JP2007044596A - Photocatalyst-containing layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocatalyst-containing layer exhibiting a high activity in a short time, and a pattern formation body or the like using the photocatalyst-containing layer. <P>SOLUTION: In order to accomplish the above object, the photocatalyst-containing layer containing at least the photocatalyst is provided, in which a cylindrical fixture for measuring an electron spin concentration formed from a material not generating a radical and not consuming the radical is installed on a surface of the photocatalyst-containing layer, a spin trapping agent solution is added into the cylinder of the fixture for measuring the electron spin concentration, the photocatalyst-containing layer is irradiated with a UV ray from a high pressure mercury lamp having illuminance of 550 lux until an integrated energy amount becomes 2,000 mJ/m<SP>2</SP>to generate the radial from the photocatalyst-containing layer, and thereafter, when measurement by an electron spin resonance method is performed relative to the spin trapping agent solution that the radical is trapped, the electron spin concentration derived from a hydroxy radical is 1.0×10<SP>20</SP>spin or more per m<SP>2</SP>of the photocatalyst-containing layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photocatalyst-containing layer used for various applications such as patterning of an organic layer, and a pattern forming body using the photocatalyst-containing layer.

  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, by forming a photocatalyst-containing layer containing a photocatalyst and a binder on a substrate and exposing from a predetermined direction, a pattern that forms a pattern in which the characteristics of the photocatalyst-containing layer are changed by the action of the photocatalyst accompanying energy irradiation A method for manufacturing a formed body has been proposed (Patent Document 1). According to this method, by the action of the photocatalyst accompanying energy irradiation, the characteristics of the photocatalyst-containing layer can be easily changed, and a pattern forming body capable of forming a functional part using the difference in characteristics I can do it. This method also has the advantage that it is not necessary to use a developer or the like. 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, depending on the type of the photocatalyst-containing layer, the photocatalyst activity is low, and it takes time to form a pattern. At this time, when the photocatalyst-containing layer is irradiated with energy for a long time, there is a problem that the pattern becomes thick due to wraparound of energy and it is difficult to form a high-definition pattern.

JP 2000-249821 A

  Therefore, it is desired to provide a photocatalyst-containing layer exhibiting high activity in a short time, and a pattern forming body using the photocatalyst-containing layer.

The present invention is a photocatalyst-containing layer containing at least a photocatalyst, and a cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals on the surface of the photocatalyst-containing layer. Install and add a spin trap solution to the inside of the electron spin concentration measurement jig, and irradiate the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ^2. Then, after generating radicals from the photocatalyst-containing layer, when the spin trapping agent solution in which the radicals are trapped is measured by an electron spin resonance method, the electron spin concentration derived from a hydroxy radical is determined by the photocatalyst-containing layer. Provided is a photocatalyst-containing layer characterized by having 1.0 × 10 ²⁰ spins or more per 1 m ² .

  According to the present invention, the concentration of electron spins derived from hydroxy radicals when irradiated with the ultraviolet rays is not less than a predetermined value, so that the photocatalytic activity in the photocatalyst-containing layer is high, and active oxygen in a short time The seed generation efficiency can be high. Therefore, it can be set as the photocatalyst containing layer which can decompose and modify | denaturate organic substance efficiently in a short time, and can be used for formation of various high-definition patterns.

The present invention is a pattern forming body comprising a base material and a photocatalyst-containing layer which is formed on the base material, contains at least a photocatalyst and a binder, and whose properties change due to the action of the photocatalyst accompanying energy irradiation, A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the photocatalyst containing layer, and a spin trap is placed inside the electron spin concentration measuring jig. solution was added, after the cumulative energy amount from a high pressure mercury lamp of the illuminance 550 lux was irradiated with ultraviolet rays to generate radicals from the photocatalyst-containing layer in the photocatalyst-containing layer until 2000 mJ / m ^2, the radicals When the trapped spin trap solution is measured by electron spin resonance, the electron spin derived from the hydroxyl radical is measured. The pattern forming body is characterized in that the concentration is 1.0 × 10 ²⁰ spins per 1 m ^{2 of the} photocatalyst containing layer.

  According to the present invention, since the electron spin concentration derived from hydroxy radicals when the ultraviolet ray is irradiated on the photocatalyst-containing layer is not less than a predetermined value, the photocatalyst activity in the photocatalyst-containing layer is high and short. The generation efficiency of active oxygen species in time can be high. Therefore, the characteristics of the photocatalyst-containing layer can be efficiently changed into a pattern in a short time, and a pattern formed body having a pattern whose characteristics have been changed with high definition can be obtained.

In addition, the present invention provides a base material, a photocatalyst-containing layer formed on the base material and containing at least a photocatalyst, and the photocatalyst-containing layer formed on the photocatalyst, and the characteristics are changed by the action of the photocatalyst upon energy irradiation. A pattern forming body having a characteristic change layer, wherein a cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the characteristic change layer. The photocatalyst-containing layer is irradiated with ultraviolet rays from a high-pressure mercury lamp having an illuminance of 550 lux until the accumulated energy amount reaches 2000 mJ / m ² by adding a spin trap solution to the inside of the electron spin concentration measuring jig. After the radical is generated from the containing layer, the spin trapping agent solution in which the radical is trapped is measured by the electron spin resonance method. The pattern forming body is characterized in that the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins per 1 m ^{2 of the} photocatalyst containing layer.

  According to the present invention, when the photocatalyst-containing layer is irradiated with the ultraviolet rays, the electron spin concentration derived from hydroxy radicals is not less than a predetermined value, so that the photocatalyst activity in the photocatalyst-containing layer is high and short. The generation efficiency of active oxygen species in time can be high. For this reason, the characteristics of the characteristic change layer can be efficiently changed in a pattern in a short time by energy irradiation, and a pattern formed body having a pattern whose characteristics have been changed with high definition can be obtained.

The present invention also includes a substrate and a photocatalyst-containing layer that is formed on the substrate and contains at least a photocatalyst, and exerts the action of the photocatalyst upon energy irradiation on a counter substrate disposed to face the substrate. , A photocatalyst-containing layer side substrate used for forming a characteristic change pattern having changed characteristics, wherein the surface of the photocatalyst-containing layer is formed of a material that does not generate radicals and does not consume radicals. The above-mentioned electron spin concentration measuring jig is installed, a spin trap agent solution is added to the inside of the electron spin concentration measuring jig, and the accumulated energy amount reaches 2000 mJ / m ² from a high pressure mercury lamp with an illuminance of 550 lux. After irradiating the photocatalyst-containing layer with ultraviolet rays to generate radicals from the photocatalyst-containing layer, the spin trap agent solution in which the radicals are trapped is applied. Thus, there is provided a photocatalyst-containing layer side substrate characterized in that an electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins per 1 m ^{2 of the} photocatalyst-containing layer when measurement is performed by an electron spin resonance method. .

  According to the present invention, the electron spin concentration derived from hydroxy radicals when the photocatalyst-containing layer is irradiated with the ultraviolet rays is not less than a predetermined value, so that the photocatalyst activity in the photocatalyst-containing layer is high. can do. Therefore, when the photocatalyst containing layer side substrate and the counter substrate are arranged to face each other and irradiated with energy, the characteristics of the counter substrate can be efficiently changed in a short time.

The present invention also provides a patterning substrate having a base material and a photocatalyst-containing layer that is formed on the base material, contains at least a photocatalyst and a binder, and whose properties change due to the action of the photocatalyst accompanying energy irradiation. A pattern forming body manufacturing method for manufacturing a pattern forming body by forming a characteristic change pattern in which the characteristics of the photocatalyst containing layer are changed by irradiating energy in a pattern, wherein a radical is formed on the surface of the photocatalyst containing layer. A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is added, and a spin trapping agent solution is added to the inside of the electron spin concentration measuring jig, and the illuminance is 550 lux. The photocatalyst-containing layer is irradiated with ultraviolet rays from the high-pressure mercury lamp until the accumulated energy amount reaches 2000 mJ / m ^2. After generating radicals from the containing layer, when the spin trapping agent solution in which the radicals are trapped is measured by an electron spin resonance method, the electron spin concentration derived from hydroxy radicals is per 1 m ^{2 of the} photocatalyst containing layer. There is provided a method for producing a pattern forming body, comprising an inspection step of selecting only the patterning substrate having 1.0 × 10 ²⁰ spins.

  According to the present invention, the photocatalytic activity is high because only the patterning substrate in which the concentration of electron spins derived from hydroxy radicals when irradiated with the ultraviolet rays is equal to or higher than a predetermined value in the inspection step is selected. Only the patterning substrate capable of changing the characteristics of the photocatalyst-containing layer into a high-definition pattern efficiently in a short time can be used for the production of the pattern forming body. Therefore, a high-definition pattern forming body can be efficiently manufactured in a short time.

The present invention includes a base material, a photocatalyst-containing layer that is formed on the base material and contains at least a photocatalyst, and a characteristic change that is formed on the photocatalyst-containing layer and that changes in characteristics due to the action of the photocatalyst upon energy irradiation. A pattern forming body manufacturing method for manufacturing a pattern forming body by forming a characteristic changing pattern in which the characteristics of the characteristic changing layer are changed by irradiating a patterning substrate having a layer with energy in a pattern. A cylindrical electron spin concentration measuring jig made of a material that does not generate radicals and does not consume radicals is installed on the surface of the characteristic change layer, and spins are formed inside the electron spin concentration measuring jig. A trapping agent solution is added, and ultraviolet light is applied to the photocatalyst-containing layer from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ^2. After generating a radical from the photocatalyst-containing layer by irradiating a line, when the spin trapping agent solution in which the radical is trapped is measured by an electron spin resonance method, the electron spin concentration derived from the hydroxy radical is There is provided a method for producing a pattern forming body, comprising an inspection step of selecting only the patterning substrate having 1.0 × 10 ²⁰ spins per 1 m ^{2 of the} photocatalyst-containing layer.

  According to the present invention, the photocatalytic activity is high because only the patterning substrate in which the concentration of electron spins derived from hydroxy radicals when irradiated with the ultraviolet rays is equal to or higher than a predetermined value is selected by the inspection step. Only the patterning substrate having the photocatalyst-containing layer can be used for the production of the pattern forming body. Therefore, a high-definition pattern forming body can be efficiently manufactured in a short time.

