JP4752391B2 - Method for producing pattern forming body - Google Patents

Description

  The present invention relates to a manufacturing method of a pattern forming body whose surface characteristics are changed into a pattern, for example, used for manufacturing a color filter and the like, and a pattern forming body manufacturing apparatus used for the manufacturing method.

  Conventionally, various methods have been proposed as a method for producing a pattern forming body for forming various patterns such as designs, images, characters, and circuits on a substrate. For example, lithographic printing, offset printing, and heat mode are proposed. A printing method for producing a lithographic printing original plate using a recording material is also used. In addition, for example, pattern exposure is performed on a photoresist layer coated on a substrate, and after exposure, the photoresist is developed and further etched, or the photoresist is exposed using a substance having functionality to the photoresist. There is also known a method of manufacturing a pattern forming body by photolithography, such as directly forming a target pattern by the above.

  However, when manufacturing a high-definition pattern forming body used for, for example, a color filter or the like, the printing method has a problem such as low positional accuracy, and is difficult to use. Further, in the photolithography method, there is a problem that a waste liquid needs to be processed because it is necessary to use a photoresist and to perform development or etching with a liquid developer after exposure. In addition, when a functional substance is used as a photoresist, there is a problem that it deteriorates due to an alkaline solution or the like used during development.

  Therefore, a photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing at least a photocatalyst and a pattern forming substrate whose characteristics change due to the action of the photocatalyst accompanying energy irradiation are arranged facing each other, and then exposed from a predetermined direction. Thus, the inventors have studied a method for producing a pattern forming body that changes the characteristics of the surface of the pattern forming substrate (Patent Document 1). According to this method, by irradiating the photocatalyst-containing layer with energy in a pattern, the characteristics of the surface of the pattern forming substrate can be changed into a pattern, and along the pattern with the changed characteristics, This makes it possible to easily form a functional part such as a colored layer with high definition. The mechanism of action of such a photocatalyst is not necessarily clear, but carriers generated by irradiation of energy react directly with nearby compounds, or by active oxygen species generated in the presence of oxygen and water, It is thought to change the chemical structure of organic matter.

  However, when the pattern forming body is continuously produced using the photocatalyst-containing layer side substrate, decomposition products generated on the pattern forming substrate adhere to the photocatalyst-containing layer, and this deposit May interfere with the action of the active oxygen species, or the attached substances may become radicals and contribute to the change of characteristics, etc., and form a pattern with a constant line width on the pattern forming substrate. There was a problem that it was difficult.

JP 2000-249821 A

  Therefore, even when the pattern forming body is continuously manufactured, the pattern forming body is capable of forming a characteristic change pattern with high definition in the shape of the target pattern, and is used in the manufacturing method. It is desired to provide an apparatus for producing a pattern forming body.

  The present invention has a surface property due to the action of the photocatalyst containing layer on the substrate and the photocatalyst containing layer side substrate having the photocatalyst containing layer containing at least the photocatalyst formed on the base material and the photocatalyst accompanying energy irradiation. A pattern forming body is formed by forming a characteristic change pattern having changed characteristics on the surface of the pattern forming substrate by irradiating the photocatalyst-containing layer with energy by placing the changing pattern forming substrate facing the substrate. A pattern forming body manufacturing method in which a pattern forming process to be formed is performed a plurality of times to produce a plurality of pattern forming bodies, and deposits attached to the photocatalyst-containing layer are removed during the pattern forming process to be performed a plurality of times. There is provided a method for producing a pattern forming body, wherein the deposit removing step is performed.

  According to the present invention, an adhering matter removing step for removing the adhering matter adhering to the surface of the photocatalyst containing layer is performed between the pattern forming step and the pattern forming step. It can prevent that the sensitivity of a content layer changes. Therefore, according to the present invention, in the pattern forming step, the characteristics of the pattern forming substrate can be changed with high definition into the target pattern, and a plurality of high-quality pattern forming bodies can be manufactured. .

  In the above invention, the deposit removal step leaves the photocatalyst-containing layer side substrate for the time determined by the standing time determining step for determining the time to leave the photocatalyst-containing layer side substrate, and forms the photocatalyst-containing layer on the photocatalyst-containing layer. It can be set as the process of removing the adhering deposit | attachment. This is because, by leaving the photocatalyst-containing layer side substrate for a certain period of time or longer, it is possible to remove the deposits attached to the surface of the photocatalyst-containing layer.

  In the above invention, the deposit removing step may be a step of sucking and removing the deposit attached to the surface of the photocatalyst containing layer, and the deposit removing step may be a deposit attached to the surface of the photocatalyst containing layer. May be a step of washing with a liquid. Furthermore, the deposit removal step may be a step of adsorbing and removing deposits adhering to the surface of the photocatalyst containing layer with an adsorption plate, and the deposit removal step is performed by irradiating the photocatalyst containing layer with thermal energy. Further, it may be a step of removing deposits attached to the surface of the photocatalyst-containing layer. This is because, according to these methods, it is possible to efficiently remove the deposit attached to the surface of the photocatalyst containing layer.

  Still further, in the above invention, the deposit removing step may be a step of irradiating the photocatalyst containing layer with plasma to remove the deposit adhering to the surface of the photocatalyst containing layer, and the deposit removing step. The step of irradiating the photocatalyst-containing layer with an electron beam to remove deposits attached to the surface of the photocatalyst-containing layer is also possible. This is because according to these methods, it is possible to efficiently decompose and remove the deposits attached to the surface of the photocatalyst containing layer.

  In addition, the present invention provides the above-mentioned photocatalyst-containing layer of the photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing at least a photocatalyst formed on the base material, and surface characteristics by the action of the photocatalyst accompanying energy irradiation. The pattern forming substrate is arranged so as to face the pattern forming substrate that changes, and by irradiating the photocatalyst-containing layer with energy, a characteristic changing pattern having changed characteristics is formed on the surface of the pattern forming substrate. A pattern forming body manufacturing apparatus used when a plurality of pattern forming bodies are manufactured by performing a pattern forming step of forming a plurality of pattern forming bodies, the pattern forming substrate support section supporting the pattern forming substrate, and the above A photocatalyst-containing layer side substrate support for supporting the photocatalyst-containing layer so as to face the pattern forming substrate; and an energy source on the photocatalyst-containing layer side substrate. Providing an energy irradiation unit that irradiates the ghee, the patterning device manufacturing apparatus characterized by having a deposit removal means for removing deposits adhering to the photocatalyst-containing layer.

  In the present invention, since the apparatus for producing a pattern forming body has the above-mentioned deposit removing means, the deposit adhering to the surface of the photocatalyst containing layer side substrate is removed between the pattern forming step and the pattern forming step. It becomes possible. Therefore, by using the apparatus for producing a patterned product of the present invention, the characteristics of the substrate for pattern formation were changed into a pattern using the above-mentioned photocatalyst-containing layer side substrate, and the patterned product was produced continuously. However, it is possible to prevent the sensitivity from changing due to deposits or the like adhering to the photocatalyst-containing layer, and manufacture a pattern forming body in which a characteristic change pattern is formed in a desired pattern shape with high definition. It becomes possible to do.

  In the above invention, the deposit removal means may be a suction means for sucking deposits attached to the photocatalyst-containing layer, and the deposit removal means cleans the photocatalyst-containing layer with a liquid. It may be a means. Still further, the deposit removal means may be an adsorption means for removing the deposit by bringing an adsorption plate into contact with the photocatalyst containing layer, and the deposit removal means irradiates the photocatalyst containing layer with thermal energy. It may be a thermal energy irradiation means. This is because by providing such means, it is possible to efficiently remove the deposits attached to the photocatalyst containing layer.

  ADVANTAGE OF THE INVENTION According to this invention, patterning can be performed using the photocatalyst containing layer side board | substrate from which the deposit | attachment adhering to the surface was removed, and the pattern formation body in which the characteristic changed to the target pattern shape with high definition is manufactured. There is an effect that it is possible.

  The present invention relates to a manufacturing method of a pattern forming body whose surface characteristics are changed into a pattern, for example, used for manufacturing a color filter and the like, and a pattern forming body manufacturing apparatus used for the manufacturing method. Each will be described separately below.

A. First, the manufacturing method of the pattern formation body of this invention is demonstrated. The method for producing a patterned product of the present invention includes a base material and the photocatalyst-containing layer of the photocatalyst-containing layer side substrate formed on the base material and having a photocatalyst-containing layer containing at least a photocatalyst, and a photocatalyst accompanying energy irradiation The pattern forming substrate whose surface characteristics change due to the action of the above is disposed opposite to the substrate, and the photocatalyst-containing layer is irradiated with energy, whereby a characteristic change pattern having changed characteristics is formed on the surface of the pattern forming substrate. A pattern forming process for forming a pattern forming body by performing a pattern forming process for forming a pattern forming body a plurality of times, wherein the photocatalyst-containing layer is formed between the pattern forming processes performed a plurality of times. An adhering matter removing process for removing adhering matter adhering to the substrate is performed.

