JP2005091849A - Photomask, method for manufacturing photomask, wiring board, color filter, and electrooptical equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photomask which can easily and inexpensively be formed, a method for manufacturing the photomask, and a writing board using the photomask, a color filter, and electrooptical equipment . <P>SOLUTION: The photomask is provided with a light-transmissive flexible substrate 1 and a transfer layer 3 which is arranged on the flexible substrate 1 and contains sublimable coloring matter or thermal transition coloring matter, and a pattern 4 is formed on the transfer layer 3 according to the presence or absence of the sublimable coloring matter or thermal transition coloring matter is present. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photomask, a photomask manufacturing method, a wiring board, a color filter, and an electro-optical device.

2. Description of the Related Art Conventionally, it is widely performed to create a photomask by directly drawing on a metal film such as chromium or gold using an electron beam. By using this method, it is possible to create a photomask with a fine pattern. Patent Document 1 below discloses a technique for forming a photomask on a metal film by irradiating the metal film with an electron beam. Has been.
JP-A-5-259041

  As described above, in the conventional photomask manufacturing method, the apparatus for irradiating the electron beam becomes a large and expensive apparatus, and it takes time to create the photomask. Therefore, the photomask produced by this apparatus is also expensive. There was a problem of becoming something.

  The present invention has been made to solve the above-described problems, and is a photomask that can be easily and inexpensively produced, a method for manufacturing the photomask, and a wiring board, a color filter, and an electro-optic using the photomask. The purpose is to provide equipment.

  In order to achieve the above object, a first photomask of the present invention includes a flexible substrate having light transmittance, and a transfer layer containing a sublimable dye or a heat transferable dye disposed on the flexible substrate. And the transfer layer is characterized in that a pattern is formed by the presence or absence of a sublimable dye or a heat transferable dye.

That is, in the first photomask of the present invention, the light shielding pattern of the photomask is formed depending on the presence or absence of the sublimable dye or the heat transferable dye in the transfer layer. Therefore, a photomask can be manufactured by sublimating a sublimable dye or applying heat to a heat transferable dye to form a region without the dye, which is more than a photomask manufactured by a conventional electron beam. Can be easily and inexpensively manufactured.
In addition, since the flexible substrate is used, the photomask is also flexible, the photomask can be brought into close contact with the exposure target, and the pattern can be accurately exposed to the exposure target.

  In order to achieve the above object, a second photomask of the present invention comprises a flexible substrate having optical transparency, and a transfer layer containing metal particles disposed on the flexible substrate, and is transferred. A pattern is formed on the layer depending on the presence or absence of metal particles.

That is, in the second photomask of the present invention, the light shielding pattern of the photomask is formed depending on the presence or absence of the metal particles in the transfer layer. Therefore, by ablating the metal particles, a region free of metal particles can be formed to manufacture a photomask, which can be manufactured more easily and cheaply than a photomask manufactured by a conventional electron beam.
Since the metal particles have a good light shielding property, they can be shielded more reliably. In addition, since the metal particles hardly change in quality, the metal particles have good durability and can maintain light-shielding properties for a long time.

In order to realize the above configuration, more specifically, the flexible substrate may be made of a transparent polymer.
According to this configuration, since the flexible substrate is formed using an inexpensive transparent polymer, a photomask can be manufactured at low cost. Examples of the transparent polymer include polyethylene terephthalate and polyester such as polyethylene naphthalate.

  The first photomask manufacturing method of the present invention includes a transfer layer forming step of forming a transfer layer containing a sublimable dye or a heat transferable dye on a light-transmitting substrate, and a predetermined region of the transfer layer. A photomask is manufactured by a pattern forming step of forming a pattern by irradiating a laser beam.

  That is, according to the first photomask manufacturing method of the present invention, the sublimable dye or heat transferable dye in the predetermined region is sublimated or transferred by heat generated by irradiating the predetermined region of the transfer layer with laser light. A pattern in which light is shielded by forming a region where the dye is present and a region where the dye is not present is formed. Therefore, a photomask can be manufactured with a laser beam that is easier to handle than a conventional electron beam, and a photomask can be manufactured easily and inexpensively.

  The second photomask manufacturing method of the present invention includes a transfer layer forming step of forming a transfer layer containing metal particles on a light transmissive substrate, and irradiating a predetermined region of the transfer layer with laser light. A photomask is manufactured by a pattern forming step of forming a pattern.

  That is, in the second photomask manufacturing method of the present invention, a predetermined region of the transfer layer is irradiated with laser light, and the metal particles are ablated by generated heat or light energy of the laser light, so that the presence of the metal particles is present. The pattern which shields light by forming the area | region which does and does not exist is formed. Therefore, a photomask can be manufactured with a laser beam that is easier to handle than a conventional electron beam, and a photomask can be manufactured easily and inexpensively.

In order to realize the above-described configuration, more specifically, the transfer layer forming step may be performed by applying a metal ink in which metal particles are dispersed in a solvent on a substrate.
According to this configuration, a transfer layer containing metal particles can be easily formed by applying metal ink on the substrate. Examples of the method for applying the metal ink on the substrate include a spin coating method in which the metal ink is dropped on the substrate while rotating the substrate, and an immersion method in which the substrate is immersed in the metal ink.

In order to realize the above configuration, more specifically, the transfer layer forming step may be performed by vapor-depositing metal particles on the substrate.
According to this configuration, a transfer layer containing metal particles can be formed by vapor-depositing metal particles on the substrate.

In order to realize the above configuration, more specifically, the transfer layer forming step may be performed by depositing metal particles on the substrate by a sputtering method.
According to this configuration, the transfer layer containing the metal particles can be formed by depositing the metal particles on the substrate by sputtering.

In order to realize the above configuration, more specifically, the laser beam may be a semiconductor laser beam emitted from a semiconductor.
According to this configuration, since the semiconductor laser light emitted from the semiconductor is used, the semiconductor laser light can be obtained at a lower cost than a conventional electron beam, and the photomask can be manufactured at a lower cost.