According to the present invention, a counter substrate, a base, and a photocatalyst-containing layer side substrate having a photocatalyst-containing layer formed on the base and containing at least a photocatalyst are disposed facing each other, and energy irradiation is performed in a pattern. A pattern forming body manufacturing method for forming a pattern forming body by forming a characteristic change pattern having changed characteristics on the counter substrate, wherein the photocatalyst containing layer generates radicals on the surface of the photocatalyst containing layer. In addition, a cylindrical electron spin concentration measuring jig formed of a material that does not consume radicals is installed, a spin trapping agent solution is added to the inside of the electron spin concentration measuring jig, and high pressure mercury with an illuminance of 550 lux. after the integrated energy amount from the lamp was irradiated with ultraviolet rays until 2000 mJ / m ^2, a spin trapping agent hydroxyl radicals are trapped When the solution is measured by the electron spin resonance method, only the photocatalyst-containing layer side substrate in which the concentration of electron spins derived from hydroxy radicals is 1.0 × 10 ²⁰ spins per 1 m ^{2 of the} photocatalyst-containing layer is selected. There is provided a method of manufacturing a pattern forming body characterized by having an inspection step.

  According to the present invention, in the inspection step, when the electron spin resonance spectrum of the photocatalyst-containing layer is measured, the concentration of electron spins derived from hydroxy radicals when irradiated with the ultraviolet rays is a predetermined value or more. Only the inclusion layer side substrate is selected. Therefore, only the photocatalyst-containing layer side substrate having a photocatalyst-containing layer with high photocatalytic activity is used for the production of a pattern-forming body, and a pattern-forming body having a high-definition characteristic change pattern can be efficiently produced in a short time. it can.

  According to the present invention, the activity of the photocatalyst contained in the photocatalyst containing layer is high, and the generation efficiency of active oxygen species by the photocatalyst in a short time can be made high. Therefore, the effect of the photocatalyst can be exhibited efficiently in a short time, and an effect is obtained that the photocatalyst-containing layer can be used for various applications.

  The present invention relates to a photocatalyst containing layer used for various applications such as patterning of an organic layer, and a pattern forming body using the photocatalyst containing layer. Each will be described separately below.

A. First, the photocatalyst containing layer of the present invention will be described. The photocatalyst-containing layer of the present invention is a photocatalyst-containing layer containing at least a photocatalyst, and has a cylindrical electron spin concentration formed from a material that does not generate radicals and does not consume radicals on the surface of the photocatalyst-containing layer. A measuring jig is installed and a spin trap solution is added to the inside of the electron spin concentration measuring jig. From the high-pressure mercury lamp with an illuminance of 550 lux, the accumulated energy amount reaches 2000 mJ / m ² to the photocatalyst containing layer. After generating radicals from the photocatalyst-containing layer by irradiating with ultraviolet rays, when the spin trapping agent solution in which the radicals are trapped is measured by an electron spin resonance method, the electron spin concentration derived from hydroxy radicals is The photocatalyst-containing layer has 1.0 × 10 ²⁰ spins or more per 1 m ² .

  When the photocatalyst-containing layer containing photocatalyst is irradiated with energy in the presence of oxygen or water, active oxygen species are generated, and this active oxygen species contributes to decomposition and modification of organic matter. Therefore, if the photocatalyst-containing layer has a high photocatalytic activity and a large amount of active oxygen species generated in a short time, the photocatalytic effect can be efficiently exhibited in a short time, such as patterning a layer made of an organic substance, It can be used for various applications.

  Here, the evaluation of the activity of the photocatalyst accompanying such energy irradiation can be performed by an electron spin resonance (ESR) method. Specifically, the amount of active oxygen species generated when a certain amount of energy is applied to the photocatalyst containing layer by irradiating ultraviolet rays from a predetermined light source by electron spin resonance, that is, the concentration of electron spins derived from hydroxy radicals is determined. This can be done by calculating. It can be said that the photocatalyst-containing layer having a higher electron spin concentration can generate a larger amount of active oxygen species in a shorter time and has a higher photocatalytic activity.

In the photocatalyst-containing layer of the present invention, when the photocatalyst-containing layer is irradiated with ultraviolet rays and measured by an electron spin resonance method by a predetermined method, the electron spin concentration derived from hydroxy radicals per 1 m ^{2 of the} photocatalyst-containing layer is Since it is not less than the predetermined value, the activity of the photocatalyst contained in the photocatalyst-containing layer is high, and the production efficiency of active oxygen species in a short time can be increased. Therefore, by using the photocatalyst-containing layer of the present invention, it is possible to efficiently decompose or modify organic substances in a short time, and the photocatalyst-containing layer of the present invention can be used in various ways such as patterning of layers made of organic substances. It can be used for applications.

Here, the photocatalyst-containing layer in the present invention is a photocatalyst-containing layer containing at least a photocatalyst, and has a cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals. The spin trapping agent solution is added to the inside of the electron spin concentration measurement jig, and the photocatalyst-containing layer is irradiated with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ^2. Then, after generating radicals from the photocatalyst-containing layer, when the spin trapping agent solution in which the radicals are trapped is measured by an electron spin resonance method, the electron spin concentration derived from hydroxy radicals is It is intended to be the layer 1 m ² per 1.0 × ^{10 20} spins above, in the present invention, among the above-mentioned 5. × ^{10 20} spins above, it is preferred that in particular the 1.0 × ^{10 21} spin more. Thereby, it can be said that the activity of the photocatalyst in the photocatalyst containing layer is high, and it can be a photocatalyst containing layer capable of efficiently decomposing organic matter in a short time. Also, if the concentration of electron spin is above the above range, when the photocatalyst-containing layer is used for patterning of a layer made of an organic material, for example, a high-definition pattern is formed without the pattern becoming thick due to entrainment of energy, etc. Because it becomes possible to do. The cumulative energy amount refers to the total amount of energy irradiated after the irradiation of ultraviolet rays on the photocatalyst containing layer is started.

Also the concentration of the electron spin is equal to or greater than the value, the accumulated amount of energy irradiated from the light source is 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, it is particularly when the 1000 mJ / ^{m 2} or less Is preferred. Thereby, the photocatalyst in the photocatalyst-containing layer can be activated with a smaller amount of energy, the time required for decomposition and modification of organic matter can be shortened, and the cost can be reduced as a result. .

  The light source used in the present invention is not particularly limited as long as it is a high-pressure mercury lamp with an illuminance of 550 lux, and can irradiate the energy amount ultraviolet rays.

  Here, a method for measuring the electron spin concentration will be described with reference to the drawings. FIG. 1 is an explanatory diagram showing the steps of the method for measuring the electron spin concentration in the photocatalyst-containing layer of this embodiment. First, as shown in FIG. 1A, an electron spin concentration measuring jig 11 is installed on the surface of the photocatalyst containing layer 1, and thereafter, as shown in FIG. A spin trap agent solution 12 is added to the inside of the cylinder. Further, as shown in FIG. 1C, a certain amount of ultraviolet rays 13 are irradiated to the photocatalyst containing layer 1 to generate radicals from the photocatalyst containing layer 1. Here, the region irradiated with the ultraviolet rays 13 in the photocatalyst containing layer 1 includes the inside of the cylinder of the electron spin concentration measuring jig 11, that is, the region where the spin trap agent 12 is in contact with the photocatalyst containing layer 1. . Thereafter, a spin trap agent solution 12 ′ trapping radicals generated from the photocatalyst-containing layer 1 is obtained, and the spin trap agent solution 12 ′ is measured with an electron spin resonance apparatus. The electron spin concentration derived from radicals is obtained.

  At this time, the electron spin concentration can be obtained by comparing the signal intensity derived from the radical obtained by the measurement with the signal intensity obtained by measuring a DPPH standard reagent having a known spin concentration. As a detailed calculation method, a method described in “Electron Spin Resonance” (Kodansha 1991) is used.

  In the case where the photocatalyst-containing layer contains a substance that reacts with the hydroxy radical generated by the action of the photocatalyst, the signal intensity derived from the hydroxy radical and the substance that reacts with the hydroxy radical The electron spin concentration derived from the hydroxy radical can be determined from the signal intensity derived from the generated radical.

Here, the electron spin concentration measuring jig used in this embodiment is formed of a material that does not generate radicals and does not consume radicals, and is disposed in close contact with the photocatalyst-containing layer. The spin trapping agent solution added to the cylinder is not particularly limited as long as it can hold the solution. In this embodiment, “do not generate radicals” means that the radicals generated by irradiating the photocatalyst-containing layer with ultraviolet rays have a substantial effect on the measured value of the electron spin concentration from the electron spin concentration measurement jig. It means that radicals are not generated to the extent that it is given. “Don't consume radicals” means that the radicals generated from the photocatalyst-containing layer change the electron spin concentration measurement tool to the extent that it substantially affects the measured value of the electron spin concentration. It means not to do. Specifically, using the above-mentioned jig for measuring electron spin concentration made of quartz, a spin trap agent solution is added into this jig for measuring electron spin concentration, and an integrated energy amount is 2000 mJ / mm from a high-pressure mercury lamp with an illuminance of 550 lux. when irradiated with ultraviolet rays until m ^2, relative to the reference plate with a 1.0 × ^{10 19} spins ^/ m 2 ^~5.0 × ^{10 19} in the range of spin / ^{m 2,} the electrons made of the material When the same measurement is performed using a jig for measuring spin concentration, the material has a spin concentration error of 5% or less compared to the case of using quartz.

  The material for such an electron spin concentration measuring jig is not particularly limited as long as it does not generate radicals and does not consume radicals. Specific examples include natural quartz and synthetic quartz. Among them, high-purity synthetic quartz is preferably used. This is because they are easy to process, do not generate radicals, and are stable against radicals.

  The shape of the electron spin concentration measuring jig is not particularly limited as long as it is cylindrical and can contact the photocatalyst-containing layer and the spin trap agent solution. Specific examples include a cylindrical shape or a cylindrical shape having a polygonal cross section, and a cylindrical shape is particularly preferable. This is because the spin trapping agent solution can trap radicals uniformly. The jig for measuring electron spin concentration may have a lid in order to prevent evaporation of the spin trap agent solution, contamination from the external environment, and the like. In addition, when it has a lid | cover, it is preferable that the said lid | cover has the permeability | transmittance which permeate | transmits the said ultraviolet-ray.

Also, when the electron spin concentration measuring jig is placed on the surface of the photocatalyst containing layer and the spin trapping agent solution is added to the inside of the electron spin concentration measuring jig, the photocatalyst containing layer and the spin trapping agent contact each other. the contact area of, but are not particularly limited, for example in the range of 1 to 10 cm ^2, preferably in the range of these the 3~8cm ^2.