  For example, as shown in FIG. 1, the method for producing a pattern forming body of the present invention includes a base material 1 and a photocatalyst containing layer 2 of a photocatalyst containing layer side substrate 3 having a photocatalyst containing layer 2 formed on the base material 1. And a pattern-forming substrate 4 whose surface characteristics are changed by the action of the photocatalyst accompanying the energy irradiation, are arranged facing each other, and irradiated with energy 6 using, for example, a photomask 5 or the like (FIG. 1A). A method of manufacturing a plurality of pattern forming bodies by performing a pattern forming step a plurality of times, by forming a characteristic changing pattern 7 having changed characteristics on the surface of the pattern forming substrate 4 in a pattern (FIG. 1B). And the deposit | attachment removal process which removes the deposit | attachment adhering to the photocatalyst containing layer is performed between the said pattern formation process and a pattern formation process.

  Here, when the pattern forming substrate is patterned using the photocatalyst-containing layer side substrate, the photocatalyst-containing layer is disposed so as to be vaporized and decomposed on the pattern forming substrate. May adhere to the surface. As a result, when patterning is subsequently performed on another pattern forming substrate, the deposits attached to the photocatalyst-containing layer may become radicals and contribute to changes in the characteristics of the pattern forming substrate. In some cases, the deposits obstruct the action of the active oxygen species generated by the photocatalyst. Therefore, when a pattern formed body is manufactured a plurality of times, there is a problem that it is difficult to form a characteristic change pattern formed on the pattern formed body in a desired pattern shape with a uniform width.

However, in the present invention, an adhering matter removing step for removing the adhering matter adhering to the photocatalyst containing layer is performed between the pattern forming step and the pattern forming step, so that the pattern is formed using the photocatalyst containing layer side substrate. When the forming step is performed, it is possible to prevent the line width or the like of the characteristic change pattern from being changed by the deposits attached to the photocatalyst containing layer. Therefore, even when the pattern forming body is manufactured continuously, the characteristic change pattern can be formed with high definition in the target pattern shape. As a result, according to the present invention, a plurality of pattern forming bodies capable of forming various functional portions can be stably manufactured along the characteristic change pattern.
Hereinafter, each process of the manufacturing method of the pattern formation body of this invention is demonstrated.

1. Adhering matter removing step First, the adhering matter removing step of the present invention will be described. The deposit removal process of the present invention is a process that is performed during a pattern forming process that is performed a plurality of times, and is a process that removes the deposit adhered to the photocatalyst-containing layer. Here, the interval between the pattern forming steps performed a plurality of times is not particularly limited as long as it is between the pattern forming step and the pattern forming step. For example, this step is performed every time the pattern forming step is performed once. Alternatively, this step may be performed every time the pattern forming step is performed a plurality of times.
Hereinafter, the method for removing deposits from the photocatalyst containing layer in this step and the photocatalyst containing layer side substrate having the photocatalyst containing layer from which deposits are removed in this step will be described in detail.

(Method of removing deposits from the photocatalyst containing layer)
First, a method for removing the deposits attached to the photocatalyst containing layer in this step will be described. In the present invention, the method for removing the deposit from the photocatalyst-containing layer is not particularly limited as long as it is a method capable of removing the deposit. Examples of such a method include a method of leaving the photocatalyst-containing layer side substrate for a predetermined time, a method of removing deposits from the photocatalyst-containing layer using gas, and a deposit from the photocatalyst-containing layer using liquid. And the like. A method of removing deposits from the photocatalyst containing layer using a solid substance, a method of removing deposits from the photocatalyst containing layer using energy, and the like. This step may be performed by any one of the methods described above, or may be performed by combining two or more methods. Moreover, the said method will be suitably selected according to the kind etc. of the deposit | attachment adhering to the photocatalyst content layer.
Hereinafter, each of the above methods will be described in detail.

(1) Method of leaving the photocatalyst-containing layer for a predetermined time First, a method of removing deposits from the photocatalyst-containing layer by leaving the photocatalyst-containing layer for a predetermined time in this step will be described. Here, the above-mentioned leaving means that the photocatalyst-containing layer is allowed to stand, and it may be a method of leaving it as it is in a pattern forming body manufacturing apparatus for manufacturing a pattern forming body. It may be a method of removing it from the apparatus for producing a pattern forming body and allowing it to stand still. The environment in which the photocatalyst-containing layer is allowed to stand is not particularly limited, and the temperature, humidity, atmospheric pressure, and the like are appropriately selected depending on the type of deposit.

  In addition, the time until the deposit is removed from the photocatalyst-containing layer varies depending on the type of deposit and the like, and thus is determined by the standing time determination step performed before this step.

  The standing time determining step is a step for determining the time for leaving the photocatalyst-containing layer side substrate in the deposit removing step, and can be performed by the following procedure. First, using the unused photocatalyst-containing layer under the same conditions as in the pattern formation step described later, a characteristic change pattern is formed on the pattern formation substrate to form a pattern formation body. Thereafter, the formed pattern forming body is removed from the pattern forming body manufacturing apparatus, and the photocatalyst-containing layer is left in the pattern forming body manufacturing apparatus for a predetermined time. Subsequently, another pattern forming substrate is patterned in a pattern forming body manufacturing apparatus under the same conditions as described above to form a pattern forming body.

  After that, the time for which the photocatalyst-containing layer is left is changed, and the same inspection is performed a plurality of times. The characteristic change pattern of the pattern forming body formed first time and the characteristic change of the pattern forming body formed second time Compare the pattern. As a result, the standing time of the photocatalyst-containing layer in which the characteristic change pattern of the pattern formed body formed at the second time is the same as the characteristic change pattern of the pattern formed body formed at the first time is determined, and the photocatalyst is removed in the deposit removal step. The time for which the containing layer is left is determined. In addition, the time for which the photocatalyst-containing layer is allowed to stand in the deposit removal step is set to be the same as or longer than the time determined by the above method. Moreover, the characteristic change pattern of the formed pattern forming body is observed by observing the surface state of the pattern forming body with a scanning electron microscope (SEM).

(2) Method of removing deposits from the photocatalyst containing layer using gas Next, a method of removing deposits from the photocatalyst containing layer using gas will be described. As a method of removing deposits from the photocatalyst containing layer using gas, for example, by blowing an inert gas to the photocatalyst containing layer and removing the deposits by wind pressure, or from the surface of the photocatalyst containing layer, A method of removing the deposit by sucking the deposit, a method of removing the deposit adhering to the surface of the photocatalyst containing layer by wind pressure, and sucking the deposit. According to these methods, deposits can be efficiently removed without requiring a special apparatus.

  Here, when removing deposits by wind pressure, a method of blowing gas to the photocatalyst containing layer may be a method using an air blow nozzle or the like generally used for cleaning the apparatus. Moreover, as an inert gas sprayed on the said photocatalyst content layer, air, argon gas, nitrogen gas etc. are mentioned, for example. Moreover, in this invention, gas may be sprayed on the photocatalyst containing layer whole surface at once, and gas may be sprayed to each one part of photocatalyst containing layer. In addition, about the time, wind pressure, etc. which spray the said gas to a photocatalyst content layer, it will be suitably selected by the kind, quantity, etc. of the deposit | attachment adhering to a photocatalyst content layer.

  In addition, as a method for sucking the deposits attached to the photocatalyst-containing layer, for example, a method of sucking the deposits by placing the photocatalyst-containing layer side substrate in a vacuum apparatus may be used. The method is preferably a method in which deposits adhering to the surface of the photocatalyst containing layer are sucked with a nozzle or the like. Thereby, the deposits can be efficiently removed from the photocatalyst containing layer. Further, by using “B. pattern forming body manufacturing apparatus” described later, it is not necessary to remove the photocatalyst-containing layer side substrate from the pattern forming body manufacturing apparatus, and there is also an advantage that deposit removal can be performed efficiently. Because. The intake nozzle may be the same as, for example, a nozzle used in a general cleaner, and may have a shape that sucks deposits from the entire surface of the photocatalyst-containing layer at a time. What adsorb | sucks a deposit from a part of layer may be used. The suction time, suction pressure, and the like are appropriately selected depending on the type of deposits attached to the photocatalyst-containing layer.

  In addition, as a method for removing the adhered matter adhering to the surface of the photocatalyst containing layer by wind pressure and sucking the adhered matter, for example, a combination of a nozzle for blowing the gas and the intake nozzle can be used. .

(3) Method of removing deposits from the photocatalyst containing layer using a liquid Next, a method of removing deposits from the photocatalyst containing layer using a liquid will be described. In the present invention, a method for removing the deposits using a liquid may be, for example, a method of washing the photocatalyst-containing layer with a liquid. Specifically, the photocatalyst-containing layer side substrate is immersed in a liquid and removed using the solubility of the deposit in the liquid, or the photocatalyst-containing layer side substrate is sprayed with a nozzle or the like. Examples thereof include a method for removing the deposit by utilizing the solubility of the deposit in the liquid and the pressure of the liquid. In the present invention, among these, a method of spraying a liquid from a nozzle or the like to remove deposits is preferable. This is because the deposits can be removed efficiently. Further, by using “B. pattern forming body manufacturing apparatus” described later, it is not necessary to remove the photocatalyst-containing layer side substrate from the pattern forming body manufacturing apparatus, and it is possible to efficiently perform the deposit removing means. It also has advantages.

