JP4752392B2 - Method for producing pattern forming body - Google Patents

Description

  The present invention relates to a method for manufacturing a pattern forming body having surface characteristics changed into a pattern, for example, used for manufacturing color filters.

  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, It is 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, it is desired to provide a manufacturing method of a pattern forming body capable of forming a characteristic change pattern with high definition in a target pattern shape even when the pattern forming body is manufactured continuously.

  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 process for forming a plurality of pattern forming bodies by performing a plurality of pattern forming processes to form, wherein the photocatalyst-containing layer side substrate and the pattern formation are performed during the pattern forming processes performed a plurality of times. The photocatalyst-containing layer is irradiated with energy by the same light source as that used in the pattern formation step without facing the substrate for use in the pattern. And, to provide a method of manufacturing a patterned product characterized by having an energy radiation step of removing the deposit adhering to the photocatalyst-containing layer.

  According to the present invention, the adhering matter adhering to the surface of the photocatalyst containing layer is removed by the energy irradiation step between the pattern forming body step and the pattern forming step. Can prevent the sensitivity of the photocatalyst-containing layer from changing. 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. . Moreover, in this invention, since the same light source as the light source used for the said pattern formation process is used for the energy irradiation in the said energy irradiation process, the apparatus for manufacturing the said pattern formation body using the said photocatalyst containing layer side board | substrate. The above-mentioned energy irradiation process can be performed without removing from the substrate and without using a special member, and the pattern formed body can be manufactured efficiently.

  In the said invention, the said energy irradiation process may make energy irradiation by making the said photocatalyst content layer and the reflecting plate which reflects the energy from the said light source oppose. Thereby, in the said energy irradiation process, it becomes possible to excite the photocatalyst in a photocatalyst content layer not only with the irradiated energy but with the energy reflected by the reflecting plate. Therefore, it is possible to remove the deposits more efficiently.

  According to the present invention, it is possible to perform patterning using a photocatalyst-containing layer side substrate from which deposits adhered to the surface have been removed, and to produce a plurality of pattern formed bodies whose characteristics have been changed to a desired pattern shape with high definition The effect that it can be done is produced.

The present invention relates to a method for manufacturing a pattern forming body having surface characteristics changed into a pattern, for example, used for manufacturing color filters.
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 plurality of pattern forming bodies by performing a pattern forming process to form a pattern forming body a plurality of times, wherein the photocatalyst containing is performed during the pattern forming process performed a plurality of times. The light source is the same as the light source used in the pattern forming step, with the layer side substrate and the pattern forming substrate not facing each other. Irradiating energy to the medium containing layer, those having an energy radiation step of removing the deposit adhering to the photocatalyst-containing layer.

  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). Then, a pattern forming process for forming a pattern forming body having the characteristic change pattern 7 in which the surface characteristics of the pattern forming substrate 4 are changed is performed. In the present invention, the pattern formation step is performed a plurality of times, and the photocatalyst-containing layer 2 is irradiated with energy 5 between the pattern formation step and the pattern formation step, for example, as shown in FIG. An energy irradiation process for removing deposits attached to the containing layer 2 is performed.

  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 the pattern forming body is continuously manufactured, there is a problem that it is difficult to form the characteristic change pattern in a desired pattern shape with a uniform width.

  However, in the present invention, an energy irradiation process for removing deposits adhering to the photocatalyst containing layer is performed between the pattern forming process and the pattern forming process, so that a 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. Thereby, even if it is a case where a pattern formation body is manufactured continuously, a characteristic change pattern can be formed in the target pattern shape with high definition. Therefore, according to the present invention, it is possible to stably manufacture a plurality of pattern forming bodies capable of forming various functional portions in a desired pattern shape along the characteristic change pattern.

In the present invention, since the same light source as that used in the pattern forming step is used in the energy irradiation step, the photocatalyst containing layer side substrate is removed from the apparatus for manufacturing the pattern forming body. The energy irradiation process can be performed without any problem, and the pattern forming body can be manufactured efficiently. At this time, there is also an advantage that it is not necessary to provide a special member in the apparatus for manufacturing the pattern forming body.
Hereinafter, each process of the manufacturing method of the pattern formation body of this invention is demonstrated.

1. Energy Irradiation Step First, the energy irradiation step in the present invention will be described. The energy irradiation step in the present invention is the same light source as the light source used in the pattern formation step in a state where the photocatalyst-containing layer side substrate and the pattern formation substrate are not opposed during the pattern formation step performed a plurality of times. Is a step of irradiating the photocatalyst-containing layer with energy to remove deposits adhering to the photocatalyst-containing layer.

  Here, “between the pattern forming process performed a plurality of times” means between the pattern forming process and the pattern forming process. In the present invention, for example, this process is performed every time the pattern forming process is performed once. Alternatively, this step may be performed every time the pattern forming step is performed a plurality of times. In addition, the state in which the photocatalyst-containing layer side substrate and the pattern forming body are not opposed to each other means that the pattern forming substrate is not disposed within a range in which the photocatalyst of the photocatalyst containing layer on the photocatalyst containing layer side substrate can reach the action. Let's say the state.