  In this embodiment, the outflow prevention means for improving the adhesion between the electron spin concentration measuring jig and the photocatalyst containing layer is used in a region where the electron spin concentration measuring jig contacts the photocatalyst containing layer. It is preferable. This is because the adhesion between the photocatalyst-containing layer and the electron spin concentration measurement jig is improved, and the outflow of the spin trap agent solution can be prevented. As such an outflow prevention means, for example, a seal member formed on the electron spin concentration measurement jig side may be used, and a sealant applied to the electron spin concentration measurement jig side and / or the photocatalyst containing layer side. Etc.

  The seal member formed on the electron spin concentration measurement jig side as the outflow prevention means is made of a material that does not generate radicals and does not consume radicals, and includes a photocatalyst containing layer and an electron spin concentration measurement jig As long as the adhesiveness is good, it is not particularly limited. Such a seal member may be formed integrally with the electron spin concentration measuring jig, or may be detachable from the electron spin concentration measuring jig.

  The shape of the sealing member is not particularly limited as long as it can be brought into close contact with the photocatalyst-containing layer and the electron spin concentration measuring jig. Usually, the electron spin concentration measuring jig is formed over the entire region facing the photocatalyst containing layer.

  The sealing agent applied to the electron spin concentration measuring jig side and / or the photocatalyst containing layer side as the outflow prevention means is not particularly limited as long as it does not generate radicals and does not consume radicals. Instead, for example, inorganic grease such as silicone grease can be used. In addition, the amount of the sealant used is preferably selected appropriately in consideration of the shape and size of the electron spin concentration measuring jig, the type of the spin trap agent, and the like.

  The spin trap agent solution usually contains at least a spin trap agent and a solvent. The spin trapping agent is not particularly limited as long as it can trap radicals generated from the photocatalyst containing layer by the ultraviolet irradiation, and is appropriately selected according to the radical for measuring the signal intensity. Is. For example, when measuring the signal intensity derived from a hydroxyl radical generated from the photocatalyst-containing layer, it is preferable to use 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap agent.

  In addition, when the radical generated from the substance that has reacted with the hydroxy radical is, for example, a carbon radical, it is preferable to use 3,5-dibromo-4-nitrosobenzenesulfonic acid (DBNBS) or the like as a spin trap agent.

  The solvent for dissolving or dispersing the spin trap agent is not particularly limited as long as it can dissolve or disperse the spin trap agent, and water can be usually used.

  Further, the concentration of the spin trapping agent in the spin trapping agent solution is not particularly limited as long as it is a concentration capable of trapping radicals generated by ultraviolet irradiation, but is usually about 0.01 to 1% by mass, especially 0.1. It can be set to about ˜1% by mass. If the concentration is too low, radicals generated by ultraviolet irradiation may not be trapped. If the concentration is too high, the obtained effect does not change and is not preferable in terms of cost.

  In this embodiment, as a method for setting the concentration of electron spins derived from hydroxy radicals in the photocatalyst containing layer to the above value or more, for example, by adding an additive for improving photocatalytic activity in the photocatalyst containing layer, Examples thereof include a method for improving photocatalytic activity, a method for improving the dispersibility of the photocatalyst in the photocatalyst-containing layer, and generating active oxygen species efficiently.

  Examples of the additive for improving the photocatalytic activity include metal oxides, chlorides, sulfides, sulfates, nitrates, and organic acid salts, and more specifically, tin oxide, iron chloride, zinc nitrate. And silver acetate.

  Moreover, as a method for improving the dispersibility of the photocatalyst in the photocatalyst-containing layer, for example, when forming the photocatalyst-containing layer, the liquidity of the photocatalyst-containing layer-forming coating liquid is made acidic, so A method of improving dispersibility by using the electric repulsive force of the material, a method of adding a dispersant or an anti-agglomeration agent so that the photocatalyst does not aggregate, and stirring under constant conditions so that each component is uniformly dispersed , A method of dispersing, a method of preventing agglomeration by increasing the volume of the binder component surrounding the photocatalyst.

  In addition, by appropriately selecting a cleaning method after forming the photocatalyst-containing layer, a drying method when forming the photocatalyst-containing layer, and the like, the electron spin concentration derived from the hydroxy radical of the photocatalyst-containing layer is set to the above value or more. Also good.

  As the washing method, for example, a method of washing the surface with pure water after forming the photocatalyst containing layer is preferably used while taking care not to damage the photocatalyst containing layer. Here, when washing the surface, if high-pressure running water is used, the photocatalyst-containing layer is deteriorated in film quality or photocatalytic activity is lowered. The method of rinsing with is preferable. This is because by using such a cleaning method, impurities adsorbed on the surface of the photocatalyst and trapping active oxygen species can be removed.

  In addition, as a drying method when forming the photocatalyst-containing layer, after applying the photocatalyst-containing layer forming coating solution by the method described later, etc., it is allowed to stand at room temperature for a while and then gradually heated on a hot plate. However, it is preferable to use a method in which the temperature is raised to the boiling point of water or more, and is heated and dried as it is for 1 hour, followed by washing using the above-described washing method, and further heated and dried for 1 hour. This is because moisture can be removed without the photocatalyst agglomerating.

Further, the photocatalyst-containing layer as described above may be one containing at least a photocatalyst, may be a film formed of a single photocatalyst, and is composed of a photocatalyst and a binder. Also good. Further, as the photocatalyst, such as titanium dioxide _(TiO 2) it is known as a semiconductor, a zinc oxide (ZnO), tin oxide _(SnO 2), strontium titanate (SrTiO _3), tungsten oxide _(WO 3), bismuth oxide ( Bi ₂ O ₃ ) and iron oxide (Fe ₂ O ₃ ). In addition to semiconductors, metal complexes, silver, and the like can also be used, and one or a mixture of two or more selected from these can be used.

  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.

  The smaller the particle size of the photocatalyst, the better. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less. As described above, the smaller the particle size of the photocatalyst, the larger the surface area of the photocatalyst in the photocatalyst-containing layer, and the higher the electron spin concentration.

  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.

  Examples of a method for forming a photocatalyst-containing layer consisting of only a photocatalyst include a method in which amorphous titania is formed on a substrate and then phase-changed to crystalline titania by firing when the photocatalyst is titanium dioxide. . 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.

  On the other hand, when a binder is used for the photocatalyst-containing layer, one having a high binding energy such that the main skeleton of the binder is not decomposed by photoexcitation of the photocatalyst is preferable, and examples thereof include organopolysiloxane.

  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 contained in the photocatalyst containing layer, the amount of the photocatalyst contained in the solid content of the photocatalyst containing layer is in the range of 50 to 90% by mass, preferably 70 to 90% by mass. Is preferred.

  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.

  In addition to the photocatalyst, binder, and surfactant, the photocatalyst-containing layer includes metal salts, metal oxides such as iron chloride, copper nitrate, tin oxide, and silver acetate, gold, silver, copper, iron, and the like. Metal fine particles and ultraviolet absorbing pigments such as triazole can be contained.

B. Next, the pattern forming body of the present invention will be described. The pattern forming body of the present invention has two embodiments depending on the layer structure. Hereinafter, each embodiment will be described in detail.

1. First Embodiment First, the pattern forming body in the first embodiment of the present invention will be described. The pattern forming body of this embodiment includes a base material, and a pattern formation formed on the base material, including at least a photocatalyst and a binder, and a photocatalyst-containing layer whose characteristics are changed by the action of the photocatalyst upon energy irradiation. A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals on the surface of the photocatalyst-containing layer, and A spin trap agent solution was added to the inside of the cylinder, and the photocatalyst-containing layer was irradiated with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount was 2000 mJ / m ² to generate radicals from the photocatalyst-containing layer. Later, when the spin trapping agent solution in which the radicals were trapped was measured by electron spin resonance, The electron spin concentration derived from dical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst containing layer.

  An example of the pattern forming body of this embodiment will be described with reference to FIG. The pattern formation body of this embodiment has the base material 2 and the photocatalyst containing layer 1 which is formed on the base material 2 and whose characteristics are changed by the action of the photocatalyst accompanying the energy irradiation. The photocatalyst-containing layer has an electron spin concentration derived from a hydroxy radical that is equal to or higher than a predetermined value when the photocatalyst-containing layer is irradiated with ultraviolet rays and measured by an electron spin resonance method using a predetermined method. It is said.

In this embodiment, when the photocatalyst-containing layer is irradiated with ultraviolet rays by a predetermined method and measured by an electron spin resonance method, the electron spin concentration derived from hydroxy radicals per 1 m ^{2 of the} photocatalyst-containing layer is a predetermined value. Above the value. Therefore, the generation efficiency of the active oxygen species of the photocatalyst contained in the photocatalyst-containing layer is high, and a pattern forming body in which the characteristic change pattern is efficiently formed in a short time by energy irradiation can be obtained.

In addition, when the photocatalyst activity is low, it is necessary to irradiate the energy for a long time when patterning the photocatalyst-containing layer. In this case, the pattern may become thick due to wraparound of energy, etc. In the embodiment, as described above, since the photocatalyst-containing layer has a high activity in the photocatalyst-containing layer, when the photocatalyst-containing layer is patterned, the patterning can be performed in a short time, and a high-definition pattern can be formed. It can be. Therefore, it is possible to obtain a high-quality pattern forming body having a pattern whose characteristics are changed with high definition without causing the characteristic change patterns to become fat.
Hereinafter, the pattern formation body of this embodiment is demonstrated in detail for every structure.

a. Photocatalyst containing layer First, the photocatalyst containing layer used for this embodiment is demonstrated. The photocatalyst-containing layer used in the present embodiment is formed on a substrate to be described later, and has at least a photocatalyst and a binder, and its characteristics change due to the action of the photocatalyst accompanying energy irradiation. . Here, the property changes due to the action of the photocatalyst accompanying the energy irradiation means that when the photocatalyst-containing layer is irradiated with energy as described later, the organic groups on the surface are decomposed by the active oxygen species generated by the action of the photocatalyst or the like. It means that the surface characteristics change due to modification. In addition, the kind of characteristic change of the photocatalyst containing layer in this embodiment is not particularly limited. For example, the organic group present on the surface of the photocatalyst containing layer may be decomposed or modified to change the wettability, and the photocatalyst containing layer surface may change the adhesiveness.

  In this embodiment, among the above, the photocatalyst-containing layer is particularly preferably a layer whose contact angle with the liquid on the surface is lowered by the action of the photocatalyst accompanying energy irradiation. This makes it possible to form a functional part with high definition along the characteristic change pattern by utilizing the difference in wettability between the characteristic change pattern whose characteristic has changed and the other part. is there.