In order to realize the above configuration, more specifically, the semiconductor laser beam may be an infrared laser beam.
According to this configuration, since the semiconductor laser light is infrared laser light, it can be obtained at a lower cost than conventional electron beams or ultraviolet laser light, and a photomask can be manufactured at low cost. Infrared laser light can be easily converted into heat, so that the sublimable dye and metal ink in the transfer layer can be easily sublimated, and the heat transferable dye can be easily transferred.

In order to implement | achieve said structure, the photothermal conversion layer containing the photothermal conversion material which converts a light energy into a thermal energy may be provided in the board | substrate more specifically.
According to this configuration, since the photothermal conversion layer is provided, the light energy of the irradiated laser light can be efficiently converted into heat energy. Therefore, it is possible to facilitate sublimation of the sublimable dye and the metal ink in the transfer layer, and to facilitate the transfer of the heat transferable dye. Examples of the photothermal conversion material include carbon black and aluminum.

  The third method for producing a photomask of the present invention includes a transfer layer forming step of forming a transfer layer containing a sublimable dye or a heat transferable dye on a light-transmitting flexible substrate, and a predetermined transfer layer. And a pattern forming step of forming a pattern by irradiating the region with laser light, and a disposing step of disposing a transfer layer on a light-transmitting substrate.

  That is, in the third photomask manufacturing method of the present invention, a transfer layer containing a sublimation dye or a heat transfer dye is formed on a flexible substrate, and the transfer layer on which the pattern is formed is disposed on the substrate. ing. Therefore, even if it is the said board | substrate which cannot form the transfer layer containing a sublimation pigment | dye or a heat transfer pigment | dye directly, a photomask can be manufactured.

  A fourth photomask manufacturing method of the present invention includes a transfer layer forming step of forming a transfer layer containing metal particles on a light-transmitting flexible substrate, and laser light is applied to a predetermined region of the transfer layer. It is characterized in that it is manufactured by a pattern forming step of forming a pattern by irradiation and a disposing step of disposing a transfer layer on a light-transmitting substrate.

  That is, in the fourth method for producing a photomask of the present invention, a transfer layer containing metal particles is formed on a flexible substrate, and the transfer layer on which the pattern is formed is disposed on the substrate. Therefore, a photomask can be manufactured even with the above-mentioned substrate that cannot directly form a transfer layer containing metal particles.

  The color filter of the present invention is manufactured using the photomask of the present invention or the photomask manufactured by the method of manufacturing the photomask of the present invention.

  That is, since the color filter of the present invention is manufactured using the photomask of the present invention or the photomask manufactured by the method of manufacturing the photomask of the present invention, it can be manufactured easily and inexpensively. it can.

  The wiring board of the present invention is manufactured using the photomask of the present invention or the photomask manufactured by the method of manufacturing the photomask of the present invention.

  That is, since the wiring board of the present invention is manufactured using the photomask of the present invention or the photomask manufactured by the method of manufacturing the photomask of the present invention, it can be manufactured easily and inexpensively. it can.

  An electro-optical device of the present invention is characterized in that the wiring board of the present invention is mounted.

  That is, the electro-optical device of the present invention can be manufactured at a low cost since the wiring board of the present invention is mounted.

[Photomask manufacturing method]
Embodiments of a photomask manufacturing method according to the present invention will be described below with reference to FIGS.
FIG. 1 is a flowchart showing one embodiment of a photomask forming method according to the present invention.
In FIG. 1, the photomask manufacturing method according to the present embodiment includes a first material placement step (step S1) for applying a functional liquid containing a photothermal conversion material on a substrate, and a photothermal conversion applied on the substrate. A first intermediate drying step (step S2) in which a functional liquid containing a material is dried to form a photothermal conversion layer, and a second material arrangement step (transfer layer) in which a functional liquid containing a sublimable dye is applied on the photothermal conversion layer. Forming step) (step S3), a second intermediate drying step (transfer layer forming step) (step S4) for drying the functional liquid containing the sublimable dye applied on the substrate to form a transfer layer, A pattern forming step (step S5) of irradiating the substrate with laser light and sublimating at least a part of the transfer layer using a photothermal conversion material.
Hereinafter, each step will be described.

(First material placement process)
First, the base material is washed using a predetermined solvent or the like. Thereby, organic residue etc. on a base material are removed. In addition, an organic residue etc. can be removed also by irradiating the base-material surface with ultraviolet light. By irradiating with ultraviolet light (UV), lyophilicity can be imparted to the surface of the substrate. Further, the base material can be washed and lyophilic can be imparted also by O ₂ plasma treatment using a gas containing oxygen (O ₂ ) as a treatment gas. And the functional liquid containing a photothermal conversion material is apply | coated on a base material using a predetermined | prescribed coating method.

  As the substrate, for example, a transparent polymer that can transmit a laser beam and is flexible can be used. Examples of the transparent polymer include polyesters such as polyethylene terephthalate and polyethylene naphthalate, and internal polymerization derived from 9,9-bis (4-hydroxyphenyl) fluorein and isophthalic acid, terephthalic acid or a polymer thereof. Fluorene polyester polymer, polyethylene, polypropylene, polyvinyl chloride, polyacryl, polyepoxy, polystyrene, polycarbonate, polysulfone, polyimide and copolymers thereof, hydrolyzed and non-hydrolyzed cellulose acetate, and the like. In addition, a fluorine-based resin containing fluorine can also be used. When the substrate is formed of a transparent polymer, the thickness is preferably 10 to 500 μm. By doing so, for example, the base material can be formed in a belt shape and wound in a roll shape, and can be transported (moved) while being wound and held on a rotating drum or the like.

  The photothermal conversion material converts light energy into heat energy. A known material can be used as the photothermal conversion material, and it is not particularly limited as long as it is a material that can efficiently convert light into heat. For example, aluminum, an oxide thereof and / or a metal made of sulfide thereof, Examples thereof include an organic substance composed of a polymer to which carbon black, graphite, an infrared absorbing dye or the like is added. Examples of infrared absorbing dyes include anthraquinone series, dithiol nickel complex series, cyanine series, azocobalt complex series, diimmonium series, squarylium series, phthalocyanine series, naphthalocyanine series, tetraarylpolymethylene series, aniline series, and phenylenediamine series. . Alternatively, a synthetic resin such as an epoxy resin may be used as a binder, and the photothermal conversion material may be dissolved or dispersed in the binder resin and provided on the substrate. In this case, the epoxy resin has a function as a curing agent, and the photothermal conversion material can be fixed on the substrate by curing. It is of course possible to provide the photothermal conversion material on the substrate without dissolving or dispersing in the binder.

