the upper limit, the transparency may be insufficient and the emitted EL light may not be sufficiently extracted to the outside. As a method for laminating the transparent electrode 92, a known method such as a vapor deposition method, a sputtering method, or a spin coating method can be appropriately employed. Among these methods, the sputtering method is preferable from the viewpoint of improving adhesion, and after that, a photoresist is applied and exposed with an electrode mask pattern, and then etched with a developer to obtain a transparent electrode having a predetermined pattern. . Note that the substrate is exposed to a high temperature of about 300 ° C. during sputtering. It is desirable to clean the obtained transparent electrode with a brush, remove organic matter with an alkaline cleaner and an organic solvent, and then perform UV ozone treatment.

  Next, the organic layer 94 shown in FIG. 8 is laminated on the transparent electrode 92. Such an organic layer 94 is not particularly limited as long as it can be used for the organic layer of the organic EL element, and a known organic layer can be appropriately used. Such an organic layer 94 may be a laminate of various organic thin films. For example, a laminate comprising a hole transport layer 95, a light emitting layer 96, and an electron transport layer 97 as shown in FIG. It may be. Here, as a material of the hole transport layer 95, a phthalocyanine derivative, a naphthalocyanine derivative, a porphyrin derivative, N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine ( Aromatic diamine compounds such as TPD) and 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl (α-NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivatives, Examples include pyrazoline derivatives, tetrahydroimidazole, polyarylalkanes, butadiene, 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA). It is not limited.

  The light emitting layer 96 is provided to recombine the holes injected from the transparent electrode 92 and the electrons injected from the metal electrode 98 to emit light. Materials that can be used for the light emitting layer 96 include anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, aluminum Organometallic complexes such as quinolinol complex (Alq3), tri- (p-terphenyl-4-yl) amine, 1-aryl-2,5-di (2-thienyl) pyrrole derivatives, pyran, quinacridone, rubrene, distyryl Benzene derivatives, distyrylarylene derivatives, distyrylamine derivatives and various fluorescent dyes can be used. Moreover, it is also preferable to mix and use the light emitting material selected from these compounds suitably. In addition, a material system that emits light from a spin multiplet, for example, a phosphorescent material that emits phosphorescence, and a compound that includes a part thereof in a part of the molecule can be preferably used. The phosphorescent material preferably contains a heavy metal such as iridium. Even if the above-described light emitting material is doped as a guest material in a host material having a high carrier mobility, light is emitted using a dipole-dipole interaction (Felster mechanism) or an electron exchange interaction (Dexter mechanism). good. The material for the electron transport layer 97 includes nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane. And organometallic complexes such as anthrone derivatives, oxadiazole derivatives, aluminum quinolinol complexes (Alq3), and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. Note that the hole transport layer 95 or the electron transport layer 97 may also serve as the light emitting layer 96. In this case, the organic layer between the transparent electrode 92 and the metal electrode 98 is two layers.

Furthermore, from the viewpoint of facilitating the injection of electrons from the metal electrode 98, a metal fluoride such as lithium fluoride (LiF) or Li ₂ O ₃ or a metal oxide is used as an electron injection layer between the organic layer 94 and the metal electrode 98. Further, a layer made of a highly active alkaline earth metal such as Ca, Ba, or Cs, an organic insulating material, or the like may be provided. From the viewpoint of facilitating hole injection from the transparent electrode 92, a triazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, as a hole injection layer between the organic layer 94 and the transparent electrode 92, Pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, or conductive polymer oligomers In particular, a layer made of a thiophene oligomer or the like may be provided.

  Further, when the organic layer 94 is a stacked body including the hole transport layer 95, the light emitting layer 96, and the electron transport layer 97, the thickness of the hole transport layer 95, the light emitting layer 96, and the electron transport layer 97 is 1 respectively. It is preferable that it is the range of -200 nm, the range of 5-100 nm, and the range of 5-200 nm. As a method for laminating the organic layer 94, a known method such as an evaporation method, a sputtering method, a spin coating method, or a die coating method can be appropriately employed.