  The light source used for energy irradiation in this step is the same as the light source used in the pattern forming step described later, and is a light source capable of irradiating with a wavelength that can excite the photocatalyst in the photocatalyst containing layer.

  The wavelength of light emitted from such a light source 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. Specific examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and other various light sources. It is also possible to use a laser such as an excimer or YAG as a light source. The energy irradiation time, irradiation intensity, and the like are appropriately selected depending on the type of the light source and the type of deposit.

  In addition, when irradiating energy, it is preferable to irradiate energy while heating the photocatalyst-containing layer, whereby sensitivity can be increased and a characteristic change pattern can be efficiently formed. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

  Here, in this invention, you may perform the said energy irradiation in the state which made the said photocatalyst content layer and the reflecting plate which can reflect the energy from the said light source face each other. As a result, the photocatalyst in the photocatalyst containing layer can be excited not only by the energy from the light source but also by the energy reflected by the reflecting plate, and the deposits can be removed more efficiently. is there.

  The reflecting plate may be disposed instead of the pattern forming substrate, for example, at a position where the pattern forming substrate is disposed in the pattern forming step to be described later. For example, in the apparatus for manufacturing the pattern forming body Alternatively, it may be formed in advance. Such a reflective plate may be composed of a single reflective layer that is self-supporting and capable of reflecting energy, and a reflective layer capable of reflecting energy is formed on the substrate. It may be a thing. Although it does not specifically limit as a material used for such a reflection layer, A metal material is used suitably, Specifically, aluminum, silver, iron, etc. are mentioned.

  As a method for forming the reflective plate, when a reflective layer is formed on the substrate, a method of vapor-depositing the above-described metal on the substrate surface by a vacuum vapor deposition method or the like is usually used. In addition, when the reflective layer has self-supporting properties, a method of mirror-finishing one surface of the metal plate made of the metal is used. The substrate is not particularly limited as long as it can support the reflective layer, and may be made of an organic material or an inorganic material.

(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 the present invention, as shown in FIG. 1, the photocatalyst containing layer side substrate 3 has at least a base material 1 and a photocatalyst containing layer 2 formed on the base material 1.

  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 the present invention, since the energy irradiation step is performed between the pattern formation step and the pattern formation step, the above characteristic change in each pattern formation body even when the pattern formation body is manufactured continuously. The pattern width and the like are unlikely to change, and the characteristic change pattern can be formed with high definition in the target pattern shape. 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.

  The light source used for such energy irradiation can be the same as the light source used in the above-described energy irradiation step, and thus detailed description thereof is omitted here. In this step, energy irradiation may be performed using, for example, a photomask.

  At this time, the energy irradiation amount at the time of energy irradiation is set to 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 energy irradiation step and the pattern forming step. In addition to the above steps, for example, a step of producing a pattern forming substrate, etc. You may have.

  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.

  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]
(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 240 ° C. and holding it for 1 hour, the inside of the heat-resistant container is made into a decylmethoxysilane atmosphere, and decylmethoxysilane is vapor-deposited on the surface of the glass substrate. 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.

(Pattern formation process)
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 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. The width of the unexposed part was 48 μm, and the width of the exposed part was 52 μm. The width of the wettability change pattern was determined by observing the surface of the pattern forming body with a scanning electron microscope.

(Energy irradiation process and pattern formation process)
Subsequently, as an energy irradiation process, ultraviolet light having a wavelength of 365 nm is applied to the photocatalyst-containing layer after exposure from the photomask side with the same ultrahigh pressure mercury lamp as the light source in the pattern formation process, and an illuminance of 38 mW / cm ² . For 90 s to remove deposits adhering 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 energy irradiation 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 51 μm and the width of the exposed area was 49 μm. The average line width of the exposed portions of the 50 wettability change patterns was 48 μm.

[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 energy irradiation 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Photocatalyst containing layer 3 ... Photocatalyst containing layer side board | substrate 4 ... Substrate for pattern formation 7 ... Characteristic change pattern

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 pattern forming process performed a plurality of times, energy is applied to the photocatalyst containing layer by the same light source as that used in the pattern forming process in a state where the photocatalyst containing layer side substrate and the pattern forming substrate are not opposed to each other. the irradiated, possess an energy radiation step of removing the deposit adhering to the photocatalyst-containing layer,
In the energy irradiation step, the photocatalyst-containing layer is opposed to a reflecting plate that reflects energy from the light source, and energy irradiation is performed.
The manufacturing method of the pattern formation body characterized by the said reflecting plate being arrange | positioned instead of the said pattern formation board | substrate in the position where the said pattern formation board | substrate is arrange | positioned in the said pattern formation process.

Images