Here, the photocatalyst-containing layer has a cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals on the surface, and the inside of the electron spin concentration measuring jig inside the cylinder After adding a spin trap agent solution to the photocatalyst-containing layer by irradiating the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount is 2000 mJ / m ² , When the spin trapping agent solution in which the radical is trapped is measured by an electron spin resonance method, the electron spin concentration derived from the hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst containing layer. It is those, in the present embodiment, 5.0 × ^{10 20} spins or more among the above, particularly 1.0 × ^{10 21} spin more It is preferably made ones. Thereby, the activity of the photocatalyst in the photocatalyst-containing layer can be increased, and a photocatalyst-containing layer capable of changing the surface characteristics efficiently in a short time can be obtained. In addition, if the electron spin concentration is equal to or higher than the above value, the pattern does not become thick due to wraparound of energy during patterning, and a high-definition pattern can be formed. The cumulative energy amount refers to the total amount of energy irradiated after the irradiation of ultraviolet rays on the photocatalyst containing layer is started.

In the present embodiment, the above-mentioned electron spin density is equal to or greater than the value, the accumulated amount of energy emitted from the high-pressure mercury lamp, 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, particularly 1000 mJ / ^{m 2} It is preferable that Thereby, the photocatalyst in the photocatalyst containing layer can be activated with a smaller amount of energy, the time required for patterning can be shortened, and the cost can be reduced as a result.

  Here, in this embodiment, the photocatalyst-containing layer contains a substance that changes the characteristics of the surface of the photocatalyst-containing layer, that is, a substance that reacts with a hydroxy radical generated by the action of the photocatalyst. Therefore, when determining the electron spin concentration derived from the hydroxy radical, the electron spin concentration derived from the hydroxy radical is calculated from the signal intensity derived from the hydroxy radical and the signal intensity derived from the radical generated from the substance that has reacted with the hydroxy radical. Can be requested. In addition, the electron spin concentration calculation method, the electron spin concentration measurement jig, the spin trap agent, and the high-pressure mercury lamp used for the measurement are the same as those described in the above section “A. Photocatalyst-containing layer”. Therefore, the detailed explanation here is omitted.

  Moreover, as a method of setting the electron spin concentration derived from hydroxy radicals in the photocatalyst-containing layer to the above value or more, for example, a method for improving the photocatalytic activity on the photocatalyst surface by adding an additive for improving the photocatalytic activity in the photocatalyst-containing layer And a method of generating active oxygen species efficiently by improving the dispersibility of the photocatalyst in the photocatalyst-containing layer. Such a method can be the same as the method described in the above-mentioned section “A. Photocatalyst-containing layer”, and thus a detailed description thereof is omitted here.

  The binder used in the photocatalyst-containing layer is preferably one having a high binding energy such that the main skeleton is not decomposed by photoexcitation of the photocatalyst. For example, the characteristics change due to the action of the photocatalyst accompanying energy irradiation. It may be present or its characteristics do not change. If the binder does not change its properties due to the action of the photocatalyst associated with energy irradiation, it is necessary to contain a material whose characteristics change due to the action of the photocatalyst associated with energy irradiation, in addition to the photocatalyst and binder. There is.

  In the present embodiment, it is particularly preferable that the binder has characteristics that change due to the action of the photocatalyst accompanying energy irradiation. This is because it is not necessary to separately contain a substance for changing the characteristics of the photocatalyst containing layer surface in the photocatalyst containing layer.

  The binder whose characteristics change due to the action of the photocatalyst accompanying such energy irradiation is appropriately selected according to the type of characteristic change of the photocatalyst containing layer. Here, in this embodiment, as described above, the photocatalyst-containing layer is preferably one whose wettability is changed by the action of the photocatalyst accompanying energy irradiation, and as a binder used in such a photocatalyst-containing layer. For example, organopolysiloxane having a fluoroalkyl group described in JP-A No. 2000-249821 can be used.

  Moreover, it is preferable that content of the binder in the said photocatalyst content layer shall be usually in the range of 10-50 mass%, especially in the range of 10-30 mass%.

  In addition, about the photocatalyst used for this embodiment, it can be made to be the same as that of what was demonstrated by the term of the "A. photocatalyst containing layer" mentioned above. Also, the method for forming the photocatalyst-containing layer in the present embodiment can be the same as that described in the above-mentioned section “A.

  Here, the thickness of the photocatalyst-containing layer as described above is preferably in the range of usually 10 nm to 10 μm.

b. Next, the base material used for the pattern forming body of this embodiment will be described. The base material used in this embodiment is not particularly limited as long as it can form the photocatalyst-containing layer, and is appropriately selected depending on, for example, the use of the pattern forming body, the energy irradiation direction, and the like. Specific examples of such a base material include non-flexible transparent rigid materials such as quartz glass, Pyrex (registered trademark) glass, and synthetic quartz plates, or flexibility such as transparent resin films and optical resin plates. A transparent flexible material having Further, the base material may be subjected to surface treatment for preventing alkali elution, imparting gas barrier properties or other purposes as required.

  Furthermore, an anchor layer may be formed on the base material in order to improve the adhesion between the base material surface and the photocatalyst-containing layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.

c. Pattern-formed body The pattern-formed body of the present embodiment is not particularly limited as long as it has the above-described base material and photocatalyst-containing layer, and may have, for example, a light-shielding part as necessary. Good.

  Here, the pattern formed body of the present embodiment may have a characteristic change pattern in which the characteristics of the photocatalyst-containing layer are changed in a pattern, or the characteristics are not changed. Also good.

  As a method for forming the characteristic change pattern, for example, as shown in FIG. 3, the photocatalyst containing layer 1 is irradiated with energy 22 in a pattern using, for example, a photomask 21 or the like (FIG. 3A), Examples include a method of changing the characteristics of the layer 1 to form the characteristic change pattern 8 (FIG. 3B).

  Here, the energy used when forming the above-described characteristic change pattern is a concept including any energy ray that can change the characteristics of the photocatalyst-containing layer surface, and is not limited to visible light. Absent.

  Usually, the wavelength of light used as such energy is set in the range of 400 nm or less, preferably in the range of 150 nm or more and 380 nm or less. 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 as such energy include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and other various light sources. In addition to the method of performing pattern irradiation using a light mask using a light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.

  Further, when the characteristic change pattern is formed using the energy, the irradiation direction of the energy may be from the substrate side when the substrate is transparent, or from the photocatalyst containing layer side. May be. On the other hand, when the substrate is opaque, it is necessary to irradiate energy from the photocatalyst containing layer side.

  Note that, when forming the characteristic change pattern, the irradiation amount of energy used is an irradiation amount necessary to change the characteristics of the surface of the photocatalyst containing layer. In addition, in this embodiment, since the activity of the photocatalyst contained in the photocatalyst containing layer is high, the characteristic change pattern can be formed in a short time.

  Further, at this time, it is preferable in that the sensitivity can be further increased by irradiating the photocatalyst-containing layer with energy while heating and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

2. Second Embodiment Next, the pattern forming body in the second embodiment of the present invention will be described. The pattern forming body of this embodiment is characterized by the action of the photocatalyst that is formed on the base material, the photocatalyst-containing layer that is formed on the base material and contains at least a photocatalyst, and the photocatalyst-containing layer and that is irradiated with energy. A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals on the surface of the characteristic changing layer. Install and add a spin trap solution to the inside of the electron spin concentration measuring jig, and irradiate the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ^2. After generating radicals from the photocatalyst-containing layer, the spin trapping agent solution in which the radicals are trapped is subjected to electron spin resonance. When the measurement is performed, the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst containing layer.

  An example of the pattern forming body of this embodiment will be described with reference to FIG. The pattern-formed body of this embodiment is formed on the base material 2, the photocatalyst-containing layer 1 formed on the base material 2, and the photocatalyst-containing layer 1, and the characteristics change due to the action of the photocatalyst accompanying energy irradiation. The characteristic change layer 4 is included. Further, when the photocatalyst-containing layer is irradiated with ultraviolet rays using a predetermined method and measured by the electron spin resonance method, the electron spin concentration derived from the hydroxy radical is set to a predetermined value or more.

In this embodiment, when the photocatalyst-containing layer is irradiated with ultraviolet rays by a predetermined method and measured by an electron spin resonance method, the electron spin concentration derived from hydroxy radicals per 1 m ^{2 of the} photocatalyst-containing layer is a predetermined value. Above the value. Therefore, the generation efficiency of the active oxygen species of the photocatalyst contained in the photocatalyst-containing layer is high, and a pattern formed body in which a pattern whose characteristics are changed by energy irradiation can be efficiently formed in a short time can be obtained.

In addition, when the photocatalytic activity is low, it is necessary to irradiate energy for a long time when patterning the property change layer. In this case, the pattern may become thick due to wraparound of energy, etc. In the embodiment, since the activity of the photocatalyst in the photocatalyst-containing layer is high as described above, the characteristics can be efficiently and precisely changed in a pattern in a short time. Therefore, it is possible to obtain a high-quality pattern forming body in which a pattern with changed characteristics is formed with high definition without causing a pattern with changed characteristics to become fat.
Hereinafter, each structure of the pattern formation body of this embodiment is demonstrated in detail. In addition, about the base material used for this embodiment, since it is the same as that used in the 1st embodiment mentioned above, detailed description here is abbreviate | omitted.

a. Photocatalyst containing layer First, the photocatalyst containing layer used for this embodiment is demonstrated. The photocatalyst-containing layer used in this embodiment is formed on a substrate and is used to change the characteristics of a characteristic change layer described later.

In addition, the photocatalyst-containing layer includes a cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals on the surface of the characteristic change layer. spin trapping agent solution is added to the inner cylindrical portion of the measuring jig, radicals from the photocatalyst-containing layer was irradiated with ultraviolet rays to the photocatalyst-containing layer to the cumulative energy amount from a high pressure mercury lamp illumination 550 lux is 2000 mJ / m ² Then, when the spin trapping agent solution in which the radical is trapped is measured by an electron spin resonance method, the electron spin concentration derived from the hydroxy radical is 1.0 × per 1 m ^{2 of the} photocatalyst containing layer. 10 ²⁰ Although made of a spin above, in the present embodiment, among the above 5.0 × ^{10 20} spin more, especially 1. × It is preferred that the 10 ²¹ spin more. Thereby, the activity of the photocatalyst in the photocatalyst-containing layer can be increased, and the surface characteristics of the characteristic change layer can be changed efficiently in a short time. In addition, if the electron spin concentration is equal to or higher than the above value, the pattern may become thick due to wraparound of energy when the photocatalyst-containing layer is irradiated with energy to form a pattern with changed characteristics in the characteristic change layer. This is because a high-definition pattern can be formed. In addition, the said integrated energy amount means the total amount of the energy amount irradiated after starting the irradiation of an ultraviolet-ray to the said photocatalyst content layer.