  In the present embodiment, the photothermal conversion material is dissolved (dispersed) in a solvent (dispersion medium) to generate a functional liquid, and then the functional liquid is subjected to a general film coating method, for example, an extrusion coating method, a spin coating method, It is applied on a substrate by a gravure coating method, a reverse roll coating method, a rod coating method, a micro gravure coating method, a knife coating method or the like. In the coating method of the photothermal conversion material, it is preferable to remove static electricity charged on the surface of the base material to form the functional liquid for forming the photothermal conversion layer uniformly on the base material. Is preferably attached. Such a coating method is particularly preferable when the organic material is used as a photothermal conversion material. On the other hand, when using the said metal as a photothermal conversion material, it can provide on a base material using a vacuum evaporation method, an electron beam evaporation method, or sputtering. Moreover, it is also possible to arrange | position the functional liquid containing a photothermal conversion material on a base material based on the droplet discharge method (inkjet method).

In the droplet discharge method, droplets of functional liquid are discharged from the discharge head in a state where the discharge head and the base material face each other. Examples of the discharge technique of the droplet discharge method include a charge control method, a pressure vibration method, an electrothermal conversion method, an electrostatic suction method, and an electromechanical conversion method. In the charge control method, a charge is applied to a material with a charging electrode, and the flight direction of the material is controlled with a deflection electrode to be discharged from a discharge nozzle. In addition, the pressure vibration method is a method in which an ultra-high pressure of about 30 kg / cm ² is applied to the material to discharge the material to the nozzle tip side, and when the control voltage is not applied, the material moves straight from the discharge nozzle. When discharged and a control voltage is applied, electrostatic repulsion occurs between the materials, and the materials are scattered and are not discharged from the discharge nozzle. In the electrothermal conversion method, a material is rapidly vaporized by a heater provided in a space in which the material is stored to generate bubbles, and the material in the space is discharged by the pressure of the bubbles. In the electrostatic attraction method, a minute pressure is applied to a space in which a material is stored, a meniscus of material is formed on the discharge nozzle, and an electrostatic attractive force is applied in this state before the material is drawn out. The electromechanical conversion method utilizes the property that a piezo element (piezoelectric element) deforms in response to a pulsed electric signal, and the piezoelectric element is deformed by pressure through a flexible substance in a space where material is stored. The material is extruded from this space and discharged from the discharge nozzle. In addition to this, it is also possible to apply a technique such as a method using the viscosity change of a fluid due to an electric field or a method using a discharge spark. The droplet discharge method has an advantage that the use of the material is less wasteful and a desired amount of the material can be accurately disposed at a desired position. In addition, the amount of one drop of the liquid material discharged by the droplet discharge method is 1 to 300 nanograms, for example. In this embodiment, an electromechanical conversion method (piezo method) is used.

FIG. 2 is a diagram for explaining the discharge principle of the functional liquid (liquid material) by the piezo method.
In FIG. 2, the ejection head 20 includes a liquid chamber 21 that stores a functional liquid, and a piezo element 22 that is installed adjacent to the liquid chamber 21. The functional liquid is supplied to the liquid chamber 21 via a supply system 23 including a material tank that stores the functional liquid. The piezo element 22 is connected to a drive circuit 24, and a voltage is applied to the piezo element 22 via the drive circuit 24 to deform the piezo element 22, whereby the liquid chamber 21 is deformed and functions from the discharge nozzle 25. Liquid is discharged. In this case, the amount of distortion of the piezo element 22 is controlled by changing the value of the applied voltage. Further, the strain rate of the piezo element 22 is controlled by changing the frequency of the applied voltage. Since the droplet discharge by the piezo method does not apply heat to the material, it has an advantage of hardly affecting the composition of the material.

(First intermediate drying step)
FIG. 3 is a diagram showing a photomask manufacturing process according to the present invention.
After the functional liquid containing the photothermal conversion material is applied to the base material (flexible substrate) 1, a drying process is performed as necessary to remove the solvent (dispersion medium) and ensure the film thickness. The drying process can be performed, for example, by lamp annealing in addition to a process using a normal hot plate or an electric furnace for heating the substrate. And at least one part of the liquid component of the functional liquid apply | coated on the base material by the 1st intermediate drying process is removed, and as shown to Fig.3 (a), the photothermal conversion which contains a photothermal conversion material on the base material 1 Layer 2 is formed. Here, by repeating the first material arranging step and the first intermediate drying step a plurality of times, the surface of the functional liquid previously arranged on the substrate 1 is formed into a film, and then the next function is formed thereon. Since the liquid can be satisfactorily stacked, the thickness of the photothermal conversion layer 2 to be formed can be set to a desired thickness. The first intermediate drying step can be omitted.

(Second material placement process)
Next, a functional liquid containing a sublimable dye is applied onto the photothermal conversion layer 2 of the substrate 1. In the present embodiment, as the functional liquid for forming the transfer layer 3, one or more types of sublimable pigments or dyes dissolved or dispersed in a solvent (dispersion medium) are used. Examples of pigments or dyes that can be used include "RAVEN" 450 (registered trademark), 769 ULTRA (registered trademark), 890 (registered trademark), 1020 (registered trademark), 1250 (registered trademark), Black Pearls 480 (registered trademark). , Vulcan XC72 (registered trademark), Black Pearls 1100 (registered trademark), "NEPTUN" Black X60 (registered trademark), "PALIOGEN" Black S 0084 (registered trademark), Microlith Violet B-K (registered trademark), "ORASOL" Black (Registered trademark), “NIGROSINE” Black (registered trademark), “PALIOTOL” Black K0080 (registered trademark), “SANDOLAN” Black E-HL (registered trademark), “NEAZOPAN” Bl ck L 0080 (TM), "SOLANTINE" Black L (registered trademark), and the like can be exemplified.