  The nozzle used for spraying the liquid can be the same as the nozzle generally used for spray cleaning or the like. The liquid used in the above method is preferably a liquid in which the deposit is highly soluble, and the type of the solution is appropriately selected depending on the type of deposit adhering to the photocatalyst-containing layer. As such a solution, water, various organic solvents, etc. can be used, for example. Further, the nozzle may be capable of spraying a solution on the entire surface of the photocatalyst-containing layer at a time, or may be capable of spraying the solution to each part of the photocatalyst-containing layer. Moreover, about the spraying time of the said solution, spraying pressure, etc., it will select suitably by the kind etc. of the deposit | attachment adhering to the photocatalyst content layer. In this case, after wiping the solution by the above method, a step of wiping the solution from the photocatalyst containing layer side substrate, a step of drying the photocatalyst containing layer side substrate, or the like may be appropriately performed.

(4) Method for removing deposits from the photocatalyst-containing layer by contacting a solid substance Next, a method for removing deposits from the photocatalyst-containing layer by contacting a solid substance in this step explain. As a method for removing deposits from the photocatalyst-containing layer by bringing the solid into contact with the photocatalyst-containing layer, for example, an adsorbing adsorption plate is brought into contact with the photocatalyst-containing layer and attached from the photocatalyst-containing layer side substrate. Examples include a method of adsorbing and removing the adsorbate and a method of sweeping off deposits from the photocatalyst containing layer side substrate using a brush.

  The adsorption plate having the adsorptivity can be, for example, an adhesive substrate or sheet, and when such an adsorption plate is used, the adsorbing plate is brought into contact with the photocatalyst-containing layer surface, By separating the adsorption plate from the photocatalyst containing layer, the adhering matter adhering to the photocatalyst containing layer can be transferred to the adsorption plate side. The type of the adsorbing plate is not particularly limited as long as it has adhesiveness to the deposit and can be peeled off from the photocatalyst-containing layer. For example, a general adhesive layer formed on a substrate can be used.

  The brush is not particularly limited as long as it does not damage the photocatalyst-containing layer, and can be the same as a brush used for cleaning a general apparatus.

(5) Method of removing deposits from the photocatalyst containing layer using energy Next, a method of removing deposits from the photocatalyst containing layer using energy will be described. Such a method includes, for example, a method of irradiating the photocatalyst containing layer with thermal energy and volatilizing the deposit attached to the photocatalyst containing layer, or irradiating the photocatalyst containing layer with ultrasonic energy to deposit from the photocatalyst containing layer. For example, a method of irradiating the photocatalyst-containing layer with plasma, a method of irradiating the photocatalyst-containing layer with an electron beam, and a method of irradiating the photocatalyst-containing layer with light energy.

  As the method using the thermal energy, for example, the deposit attached to the photocatalyst containing layer can be volatilized and removed from the photocatalyst containing layer. A method of heating the substrate can be employed. Such a temperature is appropriately selected depending on the kind of deposits and the like, but is usually about 20 ° C. to 300 ° C., particularly about 50 ° C. to 200 ° C. As the heating method, for example, a hot plate, an infrared heater, an oven, or the like can be used. In addition, about heating time, it will select suitably according to the kind, quantity, etc. of the said deposit | attachment.

  The method of irradiating the ultrasonic wave may be the same as a general ultrasonic cleaning method, for example, after immersing the photocatalyst-containing layer in a cleaning liquid holding tank into which a cleaning liquid is injected, A method of irradiating the layer with ultrasonic waves can be used.

  The method of irradiating the photocatalyst-containing layer with plasma is not particularly limited as long as it is a method capable of removing the deposits attached to the surface of the photocatalyst-containing layer. There may be a method of plasma irradiation under atmospheric pressure. Usually, the plasma irradiation direction is from the photocatalyst containing layer side of the photocatalyst containing layer side substrate.

  In the present invention, the plasma irradiation is particularly preferably plasma irradiation under atmospheric pressure. This is because an apparatus for decompression or the like is not necessary, which can be preferable in terms of cost, manufacturing efficiency, and the like. The irradiation conditions of such atmospheric pressure plasma can be as follows. For example, the power output can be the same as that used in a general atmospheric pressure plasma irradiation apparatus. At this time, the distance between the irradiated plasma electrode and the photocatalyst-containing layer is preferably about 0.2 mm to 20 mm, and more preferably about 1 mm to 5 mm. The substrate transport speed is preferably about 0.1 m / min to 10 m / min, and more preferably about 0.5 m / min to 5 m / min.

  Further, the method for irradiating the photocatalyst-containing layer with an electron beam is not particularly limited as long as it is a method capable of irradiating the adhering matter attached to the photocatalyst-containing layer surface with a removable electron beam. Absent. Specific examples of such an electron beam irradiation method include a device capable of irradiating a uniform electron beam in the form of a curtain from a linear filament (for example, an electrocurtain type device), an electron beam exposure device for creating a photomask, etc. Any known device can be used. The electron beam irradiation dose at this time is appropriately determined depending on the kind and amount of the deposit, but usually when the electron beam having an acceleration energy of 1 to 30 MRad is irradiated onto the substrate surface, the deposit on the surface Is preferably within this range. This is because if the electron beam dose is too low, the expected effect cannot be obtained, while if the electron beam dose is too high, the surface of the photocatalyst layer may be damaged.

  The method of irradiating the photocatalyst-containing layer with light energy may be a method of removing the deposits from the photocatalyst-containing layer by the action of light energy. In the present invention, the photocatalyst-containing layer is particularly produced with light energy. The method is preferably a method in which the photocatalyst contained therein is excited and the action of this photocatalyst is also used to remove the deposits. The light energy used in such a method is not particularly limited as long as it can excite the photocatalyst, and is not limited to visible light. The wavelength of light energy used in such a method is usually set in the range of 400 nm or less, preferably in the range of 150 nm to 380 nm. This is because the preferable photocatalyst used in the photocatalyst-containing layer is titanium dioxide as described later, and light having the above-described wavelength is preferable as energy for activating the photocatalytic action by the titanium dioxide.

  Examples of light sources that can be used for such light energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources. In addition to the above-described method of irradiating light energy using a light source, a method of drawing and irradiating in a pattern using a laser such as an excimer or YAG can also be used.

  Further, the irradiation direction of the light energy is not particularly limited as long as it is a direction in which the light energy can be irradiated to the region where the deposit is attached to the photocatalyst containing layer. For example, the photocatalyst containing layer side substrate described later Although energy may be irradiated from the base material side, it is preferable to irradiate energy from the photocatalyst containing layer side of the photocatalyst containing layer side substrate in the present invention. Thereby, for example, even when a light-shielding portion or the like is formed in the photocatalyst-containing layer side substrate, it is possible to irradiate the entire surface of the photocatalyst-containing layer with light energy.

  Here, the irradiation amount of light energy at the time of irradiation with light energy is set to an irradiation amount necessary for removing deposits adhering to the surface of the pattern forming substrate. In this case, it is preferable in that the photocatalyst-containing layer is irradiated with light energy while being heated, so that the sensitivity of the photocatalyst can be increased and the deposits can be efficiently decomposed and removed. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

(Photocatalyst containing layer side substrate)
Next, the photocatalyst containing layer side substrate having the photocatalyst containing layer from which deposits are removed by this step will be described. The photocatalyst containing layer side substrate used in this step has a photocatalyst containing layer and a base material containing a photocatalyst, and is usually a base material and a photocatalyst containing layer formed on the base material. . Hereinafter, each structure of the photocatalyst containing layer side board | substrate used for this process is demonstrated.

(1) Photocatalyst containing layer First, the photocatalyst containing layer used for a photocatalyst containing layer side board | substrate is demonstrated. The photocatalyst-containing layer used in this step is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer can change the characteristics of the pattern forming substrate disposed to face each other. And a binder, or a film formed of a single photocatalyst. Further, the surface characteristics may be particularly lyophilic or lyophobic.

As the photocatalyst used in the present invention, known as semiconductors, for example, titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide _{(Bi 2 O} 3), and the like, and iron oxide _(Fe 2 _{O 3).} In addition to semiconductors, metal complexes and silver can also be used. In this invention, it can select from these and can use 1 type or in mixture of 2 or more types.

  In the present invention, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type and a rutile type, and both can be used in the present invention, but anatase type titanium dioxide is preferred. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.

  Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.

  Further, a visible light responsive type may be used as the titanium oxide. Visible light responsive titanium oxide is also excited by the energy of visible light. Examples of such a visible light responsive method include a method of nitriding titanium oxide.