  In the organic EL element forming step, a metal electrode 98 is then laminated on the organic layer 94 as shown in FIG. As a material of the metal electrode 98, a substance having a small work function can be used as appropriate, and is not particularly limited, and examples thereof include aluminum, MgAg, MgIn, and AlLi. The thickness of the metal electrode 98 is preferably in the range of 50 to 500 nm. If the thickness is less than the lower limit, the conductivity tends to decrease, and if the thickness exceeds the upper limit, it may be difficult to repair when a short circuit occurs between the electrodes. The metal electrode 98 can be laminated by employing a known method such as vapor deposition or sputtering. Thus, an organic EL element 200 having a structure as shown in FIG. 8 is obtained.

  As described above, since the concavo-convex pattern of the optical substrate manufactured according to the method of the present invention is formed from a sol-gel material, the concavo-convex pattern is formed from a curable resin at various points as described below. It becomes advantageous compared with. Since the sol-gel material is excellent in mechanical strength, scratches, adhesion of foreign matter, protrusions on the transparent electrode, etc. are unlikely to occur even if the concavo-convex pattern surface is washed after forming the substrate and the transparent electrode in the manufacturing process of the organic EL element. , Device defects caused by them can be suppressed. Therefore, the organic EL element obtained by the method of the present invention is superior to the case of using a curable resin substrate in terms of the mechanical strength of the substrate having an uneven pattern.

  The substrate formed from the sol-gel material manufactured according to the method of the present invention is excellent in chemical resistance. Therefore, it is relatively corrosion resistant to the alkaline liquid and organic solvent used in the cleaning process of the substrate and the transparent electrode, and various cleaning liquids can be used. Further, as described above, an alkaline developer may be used during patterning of the transparent substrate, and the developer is also resistant to corrosion. This is advantageous compared to a curable resin substrate having a relatively low resistance to an alkaline solution.

  The substrate formed from the sol-gel material manufactured according to the method of the present invention is excellent in heat resistance. For this reason, it can endure the high temperature atmosphere of the sputtering process in the transparent electrode manufacturing process of an organic EL element. Furthermore, the substrate formed from the sol-gel material manufactured according to the method of the present invention is excellent in UV resistance and weather resistance as compared with the curable resin substrate. For this reason, it has tolerance also to the UV ozone cleaning process after transparent electrode formation.

  When the organic EL element manufactured by the method of the present invention is used outdoors, deterioration due to sunlight can be suppressed as compared with the case where a curable resin substrate is used. Further, the cured resin as described above may deteriorate when left for a long period of time due to heat generated during light emission, and may cause yellowing or generation of gas. Although it is difficult to use, deterioration is suppressed in an organic EL element including a substrate manufactured using a sol-gel material.

  The present invention has been described with reference to the examples. However, the optical substrate manufacturing method and the manufacturing apparatus of the present invention are not limited to the above-described embodiments, and may be appropriately modified within the scope of the technical idea described in the claims. Can do.

  In addition, the optical substrate has been described as an example of the “substrate having a concavo-convex pattern” as a manufacturing target, but the manufacturing method of the present invention can be applied to substrates having various uses without being limited thereto. For example, optical elements such as microlens arrays, nanoprism arrays, optical waveguides, optical components such as lenses, solar cells, antireflection films, semiconductor chips, patterned media, data storage, electronic paper, LSI manufacturing, paper manufacturing, The present invention can also be applied to substrates used in applications in the bio field such as food production, immunoassay chips, and cell culture sheets.