  And after producing | generating the functional liquid containing a sublimable pigment | dye, the general liquid coating method, for example, an extrusion coating method, a spin coating method, a gravure coating method, a reverse roll, like the said 1st material arrangement | positioning process. It can apply | coat on the photothermal conversion layer 2 (base material 1) by the coating method, the rod coating method, the micro gravure coating method, the knife coating method, etc. Also in this case, it is preferable that the transfer layer forming functional liquid is uniformly formed on the photothermal conversion layer 2 (base material 1) by removing static electricity charged on the surface of the base material 1 as in the first material arranging step. It is preferable that a static eliminator is attached to the device used for each method. It is of course possible to dispose a functional liquid containing a conductive material on the photothermal conversion layer 2 (base material 1) based on the above-described droplet discharge method (inkjet method).

(Second intermediate drying step)
After applying a functional liquid containing a sublimable dye, a drying process is performed as necessary to remove the solvent (dispersion medium) and secure the film thickness. Similar to the first intermediate drying step, the second intermediate drying step can be performed, for example, by treatment with a normal hot plate or an electric furnace for heating the substrate, or lamp annealing. And at least one part of the liquid component of the functional liquid apply | coated on the photothermal conversion layer 2 (base material 1) by the 2nd intermediate drying process is removed, as shown in FIG.3 (b), on the photothermal conversion layer 2 The transfer layer 3 containing a sublimable dye is formed. Here, by repeatedly performing the second material placement step and the second intermediate drying step a plurality of times, after the surface of the functional liquid previously placed on the photothermal conversion layer 2 (base material 1) is formed into a film, Since the next functional liquid can be satisfactorily stacked thereon, the thickness of the transfer layer 3 to be formed can be set to a desired thickness. This second intermediate drying step can also be omitted.
In this embodiment, as shown in FIG. 3B, the photothermal conversion layer 2 is provided on the base material 1 independently of the base material 1, and the photothermal conversion layer 2 and the transfer layer are formed on the base material 1. 3 are stacked adjacent to each other.

(Pattern formation process)
FIG. 4 is a schematic configuration diagram showing an embodiment of an irradiation apparatus used for pattern formation according to the present invention.
In FIG. 4, the irradiation device 10 includes a laser light source 11 that emits a laser beam having a predetermined wavelength, and a drum 12 that winds and supports the substrate 1 having the photothermal conversion layer 2 and the transfer layer 3. In the present embodiment, the substrate 1 is supported by the drum 12 so that the transfer layer 3 and the drum 12 face each other. The laser light source 11 and the drum 12 are disposed in the chamber 14. A suction device 13 capable of sucking the gas in the chamber 14 is connected to the chamber 14. In the present embodiment, a near-infrared semiconductor laser (wavelength 830 nm) is used as the laser light source 11.

  Here, in the following description, the predetermined direction in the horizontal plane is the X axis direction, the direction orthogonal to the X axis direction in the horizontal plane is the Y axis direction, and the direction (vertical direction) orthogonal to each of the X axis and Y axis is Z. Axial direction.

  The drum 12 is provided so as to be movable in the horizontal translation direction (scanning direction, X direction), the rotation direction (Y direction), and the vertical direction (Z axis direction) while supporting the base material 1. Is movable with respect to the light beam emitted from the light source 11 by the movement of the drum 12. Here, an optical system (not shown) is disposed between the light source 11 and the substrate 1 supported by the drum 12. The drum 12 that supports the substrate 1 moves in the Z-axis direction, so that the position of the substrate 1 with respect to the focal point of the optical system can be adjusted. Then, the light beam emitted from the light source 11 irradiates the base material 1 supported by the drum 12.

  Here, the base material 1 is supported by the drum 12 that can move in the horizontal translation direction, the rotation direction, and the vertical direction, but the base material 1 may be supported by a stage that translates in the XYZ directions. In this case, not only the plastic film formed from the flexible material described above but also a glass plate such as a quartz plate can be used as the substrate 1.

When the pattern is formed, laser light having a predetermined light beam diameter is irradiated from the light source 11 from the side of the substrate 1 on which the transfer layer 3 is provided, as shown in the schematic diagram of FIG. The By irradiating the laser beam, the substrate 1 and the photothermal conversion layer 2 corresponding to the irradiated region are heated. The photothermal conversion layer 2 converts the light energy of the irradiated laser beam into heat energy, and supplies the heat energy to the transfer layer 3. Thereby, thermal energy is provided to a part of the transfer layer 3 corresponding to the light irradiation region.
Then, in a part of the transfer layer 3 to which thermal energy has been supplied, the sublimable dye is sublimated by the heated heat, so that light transmission is ensured in the part of the region, and FIG. As shown in d), it is converted into a light shielding pattern (pattern) 4 composed of a light transmission region and a light shielding region.

At this time, by moving the drum 12 in the X and Y directions with respect to the laser beam to be irradiated, the sublimation dye in the region corresponding to the movement locus of the stage 12 can be sublimated, and the sublimation region of the sublimation dye is patterned. can do.
Here, in order to transmit the light in the sublimation region of the sublimable dye and shield the light in the region where the sublimable dye is not sublimated, the drum 12 is moved on the base 1 by moving in a preset movement locus. An arbitrary light shielding pattern 4 can be formed. Note that the laser beam may be moved relative to the base material 1 without moving the drum 12, or both the laser beam and the drum 12 may be moved.

According to the above configuration, the sublimable dye in the predetermined region is sublimated by the heat generated by irradiating the predetermined region of the transfer layer 3 with the laser beam, and the region where the sublimable dye is present and the region where the sublimable dye is present are formed. Thus, a light shielding pattern such as a light transmitting region and a light shielding region can be formed. Therefore, a photomask can be manufactured with a laser beam that is easier to handle than conventionally used electron beams, and a photomask can be manufactured easily and inexpensively.
Moreover, since the photothermal conversion layer 2 is provided on the base material 1, the light energy of the irradiated laser beam can be efficiently converted into heat energy. Therefore, sufficient heat energy for sublimating the sublimable dye of the transfer layer 3 can be given to the transfer layer 3, and the sublimable dye can be easily sublimated.

