JP4849162B2 - Method for producing pattern forming body - Google Patents

Description

  The present invention relates to a method for producing a pattern forming body having a pattern with different characteristics on the surface, which can be used for various applications including a color filter.

  Conventionally, various methods for producing a pattern forming body for forming various patterns such as designs, images, characters, and circuits on a substrate have been produced.

  As such a high-definition pattern forming body, a pattern forming body using a photocatalyst by the present inventors and a manufacturing method thereof have been proposed (for example, Patent Document 1). According to this, since it is possible to obtain a pattern formed body on which patterns having different characteristics are formed by pattern exposure, the pattern formed body can be obtained easily and accurately. Since various functional elements can be manufactured by utilizing the difference in characteristics of pattern forming bodies having patterns having different characteristics, functional elements such as color filters and microlenses can be efficiently and high-quality. There is an effect that it can be obtained.

  However, the above-described pattern forming body changes the characteristics of the portion irradiated with energy by using the action of the photocatalyst to form patterns having different characteristics. It takes a certain amount of time to generate. If this time can be shortened, further efficiency can be achieved.

  In order to obtain a functional element with high accuracy, it is preferable to form a large characteristic difference on the pattern forming body. However, such a large characteristic difference is allowed within a predetermined time allowed for efficiency. In order to form it, it is necessary to improve the rate of change of critical surface tension due to exposure on the surface of the pattern forming body.

JP 2000-249821 A

  From the above, it is desired to provide an efficient manufacturing method of a pattern forming body in which patterns having different characteristics are formed.

  The present invention provides a photocatalyst-containing layer-side substrate having a photocatalyst-containing layer and a substrate containing a photocatalyst, and a substrate for a pattern forming body having a characteristic change layer whose properties change due to the action of the photocatalyst in the photocatalyst-containing layer. After the photocatalyst-containing layer and the characteristic change layer are arranged with a gap so that the thickness is 200 μm or less, a characteristic change pattern with changed characteristics is formed on the surface of the characteristic change layer by irradiating an electron beam from a predetermined direction. The manufacturing method of the pattern formation body characterized by doing is provided.

  According to the present invention, by irradiating the characteristic change layer whose characteristic is changed by the action of the photocatalyst using the photocatalyst-containing layer side substrate, the action of the photocatalyst efficiently activated by the electron beam. This makes it possible to change the characteristics on the characteristic change layer in a short time. Also, the electron beam has high energy, and the characteristics of the property change layer are changed by, for example, cutting the molecular chain constituting the property change layer by the electron beam itself that has passed through the photocatalyst containing layer side substrate. It becomes possible. Thereby, it becomes possible to manufacture a pattern formation body efficiently by the effect of both a photocatalyst and an electron beam.

  In this invention, the said board | substrate for pattern formation bodies may have a base material and the characteristic change layer formed on the said base material. The substrate for a pattern forming body may have a characteristic change layer having self-supporting property and does not require a base material. When strength is required for the body substrate, the characteristic change layer may be formed on a base material.

  In the present invention, the photocatalyst-containing layer may be a layer made of a photocatalyst. This is because, when the photocatalyst-containing layer is a layer composed only of a photocatalyst, it is possible to enhance the effect of the photocatalyst associated with the irradiation of the electron beam, and to efficiently produce a pattern-formed body. .

  In the present invention, the photocatalyst-containing layer is preferably a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. This is because the photocatalyst-containing layer can be made uniform with no irregularities, and the characteristics of the characteristic change layer can be changed uniformly and efficiently.

  In the present invention, the photocatalyst-containing layer may be a layer having a photocatalyst and a binder. By using the binder in this manner, it becomes possible to form the photocatalyst-containing layer relatively easily, and as a result, the pattern formed body can be manufactured at a low cost.

In the present invention, the photocatalyst is titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O). _3), and a one or more substances selected from iron oxide (Fe 2 _{O 3)} may, as described above claim 7, the photocatalyst is titanium oxide (TiO ₂₎ Preferably there is. This is because titanium dioxide has a high band gap energy and is effective as a photocatalyst, and is chemically stable, non-toxic and easily available.

  In the present invention, when the surface of the property change layer is irradiated with an electron beam, the distance between the photocatalyst-containing layer and the property change layer surface is preferably in the range of 0.2 μm to 10 μm. . This is because, when irradiating the electron beam, the characteristics of the property change layer can be changed more effectively by irradiating the electron beam with the above-mentioned minute intervals.