Here, the nitriding treatment of titanium oxide referred to in the present invention is a treatment for replacing part of the oxygen sites of the titanium oxide (TiO ₂ ) crystal with nitrogen atoms, or between the lattices of the titanium oxide (TiO ₂ ) crystal. A treatment of doping nitrogen atoms or a treatment of arranging nitrogen atoms at the grain boundaries of a polycrystalline aggregate of titanium oxide (TiO ₂ ) crystals.

The method of nitriding titanium oxide (TiO ₂ ) is not particularly limited. For example, crystalline titanium oxide fine particles are doped with nitrogen by heat treatment at 700 ° C. in an ammonia atmosphere, and the nitrogen is doped. Examples thereof include a method of forming a dispersion using fine particles and an inorganic binder, a solvent, or the like.

  The smaller the particle size of the photocatalyst in the photocatalyst-containing layer is, the more effective the photocatalytic reaction takes place. The average particle size is preferably 50 nm or less, and particularly preferably 20 nm or less.

  The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder.

  Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, thereby efficiently changing the characteristics of the substrate for pattern formation. It becomes possible.

  In addition, as another example of a method for forming a photocatalyst-containing layer comprising only a photocatalyst, for example, when the photocatalyst is titanium dioxide, a method of forming amorphous titania on a substrate and then changing the phase to crystalline titania by firing. Etc. As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.

  Moreover, when using a binder, what has the high bond energy that the main frame | skeleton of a binder is not decomposed | disassembled by photoexcitation of said photocatalyst is preferable, for example, organopolysiloxane etc. can be mentioned.

  When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. It can be formed by applying this coating solution on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.

An amorphous silica precursor can be used as the binder. This amorphous silica precursor is represented by the general formula SiX _4, X is a halogen, a methoxy group, an ethoxy group or a silicon compound an acetyl group or the like, and silanol or average molecular weight of 3,000 or less, their hydrolysates Polysiloxane is preferred.

  Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration-condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.

  When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.

  In addition to the photocatalyst and the binder, the photocatalyst containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the photocatalyst-containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.

  Here, in the present invention, the photocatalyst-containing layer may be formed on the entire surface of the substrate, but may be formed in a pattern, for example, in a shape that forms a characteristic change pattern. Thereby, even when energy is irradiated to the entire surface of the photocatalyst containing layer, the characteristic change pattern can be formed only in the target region of the pattern forming substrate. The patterning method of such a photocatalyst-containing layer is not particularly limited, but can be performed by, for example, a photolithography method.

  In the present invention, a light shielding part may be formed on the photocatalyst containing layer, or a light shielding part may be formed between the photocatalyst containing layer and the substrate. In this case, there is an advantage that even if the entire surface of the photocatalyst containing layer is irradiated with energy, it is not necessary to use a photomask or the like. In addition, such a light shielding part can be formed by the same material and forming method as the light shielding part in a general color filter.

(2) Base material Next, the base material used for a photocatalyst content layer side substrate is explained. In this invention, as shown to Fig.1 (a), the photocatalyst containing layer side board | substrate 3 has the base material 1 and the photocatalyst containing layer 2 formed on this base material 1 at least.

  The base material used in the present invention is not particularly limited as long as it can form the photocatalyst-containing layer. For example, a flexible resin film or the like may be used. For example, a glass substrate or the like may be used.

  An intermediate layer may be formed on the base material in order to improve the adhesion between the base material surface and the photocatalyst-containing layer and to prevent the base material from being deteriorated by the action of the photocatalyst. Examples of such an intermediate layer include silane-based and titanium-based coupling agents, silica films prepared by a reactive sputtering method, a CVD method, and the like.

2. Pattern Formation Step Next, the pattern formation step in the present invention will be described. The pattern formation process in this invention is based on the said photocatalyst containing layer of the photocatalyst containing layer side board | substrate which has a photocatalyst containing layer formed on a base material and the said base material and contains a photocatalyst at least, and the effect | action of the photocatalyst accompanying energy irradiation. A pattern-forming substrate whose surface characteristics change is placed opposite to it, and the photocatalyst-containing layer is irradiated with energy in a pattern, whereby a characteristic-changing pattern with changed characteristics is formed on the surface of the pattern-forming substrate. Forming a pattern forming body. In the present invention, the pattern forming step may be performed at least twice, and the number of times is not particularly limited.

  In this invention, since the said deposit removal process is performed between the said pattern formation process and a pattern formation process, the sensitivity of the photocatalyst of the photocatalyst containing layer side board | substrate used for the said pattern formation process will change. This makes it possible to manufacture a plurality of pattern-formed bodies in which characteristic change patterns are formed in a target pattern with high definition. Hereinafter, the substrate for pattern formation used in this step and the energy irradiation method will be described.

(Pattern for forming a pattern)
First, the pattern forming substrate used in the present invention will be described. The substrate for pattern formation used in the present invention may be any substrate as long as its surface characteristics are changed by the action of the photocatalyst associated with energy irradiation when irradiated with energy while facing the above-mentioned photocatalyst-containing layer side substrate. The configuration is not particularly limited.

  For example, it may have a support substrate and a characteristic change layer formed on the support substrate and whose surface characteristics change due to the action of the photocatalyst accompanying the energy irradiation, and the characteristic due to the action of the photocatalyst accompanying the energy irradiation. It may be composed only of a characteristic change layer in which changes. In the present invention, the characteristic change layer is particularly preferably a layer containing an organic substance. This is because, when the characteristic change layer contains an organic substance, the deposit easily adheres to the photocatalyst-containing layer when patterning is performed using the above-described photocatalyst-containing layer side substrate, so that the advantages of the present invention can be particularly utilized. .

  Also, the type of characteristic change of the characteristic change layer in the pattern forming substrate is not particularly limited, and for example, the wettability of the surface may be changed by the action of a photocatalyst accompanying energy irradiation, For example, the adhesiveness with a specific substance may change due to the action of a photocatalyst accompanying energy irradiation. In the present invention, it is particularly preferred that the wettability of the surface is changed by the action of the photocatalyst accompanying the energy irradiation, and in particular, the wettability changing layer in which the contact angle with the liquid is lowered by the action of the photocatalyst accompanying the energy irradiation. preferable. Thereby, the area where wettability has changed by this process can be made a lyophilic area, and the area where wettability has not changed by this process can be made a liquid repellent area. Therefore, when the functional part forming coating liquid is applied to the pattern formed body manufactured according to the present invention by, for example, a coating method, the functional part forming coating liquid is applied only to the characteristic change pattern which is a lyophilic region. This is because the functional part can be formed in a highly fine pattern.

  Here, the lyophilic region refers to a region having a contact angle with the liquid of 1 ° or more lower than that of the adjacent region, and is a region having a small contact angle with the liquid, and the functionality that forms the functional part. The region having good wettability with respect to the coating liquid for part formation will be referred to. Further, the liquid repellent region is a region having a large contact angle with the liquid, and refers to a region having poor wettability with respect to the functional part forming coating liquid.

  When the wettability changing layer used for the pattern forming substrate is not changed in wettability, the contact angle with a liquid having a surface tension of 40 mN / m is 10 ° or more, particularly a liquid having a surface tension of 20 mN / m. It is preferable to show wettability with a contact angle of 10 ° or more. This is because the area where the wettability is not changed is an area where liquid repellency is required. Therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient. This is because there is a possibility that the functional part forming coating liquid may remain on the liquid repellent region when the coating liquid is applied.

  Further, when the photocatalytic action is exerted on the wettability changing layer by this step, the contact angle with the liquid of the portion where the wettability has changed is 9 ° or less with the liquid with the surface tension of 40 mN / m. In particular, the contact angle with a liquid having a surface tension of 60 mN / m is preferably 10 ° or less. When the wettability has changed, that is, when the contact angle with the liquid in the lyophilic area is high, for example, when the functional part forming coating liquid is applied, the functional part is formed also in the lyophilic area. This is because the coating liquid may be repelled and it may be difficult to pattern the functional part on the lyophilic region.

  In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.

  As the wettability changing layer in which the wettability is changed by the action of the photocatalyst associated with the energy irradiation, for example, a layer containing an organopolysiloxane can be used. Specifically, Japanese Patent Application Laid-Open No. 2001-074928 discloses. It can be set as the layer containing organopolysiloxane etc. which are described.

  In addition to the organopolysiloxane, a surfactant, an additive, and the like can be used. For example, those described in JP-A-2001-074928 can be used.

  The film thickness of the characteristic change layer is appropriately selected according to the type of the characteristic change layer, the type and application of the pattern forming substrate, etc., but is usually about 0.01 μm to 1 mm, especially 0.1 μm. It can be about 0.1 mm.

  In addition, when the pattern forming substrate has a support substrate, the support substrate is not particularly limited as long as it can support the characteristic changing layer whose characteristics change, and it depends on the use of the pattern forming body. The type, flexibility, transparency, etc. are appropriately selected. In the present invention, the support substrate may be made of an organic material, or may be made of an inorganic material. Specifically, a film made of resin, glass, ceramic, metal, or the like can be used, and a plate-like one is preferable.