In the present embodiment, the above-mentioned electron spin density is equal to or greater than the value, the accumulated amount of energy emitted from the high-pressure mercury lamp, 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, particularly 1000 mJ / ^{m 2} It is preferable that Thereby, the photocatalyst in the photocatalyst containing layer can be activated with a smaller amount of energy, the time required for patterning can be shortened, and the cost can be reduced as a result. The electron spin concentration can be measured by the method described above.

  Here, in this embodiment, since the electron spin concentration measurement is performed by installing an electron spin concentration measurement jig on the surface of the property change layer, the signal intensity derived from the hydroxy radical, and the reaction with the hydroxy radical The electron spin concentration derived from the hydroxy radical can be obtained from the signal intensity derived from the radical generated from the substance that has caused the oxidization. In addition, the electron spin concentration calculation method, the electron spin concentration measurement jig, the spin trap agent, and the high-pressure mercury lamp used for the measurement are the same as those described in the above section “A. Photocatalyst-containing layer”. Therefore, the detailed explanation here is omitted. In the present embodiment, the electron spin concentration measuring jig may be installed on the surface of the photocatalyst containing layer to measure the electron spin concentration.

  Moreover, as a method of setting the electron spin concentration derived from hydroxy radicals in the photocatalyst-containing layer to the above value or more, for example, a method for improving the photocatalytic activity on the photocatalyst surface by adding an additive for improving the photocatalytic activity in the photocatalyst-containing layer And a method of generating active oxygen species efficiently by improving the dispersibility of the photocatalyst in the photocatalyst-containing layer. Such a method can be the same as the method described in the above-mentioned section “A. Photocatalyst-containing layer”, and thus a detailed description thereof is omitted here.

  The photocatalyst-containing layer may be formed of a photocatalyst alone or may be formed by mixing a photocatalyst and a binder. The photocatalyst and binder used in such a photocatalyst-containing layer and the method for forming the photocatalyst-containing layer can be the same as those described in the above-mentioned section “A. Photocatalyst-containing layer”. Description is omitted.

  In addition, when the binder is contained in the photocatalyst-containing layer, the amount of the photocatalyst contained in the solid content of the photocatalyst-containing layer is usually in the range of 50 to 90% by mass, particularly in the range of 70 to 90% by mass. It is preferable to be within. This is because the electron spin concentration derived from the hydroxy radical can be set within the above-described range.

  Here, the thickness of the photocatalyst-containing layer as described above is preferably in the range of usually 10 nm to 10 μm.

b. Characteristic Change Layer The characteristic change layer used in the present embodiment is formed on the photocatalyst-containing layer, and the characteristics change due to the action of the photocatalyst accompanying energy irradiation. Here, the characteristic changes due to the action of the photocatalyst accompanying the above-mentioned energy irradiation means that when the energy is irradiated, the organic groups on the surface are decomposed or modified by the active oxygen species generated by the action of the photocatalyst in the photocatalyst-containing layer. It means that the surface properties change. In addition, the kind of characteristic change of the characteristic change layer in this embodiment is not specifically limited. For example, an organic group present on the surface of the property change layer may be decomposed or modified to change the wettability, and the property change layer surface may have a different adhesive property.

  In the present embodiment, among the above, the characteristic change layer is preferably a layer whose contact angle with the liquid on the surface is lowered by the action of the photocatalyst accompanying the energy irradiation. This makes it possible to form a functional part with high definition along the characteristic change pattern by utilizing the difference in wettability between the characteristic change pattern whose characteristic has changed and the other part. is there.

  Such a characteristic change layer can be a layer formed of the same material as the binder used in the photocatalyst-containing layer of the first embodiment described above and whose characteristics change due to the action of the photocatalyst accompanying energy irradiation. Therefore, detailed explanation here is omitted.

c. Pattern Forming Body The pattern forming body of the present embodiment is not particularly limited as long as it has the base material, the photocatalyst-containing layer, and the characteristic change layer. You may have.

  In addition, about the energy used when changing the characteristic of the said characteristic change layer of the pattern formation body in this embodiment, its energy irradiation method, etc., it can be made the same as that of the 1st embodiment mentioned above.

C. Next, the photocatalyst containing layer side substrate of the present invention will be described. The photocatalyst-containing layer side substrate of the present invention has a base and a photocatalyst-containing layer that is formed on the base and contains at least a photocatalyst. A photocatalyst-containing layer-side substrate that is used to form a characteristic change pattern that has changed properties and is formed from a material that does not generate radicals and does not consume radicals on the surface of the photocatalyst-containing layer. A cylindrical electron spin concentration measuring jig is installed, a spin trap agent solution is added to the inside of the electron spin concentration measuring jig, and an integrated energy amount is 2000 mJ / m ² from a high pressure mercury lamp with an illuminance of 550 lux. Until the photocatalyst-containing layer is irradiated with ultraviolet rays until radicals are generated from the photocatalyst-containing layer, the spin trap where the radicals are trapped is generated. Against flop solution, when was measured by electron spin resonance method, in which an electron spin concentration of from hydroxyl radical is characterized in that it is 1.0 × 10 ²⁰ spin or the photocatalyst-containing layer 1 m ² per is there.

  The photocatalyst-containing layer side substrate of the present invention has a base 5 and a photocatalyst-containing layer 1 formed on the base 5 as shown in FIG. 5, for example. The photocatalyst-containing layer 1 is a predetermined method. When the photocatalyst-containing layer 1 is irradiated with ultraviolet rays and measured by the electron spin resonance method, the electron spin concentration derived from the hydroxy radical is set to a predetermined value or more.

  Further, the photocatalyst containing layer side substrate of the present invention includes, for example, as shown in FIG. 6, a counter substrate 9 whose characteristics are changed by decomposition or modification of surface organic groups by active oxygen species and the like, and a photocatalyst containing layer side substrate. 7 is used so as to face the photocatalyst-containing layer 1 (FIG. 6A). In this state, for example, the photomask 21 is used to irradiate energy 22 from a predetermined direction. Then, the characteristic change pattern 8 in which the characteristic of the counter substrate 9 is changed in a pattern shape can be formed (FIG. 6B).

In the present invention, when the photocatalyst-containing layer is irradiated with ultraviolet rays by a predetermined method and measured by the electron spin resonance method, the electron spin concentration derived from hydroxy radicals per 1 m ^{2 of the} photocatalyst-containing layer has a predetermined value. It is said above. Therefore, the photocatalyst-containing layer side substrate can generate a reactive oxygen species of the photocatalyst contained in the photocatalyst-containing layer with high generation efficiency and can efficiently change the characteristics of the counter substrate in a short time.

Conventionally, when the activity of the photocatalyst in the photocatalyst containing layer side substrate is low, it is necessary to irradiate energy for a long time, and there is a problem that a high-definition pattern cannot be formed due to entrainment of energy. However, in the present invention, as described above, since the photocatalyst in the photocatalyst-containing layer has high activity and high generation efficiency of active oxygen species, it is possible to change the characteristics of the counter substrate in a short time. The photocatalyst-containing layer side substrate can form a high-definition pattern.
Hereinafter, the photocatalyst-containing layer side substrate of the present invention will be described separately for each configuration.

a. Photocatalyst containing layer First, the photocatalyst containing layer used for this invention is demonstrated. The photocatalyst-containing layer used in the present invention is formed on a substrate to be described later, and has a cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals on the surface. The spin trap agent solution is added to the inside of the electron spin concentration measurement jig, and the photocatalyst-containing layer is irradiated with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ^2. Then, after generating radicals from the photocatalyst-containing layer, when the spin trapping agent solution in which the radicals are trapped is measured by an electron spin resonance method, the electron spin concentration derived from the hydroxy radical is determined by the photocatalyst-containing layer. Although it made of a 1 m ² per 1.0 × ^{10 20} spins above, in the present invention, 5.0 × ^{10 20} among the above Pin above, it is preferred that in particular the 1.0 × ^{10 21} spin more. Thereby, the activity of the photocatalyst in the photocatalyst-containing layer can be increased, and a photocatalyst-containing layer that can efficiently change the characteristics of the counter substrate surface in a short time can be obtained. In addition, if the electron spin concentration is equal to or higher than the above value, the pattern does not become thick due to wraparound of energy during patterning, and a high-definition pattern can be formed. The cumulative energy amount refers to the total amount of energy irradiated after the irradiation of ultraviolet rays on the photocatalyst containing layer is started.

In the present invention, the above-mentioned electron spin density is equal to or greater than the value, the accumulated amount of energy emitted from the high-pressure mercury lamp, 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, particularly 1000 mJ / ^{m 2} or less It is preferable that Thereby, the photocatalyst in the photocatalyst containing layer can be activated with a smaller amount of energy, the time required for patterning can be shortened, and the cost can be reduced as a result.

  In addition, the electron spin concentration calculation method, the electron spin concentration measurement jig, the spin trap agent, and the high-pressure mercury lamp used for the measurement are the same as those described in the above section “A. Photocatalyst-containing layer”. Therefore, the detailed explanation here is omitted.

  Moreover, as a method of setting the electron spin concentration derived from hydroxy radicals in the photocatalyst-containing layer to the above value or more, for example, a method for improving the photocatalytic activity on the photocatalyst surface by adding an additive for improving the photocatalytic activity in the photocatalyst-containing layer And a method of generating active oxygen species efficiently by improving the dispersibility of the photocatalyst in the photocatalyst-containing layer. Such a method can be the same as the method described in the above-mentioned section “A. Photocatalyst-containing layer”, and thus a detailed description thereof is omitted here.

  Further, the photocatalyst-containing layer may be formed by a photocatalyst alone or may be formed by mixing a photocatalyst and a binder. The photocatalyst and binder used in such a photocatalyst-containing layer and the method for forming the photocatalyst-containing layer can be the same as those described in the above-mentioned section “A. Photocatalyst-containing layer”. Description is omitted.