  In the present invention, the characteristic change layer is preferably a layer not containing a photocatalyst. This is because it is possible to obtain a high-quality pattern forming body that does not include the photocatalyst in the manufactured pattern forming body and that is not affected by the photocatalyst over time.

  In the present invention, the property change layer may be a wettability change layer in which the wettability changes so that the contact angle with the liquid decreases due to the action of the photocatalyst accompanying irradiation of the electron beam. When the property change layer is a wettability change layer, the region irradiated with the electron beam is lyophilic and the region not irradiated with the electron beam is lyophobic due to the action of the photocatalyst accompanying the electron beam irradiation. It is possible to obtain a pattern forming body that can easily form a functional part by utilizing the difference in wettability.

  Further, in the present invention, the contact angle with the liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in the portion not irradiated with the electron beam, and in the portion irradiated with the electron beam. It is preferably 9 ° or less. When the contact angle of the wettability changing layer with the portion of the liquid not irradiated with the electron beam is 10 ° or less, the liquid repellency is insufficient, and the liquid with the portion irradiated with the electron beam In the case where the contact angle is 10 ° or more, for example, when a functional element is formed on the pattern forming body by utilizing the difference in wettability, the functional part composition that forms the functional part. This is because there is a possibility that the spread of etc. is inferior.

  In the present invention, the wettability changing layer is preferably a layer containing an organopolysiloxane. In the present invention, the wettability changing layer is required for the wettability changing layer to be liquid repellent when it is not irradiated with an electron beam, and contains a photocatalyst that is contacted when irradiated with an electron beam. It is a characteristic that it becomes lyophilic by the action of the photocatalyst in the layer. This is because it is preferable to use organopolysiloxane as a material for imparting such characteristics to the wettability changing layer.

  In the present invention, the organopolysiloxane is preferably a polysiloxane containing a fluoroalkyl group. This is because if it contains a fluoroalkyl group, the difference in wettability between the electron beam irradiated portion and the electron beam non-irradiated portion can be increased.

In the present invention, the organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group, or an epoxy group, and X represents an alkoxyl group. Or n represents an integer from 0 to 3. It is preferably an organopolysiloxane that is a hydrolytic condensate or a cohydrolytic condensate of one or more of the silicon compounds represented by .

  This is because by using such an organopolysiloxane, it is possible to exhibit the characteristics against the change in wettability as described above.

In the present invention, the wettability changing layer may have a self-supporting property. Since the wettability changing layer has a self-supporting property, it is possible to easily form a substrate for a pattern forming body using a commercially available resinous film or the like, which is preferable in terms of manufacturing efficiency and cost. Because.
In the present invention, the property change layer may be a decomposition / removal layer that is decomposed and removed by the action of a photocatalyst accompanying irradiation of an electron beam. Since the characteristic change layer is a decomposition removal layer, it is possible to form irregularities on the substrate for pattern forming bodies, and a pattern forming body capable of easily forming a functional part using the irregularities. This is because it becomes possible.

  In the present invention, the contact angle of the liquid with respect to the decomposition / removal layer is preferably different from the contact angle of the liquid with respect to the substrate exposed when the decomposition / removal layer is decomposed and removed. This is because the functional part can be formed on the pattern forming body to be a pattern forming body that can utilize not only surface irregularities but also a difference in wettability.

  In the present invention, the decomposition removal layer is preferably a self-assembled monomolecular film, a Langmuir-Blodgett film, or an alternately adsorbed film. This is because, when the decomposition removal layer is the above layer, a defect-free layer having a relatively high strength can be easily formed.

  In the present invention, the contact angle of the decomposition / removal layer with a 40 mN / m liquid is preferably 10 ° or more, and preferably 9 ° or less on the substrate. In the present invention, the decomposition / removal layer is an area where liquid repellency is required. Therefore, when the contact angle with the liquid on the decomposition / removal layer is 10 ° or less, the liquid repellency is sufficient. It is not. Further, the base material exposed by the decomposition removal layer being decomposed and removed by the action of the photocatalyst accompanying the irradiation of the electron beam is an area where lyophilicity is required, and the contact angle with the liquid is 10 ° or more. In some cases, for example, when the functional part is formed on the pattern-formed body, there is a high possibility that the functional part composition for forming the functional part in the lyophilic region will not spread and spread.