(Energy irradiation)
Next, energy irradiation in this step will be described. In this step, the pattern forming substrate and the photocatalyst containing layer of the photocatalyst containing layer side substrate are arranged with a predetermined gap, and the photocatalyst containing layer is irradiated with energy in a pattern from a predetermined direction.

  Here, the above arrangement means a state in which the action of the photocatalyst substantially extends to the pattern forming substrate, and the photocatalyst-containing layer and the pattern forming substrate are in close contact with each other. In addition to the state, the photocatalyst-containing layer and the pattern forming substrate are arranged at a predetermined interval. This gap is preferably 200 μm or less.

  In the present invention, the gap is preferably in the range of 0.2 μm to 50 μm, preferably in the range of 1 μm to 10 μm, considering that the photocatalyst has high sensitivity and the characteristic change pattern formation efficiency is good. . Such a gap range is particularly effective for a small area pattern forming substrate capable of controlling the gap with high accuracy.

  On the other hand, when processing a pattern forming substrate having a large area of, for example, 300 mm × 300 mm or more, a fine gap as described above is formed between the photocatalyst containing layer side substrate and the pattern forming substrate. Is extremely difficult. Therefore, when the pattern forming substrate has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly in the range of 50 to 75 μm. By setting the gap within such a range, the characteristic change pattern can be further reduced without causing problems such as a decrease in pattern accuracy or a problem that the sensitivity of the photocatalyst deteriorates and the efficiency of forming the characteristic change pattern deteriorates. This is because there is an effect that unevenness does not occur.

  When energy is irradiated to the pattern forming substrate having a relatively large area as described above, the gap setting in the positioning device between the photocatalyst containing layer side substrate and the pattern forming substrate in the energy irradiation device is set in the range of 10 μm to 200 μm. Especially, it is preferable to set in the range of 25 micrometers-75 micrometers. This is because by setting the set value within such a range, it is possible to arrange the photocatalyst without significantly deteriorating the sensitivity of the photocatalyst.

  Thus, by disposing the photocatalyst-containing layer and the pattern forming substrate surface at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, when the interval between the photocatalyst-containing layer and the pattern forming substrate is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the speed of forming the characteristic change pattern may be reduced. This is not preferable. In addition, when it is arranged at a distance from the above range, the generated active oxygen species are difficult to reach the pattern forming substrate, and in this case, the speed of forming the characteristic change pattern may be reduced. It is not preferable.

  As a method for uniformly forming such a very narrow gap and arranging the photocatalyst containing layer and the pattern forming substrate, for example, a method using a spacer can be mentioned. This is because a uniform gap can be formed by using the spacer in this way. In addition, by using such a spacer, the active oxygen species generated by the action of the photocatalyst reaches the surface of the pattern forming substrate at a high concentration without diffusing, so that the characteristic change pattern can be efficiently formed. Can do.

  In the case of using a photocatalyst-containing layer side substrate formed on a flexible base material such as a resin film in which the photocatalyst-containing layer has flexibility, it is difficult to provide the gap as described above. From the viewpoint of production efficiency and the like, it is preferable that the photocatalyst-containing layer and the pattern forming substrate are disposed so as to contact each other.

  In the present invention, such an arrangement state of the photocatalyst-containing layer side substrate only needs to be maintained at least during the energy irradiation.

  The energy irradiation (exposure) referred to in the present invention is a concept including irradiation of any energy beam capable of forming a characteristic change pattern whose characteristics have changed on the surface of the pattern forming substrate, and irradiation with visible light. It is not limited to.

  Usually, the wavelength of light used for such energy irradiation is set in the range of 400 nm or less, preferably in the range of 150 nm to 380 nm. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.

  Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources. In this case, for example, by using a photomask or the like, the photocatalyst-containing layer can be irradiated with energy in a pattern. In addition to the above-described method of irradiating energy using a light source, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.

  Here, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for forming a characteristic change pattern having changed characteristics on the surface of the pattern forming substrate. In addition, the shape, area, and the like of the characteristic change pattern formed by this step are appropriately selected according to the type and application of the pattern forming body. Further, at this time, it is preferable in that the photocatalyst-containing layer is irradiated with energy while heating so that the sensitivity can be increased and the characteristic change pattern can be efficiently formed. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

3. Others The method for producing a pattern forming body of the present invention is not particularly limited as long as it has the deposit removing step and the pattern forming step. For example, a step of producing a pattern forming substrate in addition to the above steps. Etc. may be included.

  The pattern formed body produced according to the present invention includes, for example, the formation of a color filter in which a colored layer is formed on the characteristic change pattern, and the formation of an organic EL element in which an organic EL layer is formed on the characteristic change pattern. It can be used for forming a microlens in which a lens is formed on a characteristic change pattern. According to the present invention, since the characteristic change pattern can be formed in a desired pattern shape with high definition, various functional parts such as a colored layer and an organic EL layer are formed with high definition. This is because it can be done. Furthermore, the pattern forming body produced according to the present invention may be used as a cell culture substrate used for culturing cells. In this case, it becomes possible to culture the cells in a desired pattern on the above characteristic change pattern with high definition.

B. Next, an apparatus for producing a pattern forming body of the present invention will be described. The apparatus for producing a pattern forming body of the present invention includes a base material, the photocatalyst-containing layer of the photocatalyst-containing layer side substrate formed on the base material and having a photocatalyst-containing layer containing at least a photocatalyst, and a photocatalyst accompanying energy irradiation The pattern forming substrate whose surface characteristics change due to the action of the above is disposed opposite to the substrate, and the photocatalyst-containing layer is irradiated with energy, whereby a characteristic change pattern having changed characteristics is formed on the surface of the pattern forming substrate. A pattern forming body manufacturing apparatus for use in manufacturing a plurality of pattern forming bodies by performing a plurality of pattern forming steps to form a pattern forming body and forming the pattern forming body, the pattern forming body supporting the pattern forming substrate A substrate support portion, a photocatalyst-containing layer side substrate support portion that supports the photocatalyst-containing layer so as to face the pattern-forming substrate, and the light An energy irradiation unit that irradiates the energy to medium-containing layer side substrate, is characterized in that it has a deposit removal means for removing deposits adhering to the photocatalyst-containing layer.

  For example, as shown in the cross-sectional view of FIG. 2A and the perspective view of FIG. 2B, the pattern forming body manufacturing apparatus of the present invention includes a pattern forming substrate support portion 11 that supports the pattern forming substrate, and The photocatalyst containing layer side substrate support part 12 for supporting the photocatalyst containing layer side substrate, the energy irradiation part 13 for irradiating the photocatalyst containing layer side substrate with energy, and the attached to the photocatalyst containing layer of the photocatalyst containing layer side substrate And a deposit removing means 14 for removing the kimono.

  The apparatus for producing a pattern forming body of the present invention supports the pattern forming substrate on the pattern forming substrate support portion, supports the photocatalyst containing layer side substrate on the photocatalyst containing layer side substrate supporting portion, and generates energy from the energy irradiation unit. Is used for a pattern forming body manufacturing method in which a pattern changing body is manufactured by forming a characteristic change pattern having changed characteristics on a pattern forming substrate.

  Here, as described above, when the pattern forming substrate is patterned using the photocatalyst-containing layer side substrate, decomposition products generated on the pattern forming substrate are vaporized and arranged to face each other. It may adhere to the photocatalyst containing layer. As a result, when patterning is subsequently performed on another pattern forming substrate, the deposits attached to the photocatalyst-containing layer may become radicals and contribute to changes in the characteristics of the pattern forming substrate. In some cases, the deposits obstruct the action of the active oxygen species generated by the photocatalyst. Therefore, when a pattern formed body is manufactured a plurality of times, there is a problem that it is difficult to form a characteristic change pattern formed on the pattern formed body in a desired pattern shape with a uniform width.

However, in the present invention, since the apparatus for manufacturing a pattern forming body has the deposit removing means, the deposit can be removed between the pattern forming step and the pattern forming step. . Therefore, by using the apparatus for producing a patterned product of the present invention, the characteristics of the substrate for pattern formation were changed into a pattern using the above-mentioned photocatalyst-containing layer side substrate, and the patterned product was produced continuously. However, it is possible to prevent the sensitivity from changing due to deposits or the like adhering to the photocatalyst-containing layer, and manufacture a pattern forming body in which a characteristic change pattern is formed in a desired pattern shape with high definition. It becomes possible to do.
Hereinafter, the pattern forming body manufacturing apparatus of the present invention will be described in detail for each configuration.

1. First, the deposit removing means used in the present invention will be described. The deposit removing means used in the present invention is not particularly limited as long as it is a means capable of removing deposits attached to the photocatalyst containing layer of the photocatalyst containing layer side substrate used for manufacturing the pattern forming body. It is not a thing. The deposit removing means may be moved in a three-dimensional direction in the pattern forming body manufacturing apparatus, or may be fixed. Further, for example, as shown in FIG. 2, the deposit removing means may be a means for removing the deposit while the photocatalyst containing layer side substrate is supported by the photocatalyst containing layer support portion 12. In, for example, a means for removing deposits attached to the photocatalyst containing layer in a state where the photocatalyst containing layer side substrate is removed from the photocatalyst containing layer side substrate support may be used.