  In addition, when the binder is included in the photocatalyst containing layer used in the present invention, the amount of the photocatalyst contained in the photocatalyst containing layer is within the range of 50 to 90% by mass in the solid content of the photocatalyst containing layer. It is preferably within the range of 70 to 90% by mass. This is because the electron spin concentration derived from the hydroxy radical can be set within the above-described range.

b. Substrate Next, the substrate used in the present invention will be described. The substrate used in the present invention is not particularly limited as long as it can form the photocatalyst-containing layer, and may be a flexible material such as a resin film. What does not have flexibility, for example, a glass substrate etc., may be sufficient. This is appropriately selected depending on the energy irradiation method. Further, the energy permeability of the substrate is appropriately selected depending on the irradiation direction of the energy irradiated when patterning the counter substrate.

  An intermediate layer may be formed on the substrate in order to improve adhesion between the substrate surface and the photocatalyst-containing layer and to prevent deterioration of the substrate due to 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.

c. Next, the photocatalyst containing layer side substrate of the present invention will be described. The photocatalyst-containing layer side substrate of the present invention is not particularly limited as long as it has the above-described substrate and photocatalyst-containing layer. For example, a light-shielding part on the photocatalyst-containing layer or the substrate, or a primer layer or the like formed on the light-shielding part may be used.

  In addition, the counter substrate used in the present invention is not particularly limited as long as the characteristics are changed by the action of the photocatalyst accompanying the energy irradiation. For example, it may be composed of only a resin layer whose characteristics are changed by a photocatalyst accompanying energy irradiation, or may be one in which a characteristic changing layer or the like whose characteristics are changed is formed on a substrate.

  The type of the property change is not particularly limited. For example, the property change layer or the like may be one in which wettability is changed by decomposition or modification of an organic group present on the surface. It may be one that changes the adhesiveness of the surface, such as a characteristic change layer.

  Such a counter substrate can have, for example, the characteristic change layer described in the second embodiment of the “B. pattern forming body” described above, and a detailed description thereof will be omitted here.

  Here, the photocatalyst containing layer side substrate of the present invention is used by facing the counter substrate containing the organic group decomposed or modified by the action of the photocatalyst accompanying energy irradiation and the photocatalyst containing layer as described above. However, at this time, the photocatalyst-containing layer side substrate is arranged and used in a state where the action of the photocatalyst substantially reaches the surface of the counter substrate or the like. In this case, in addition to the state of physical contact with each other, it is preferable that they are arranged at a predetermined interval. In the case where they are arranged with a gap, the photocatalyst containing layer surface and the counter substrate surface The distance is preferably 200 μm or less.

  In the present invention, such a gap has an extremely good pattern accuracy, a high photocatalyst sensitivity, and a good efficiency in changing the characteristics of the counter substrate, particularly in the range of 0.2 μm to 10 μm, preferably It is preferable to be within a range of 1 μm to 5 μm. Such a gap range is particularly effective for a counter substrate having a small area that can control the gap with high accuracy.

  On the other hand, when processing is performed on a counter 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 counter substrate without contact. It is extremely difficult. Therefore, when the counter 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, there is no problem of pattern accuracy deterioration such as blurring of the pattern or problems such as deterioration of the sensitivity of the photocatalyst and deterioration of characteristic change efficiency, and the counter substrate is further reduced. This is because there is an effect that unevenness does not occur in the above characteristic change or the like.

  As described above, when the photocatalyst containing layer side substrate of the present invention is used when exposing a counter substrate having a relatively large area, the gap in the positioning device between the photocatalyst containing layer side substrate and the counter substrate in the energy irradiation apparatus is used. Is preferably set in the range of 10 μm to 200 μm, particularly in the range of 25 μm to 75 μm. By setting the set value within such a range, it is possible to arrange the photocatalyst containing layer side substrate and the counter substrate without contact with each other without causing a significant decrease in pattern accuracy or a significant deterioration in the sensitivity of the photocatalyst. This is because it becomes possible.

  Thus, by disposing the photocatalyst-containing layer side substrate and the surface of the counter substrate 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 side substrate and the counter substrate is narrower than the above range, it is difficult to desorb the active oxygen species, resulting in a possibility of slowing the characteristic change rate. It is not preferable. In addition, it is not preferable that the active oxygen species generated are difficult to reach the counter substrate if they are spaced apart from the above range, and in this case as well, there is a possibility of slowing down the characteristic change. Such an arrangement state only needs to be maintained at least during the energy irradiation.

  In addition, the energy irradiated in the patterning using the photocatalyst-containing layer side substrate is the same as the energy used in the energy irradiation described in the first embodiment of “B. Pattern formation body” described above. be able to.

C. Next, the manufacturing method of the pattern formation body of this invention is demonstrated. The manufacturing method of the pattern forming body of the present invention has three embodiments depending on the layer structure of the pattern forming body to be manufactured. Hereinafter, each embodiment will be described in detail.

1. First Embodiment First, a method for producing a pattern forming body in a first embodiment of the present invention will be described. The method for producing a pattern forming body according to this embodiment includes a base material and a photocatalyst-containing layer that is formed on the base material and contains at least a photocatalyst and a binder, and the characteristics of the photocatalyst change by the action of the photocatalyst accompanying energy irradiation. A pattern forming body manufacturing method for manufacturing a pattern forming body by forming a characteristic change pattern in which the characteristics of the photocatalyst containing layer are changed by irradiating a patterning substrate with energy in a pattern, comprising the photocatalyst containing A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the layer, and the spin trapping agent solution is placed inside the cylinder of the electron spin concentration measuring jig. Added to the photocatalyst-containing layer from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ^2. After generating a radical from the photocatalyst-containing layer by irradiating an external line, when the spin trapping agent solution in which the radical is trapped is measured by an electron spin resonance method, the electron spin concentration derived from the hydroxy radical is The method includes an inspection step of selecting only the patterning substrate having 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer.

  For example, as shown in FIG. 3, the pattern forming body according to the present embodiment includes a base material 2 and a photocatalyst containing layer 1 of a patterning substrate having a photocatalyst containing layer 1 formed on the base material 2. For example, by irradiating energy 22 using a photomask 21 or the like (FIG. 3A), the characteristics of the photocatalyst-containing layer 1 are changed into a pattern, and the pattern forming body 10 having the characteristic change pattern 8 is manufactured. This is the method (FIG. 3B). In this embodiment, when the photocatalyst-containing layer is irradiated with ultraviolet rays from the light source and measured by the electron spin resonance method using a predetermined method, the electron spin concentration derived from the hydroxy radical has a predetermined value. There is an inspection step of selecting only the patterning substrate as described above.

According to this embodiment, since only the patterning substrate in which the concentration of electron spins derived from hydroxy radicals when irradiated with the ultraviolet rays is greater than or equal to a predetermined value when the ultraviolet rays are irradiated is selected in the inspection step, the photocatalytic activity is increased. Only a patterning substrate having a high photocatalyst-containing layer can be used for the production of a pattern forming body. Therefore, a high-definition pattern forming body can be efficiently manufactured in a short time.
Hereinafter, the inspection process in the present invention will be described.

a. Inspection process The inspection process in this embodiment is a cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals on the surface of the photocatalyst-containing layer containing at least a photocatalyst and a binder. When the electron spin resonance spectrum was measured while irradiating ultraviolet rays from a high-pressure mercury lamp having an illuminance of 550 lux, the spin-trap agent solution was added to the inside of the electron spin concentration measurement jig placed on the surface, and the high-pressure mercury was measured. When the integrated energy amount irradiated from the lamp reaches 2000 mJ / m ² , the photocatalyst-containing layer has a concentration of electron spins derived from hydroxy radicals of 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer. a step of selecting a patterning substrate, in this embodiment, 5.0 × 10 ² among the above Spin above, it is preferable to select only the substrate for patterning with photocatalyst-containing layer to be a particularly 1.0 × 10 ²¹ spin more. Thereby, it can be said that the activity of the photocatalyst in the photocatalyst-containing layer is high, and a high-definition pattern forming body can be efficiently produced in a short time.

Further, the concentration of the electron spin is equal to or greater than the value, the accumulated amount of energy irradiated from the light source is 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, are particularly when a 1000 mJ / ^{m 2} or less It is preferable to select one. As a result, it is possible to select a patterning substrate having a photocatalyst-containing layer in which the photocatalyst is activated with a smaller amount of energy, and the time required for decomposition or modification of organic matter can be shortened, resulting in cost reduction. It is.

  In addition, the electron spin concentration calculation method, the electron spin concentration measurement jig, the spin trap agent, and the high-pressure mercury lamp used for the measurement are the same as those described in the above section “A. Photocatalyst-containing layer”. Therefore, the detailed explanation here is omitted.

  In this step, for example, a patterning substrate for testing is simultaneously manufactured under the same conditions as a patterning substrate for products, and the patterning substrate for products is inspected by inspecting the patterning substrate for testing. May be selected. Moreover, this process may be performed with respect to all the patterning substrates manufactured, and may be performed for every predetermined number of sheets.

  Further, the base material of the patterning substrate used in this step and the photocatalyst-containing layer can be the same as those described in the first embodiment of the above-mentioned “B. pattern forming body”. Detailed description is omitted.

b. Others In the method for producing a pattern forming body in the present invention, in addition to the inspection step, an energy irradiation step for irradiating the patterning substrate with energy to form the pattern forming body is performed. The kind of energy irradiated in the energy irradiation step and the energy irradiation method can be the same as those described in the first embodiment of “B. Pattern formation body” described above.

  In addition, in this embodiment, you may have not only the said inspection process and energy irradiation process but the photocatalyst containing layer formation process etc. which form a photocatalyst containing layer, for example. In this case, the inspection step may be performed immediately after the photocatalyst-containing layer formation step, or may be performed immediately before the energy irradiation step, for example.

2. Second Embodiment Next, a method for producing a pattern forming body in a second embodiment of the present invention will be described. The method for producing a pattern forming body according to this embodiment includes a base material, a photocatalyst-containing layer formed on the base material and containing at least a photocatalyst, the photocatalyst-containing layer formed on the photocatalyst-containing layer, and the photocatalyst associated with energy irradiation. A pattern for producing a pattern forming body by forming a characteristic change pattern in which the characteristic of the characteristic change layer is changed by irradiating energy in a pattern onto a patterning substrate having a characteristic change layer whose characteristic is changed by an action. A method for producing a formed body, wherein a cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the characteristic change layer, and the electron spin concentration A spin trap solution is added to the inside of the measuring jig, and the accumulated energy amount is 2000 mJ / m ² from a high-pressure mercury lamp with an illuminance of 550 lux. The photocatalyst-containing layer is irradiated with ultraviolet rays until radicals are generated from the photocatalyst-containing layer until the radical is trapped, and the spin trapping agent solution in which the radicals are trapped is subjected to measurement by electron spin resonance. The method includes an inspection step of selecting only the patterning substrate having a radical-derived electron spin concentration of 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer.