  In the present invention, the characteristic change layer may be an adhesion change layer in which the adhesion changes due to the action of a photocatalyst accompanying irradiation of an electron beam. Since the characteristic change layer is an adhesion change layer, it is possible to form an adhesion good region with good adhesion and an adhesion inhibition region with poor adhesion on the substrate for a pattern forming body. This is because a pattern forming body capable of forming a functional part can be obtained by utilizing the difference in adhesion.

  According to the present invention, by irradiating the characteristic change layer whose characteristic is changed by the action of the photocatalyst using the photocatalyst-containing layer side substrate, the action of the photocatalyst efficiently activated by the electron beam. This makes it possible to change the characteristics on the characteristic change layer in a short time. Also, the electron beam has high energy, and the characteristics of the property change layer are changed by, for example, cutting the molecular chain constituting the property change layer by the electron beam itself that has passed through the photocatalyst containing layer side substrate. It becomes possible. Thereby, it becomes possible to manufacture a pattern formation body efficiently by the effect of both a photocatalyst and an electron beam.

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 the other example of the photocatalyst containing layer side board | substrate used for the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the photocatalyst containing layer side board | substrate used for the manufacturing method of the pattern formation body of this invention. It is a schematic sectional drawing which shows the other example of the photocatalyst containing layer side board | substrate used for the manufacturing method of the pattern formation body of this invention.

  The present invention relates to a method for producing a pattern formed body, and will be described in detail below.

  The method for producing a pattern forming body of the present invention includes a photocatalyst-containing layer containing a photocatalyst and a substrate having a photocatalyst-containing layer side substrate, and a pattern formation having a characteristic change layer whose characteristics change due to the action of the photocatalyst in the photocatalyst-containing layer. The body substrate is disposed with a gap so that the photocatalyst-containing layer and the property change layer are 200 μm or less, and then irradiated with an electron beam from a predetermined direction, whereby the surface of the property change layer has a characteristic. It is a method characterized by forming a changed characteristic change pattern.

  For example, as shown in FIG. 1, the method for producing a pattern forming body according to the present invention includes a substrate 1 and a photocatalyst-containing layer side substrate 3 having a photocatalyst processing layer 2 formed on the substrate 1, a base material 4, and a base material 4. A pattern forming body substrate 6 having the characteristic change layer 5 formed thereon is prepared (FIG. 1A). Next, after arranging the photocatalyst containing layer 2 and the characteristic change layer 5 with a predetermined gap, the electron beam 8 is irradiated from a predetermined direction using, for example, a photomask 7 or the like (FIG. 1B). ). As a result, a pattern forming body in which the characteristic change pattern 9 in which the characteristic of the characteristic change layer 5 is changed can be formed (FIG. 1C).

  According to the present invention, the photocatalyst in the photocatalyst containing layer is excited by the energy of the electron beam by irradiating an electron beam on the photocatalyst containing layer side substrate on the characteristic change layer, and the characteristic change is performed. It is possible to change the characteristics of the layer. In addition, the electron beam has high energy, passes through the photocatalyst-containing layer side substrate, acts directly on the property change layer, for example, breaks the molecular chain constituting the property change layer, and the properties described above. It is possible to change the characteristics of the change layer. This makes it possible to efficiently change the characteristics of the characteristic change layer by both the action of the photocatalyst and the action of the electron beam. Hereinafter, each structure of the manufacturing method of the pattern formation body of this invention is demonstrated.

(Pattern for pattern formation)
First, the characteristic change layer used in the present invention will be described. The substrate for the pattern forming body used in the present invention is not particularly limited as long as it has a characteristic change layer whose characteristics change due to the action of the photocatalyst, and has only the characteristic change layer. Alternatively, for example, as shown in FIG. 1 (a), the characteristic change layer 5 may be formed on the base material 4, and may further have a light shielding portion or the like.

  Hereinafter, each configuration of the pattern forming body substrate will be described.

(1) Property changing layer The property changing layer in the present invention is not particularly limited in its kind as long as the property changes due to the action of the photocatalyst accompanying irradiation of the electron beam or the action of the electron beam itself. Absent. In addition, when forming a photocatalyst characteristic change pattern, which will be described later, when energy is irradiated from the pattern forming substrate side, the characteristic change layer is preferably a layer that transmits an electron beam.