  The method and apparatus for producing a substrate of the present invention can produce a substrate with high throughput while accurately and reliably transferring a fine pattern. The concavo-convex pattern of the substrate manufactured by the manufacturing method and manufacturing apparatus of the present invention is excellent in heat resistance, weather resistance, and corrosion resistance, and is resistant to the manufacturing process of the element in which the substrate is incorporated. Can be Therefore, the substrate obtained by the production method and production apparatus of the present invention is extremely effective for various devices such as organic EL elements and solar cells, and heat resistance and weather resistance are obtained using the substrate thus obtained. And various devices, such as an organic EL element and a solar cell excellent in corrosion resistance, can be manufactured.

DESCRIPTION OF SYMBOLS 21 Mold delivery roll, 22 Press roll 22a Heating heater, 23 Peeling roll, 24 Mold winding roll 26 Support roll, 29 Conveyance roll 30 Die coater, 35 Heat zone, 40 Substrate 42 Coating film (sol-gel material layer), 72 Film delivery roll 74 nip rolls, 76 release rolls,
80 substrate film, 80a film mold, 82 die coater,
85 UV irradiation light source 87 Film winding roll, 90 transfer roll 92 transparent electrode, 94 organic layer, 95 hole transport layer 96 light emitting layer, 97 electron transport layer, 98 metal electrode 100 optical substrate manufacturing apparatus, 142, 144, 146 Electric appliance 120 Application part, 130 Substrate transport part, 140 Mold transport part 150 Press part, 160 peeling part, 200 Organic EL element

Claims (28)