Since semiconductor laser light emitted from a semiconductor (infrared laser light in this embodiment) is used, semiconductor laser light can be obtained at a lower cost than conventionally used electron beams, and a photomask can be manufactured at low cost. be able to.
In addition, since infrared laser light is easily converted into heat, it is easy to apply heat to the sublimable dye of the transfer layer 3, and the sublimable dye can be easily sublimated.

  In addition, since the photomask uses a flexible transparent polymer for the substrate 1, the photomask itself is also flexible so that the photomask can be brought into close contact with the exposure target, and the light shielding pattern is exposed. The object can be accurately exposed.

FIG. 5 is a schematic configuration diagram showing another embodiment of an irradiation apparatus used for pattern formation of a photomask.
When a predetermined region of the transfer layer 3 is formed by patterning, as shown in FIG. 5, a configuration is employed in which light is applied to the mask 15 having a predetermined pattern, and the substrate 1 is irradiated with light through the mask 15. can do. In FIG. 5, the mask 15 is supported by a mask support portion 16 having an opening 16 </ b> A for allowing the light transmitted through the mask 15 to pass. The light beam emitted from the light source 11 is converted into illumination light having a uniform illuminance distribution by the optical system 17 and then illuminates the mask 15. The light that has passed through the mask 15 irradiates the substrate 1 supported by the drum 12. Thereby, a fine conductive film pattern having a diameter equal to or smaller than the laser beam diameter to be irradiated can be formed. On the other hand, as in the embodiment described with reference to FIG. 4, by drawing the conductive film pattern by irradiating the laser beam while irradiating the laser beam while moving the substrate 1, the labor for manufacturing the mask can be saved. be able to.

  In the present embodiment, the light-to-heat conversion layer 2 and the transfer layer 3 are laminated so as to be adjacent to each other. For example, the light-to-heat conversion layer 2 is provided on one surface side of the substrate 1 and transferred to the other surface side. Another layer may be interposed between the photothermal conversion layer 2 and the transfer layer 3, such as providing the layer 3. Also by doing this, the heat energy generated in the light-to-heat conversion layer 2 is supplied to the transfer layer 3 via the substrate 1 (another layer), and the sublimable dye of the transfer layer 3 is sublimated using the heat energy. Can be made. On the other hand, by laminating the photothermal conversion layer 2 and the transfer layer 3 so as to be adjacent to each other, the heat energy generated in the photothermal conversion layer 2 can be efficiently supplied to the transfer layer 3.

  In the above embodiment, an intermediate layer for making the photothermal conversion action of the photothermal conversion layer 2 uniform can be provided between the photothermal conversion layer 2 and the transfer layer 3, for example. Examples of the material for forming the intermediate layer that forms the intermediate layer include resin materials that can satisfy the above requirements. Such an intermediate layer is obtained by forming a photothermal conversion layer 2 on the substrate 1 (that is, after the first intermediate drying step S2), and then applying a resin composition having a predetermined composition, for example, a spin coating method, a gravure coating method, It can be formed by applying to the surface of the photothermal conversion layer 2 and drying based on a known coating method such as a die coating method. When the laser beam is irradiated, the light energy is converted into heat energy by the action of the photothermal conversion layer 2, and this heat energy is made uniform by the action of the intermediate layer. Therefore, uniform heat energy is supplied to the transfer layer 3 corresponding to the light irradiation region.

  In the above embodiment, the laser beam is irradiated from the surface side of the substrate 1 on which the transfer layer 3 is provided, but the laser beam may be irradiated from the surface side of the substrate 1 on which the transfer layer 3 is not provided. Is possible. The irradiated laser light is applied to the photothermal conversion layer 2 via the transfer layer 3, and the photothermal conversion layer 2 irradiated with the laser light converts the light energy of the light into thermal energy and supplies it to the transfer layer 3. Can do. On the other hand, by irradiating a laser beam from the surface side of the substrate 1 where the transfer layer 3 is not provided, the photothermal conversion layer 2 can be directly irradiated with the laser beam through the transparent substrate 1. The conversion layer 2 can efficiently convert the light energy of the laser light into heat energy.

  In the above-described embodiment, the photothermal conversion material is provided in a layer (photothermal conversion layer 2) independent from the base material 1, but a configuration in which the photothermal conversion material is mixed in the base material 1 is also possible. Even with such a configuration, the light energy of the irradiated laser light can be converted into heat energy, and the heat energy can be provided to the transfer layer 3. In addition, you may provide the photothermal conversion layer 2 on the base material 1 with which the photothermal conversion material was mixed separately.

  When the photothermal conversion layer 2 is provided, it is preferable to irradiate light having a wavelength corresponding to the photothermal conversion material. That is, since the wavelength band of light that is favorably absorbed differs depending on the photothermal conversion material used, light energy can be efficiently converted into thermal energy by irradiating light having a wavelength corresponding to the light conversion material. In other words, the photothermal conversion material to be used is selected according to the light to be irradiated. In this embodiment, since a near-infrared semiconductor laser (wavelength 830 nm) is used as a laser light source, a material having a property of absorbing light in the infrared to visible light region is used as the photothermal conversion material. Is preferred.

  In addition, although the light source 11 in the said embodiment is a near-infrared semiconductor laser, it is not restricted to this, A mercury lamp, a halogen lamp, a xenon lamp, a flash lamp etc. can also be used. In addition, all general-purpose lasers such as ultraviolet lasers other than near infrared lasers can be used.

In the above embodiment, the transfer layer is formed by applying a functional liquid containing a sublimable dye, but a heat transferable dye can be used in addition to the sublimable dye. Examples of the heat transfer dye include silver halide, silver behenate, silver stearate, silver oleate, silver erucate, silver laurate, silver caproate, silver myristylate, silver palmitate, silver maleate, and fumarate. Examples thereof include silver oxide, silver tartrate, silver linoleate, silver camphorate, and mixtures thereof. The dispersion medium is preferably one that can disperse the above-mentioned heat transferable dye, is transparent to the irradiated laser light, has good film-forming properties, and has yellowing resistance against long-time exposure. For example, acrylic acid, methacrylic acid (and its esters, amides and nitrile derivatives), maleic anhydride, and polymers and copolymers of vinyl monomers such as styrene, 1-alkene, vinyl halides, vinyl ethers and vinyl esters, polyesters, polycarbonates Cellulose ester, methacrylate polymer and copolymer, styrene-maleic anhydride copolymer and cellulose acetate butyrate.
Examples of photothermal conversion materials when these materials are used include cyanine, merocyanine, amine cation radical dye, squarilim dye, croconium dye, tetraarylpolymethylene dye, oxonol dye and the like.