  Here, in the present invention, when the property change layer is a wettability change layer in which the wettability changes and a pattern due to wettability is formed, the property change layer is decomposed and removed, and the pattern is formed by unevenness. Three cases are preferable: a layer, and a case where the characteristic change layer is an adhesive change layer in which the adhesiveness changes to form a pattern having a difference in adhesiveness. Hereinafter, the wettability changing layer, the decomposition removal layer, and the adhesion changing layer will be described.

a. The wettability changing layer is not particularly limited as long as the wettability changing layer used in the present invention is a layer whose surface wettability changes by the action of the photocatalyst accompanying the electron beam irradiation or the action of the electron beam itself. In general, the layer is preferably a layer whose wettability changes so that the contact angle with the liquid on the surface of the wettability changing layer is lowered by the action of the photocatalyst accompanying electron beam irradiation.

  In such a wettability changing layer, a substance having liquid repellency is formed on the surface before the electron beam irradiation, and when the electron beam is irradiated, the molecular chain on the surface, for example, the liquid repellency is reduced. The bond of fluorine, which is a substance possessed, is broken. At the same time, oxygen and water in the atmosphere are made active oxygen species by the action of the photocatalyst activated by electron beam irradiation, and reaction such as oxidation, decomposition, etc. on the wettability change layer surface easily by this active oxygen species. And a hydrophilic group is introduced.

  Usually, the above reaction is caused only by the action of the photocatalyst accompanying energy irradiation, but in the present invention, by using an electron beam, the molecular chain can be easily cleaved, Further, since the photocatalyst is efficiently activated, the reaction can be performed in a short time.

  In this way, when the wettability changing layer changes wettability so that the contact angle with the liquid is reduced by electron beam irradiation, the wettability easily changes into a pattern by performing electron beam irradiation in a pattern. Thus, it is possible to form a pattern of the lyophilic region having a small contact angle with the liquid. As a result, it is possible to obtain a pattern forming body in which a functional element can be easily formed by attaching a functional part composition or the like to the lyophilic region.

  Here, the lyophilic region is a region having a small contact angle with the liquid, for example, a region having good wettability with respect to the functional part composition or the like. The liquid repellent region is a region having a large contact angle with the liquid, and refers to a region having poor wettability with respect to the functional part composition or the like.

  In the present invention, when the contact angle with the liquid in the adjacent region is 1 ° or more lower than the contact angle with the liquid in the adjacent region, the contact with the liquid is determined from the contact angle with the liquid in the lyophilic region or the adjacent region. When the contact angle is higher than 1 °, the liquid repellent region is used.

  Here, the characteristics of the lyophilic region formed by the electron beam irradiation and the liquid repellent region not irradiated with the electron beam have a surface tension equivalent to the surface tension of the functional part composition to be applied thereafter. A pattern formed from a lyophilic region and a liquid-repellent region that differ in the contact angle with respect to the liquid by at least 1 ° or more, preferably 5 ° or more, particularly 10 ° or more.

  The wettability changing layer has a contact angle with a liquid with a surface tension of 40 mN / m of 10 ° or more, preferably a liquid with a surface tension of 30 mN / m, in a portion not irradiated with an electron beam, that is, in a water-repellent region. It is preferable that the wettability is 10 ° or more, particularly 10% or more with a liquid having a surface tension of 20 mN / m. This is because the portion not irradiated with the electron beam is a portion that requires liquid repellency in the present invention, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient. This is because the functional part composition may remain when the functional part is formed on the body, which is not preferable.

  In addition, the wettability changing layer has a contact angle with a liquid that decreases when irradiated with an electron beam, and a contact angle with a liquid with a surface tension of 40 mN / m is 9 ° or less, preferably with a liquid with a surface tension of 50 mN / m. A layer having a contact angle of 10 ° or less, particularly a contact angle with a liquid having a surface tension of 60 mN / m is preferably 10 ° or less. When the contact angle with the electron beam irradiated part, that is, the liquid in the lyophilic region is high, for example, when the functional part is formed on the pattern forming body, the spread of the functional part composition may be inferior. This is because problems such as missing functional parts may occur.

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

  Further, when the wettability changing layer as described above is used in the present invention, fluorine is contained in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer is an electron with respect to the wettability changing layer. The wettability changing layer may be formed so as to be lower than that before electron beam irradiation by the action of the photocatalyst when irradiated with the beam.

  In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with an electron beam. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a pattern of the lyophilic region in the liquid repellent region.