Examples of such deposit removing means include means for removing deposits from the photocatalyst containing layer using gas, means for removing deposits from the photocatalyst containing layer using liquid, and solid substances. Examples include a means for removing the deposit from the photocatalyst containing layer using the above, a means for removing the deposit from the photocatalyst containing layer using energy, and the like. Any one of the above means may be formed in the deposit removing means, or two or more kinds of the above means may be formed.
Hereinafter, each of the above means will be described in detail.

(1) Means for removing deposits from the photocatalyst containing layer using gas A means for removing deposits from the photocatalyst containing layer using gas will be described. Examples of means for removing deposits from the photocatalyst-containing layer using gas include, for example, a gas spraying means for removing deposits by wind pressure by blowing an inert gas on the photocatalyst-containing layer, and the photocatalyst-containing layer surface. Therefore, it is possible to use a suction unit that sucks the deposit and removes the deposit, or a combination of the gas blowing unit and the suction unit.

  As the gas spraying means, for example, as shown in FIG. 3, a nozzle part for spraying for spraying gas onto the photocatalyst containing layer 2 of the photocatalyst containing layer side substrate 3 supported by the photocatalyst containing layer side substrate supporting part 12 is used. 21 and a gas supply unit 22 for sending gas to the spray nozzle unit 21. The spray nozzle part may have a shape capable of spraying gas over the entire surface of the photocatalyst-containing layer, or may have a shape capable of spraying gas onto a part of the photocatalyst-containing layer. . As such a nozzle part for spraying, it can be the same as that of the nozzle for air blows used for general washing | cleaning. In general, the nozzle for spraying is a photocatalyst containing layer of the photocatalyst containing layer side substrate supported by the photocatalyst containing layer side substrate support after the pattern forming substrate is removed from the pattern forming substrate support described later. It has a moving mechanism for moving to the vicinity. The spray nozzle may have a moving mechanism that moves in a two-dimensional direction along the surface of the photocatalyst containing layer.

  The gas supply unit is not particularly limited as long as it can supply gas to the nozzle unit, and can be the same as a general compressor or the like. In addition, about the kind etc. of gas sprayed on the said photocatalyst content layer, it can be made to be the same as that of what was demonstrated by the term of the "A. manufacturing method of a pattern formation body" mentioned above.

  Moreover, as a suction means for sucking the deposit from the surface of the photocatalyst containing layer and removing the deposit, for example, as shown in FIG. 4, the photocatalyst containing layer side substrate supported by the photocatalyst containing layer side substrate support portion 12 is used. 3 from the surface of the photocatalyst containing layer 2, an intake nozzle portion 23 for sucking deposits, an intake portion 24 for sucking gas, a storage portion 25 for storing deposits sucked by the intake nozzle portion, and the like It can have.

  The intake nozzle portion may have a shape capable of sucking deposits from the entire surface of the photocatalyst containing layer, or a shape capable of sucking deposits from a part of the photocatalyst containing layer. It may be said. Such an intake nozzle portion may have the same structure as a nozzle used in a general cleaner. In general, the intake nozzle has a photocatalyst containing layer of the photocatalyst containing layer side substrate supported by the photocatalyst containing layer side substrate support after the pattern forming substrate is removed from the pattern forming substrate support described later. It is assumed that it has a moving mechanism that moves to the vicinity of. Further, the intake nozzle may have a moving mechanism that moves in a two-dimensional direction along the surface of the photocatalyst containing layer.

  In addition, the storage unit is disposed between the intake nozzle unit and the intake unit, and is particularly capable of storing deposits sucked from the intake nozzle unit. It is not limited. This is because, when the intake nozzle portion and the intake portion are directly connected, the adhering matter sucked from the intake nozzle portion becomes clogged in the intake portion, causing a failure or the like. Such a storage unit may have the same structure as a storage unit provided in a general cleaner.

  The intake section is not particularly limited as long as it can inhale with a predetermined intake pressure, and can be the same as the intake section provided in a general cleaner.

  The gas blowing means and the suction means are combined as a blowing nozzle part for blowing gas to the photocatalyst containing layer and an intake for sucking the deposits separated from the photocatalyst containing layer by the gas. A nozzle unit, a storage unit for storing deposits sucked from the suction nozzle unit, and a gas circulation unit for supplying the gas sucked from the suction nozzle unit to the spray nozzle unit. Can be. About the nozzle part for spraying, the nozzle part for intake, the storage part etc., it can be the same as that mentioned above. Moreover, the said gas circulation part can be made to be the same as the gas circulation part etc. which are used for the general apparatus.

(2) Means for Removing Deposits from the Photocatalyst Containing Layer Using Liquid Next, means for removing deposits from the photocatalyst containing layer using liquid will be described. In the present invention, as a means for removing the deposit using a liquid, for example, a dipping means for immersing the photocatalyst-containing layer side substrate in the liquid and removing the deposit using the solubility of the deposit in the liquid, for example. Alternatively, the photocatalyst-containing layer side substrate can be a cleaning means for cleaning the photocatalyst-containing layer by spraying a liquid with a nozzle or the like.

  As said immersion means, what has a solution holding | maintenance part which can hold | maintain the solvent etc. which can dissolve the said deposit | attachment, etc. can be used, for example. The solution holding part is not particularly limited as long as it holds a solvent capable of dissolving the deposit and can immerse the photocatalyst-containing layer side substrate. The type of the solution held in the solution holding unit is appropriately selected according to the type and amount of the deposit.

  As the cleaning means, for example, as shown in FIG. 5, a cleaning unit 26 for discharging the liquid and cleaning the surface of the photocatalyst containing layer 2, and a liquid supply unit for supplying the cleaning unit 26 with the liquid 27 and a suction drying unit 27 for drying the photocatalyst-containing layer 2 can be used. The cleaning unit is not particularly limited as long as it can discharge liquid to the surface on the photocatalyst containing layer side and can be cleaned. For example, the cleaning unit may discharge liquid over the entire surface of the photocatalyst containing layer. In addition, the liquid may be ejected to a part of the photocatalyst containing layer. Such a cleaning unit may have the same structure as a cleaning unit including a nozzle or the like used in a general spray cleaning apparatus. In addition, this washing | cleaning part is a photocatalyst containing layer of the photocatalyst containing layer side board | substrate currently supported by the said photocatalyst containing layer side board | substrate support part after the board | substrate for pattern formation is normally removed from the board | substrate support part for pattern formation mentioned later It is assumed that it has a moving mechanism that moves to the vicinity of. The cleaning unit may have a moving mechanism that moves in a two-dimensional direction along the surface of the photocatalyst containing layer.

  The solution supply unit is not particularly limited as long as a predetermined amount and a solution can be supplied to the solution discharge unit, and a solution supply unit provided in a general spray cleaning device or the like. It can have the same structure. The suction drying unit is not particularly limited as long as the photocatalyst-containing layer can be dried, and has the same structure as the suction drying unit used in a general cleaning device. It can have.

  Note that the cleaning means may include a temperature control unit for thermally drying the photocatalyst-containing layer, a pressure control unit for adjusting the pressure of the solution discharged from the cleaning unit, and the like. Here, the solution and the like discharged from the cleaning means can be the same as those described in the above-mentioned “A. Method for producing pattern forming body”.

(3) Means for removing deposits from the photocatalyst-containing layer by contacting a solid substance Next, means for removing deposits from the photocatalyst-containing layer by contacting a solid substance in this step explain. As a means for removing deposits from the photocatalyst containing layer by bringing a solid substance into contact with the photocatalyst containing layer, for example, an adsorbing adsorption plate is brought into contact with the photocatalyst containing layer and attached from the photocatalyst containing layer side substrate. Examples include adsorption means for removing the deposits, and means for sweeping off deposits from the photocatalyst containing layer side substrate using a brush.

  As the adsorption means, for example, as shown in FIG. 6, an adsorption plate 29 having an adsorptivity is provided, and the adsorption plate 29 comes into close contact with the photocatalyst containing layer 2 and then peels from the photocatalyst containing layer 2. It is assumed to have a moving mechanism. The type of the adsorbing plate is not particularly limited as long as it has adhesiveness with an attached substance and can be peeled off from the photocatalyst-containing layer. It can be formed as above, and is appropriately selected depending on the type of the deposit.

  Further, as means for using the brush, it is assumed that it has a brush part for cleaning the surface of the photocatalyst containing layer, and this brush part has a mechanism that moves along the photocatalyst containing layer after contacting the photocatalyst containing layer. Is done. Such a brush part is not particularly limited as long as it does not damage the photocatalyst-containing layer, and can be the same as that used for cleaning a general apparatus.

(4) Means for Removing Deposits from the Photocatalyst Containing Layer Using Energy Next, means for removing deposits from the photocatalyst containing layer using energy will be described. Such means include, for example, thermal energy irradiation means for irradiating the photocatalyst containing layer with thermal energy and volatilizing the adhering matter adhering to the photocatalyst containing layer, or applying ultrasonic waves to the photocatalyst containing layer. Ultrasonic irradiation means for irradiating and removing deposits adhering to the photocatalyst containing layer by vibration, light energy irradiation means for irradiating light energy, electron beam irradiation means for irradiating an electron beam, plasma irradiation means for irradiating plasma, etc. can do.