  For example, as shown in FIG. 7, the method for producing a pattern-formed body of this embodiment includes a base material 2, a photocatalyst-containing layer 1 formed on the base material 2, and a characteristic change formed on the photocatalyst-containing layer 1. The characteristic changing layer 4 of the patterning substrate having the layer 4 is irradiated with energy 22 using, for example, a photomask 21 (FIG. 7A), thereby changing the characteristic of the characteristic changing layer 4 into a pattern. Thus, the pattern forming body 10 having the characteristic change pattern 8 is manufactured (FIG. 7B). In this embodiment, when the photocatalyst-containing layer is irradiated with ultraviolet rays from the light source and measured by the electron spin resonance method using a predetermined method, the electron spin concentration derived from the hydroxy radical has a predetermined value. There is an inspection step of selecting only the patterning substrate as described above.

According to this embodiment, since only the patterning substrate in which the concentration of electron spins derived from hydroxyl radicals when irradiated with the ultraviolet rays is equal to or higher than a predetermined value when the ultraviolet rays are irradiated is selected, the photocatalytic activity is increased. Only a patterning substrate having a high photocatalyst-containing layer can be used for the production of a pattern forming body. Therefore, a high-definition pattern forming body can be efficiently manufactured in a short time.
Hereinafter, the inspection process in the present invention will be described.

a. Inspection process In the inspection process of this embodiment, a cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is arranged on the surface of the characteristic change layer of the patterning substrate. When the electron spin resonance spectrum was measured while irradiating ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux, the spin-trap agent solution was added to the inside of the electron spin concentration measuring jig and irradiated from the high-pressure mercury lamp. when the integrated amount of energy becomes 2000 mJ / m ^2, the patterning substrate having a photocatalyst-containing layer in which the concentration of electron spin from hydroxyl radicals is 1.0 × 10 ²⁰ spin or the photocatalyst-containing layer 1 m ² per a step of selecting only, in the present embodiment, among the above 5.0 × 10 ²⁰ spins or more, particularly It is preferable to select only patterning substrate having a photocatalyst-containing layer to be .0 × 10 ²¹ spins or more. Thereby, it can be said that the activity of the photocatalyst in the photocatalyst-containing layer is high, and a high-definition characteristic change pattern can be efficiently formed in a short time.

Further, the concentration of the electron spin is equal to or greater than the value, the accumulated amount of energy irradiated from the light source is 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, are particularly when a 1000 mJ / ^{m 2} or less It is preferable to select one. As a result, it is possible to select a patterning substrate having a photocatalyst-containing layer in which the photocatalyst is activated with a smaller amount of energy, and the time required for decomposition or modification of organic matter can be shortened, resulting in cost reduction. It is.

  In addition, the electron spin concentration calculation method, the electron spin concentration measurement jig, the spin trap agent, and the high-pressure mercury lamp used for the measurement are the same as those described in the above section “A. Photocatalyst-containing layer”. Therefore, the detailed explanation here is omitted.

  In this step, for example, a patterning substrate for testing is simultaneously manufactured under the same conditions as a patterning substrate for products, and the patterning substrate for products is inspected by inspecting the patterning substrate for testing. May be selected. Moreover, this process may be performed with respect to all the patterning substrates manufactured, and may be performed for every predetermined number of sheets.

  Moreover, as the base material, photocatalyst containing layer, and characteristic changing layer of the patterning substrate used in this step, it can be the same as that described in the second embodiment of “B. Pattern forming body” described above. Detailed explanation here is omitted.

b. Others In the method for producing a pattern forming body according to the present invention, in addition to the inspection step, an energy irradiation step of irradiating the patterning substrate with energy is performed, and irradiation is performed in such an energy irradiation step. The type of energy and the energy irradiation method can be the same as those described in the first embodiment of “B. Pattern forming body” described above.

  In addition, in this embodiment, you may have not only the said test | inspection process and energy irradiation process but the patterning board | substrate formation process etc. which form a patterning board | substrate, for example. In this case, the inspection step may be performed immediately after the patterning substrate forming step, or may be performed immediately before the energy irradiation step, for example.

3. Third Embodiment Next, a method for manufacturing a pattern forming body in a third embodiment of the present invention will be described. In the method for producing a pattern forming body according to this embodiment, a counter substrate, a base, and a photocatalyst-containing layer side substrate having a photocatalyst-containing layer formed on the base and containing at least a photocatalyst are arranged to face each other, and a pattern is formed. The pattern forming body is manufactured by forming a characteristic change pattern having a changed characteristic on the counter substrate by irradiating energy in a shape, wherein radicals are formed on the surface of the photocatalyst-containing layer. A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed, and a spin trap agent solution is added to the inside of the electron spin concentration measuring jig, and an illuminance of 550 lux is obtained. Spins with hydroxy radicals trapped after UV irradiation from a high-pressure mercury lamp until the accumulated energy reaches 2000 mJ / m ² The photocatalyst-containing layer side substrate in which the concentration of electron spins derived from hydroxy radicals is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst containing layer when the trapping agent solution is measured by the electron spin resonance method. It is a method characterized by having the inspection process which selects only.

  For example, as shown in FIG. 6, the method for producing a pattern forming body according to this embodiment includes a photocatalyst containing layer 1 of a substrate 5 and a photocatalyst containing layer side substrate 7 having a photocatalyst containing layer 1 formed on the substrate 5. By irradiating the energy 22 using a photomask 21 or the like from a predetermined direction, the counter substrate 9 whose characteristics change due to decomposition or modification of the surface organic groups by active oxygen species or the like is placed opposite to the counter substrate 9. (FIG. 6A) is a method of manufacturing the pattern forming body 10 having the characteristic change pattern 8 by changing the characteristic of the counter substrate 9 into a pattern (FIG. 6B). In this embodiment, an electron spin resonance spectrum is measured while irradiating the photocatalyst-containing layer with ultraviolet rays from the light source, and the concentration of electron spins when the integrated energy amount irradiated from the light source becomes a predetermined value is determined. There is an inspection step of selecting only the photocatalyst-containing layer side substrate having a predetermined value or more.

According to this embodiment, in the inspection step, the concentration of electron spins derived from hydroxy radicals per 1 m ^{2 of the} photocatalyst-containing layer when the electron spin resonance spectrum of the photocatalyst-containing layer is measured under a predetermined condition is a certain level or more. Only the photocatalyst-containing layer side substrate is selected. Therefore, according to the present invention, only a photocatalyst-containing layer-side substrate that is highly active, can be efficiently decomposed in a short time, and can decompose or modify organic substances can be produced efficiently in a short time. And a pattern forming body having a high-definition characteristic change pattern can be manufactured. In addition, since the photocatalyst-containing layer side substrate is usually repeatedly used, the photocatalyst-containing layer side substrate that has deteriorated over time can be discarded by performing the above inspection step, and a highly active photocatalyst. There is an advantage that a pattern formation object can be manufactured using only a content layer side substrate.
Hereinafter, the inspection process in this embodiment will be described.

a. Inspection Step The inspection step according to the present embodiment includes a cylindrical electron spin concentration measuring jig formed on the surface of the photocatalyst-containing layer and formed of a material that does not generate radicals and does not consume radicals. When an electron spin resonance spectrum is measured while irradiating ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux, a spin trap agent solution is added to the inside of the electron spin concentration measuring jig cylinder, and the integration irradiated from the high-pressure mercury lamp A photocatalyst-containing layer side substrate having a photocatalyst-containing layer in which the concentration of electron spins derived from hydroxy radicals is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer when the energy amount is 2000 mJ / m ^2. a step of selecting, in the present embodiment, among the above 5.0 × ^{10 20} spins or more, particularly 1.0 × ^{10 21} scan It is preferable to select a photocatalyst-containing layer side substrate having a photocatalyst-containing layer to be down more. Thereby, it can be said that the photocatalyst-containing layer side substrate can be said to have a high activity of the photocatalyst in the photocatalyst-containing layer and can efficiently change the characteristics of the counter substrate in a short time.

Further, the concentration of the electron spin is equal to or greater than the value, the accumulated amount of energy irradiated from the light source is 2000 mJ / ^{m 2} or less, preferably 1500 mJ / ^{m 2} or less, are particularly when a 1000 mJ / ^{m 2} or less It is preferable to select one. This makes it possible to select a photocatalyst-containing layer side substrate having a photocatalyst-containing layer in which the photocatalyst is activated with a smaller amount of energy, thereby shortening the time required for decomposition or modification of organic substances, resulting in cost reduction. Because it can.

  In addition, the electron spin concentration calculation method, the electron spin concentration measurement jig, the spin trap agent, and the high-pressure mercury lamp used for the measurement are the same as those described in the above section “A. Photocatalyst-containing layer”. Therefore, the detailed explanation here is omitted.

  In this step, for example, a photocatalyst-containing layer side substrate for testing is simultaneously manufactured under the same conditions as the photocatalyst-containing layer side substrate used for pattern formation, and the photocatalyst-containing layer of the photocatalyst-containing layer side substrate for testing is prepared. May be used to sort out the photocatalyst-containing layer side substrate used for pattern formation. Moreover, this process may be performed with respect to all the photocatalyst containing layer side substrates used for manufacture of a pattern formation body, and may be performed by extraction.

  The photocatalyst-containing layer side substrate used in this step is the same as that described in the above-mentioned section “C. Photocatalyst-containing layer side substrate”, and therefore detailed description thereof is omitted here.

b. Others In the method for producing a pattern forming body according to the present invention, in addition to the forming step, an energy irradiating step is performed in which the counter substrate and the photocatalyst-containing layer side substrate are arranged facing each other and irradiated with energy. However, regarding the counter substrate used in such an energy irradiation step, the type of energy to be irradiated and the method of irradiating energy, the arrangement method of the counter substrate and the photocatalyst containing layer side substrate, etc., the above-mentioned “B. This can be the same as that described in “Layer-side substrate”.

  Moreover, in this embodiment, you may have the photocatalyst containing layer side board | substrate formation process which forms a photocatalyst containing layer side board | substrate other than an energy irradiation process and an inspection process. In this case, the inspection step may be performed immediately after the photocatalyst-containing layer side substrate forming step, or may be performed immediately before the energy irradiation step, for example. Further, for example, the inspection step may be periodically performed on the stored photocatalyst-containing layer side substrate.