In the above embodiment, the transfer layer is formed by applying a functional liquid containing a sublimable dye. However, the transfer layer is also formed by applying a functional liquid containing metal particles. Also good.
As the functional liquid containing the transfer layer forming metal particles, a dispersion liquid in which silver fine particles are dispersed in a dispersion medium may be used. Examples of the metal particles include metal fine particles containing at least one of gold, silver, copper, aluminum, palladium, and nickel, oxides thereof, and fine particles of conductive polymers and superconductors. Is used. The dispersion medium is not particularly limited as long as it can disperse the metal particles and does not cause aggregation. For example, in addition to water, alcohols such as methanol, ethanol, propanol, butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydro Hydrocarbon compounds such as naphthalene and cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis (2- Methoxyethyl) ether, ether compounds such as p-dioxane, propylene carbonate, γ- Butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, can be exemplified polar compounds such as cyclohexanone. Of these, water, alcohols, hydrocarbon compounds, and ether compounds are preferable and more preferable dispersion media in terms of fine particle dispersibility, dispersion stability, and ease of application to the droplet discharge method. Examples thereof include water and hydrocarbon compounds.

Then, the functional liquid is applied to a general film coating method, for example, an extrusion coating method, a spin coating method, a gravure coating method, a reverse roll coating method, a rod coating method, a micro gravure coating method, as in the first material arranging step. It can apply | coat on the photothermal conversion layer 2 (base material 1) by the knife coating method etc.
In addition to the above-described method, the transfer layer 3 may be formed by vapor-depositing metal particles on the substrate 1, or the transfer layer 3 may be formed by depositing metal particles on the substrate 1 by a sputtering method. It may be formed.

  When the transfer layer 3 formed using the functional liquid containing metal particles is irradiated with laser light, the substrate 1 and the photothermal conversion layer 2 corresponding to the irradiated region are heated. The photothermal conversion layer 2 converts the light energy of the irradiated laser beam into heat energy, and supplies the heat energy to the transfer layer 3. In the transfer layer 3, the metal particles are sublimated by thermal energy, and light transmission is ensured in the region irradiated with the laser light, thereby forming the light shielding pattern 4 including the light transmitting region and the light shielding region. Alternatively, the metal particles of the transfer layer 3 directly receive the light energy of the laser light, cause ablation, and light transmittance is ensured in the region irradiated with the laser light, and the light shielding pattern including the light transmitting region and the light shielding region. 4 is formed.

  According to said structure, a metal particle is sublimated by the heat which generate | occur | produces with the laser beam irradiated to the predetermined area | region of the transfer layer, or a metal particle is ablated by the optical energy of a laser beam, and a metal particle exists. Regions and non-existing regions can be formed. Therefore, it is possible to form a light shielding pattern including a region that transmits light and a region that blocks light. As a result, a photomask can be manufactured with laser light that is easier to handle than conventional electron beams, and a photomask can be manufactured easily and inexpensively.

FIG. 6 is a diagram showing another manufacturing process of the photomask in the present invention.
In the above embodiment, the light shielding pattern 4 is formed on the base material 1, but as shown in FIG. 6A, for example, a sublimation dye, a heat transferable dye on the base material 1 made of a laminate film, or the like It is also possible to form a photomask by forming a light shielding pattern on the transfer layer 3 containing metal particles and laminating it on a predetermined substrate 6 made of, for example, a quartz plate, as shown in FIG. 6B.
According to this configuration, a photomask can be manufactured even on a substrate on which a transfer layer containing a direct sublimable dye, a heat transferable dye, or metal particles cannot be formed.

<Example>
A sheet made of polyethylene terephthalate was used as the substrate 1, and a thermosetting epoxy resin mixed with carbon black was used as the photothermal conversion layer 2 in the sheet. Further, a transfer layer 3 was formed by applying a functional liquid containing a sublimable dye on the substrate 1. Then, the sheet is held on a rotating drum so that the transfer layer is on the outer side, and the rotating drum is rotated at 130 rpm, and a laser beam with a wavelength of 830 nm is irradiated from the near-infrared semiconductor laser device with an output of 11 W to the sheet. did. Then, the color of the sublimable dye disappeared in the region irradiated with the laser light, and the substrate 1 can be visually recognized. Further, the color of the sublimable dye did not disappear in the region not irradiated with the laser beam, and it was confirmed that the sublimable dye was removed in the light irradiated region.

[Color filter]
Next, the manufacturing method of the color filter formed using the photomask of this invention is demonstrated.
FIG. 7 is a diagram illustrating a manufacturing process of a color filter.
First, as shown in FIG. 7A, a black matrix (bank) 52 is formed on one surface of a transparent substrate (base material) P. The black matrix 52 defines a color filter forming region. The bottom surface 52a of the concave portion of the black matrix 52 is subjected to lyophilic treatment, and the side surface 52b of the concave portion and the upper surface 52c of the convex portion are subjected to liquid repellent treatment. It has been subjected.

A procedure for the lyophilic process and the liquid repellent process of the black matrix 52 will be described.
First, a substrate P on which a black matrix 52 is formed and a bottle containing a fluorine-containing alkyl compound (for example, tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane) are combined with Teflon (registered trademark). ) Place in a container. The substrate P is placed on a fixed base, and in this state, the inside of the container is depressurized, the temperature of the entire container is increased to about 80 ° C., and the temperature is maintained for about one hour. As a result, the alkyl compound in the bottle evaporates and chemical vapor deposition is performed on the entire surface of the black matrix 52. As a result, the chemical vapor deposition surface of the black matrix 52 showed a contact angle of 72 ° with respect to tetradecane, and it was found that the liquid repellent treatment was performed.