  As said thermal energy irradiation means, it shall have a heating part for raising the temperature in the apparatus for pattern formation manufacture, for example, and a temperature adjustment part for adjusting the temperature in the apparatus for pattern formation manufacture etc. be able to. Such a heating unit and a temperature adjusting unit can be the same as those used in, for example, a general hot plate, a heater, and an oven. This energy irradiation means is used for the photocatalyst containing layer of the photocatalyst containing layer side substrate supported by the photocatalyst containing layer side substrate support after the pattern forming substrate is removed from the pattern forming substrate support described later. You may have a moving mechanism which moves to the vicinity.

  Examples of the ultrasonic irradiation means may include a cleaning liquid holding tank for immersing the photocatalyst-containing layer side substrate and an ultrasonic irradiation unit for irradiating the photocatalyst-containing layer with ultrasonic waves. . The cleaning liquid holding tank is not particularly limited as long as it is a tank that holds a cleaning liquid capable of cleaning the photocatalyst containing layer and can immerse the photocatalyst containing layer side substrate. It can be the same as the cleaning liquid holding tank used in the cleaning apparatus. Further, the ultrasonic irradiation unit is not particularly limited as long as it can irradiate ultrasonic waves capable of removing deposits from the surface of the photocatalyst-containing layer. It can be the same as the ultrasonic irradiation part used.

  Further, the light energy irradiation means may be a means for irradiating the photocatalyst-containing layer with light energy and removing deposits by the energy of the light itself. A means for removing the deposit by utilizing the action of the photocatalyst is preferable. This is because the deposits can be more efficiently removed by utilizing the action of the photocatalyst.

  Such light energy irradiation means may include, for example, a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and other various light sources. Moreover, it is good also as a means which has lasers, such as an excimer and YAG. Moreover, in order to improve the sensitivity of the said photocatalyst, you may have a temperature adjustment part etc. which heat a photocatalyst content layer. In addition, the light energy irradiation method in such a light energy irradiation means can be the same as the method described in the deposit decomposition / removal means in “A. Method for producing pattern forming body”.

  The plasma irradiation means is not particularly limited as long as it can irradiate the photocatalyst-containing layer with plasma to remove the deposit, and may be, for example, a means for plasma irradiation in a vacuum, In addition, a means for plasma irradiation under atmospheric pressure may be used, but in the present invention, a means for plasma irradiation under atmospheric pressure is particularly preferable. This is because the design of the apparatus can be facilitated. Such plasma irradiation means can be the same as the plasma irradiation means in a general plasma irradiation apparatus. Further, the plasma irradiation method using such a plasma irradiation means can be the same as the method described in the deposit decomposition and removal means in “A. Method for producing a pattern forming body”, so the description here will be given. Is omitted.

  Further, the electron beam irradiation means for irradiating the photocatalyst-containing layer with an electron beam is particularly limited as long as it can irradiate an electron beam capable of decomposing and removing the adhering matter attached to the surface of the photocatalyst-containing layer. Is not to be done. Specifically, such electron beam irradiation means can be the same as the electron beam irradiation means in a general electron beam irradiation apparatus. Moreover, the electron beam irradiation method using such an electron beam irradiation means can be the same as the method described in the deposit decomposition and removal means in “A. Method for producing pattern forming body”.

2. Next, the pattern forming substrate support in the pattern forming body manufacturing apparatus of the present invention will be described. The pattern forming substrate support portion in the pattern forming body manufacturing apparatus of the present invention is particularly limited as long as it can stably support the pattern forming substrate in the pattern forming body manufacturing apparatus. It is not a thing. The shape or the like of the substrate support portion is appropriately selected according to the shape or use of the pattern forming substrate exposed by the pattern forming body manufacturing apparatus of the present invention. For example, the entire surface of the pattern forming substrate is supported. Such a structure may be used, and a structure that supports a part of the pattern forming substrate may be used.

  Such a pattern-forming substrate support is not particularly limited as long as it has a strength capable of supporting the pattern-forming substrate. For example, an inorganic material such as a metal or ceramic is used. Alternatively, an organic material such as plastic can be used. The pattern forming substrate supported by the pattern forming substrate support section may be the same as the pattern forming substrate described in the above-mentioned “A. Method for producing pattern forming body”.

3. Next, the photocatalyst containing layer side substrate support in the apparatus for producing a pattern forming body of the present invention will be described. The photocatalyst containing layer side substrate support part in the apparatus for producing a pattern forming body of the present invention forms a pattern so that the photocatalyst containing layer side substrate faces the pattern forming substrate supported by the pattern forming substrate support part. There is no particular limitation as long as it can stably support the photocatalyst-containing layer side substrate in the body manufacturing apparatus. The shape and the like of the photocatalyst containing layer side substrate support part are appropriately selected according to the shape and use of the photocatalyst containing layer side substrate. For example, even if it has a structure that supports the entire surface of the photocatalyst containing layer side substrate. In addition, a structure that supports a part of the photocatalyst-containing layer side substrate may be used.

  Such a photocatalyst-containing layer side substrate support portion can be the same as the pattern formation substrate support portion described above. In addition, the photocatalyst-containing layer side substrate support part and the pattern formation substrate support part have a pattern formation substrate at such a distance that the action accompanying energy irradiation of the photocatalyst contained in the photocatalyst content layer reaches the pattern formation substrate. And the photocatalyst containing layer side substrate is supported. The above-mentioned distance and the photocatalyst containing layer side substrate supported by the photocatalyst containing layer side substrate supporting part can be the same as those described in the above-mentioned “A. Pattern forming body manufacturing method”.

4). Energy irradiation part Next, the energy irradiation part used for this invention is demonstrated. The energy irradiation part used for this invention will not be specifically limited if energy can be irradiated to the photocatalyst containing layer of the said photocatalyst containing layer side board | substrate. The energy irradiation part may be provided on the photocatalyst containing layer side substrate support part 13 side in the apparatus for producing a pattern forming body, for example, as shown in FIG. It may be provided on the forming substrate support part side.

  Such an energy irradiating unit may have any lamp capable of irradiating energy capable of exciting the photocatalyst in the photocatalyst-containing layer. For example, a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and other various light sources It can have. Moreover, what has lasers, such as an excimer and YAG, may be used.

5. Pattern Forming Body Manufacturing Apparatus The pattern forming body manufacturing apparatus of the present invention is particularly limited as long as it has the deposit removing means, the pattern forming substrate support section, the photocatalyst containing layer side substrate support section, and the energy irradiation section. Instead, for example, photomask support means for supporting the photomask, temperature control means for controlling the temperature in the pattern forming body manufacturing apparatus, and humidity in the pattern forming body manufacturing apparatus are controlled as necessary. May have a humidity control means or the like.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

[Example 1]
(Preparation of substrate for pattern formation)
A glass container containing 0.5 ml of decylmethoxysilane (LS-5258 manufactured by Shin-Etsu Silicone) and a glass substrate were sealed in a heat-resistant container with a lid. By putting the heat-resistant container into an oven heated to 165 ° C. and holding it for 1 hour, the inside of the heat-resistant container is made into a decylmethoxysilane atmosphere, decylmethoxysilane is vapor-deposited on the glass substrate surface, and a transparent and uniform wettability change layer A pattern forming substrate having the following was obtained.

(Preparation of photocatalyst-containing layer side substrate)
Next, an aqueous dispersion of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.) is formed on the photomask pattern side having a mask pattern in which a Cr thin film is formed in a stripe shape with a width of 50 μm and a pitch of 100 μm on a quartz glass substrate. Product name: ST-K03) was spin-coated and dried by heating to form a transparent photocatalyst-containing layer, which was used as a photocatalyst-containing layer side substrate.