  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.

  The following examples illustrate the present invention more specifically.

[Example 1]
A titanium dioxide sol solution (trade name STK-01, manufactured by Ishihara Sangyo Co., Ltd.) was coated on a washed 2 cm × 2 cm non-alkali glass substrate by a spin coating method and dried at room temperature for 3 minutes. Thereafter, the coating was transferred onto a hot plate, the temperature was gradually raised from room temperature to 200 ° C., and after reaching 200 ° C., it was heated and dried for 1 hour to obtain a photocatalyst composition coating film. Care was taken that the heating temperature of the hot plate did not exceed 200 ° C. in order to suppress deterioration of the substrate and material.
The dried photocatalyst composition coating film is immersed in a glass container filled with pure water for 1 minute, then taken out, washed with pure water, and allowed to stand for another hour on a 200 ° C. hot plate in the same manner as described above. did.
Carefully attach a cylindrical synthetic quartz jig having a ² cm diameter (area: about 3.14 cm ² ) circle with a small amount of silicone grease applied to the end to the photocatalyst-containing layer so that the surface is not scratched. It was. Inside this cylinder, 2 ml of a 1 wt% pure aqueous solution of spin trap agent (DMPO) was gently dropped accurately using a micropipette. At this time, it was confirmed that there was no leakage of the spin trap agent from the contact portion between the photocatalyst-containing layer surface and the jig. The photocatalyst-containing layer is irradiated with 2000 mJ / m ² of ultraviolet light from a vertical direction with a high-pressure mercury lamp, and 1 ml is extracted from the above-mentioned 2 ml of the pure aqueous solution of the spin trapping agent with a micropipette and put into a sample tube for measuring electron spin concentration. Then, electron spin concentration measurement was performed. From the measurement results, the electron spin concentration derived from the hydroxy radical was determined according to the method described in the book (Electronic Spin Resonance; Kodansha 1991), and found to be 2.0 × 10 ²⁰ spins / m ² per 1 m ^{2 of the} photocatalyst containing layer. ² .

[Example 2]
(Formation of photocatalyst containing layer)
In order to give wettability change characteristics to 0.5 g of titanium dioxide sol liquid (trade name STK-01, manufactured by Ishihara Sangyo Co., Ltd.) used in Example 1, 0.004 g of fluoroalkylsilane was mixed. Similarly, a photocatalyst-containing layer was formed.
Electron spin resonance spectrum measurement was performed on the photocatalyst-containing layer in the same manner as in Example 1. Similar to Example 1, signal intensity derived from hydroxy radicals and carbon radicals with respect to ultraviolet irradiation with an integrated energy amount of 2000 mJ / m ^2. The electron spin concentration derived from hydroxy radicals was determined according to the method described in the book (Electron Spin Resonance; Kodansha 1991), and found to be 1.1 × 10 ²⁰ spins per 1 m ^{2 of the} photocatalyst-containing layer. Compared to Example 1, the active species were lost due to various reactions due to the addition of the wettability change property-imparting component, but the radical generation efficiency per unit surface area with respect to a constant integrated energy amount of ultraviolet rays was determined by electron spin resonance spectrum measurement. I was able to.

(Contact angle change measurement)
As a result of investigating the degree of decrease in the toluene contact angle with respect to the energy irradiation amount of the photocatalyst-containing layer, the minimum exposure amount until the initial 50 ° (toluene repellency) changes to 10 ° (toluene affinity) is about 2200 mJ / m ² , and was found to have high sensitivity (photocatalytic activity) as a photocatalyst.

[Comparative Example 1]
A photocatalyst containing layer was formed in the same manner as in Example 2 except that the drying temperature by the hot plate was changed to 300 ° C. Similarly, the electron spin resonance spectrum was measured by the electron spin resonance method. As a result, the electron spin concentration derived from the hydroxy radical and the carbon radical derived signal intensity with respect to the ultraviolet irradiation with an integrated energy amount of 2000 mJ / m ² was determined as a photocatalyst. It was found to be 6.0 × 10 ¹⁹ spins per 1 m ^{2 of the} containing layer, and it was found that excessive alteration causes unnecessary alteration and suppresses generation of desired active species.

(Contact angle change measurement)
When the sensitivity by contact angle measurement was investigated in the same manner as in Example 2, the minimum exposure required for contact angle change was about 3000 mJ / m ² , and the photocatalyst-containing layer had low sensitivity (low photocatalytic activity). It was confirmed.

It is explanatory drawing explaining the measuring method of the electron spin density | concentration used for this invention. It is a schematic sectional drawing which shows an example of the pattern formation body of this invention. It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the pattern formation body of this invention. It is a schematic sectional drawing which shows an example of the photocatalyst containing layer side board | substrate of this invention. It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention. It is process drawing which shows an example of the manufacturing method of the pattern formation body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photocatalyst containing layer 2 ... Base material 4 ... Characteristic change layer 5 ... Base | substrate 7 ... Photocatalyst containing layer side board | substrate 8 ... Characteristic change pattern 9 ... Opposite substrate 10 ... Pattern formation body 11 ... Electron spin concentration measurement jig | tool 12 ... Spin trap Agent solution 13 UV

Claims (8)

A photocatalyst-containing layer containing at least a photocatalyst, wherein a cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the photocatalyst-containing layer, and A spin trap agent solution is added to the inside of a jig for measuring electron spin concentration, and the photocatalyst-containing layer is irradiated with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the integrated energy amount reaches 2000 mJ / m ^2. After generating radicals from the layer, when the spin trapping agent solution in which the radicals are trapped is measured by an electron spin resonance method, the electron spin concentration derived from hydroxy radicals is 1 per 1 m ^{2 of the} photocatalyst-containing layer. A photocatalyst-containing layer characterized in that it has 0 × 10 ²⁰ spins or more.   The photocatalyst-containing layer according to claim 1, wherein the photocatalyst contains at least titanium dioxide. A pattern forming body having a base material and a photocatalyst-containing layer that is formed on the base material, contains at least a photocatalyst and a binder, and whose characteristics change due to the action of the photocatalyst accompanying energy irradiation,
A cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals is installed on the surface of the photocatalyst-containing layer, and a spin trap is placed inside the electron spin concentration measuring jig. After adding an agent solution and irradiating the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount is 2000 mJ / m ² , radicals are generated from the photocatalyst-containing layer, When the trapped spin trap agent solution is measured by an electron spin resonance method, the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer. A pattern forming body. A base material; a photocatalyst-containing layer formed on the base material and containing at least a photocatalyst; and a property change layer formed on the photocatalyst-containing layer and having properties changed by the action of the photocatalyst upon energy irradiation. A pattern former,
A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the characteristic change layer, and a spin trap is placed inside the electron spin concentration measuring jig. After adding an agent solution and irradiating the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount is 2000 mJ / m ² , radicals are generated from the photocatalyst-containing layer, When the trapped spin trap agent solution is measured by an electron spin resonance method, the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer. A pattern forming body. A characteristic that has a base and a photocatalyst-containing layer that is formed on the base and contains at least a photocatalyst, and has an effect of the photocatalyst associated with energy irradiation on a counter substrate arranged to face the base, and the characteristics changed. A photocatalyst-containing layer side substrate used to form a change pattern,
A cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals is installed on the surface of the photocatalyst-containing layer, and a spin trap is placed inside the electron spin concentration measuring jig. After adding an agent solution and irradiating the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount is 2000 mJ / m ² , radicals are generated from the photocatalyst-containing layer, When the trapped spin trap agent solution is measured by an electron spin resonance method, the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer. A photocatalyst-containing layer side substrate. A patterning substrate having a base material and a photocatalyst-containing layer which is formed on the base material and contains at least a photocatalyst and a binder and whose characteristics are changed by the action of the photocatalyst upon energy irradiation is irradiated with energy in a pattern. By this, it is a manufacturing method of the pattern formation body which forms the characteristic change pattern in which the characteristic of the photocatalyst content layer changed, and manufactures a pattern formation object,
A cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals is installed on the surface of the photocatalyst-containing layer, and a spin trap is placed inside the electron spin concentration measuring jig. After adding an agent solution and irradiating the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount is 2000 mJ / m ² , radicals are generated from the photocatalyst-containing layer, When the trapped spin trap agent solution is measured by an electron spin resonance method, the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer. The manufacturing method of the pattern formation body which has the test | inspection process which selects only a board | substrate. A base material; a photocatalyst-containing layer formed on the base material and containing at least a photocatalyst; and a characteristic change layer formed on the photocatalyst-containing layer and whose characteristics are changed by the action of the photocatalyst upon energy irradiation. A pattern forming body manufacturing method for manufacturing a pattern forming body by forming a characteristic changing pattern in which the characteristics of the characteristic changing layer are changed by irradiating a patterning substrate with energy in a pattern,
A cylindrical electron spin concentration measuring jig formed of a material that does not generate radicals and does not consume radicals is installed on the surface of the characteristic change layer, and a spin trap is placed inside the electron spin concentration measuring jig. After adding an agent solution and irradiating the photocatalyst-containing layer with ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy amount is 2000 mJ / m ² , radicals are generated from the photocatalyst-containing layer, When the trapped spin trap agent solution is measured by an electron spin resonance method, the electron spin concentration derived from a hydroxy radical is 1.0 × 10 ²⁰ spins or more per 1 m ^{2 of the} photocatalyst-containing layer. The manufacturing method of the pattern formation body which has the test | inspection process which selects only a board | substrate. A counter substrate, a base, and a photocatalyst-containing layer side substrate having a photocatalyst-containing layer containing at least a photocatalyst formed on the base are arranged to face each other, and energy is irradiated in a pattern on the counter substrate. A pattern forming body manufacturing method for manufacturing a pattern forming body by forming a characteristic change pattern having changed characteristics in
A cylindrical electron spin concentration measuring jig formed from a material that does not generate radicals and does not consume radicals is installed on the surface of the photocatalyst-containing layer, and a spin trap is placed inside the electron spin concentration measuring jig. After adding an agent solution and irradiating ultraviolet rays from a high-pressure mercury lamp with an illuminance of 550 lux until the accumulated energy reaches 2000 mJ / m ² , the spin trap agent solution in which hydroxy radicals are trapped is subjected to electron spin resonance. when performing the measurement, and wherein a test step of concentration of the electron spins from hydroxy radicals to select only the photocatalyst-containing layer side substrate is the photocatalyst-containing layer 1 m ² per 1.0 × 10 ²⁰ spin more A method for producing a pattern forming body.

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