Next, as shown in FIG. 7B, a photomask M manufactured so that only the bottom surface 52a region of the black matrix 52 transmits ultraviolet light (UV light) by the manufacturing method according to the present invention is formed on the substrate P. Deploy. At this time, the photomask M is disposed so that the transfer layer 3 of the photomask faces the substrate P and the UV light transmission region and the bottom surface 52a coincide.
In this state, the substrate P is irradiated with UV light (for example, UV light of 172 nm, 254 nm, 313 nm, 365 nm, and 436 nm) for 10 minutes from a position 1.5 mm away from the photomask M side. As a result, it can be seen that the bottom surface 52a irradiated with UV light has a contact angle with respect to tetradecane of 35 ° and is lyophilic. It can be seen that the contact angle with respect to tetradecane is 65 ° on the side surface 52b and the upper surface 52c where the UV light is shielded by the photomask M, and the liquid repellency remains as compared with the bottom surface 52a.

  As described above, after the lyophilic and lyophobic treatment of the black matrix 52 is performed, as shown in FIG. 7C, droplets of the functional liquid 54 for the color filter are ejected from the ejection head. The filter element 53 is landed. The amount of the functional liquid 54 to be discharged is a sufficient quantity considering the volume reduction of the functional liquid in the overheating process (drying / firing process). Further, since the bottom surface 52a of the black matrix is made lyophilic and the side surface 52b and the upper surface 52c are lyophobic, the functional liquid 54 easily spreads on the bottom surface 52a, and the functional liquid 54 attached to the side surface 52b or the upper surface 52c It flows down toward the bottom surface 52a.

  In this way, after all the filter elements 53 on the substrate P are filled with the droplets 54, the substrate P is heated using a heater so that the substrate P reaches a predetermined temperature (for example, about 70 ° C.). By this heat treatment, the solvent of the functional liquid is evaporated and the volume of the functional liquid is reduced. When the volume reduction is severe, the droplet discharge process and the heating process are repeated until a sufficient film thickness for the color filter is obtained. By this treatment, the solvent contained in the functional liquid evaporates, and finally, only the solid content (functional material) contained in the functional liquid remains to form a film, and as shown in FIG. It becomes.

FIG. 8 is a diagram illustrating a manufacturing process of a color filter.
Next, in order to flatten the substrate P and protect the color filter 55, a protective film 56 is formed on the substrate P so as to cover the color filter 55 and the black matrix 52 as shown in FIG. In forming the protective film 56, a spin coating method, a roll coating method, a ripping method, or the like can be employed. However, similarly to the case of the color filter 55, the above-described ejection device can also be used.
Next, as shown in FIG. 8B, a transparent conductive film 57 is formed on the entire surface of the protective film 56 by a sputtering method, a vacuum deposition method, or the like. Thereafter, the transparent conductive film 57 is patterned, and the pixel electrode 58 is patterned corresponding to the filter element 53 as shown in FIG.
Note that this patterning is not necessary when a TFT (Thin Film Transistor) is used to drive the liquid crystal display panel. In the production of such a color filter, since the ejection head is used, the color filter material can be ejected continuously without hindrance, so that a good color filter can be formed and the productivity is improved. be able to.

[Plasma display]
Next, as an example of an electro-optical device having a wiring substrate formed using the photomask of the present invention, a plasma display (plasma display device) will be described with reference to FIGS.
FIG. 9 is an exploded perspective view showing the plasma display 500 in which the address electrodes 511 and the bus electrodes 512a are manufactured.
The plasma display 500 is generally configured by a glass substrate 501 and a glass substrate 502 that are arranged to face each other, and a discharge display portion 510 that is formed therebetween.

  The discharge display unit 510 includes a plurality of discharge chambers 516, and among the plurality of discharge chambers 516, three of the red discharge chamber 516 (R), the green discharge chamber 516 (G), and the blue discharge chamber 516 (B). Two discharge chambers 516 are arranged in pairs to constitute one pixel. Address electrodes 511 are formed in stripes at predetermined intervals on the upper surface of the (glass) substrate 501, a dielectric layer 519 is formed so as to cover the address electrodes 511 and the upper surface of the substrate 501, and a dielectric layer A partition wall 515 is formed on the 519 between the address electrodes 511 and 511 and along the address electrodes 511. The partition wall 515 is also partitioned at a predetermined interval in a direction perpendicular to the address electrode 511 at a predetermined position in the longitudinal direction (not shown), and is basically adjacent to the left and right sides of the address electrode 511 in the width direction. A rectangular region partitioned by the barrier ribs and the barrier ribs extending in a direction orthogonal to the address electrodes 511 is formed, and discharge chambers 516 are formed so as to correspond to the rectangular regions. One pixel is composed of three pairs. In addition, a phosphor 517 is disposed inside a rectangular region partitioned by the partition 515. The phosphor 517 emits red, green, or blue fluorescence. The red phosphor 517 (R) is located at the bottom of the red discharge chamber 516 (R), and the bottom of the green discharge chamber 516 (G). Are arranged with a green phosphor 517 (G) and a blue phosphor 517 (B) at the bottom of the blue discharge chamber 516 (B).

  Next, on the glass substrate 502 side, transparent display electrodes 512 made of a plurality of ITO are formed in stripes at a predetermined interval in a direction orthogonal to the previous address electrode 511, and in order to compensate for the high resistance ITO. Further, a bus electrode 512a made of metal is formed. Further, a dielectric layer 513 is formed so as to cover them, and a protective film 514 made of MgO or the like is further formed. The substrate 501 and the substrate 2 of the glass substrate 502 are bonded to each other so that the address electrodes 511 and the display electrodes 512 are opposed to each other so as to be orthogonal to each other, and are formed on the substrate 501, the partition wall 515, and the glass substrate 502 side. A discharge chamber 516 is formed by evacuating a space surrounded by the protective film 514 and enclosing a rare gas. Note that two display electrodes 512 formed on the glass substrate 502 side are formed so as to be arranged two by two for each discharge chamber 516. The address electrode 511 and the display electrode 512 are connected to an alternating current power supply (not shown), and the phosphor 517 is excited to emit light in the discharge display portion 510 at a necessary position by energizing each electrode, thereby enabling color display. ing.