(Formation of pattern formed body)
The photocatalyst containing layer on the photocatalyst containing layer side substrate and the wettability changing layer are opposed to each other with a gap of 50 μm, and an ultraviolet ray having a wavelength of 365 nm is applied at 38 mW / cm with a super high pressure mercury lamp from the photomask side. It exposed by irradiating with the illumination intensity of ² , and formed the wettability change pattern in the surface of the wettability change layer. The obtained wettability change pattern has a contact angle with water in an unexposed area of 102 °, a contact angle with liquid with a surface tension of 40 mN / m is 71 °, and a contact angle with water in an exposed area of 10 °. It took 150 seconds for the contact angle with a liquid having a surface tension of 40 mN / m or less to be 9 ° or less. Further, the width of the unexposed portion was 49 μm, and the width of the exposed portion was 51 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

(Adherent removal process and pattern formation process)
Subsequently, as a deposit removal step, the photocatalyst containing layer on the photocatalyst containing layer side substrate after the exposure was sucked at 0.05 MPa for 60 s to remove deposits attached to the surface of the photocatalyst containing layer. Thereafter, as a pattern forming step, exposure was performed for 150 s in the same manner as described above using the photocatalyst-containing layer side substrate on the same pattern forming substrate as the above-described pattern forming substrate.
The deposit removal process and the pattern formation process were repeated 50 times, and a pattern forming body having 50 wettability change patterns was produced. In the 50th wettability change pattern, the width of the unexposed area was 50 μm, and the width of the exposed area was 50 μm. Further, the average line width of the exposed portions of the 50 wettability change patterns was 49 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

[Example 2]
(Preparation of substrate for pattern formation)
A glass container and a glass substrate containing 0.5 ml of 1H, 1H, 2H, 2H-heptadecafluorodecyltrimethoxysilane (GE Toshiba Silicone TSL8233) were placed in a heat-resistant container with a lid and sealed. By putting the heat-resistant container in an oven heated to 240 ° C. and holding it for 1 hour, the heat-resistant container is made into 1H, 1H, 2H, 2H-heptadecafluorodecyltrimethoxysilane atmosphere, and 1H, 1H, 2H, 2H-heptadecafluorodecyltrimethoxysilane was vapor-deposited to obtain a pattern forming substrate having a transparent and uniform wettability changing layer.

(Formation of pattern formed body)
Exposure was performed using the pattern forming substrate and the same photocatalyst containing layer side substrate as in Example 1. In the obtained wettability change pattern, the contact angle with water in the unexposed area is 114 °, the contact angle with a liquid having a surface tension of 40 mN / m is 78 °, and the contact angle between the exposed area and water is 10 °. It took 185 seconds for the contact angle with the liquid having a surface tension of 40 mN / m or less to be 9 degrees or less. Moreover, as a result of measuring the line width of the said wettability change pattern by observing the surface of a pattern formation body with a scanning electron microscope, the line width of the unexposed part was 49 micrometers and the line width of the exposed part was 51 micrometers. .

(Adherent removal process and pattern formation process)
Subsequently, as a deposit removal step, the photocatalyst-containing layer on the photocatalyst-containing layer side substrate after the exposure was spray-cleaned for 30 seconds at a discharge amount of 1 L / min. And a discharge pressure of 1 MPa using a 50% methanol aqueous solution as a cleaning liquid. Thereafter, air was blown to completely remove the cleaning liquid adhering to the surface of the photocatalyst-containing layer.
Thereafter, as a pattern forming step, exposure was performed for 185 s in the same manner as described above, using the photocatalyst-containing layer on the same pattern forming substrate as that described above.
The deposit removal process and the pattern formation process were repeated 50 times, and a pattern forming body having 50 wettability change patterns was produced. In the 50th wettability change pattern, the line width of the unexposed area was 48 μm, and the line width of the exposed area was 52 μm. Further, the average line width of the exposed portions of the 50 wettability change patterns was 49 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

[Example 3]
(Adherent removal process and pattern formation process)
A pattern forming body was produced using the same pattern forming substrate and photocatalyst containing layer side substrate as in Example 1. Thereafter, as a deposit removal step, an adsorption plate made of silicon rubber was brought into contact with the photocatalyst containing layer in the photocatalyst containing layer side substrate after the exposure at an adhesion pressure of 1.2 kg / cm ² for 20 seconds.
Thereafter, as a pattern formation step, exposure was performed for 150 s in the same manner as described above, using the photocatalyst-containing layer, on the same pattern formation substrate as that described above.
The deposit removal process and the pattern formation process were repeated 50 times, and a pattern forming body having 50 wettability change patterns was produced. In the 50th wettability change pattern, the line width of the unexposed area was 48 μm, and the line width of the exposed area was 52 μm. Further, the average line width of the exposed portions of the 50 wettability change patterns was 49 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

[Example 4]
(Adherent removal process and pattern formation process)
Using the same pattern forming substrate and photocatalyst-containing layer side substrate as in Example 2, a pattern forming body was produced. Then, as a deposit removal step, the photocatalyst containing layer in the photocatalyst containing layer side substrate after the exposure was heated for 2 minutes on a hot plate at 80 ° C.
Thereafter, as a pattern formation step, exposure was performed for 150 s in the same manner as described above, using the photocatalyst-containing layer, on the same pattern formation substrate as that described above.
The deposit removal process and the pattern formation process were repeated 50 times, and a pattern forming body having 50 wettability change patterns was produced. In the 50th wettability change pattern, the line width of the unexposed area was 48 μm, and the line width of the exposed area was 52 μm. Further, the average line width of the exposed portions of the 50 wettability change patterns was 49 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

[Example 5]
(Adherent removal process and pattern formation process)
A pattern forming body was produced using the same pattern forming substrate and photocatalyst containing layer side substrate as in Example 1. Thereafter, as a deposit removing step, the photocatalyst-containing layer in the photocatalyst-containing layer side substrate after the exposure was irradiated with atmospheric pressure oxygen plasma at a power of 700 W, an irradiation distance of 5 mm, and a plasma processing rate of 20 mm / sec.
Thereafter, as a pattern formation step, exposure was performed for 150 s in the same manner as described above, using the photocatalyst-containing layer, on the same pattern formation substrate as that described above.
The deposit removal process and the pattern formation process were repeated 50 times, and a pattern forming body having 50 wettability change patterns was produced. In the 50th wettability change pattern, the line width of the unexposed area was 48 μm, and the line width of the exposed area was 52 μm. Further, the average line width of the exposed portions of the 50 wettability change patterns was 49 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

[Example 6]
(Adherent removal process and pattern formation process)
Using the same pattern forming substrate and photocatalyst-containing layer side substrate as in Example 2, a pattern forming body was produced. Thereafter, as a deposit removal step, the photocatalyst containing layer in the photocatalyst containing layer side substrate after the exposure was irradiated with an electron beam with an acceleration energy of 10 Mrad using an electron curtain type electron beam irradiation apparatus.
Thereafter, as a pattern formation step, exposure was performed for 150 s in the same manner as described above, using the photocatalyst-containing layer, on the same pattern formation substrate as that described above.
The deposit removal process and the pattern formation process were repeated 50 times, and a pattern forming body having 50 wettability change patterns was produced. In the 50th wettability change pattern, the line width of the unexposed area was 48 μm, and the line width of the exposed area was 52 μm. Further, the average line width of the exposed portions of the 50 wettability change patterns was 49 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

[Comparative Example 1]
(Formation of pattern formed body)
Exposure was carried out using the same pattern forming substrate and photocatalyst containing layer side substrate as in Example 1. The obtained wettability change pattern has a contact angle with water in an unexposed area of 108 °, a contact angle with liquid with a surface tension of 40 mN / m is 72 °, and a contact angle with water in an exposed area of 10 °. It took 150 seconds for the contact angle with a liquid having a surface tension of 40 mN / m or less to be 9 ° or less. Further, by observing the surface of the pattern forming body with a scanning electron microscope, the line width of the wettability change pattern was measured. As a result, the width of the unexposed portion was 49 μm and the width of the exposed portion was 51 μm.
Subsequently, without performing the adhering substance removing step, exposure of 150 s was performed on 20 pattern forming substrates similar to the pattern forming substrate using the photocatalyst-containing layer side substrate. As the number of exposures increases, it is confirmed that the line width when the ink is attached to the exposed part tends to be thicker than the opening of the photomask. Became wet and the pattern collapsed.

It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention. It is explanatory drawing for demonstrating the apparatus for pattern forming body manufacture of this invention. It is a schematic sectional drawing which shows an example of the apparatus for manufacturing the pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the apparatus for pattern formation body manufacture of this invention. It is a schematic sectional drawing which shows the other example of the apparatus for pattern formation body manufacture of this invention. It is a schematic sectional drawing which shows the other example of the apparatus for pattern formation body manufacture of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Photocatalyst containing layer 3 ... Photocatalyst containing layer side substrate 4 ... Pattern forming substrate 7 ... Characteristic change pattern 11 ... Pattern forming substrate support part 12 ... Photocatalyst containing layer side substrate support part 13 ... Energy irradiation part 14 ... Adherent removal means

Claims (1)

The substrate, and the photocatalyst-containing layer-side substrate of the photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing at least a photocatalyst, and pattern formation in which surface characteristics are changed by the action of the photocatalyst accompanying energy irradiation Pattern formation in which a characteristic change pattern having a changed characteristic is formed on the surface of the pattern formation substrate by irradiating the photocatalyst-containing layer with energy by placing the substrate opposite to the substrate and irradiating the photocatalyst-containing layer with energy. A process for producing a pattern forming body, wherein the process is performed a plurality of times to produce a plurality of pattern forming bodies,
During the patterning step of performing the plurality of times, it has rows deposit removing step of removing the deposit adhering to the photocatalyst-containing layer,
The deposit removal step leaves the photocatalyst-containing layer side substrate for the time determined by the standing time determination step for determining the time to leave the photocatalyst-containing layer side substrate, and deposits adhered to the photocatalyst-containing layer are removed. A method for producing a pattern forming body, which is a removing step .

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