A method of manufacturing a substrate having a concavo-convex pattern,
Preparing a long film-shaped mold having an uneven pattern surface;
Forming a sol-gel material coating on the substrate;
A step of making the concavo-convex pattern surface of the film-shaped mold and the coating film face each other, pressing a pressing roll against a surface opposite to the concavo-convex pattern surface of the film-shaped mold, and transferring the concavo-convex pattern surface to the coating film; ,
Peeling the film mold from the coating film;
And a step of curing the coating film onto which the concave / convex pattern has been transferred.   The method of manufacturing a substrate according to claim 1, wherein the substrate is an optical substrate.   The method for producing a substrate according to claim 1, wherein the step of curing the coating film is performed by baking the coating film. The step of preparing the long film mold,
Applying a concavo-convex forming material to a long film-like substrate;
The concavo-convex pattern is roll-transferred to the concavo-convex forming material by pressing the transfer roll having a concavo-convex pattern on the applied concavo-convex forming material while rotating the roll.
The board | substrate as described in any one of Claims 1-3 including obtaining the said long film-like mold of a roll form by hardening the uneven | corrugated formation material by which the said uneven | corrugated pattern was roll-transferred. Manufacturing method.   The method for producing a substrate according to claim 4, wherein the film-like base material having the cured unevenness forming material is wound up by a film winding roll.   The concavo-convex pattern of the transfer roll is transferred while transporting the film-shaped substrate using a film feeding roll for unwinding the film-shaped substrate and a film winding roll for winding. Substrate manufacturing method.   The method for producing a substrate according to claim 5 or 6, wherein the long film-shaped mold in the form of a roll wound around the film winding roll is unwound and moved with respect to the pressing roll.   The method for producing a substrate according to claim 7, wherein the peeled long film-shaped mold is wound up by a mold winding roll.   The method for manufacturing a substrate according to any one of claims 1 to 8, wherein the pressing roll is pressed against a surface opposite to the uneven pattern surface while heating the uneven forming material.   The method for manufacturing a substrate according to any one of claims 1 to 9, wherein the pressed unevenness forming material is heated between the transfer step and the peeling step or in the peeling step.   The long film-like mold is continuously fed below the pressing roll, and a plurality of substrates are conveyed to the pressing roll while forming a sol-gel material coating film at predetermined time intervals, and the coating films of the plurality of substrates are The method of manufacturing a substrate according to any one of claims 1 to 10, wherein the uneven pattern surface of the film-shaped mold is sequentially pressed with a pressing roll.   The concavo-convex pattern of the film mold is an irregular concavo-convex pattern, the average pitch of the concavo-convex is in the range of 100 to 1500 nm, and the average value of the concavo-convex depth distribution is in the range of 20 to 200 nm. The manufacturing method of the board | substrate as described in any one of Claims 1-11.   The method for manufacturing a substrate according to any one of claims 1 to 12, wherein the substrate is a glass substrate.   The method for producing a substrate according to claim 1, wherein the sol-gel material contains a silica precursor.   A diffraction grating substrate having an uneven surface as an optical substrate is produced using the method for producing a substrate according to any one of claims 1 to 14, and a transparent electrode, an organic material is formed on the uneven surface of the diffraction grating substrate. A method for producing an organic EL element, comprising sequentially laminating layers and metal electrodes to produce an organic EL element. An apparatus for manufacturing a substrate,
A coating film forming section for forming a sol-gel material coating film on the substrate;
A substrate transport unit for transporting the substrate on which the coating film is formed to a predetermined position;
A mold feeding roll for feeding out a long film-shaped mold having a concavo-convex pattern surface; and a mold winding roll for winding up the long film-shaped mold, and continuously from the mold feeding roll to the predetermined position. A mold transport unit that unwinds the film mold and winds the film mold with the mold winding roll to transport the film mold to the predetermined position;
A part of the concavo-convex pattern surface of the elongated film-shaped mold that is rotatably installed at the predetermined position and is fed out to the predetermined position by the mold conveyance unit is conveyed to the predetermined position by the substrate conveyance unit. And a pressing roll for pressing the coated film on the substrate.   The substrate manufacturing apparatus according to claim 16, wherein the substrate is an optical substrate.   Furthermore, it is equipped with the peeling roll for peeling a part of uneven | corrugated pattern surface of the said elongate film-shaped mold pressed by the said press roll from the coating film of the said board | substrate. The manufacturing apparatus of the board | substrate of description.   Furthermore, the manufacturing apparatus of the board | substrate as described in any one of Claims 16-18 provided with the heating means which heats the coating film of the said board | substrate by which a part of uneven | corrugated pattern surface of the said film-like mold is pressed.   The substrate manufacturing apparatus according to claim 19, wherein the heating means is a heater provided in the pressing roll.   Furthermore, the manufacturing apparatus of the board | substrate as described in any one of Claims 16-20 provided with the heating means which heats the said coating film when the said film-like mold is peeled from the said coating film.   The apparatus for manufacturing a substrate according to any one of claims 16 to 21, further comprising a support roll that is provided at a position facing the pressing roll and supports the substrate from below.   The said coating-film formation part is equipped with the substrate stage moved while hold | maintaining a board | substrate, The manufacturing apparatus of the board | substrate as described in any one of Claims 16-22 characterized by the above-mentioned.   The concavo-convex pattern of the film mold is an irregular concavo-convex pattern, the average pitch of the concavo-convex is in the range of 100 to 1500 nm, and the average value of the concavo-convex depth distribution is in the range of 20 to 200 nm. The substrate manufacturing apparatus according to any one of claims 16 to 23.   The apparatus for manufacturing a substrate according to any one of claims 16 to 24, wherein the substrate is a glass substrate and the sol-gel material contains a silica precursor.   Furthermore, a roll process device for forming the long film mold is provided, the roll process device transporting a substrate film, a coating machine for applying an unevenness forming material to the substrate film being transported, It has a transfer roll which is located in the downstream of a coating machine, and transfers a pattern, and an irradiation light source for irradiating the said substrate film with light, It is characterized by the above-mentioned. Equipment for manufacturing substrates.   The pattern is transferred by the transport system, a film feeding roll that feeds the substrate film, a nip roll that urges the substrate film to the transfer roll, a peeling roll that promotes peeling of the substrate film from the transfer roll, and the pattern. 27. A substrate manufacturing apparatus according to claim 26, further comprising a film winding roll for winding the substrate film.   28. The apparatus for manufacturing a substrate according to claim 27, wherein the film take-up roll on which the substrate film is taken up is used as a mold feeding roll for feeding out the film-shaped mold.

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