FIG. 10 is a diagram showing a part of the manufacturing process of the plasma display.
In this example, the address electrodes 511 and the bus electrodes 512a are formed in a predetermined pattern using the photomask according to the present invention. Since the address electrode 511 and the bus electrode 512a are formed in substantially the same procedure, the procedure for forming the address electrode 511 will be described, and the description of the procedure for forming the bus electrode 512a will be omitted.
First, a glass substrate 501 and a bottle containing a fluorine-containing alkyl compound (for example, tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane) are placed in a Teflon (registered trademark) container. Put in. The glass substrate 501 is installed on a fixed base. In this state, the inside of the container is depressurized, and the temperature of the entire container is increased to approximately 80 ° C. and the temperature is maintained for approximately one hour. As a result, the alkyl compound in the bottle evaporates, and chemical vapor deposition is performed on the surface of the glass substrate 501 to form the liquid repellent layer 501a, whereby the liquid repellent treatment is performed.
Next, as shown in FIG. 10A, a photomask M manufactured so that only the wiring pattern region of the address electrode 511 transmits ultraviolet light (UV light) by the manufacturing method according to the present invention is formed on a glass substrate 501. To place. At this time, the photomask M is arranged so that the transfer layer 3 faces the glass substrate 501 side.
In this state, the glass substrate 501 is irradiated with UV light (for example, UV light of 172 nm, 313 nm, 365 nm, and 436 nm) from the position 1.5 mm away from the photomask side for 10 minutes. As a result, the wiring pattern region of the address electrode 511 of the liquid repellent layer 501a irradiated with UV light is made lyophilic.

As described above, after the lyophilic and lyophobic treatment of the substrate 501, the metal colloid material (for example, gold colloid or silver colloid) or conductive fine particles (for example, gold colloid or silver colloid) is discharged from the ejection head as shown in FIG. The functional liquid 511a in which the metal fine particles) are dispersed is discharged and landed on the substrate 501. The functional liquid 511a that has landed on the lyophilic region of the substrate 501 is likely to spread and does not spread to the lyophobic region. Therefore, the wiring pattern of the address electrode 511 can be drawn accurately, and the line width of the wiring can be drawn accurately.
The phosphor 517 can also be formed by discharging a functional liquid in which a phosphor material is dissolved in a solvent or dispersed in a dispersion medium from the discharge head 20 and drying and baking.

  Although the plasma display device has been described as an example of the electro-optical device here, the method for forming a conductive film pattern of the present invention is also applied when forming a wiring pattern constituting an organic EL display device or a liquid crystal display device. be able to.

It is a flowchart figure which shows one Embodiment of the formation method of the photomask in this invention. It is a figure for demonstrating the discharge principle of the functional liquid by a piezo method. It is a figure which shows the manufacturing process of the photomask in this invention. It is a schematic block diagram which shows an example of the irradiation apparatus used for pattern formation of a photomask. It is a schematic block diagram which shows another embodiment of the irradiation apparatus used for pattern formation of a photomask. It is a figure which shows another manufacturing process of the photomask in this invention. It is a figure which shows the manufacturing process of a color filter. It is a figure which shows the manufacturing process of a color filter. It is a disassembled perspective view which shows the plasma display with which the address electrode and the bus electrode were manufactured. It is a figure which shows a part of manufacturing process of a plasma display.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material (flexible board | substrate), 2 ... Photothermal conversion layer, 3 ... Transfer layer, 4 ... Light-shielding pattern (pattern)

Claims (16)

A flexible substrate having light permeability, and a transfer layer containing a sublimation dye or a heat transfer dye disposed on the flexible substrate,
A pattern is formed on the transfer layer depending on the presence or absence of the sublimable dye or the heat transferable dye. A flexible substrate having light permeability, and a transfer layer containing metal particles disposed on the flexible substrate,
A pattern is formed on the transfer layer depending on the presence or absence of the metal particles.   The photomask according to claim 1, wherein the flexible substrate is made of a transparent polymer. A transfer layer forming step of forming a transfer layer containing a sublimable dye or a heat transferable dye on a substrate having light permeability;
A photomask manufacturing method comprising manufacturing a photomask by a pattern forming step of irradiating a predetermined region of the transfer layer with a laser beam to form a pattern. A transfer layer forming step of forming a transfer layer containing metal particles on a substrate having optical transparency;
A photomask manufacturing method comprising manufacturing a photomask by a pattern forming step of irradiating a predetermined region of the transfer layer with a laser beam to form a pattern.   6. The method for producing a photomask according to claim 5, wherein the transfer layer forming step is performed by applying a metal ink in which the metal particles are dispersed in a solvent on the substrate.   6. The method of manufacturing a photomask according to claim 5, wherein the transfer layer forming step is performed by vapor-depositing the metal particles on the substrate.   The photomask manufacturing method according to claim 5, wherein the transfer layer forming step is performed by depositing the metal particles on the substrate by a sputtering method.   9. The method for manufacturing a photomask according to claim 4, wherein the laser beam is a semiconductor laser beam emitted from a semiconductor.   The photomask manufacturing method according to claim 9, wherein the semiconductor laser light is an infrared laser light.   The photomask manufacturing method according to claim 5, wherein the substrate is provided with a photothermal conversion layer containing a photothermal conversion material that converts optical energy into thermal energy. A transfer layer forming step of forming a transfer layer containing a sublimable dye or a heat transferable dye on a light-transmitting flexible substrate;
A pattern forming step of forming a pattern by irradiating a predetermined region of the transfer layer with laser light;
A method of manufacturing a photomask, comprising: arranging the transfer layer on a light-transmitting substrate. A transfer layer forming step of forming a transfer layer containing metal particles on a flexible substrate having optical transparency;
A pattern forming step of forming a pattern by irradiating a predetermined region of the transfer layer with laser light;
A method of manufacturing a photomask, comprising: arranging the transfer layer on a light-transmitting substrate.   A color filter manufactured using the photomask according to any one of claims 1 to 3 or the photomask manufactured by the method for manufacturing a photomask according to any one of claims 4 to 13. .   A wiring board manufactured using the photomask according to any one of claims 1 to 3 or the photomask manufactured by the method for manufacturing a photomask according to any one of claims 4 to 13. .   An electro-optical device having the wiring board according to claim 15 mounted thereon.

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