  Therefore, when such a wettability changing layer is used, the pattern of the lyophilic region can be easily formed in the lyophobic region by pattern irradiation with an electron beam. It is possible to obtain a pattern forming body capable of forming a functional part only in the region.

  As described above, the fluorine content contained in the wettability changing layer containing fluorine is the fluorine content in the lyophilic region formed by electron beam irradiation and having a low fluorine content. When the fluorine content of the unexposed portion is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.

  By setting it within such a range, it is possible to make a great difference in wettability between the electron beam irradiated portion and the electron beam non-irradiated portion. Therefore, by forming the functional part in such a wettability changing layer, it becomes possible to accurately form the functional part only in the lyophilic region where the fluorine content is reduced, and the functional element can be accurately formed. Because it can be obtained. This rate of decrease is based on weight.

  The fluorine content in such a wettability changing layer can be measured by various commonly used methods. For example, X-ray photoelectron spectroscopy (ESCA) (Electron Spectroscopy, ESCA) Spectroscopy for Chemical Analysis)), and any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.

  The material used for such a wettability changing layer is a material whose wettability changing layer has the characteristics described above, that is, a material whose wettability is changed by the photocatalyst in the photocatalyst-containing layer that is contacted by electron beam irradiation, and due to the action of the photocatalyst. The main chain is not particularly limited as long as it has a main chain that is difficult to be degraded and decomposed. For example, (1) chloro- or alkoxysilane is hydrolyzed and polycondensed by sol-gel reaction or the like to exhibit high strength. Examples include organopolysiloxanes, and (2) organopolysiloxanes crosslinked with reactive silicones having excellent water and oil repellency.

In the case of (1) above, the general formula:
Y _n SiX _(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.

In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used. Specifically, one or two of the following fluoroalkylsilanes can be used.
Hydrolysis condensates and co-hydrolysis condensates of more than one species can be mentioned, and those generally known as fluorine-based silane coupling agents can be used.

_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 3) 3;
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
_{(CF 3) 2 CF (CF} 2) 6 CH 2 CH 2 Si (OCH 3) 3;
_{(CF 3) 2 CF (CF} 2) 8 CH 2 CH 2 Si (OCH 3) 3;
_{CF 3 (C 6 H 4)} C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 9 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{(CF 3) 2 CF (CF} 2) 4 CH 2 CH 2 SiCH 3 (OCH 3) 2;
_{(CF 3) 2 CF (CF} 2) 6 CH 2 CH 2 Si CH 3 (OCH 3) 2;
_{(CF 3) 2 CF (CF} 2) 8 CH 2 CH 2 Si CH 3 (OCH 3) 2;
_{CF 3 (C 6 H 4)} C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 2 CH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 2 CH 3) 3; and _{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) C 2 H 4 CH 2 Si (OCH 3) 3.

  By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-irradiated portion of the wettability changing layer is greatly improved, for example, forming a pixel portion on the pattern forming body, In the case of a color filter, a function of preventing adhesion of the functional part composition such as pixel part coloring ink and pixel part coloring ink is developed.

  Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.

However, n is an integer of 2 or more, R ^1, R ² are each a substituted or unsubstituted alkyl having 1 to 10 carbon atoms, alkenyl, aryl or cyanoalkyl group, the total molar ratio of 40% or less Vinyl, phenyl and phenyl halide. Further, those in which R ¹ and R ² are methyl groups are preferable because the surface energy becomes the smallest, and the methyl groups are preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.

  Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.

  In the present invention, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.

  The wettability changing layer in the present invention may further 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 wettability changing 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. Can be contained.

  Such a wettability changing layer can be formed by preparing a coating solution by dispersing the above-described components in a solvent together with other additives as necessary, and coating the coating solution on a substrate. . As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.

  Further, the wettability changing layer used in the present invention may be a self-supporting material as long as it is formed of a material whose surface wettability can be changed by the action of a photocatalyst. The material which does not have property may be sufficient. In addition, having self-supporting property as used in the field of this invention means that it can exist in a tangible state without another support material.

  Further, as described above, the wettability changing layer of the present invention may be a material having self-supporting property, and as the material having self-supporting property, a material obtained by depositing the above-described material has self-supporting property. However, for example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyvinylidene fluoride , Polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, silicone and the like.

  In the present invention, a wettability changing layer having no self-supporting property is preferable. The wettability changing layer formed of a material whose characteristics change greatly as described above usually has few self-supporting materials. By forming it on a substrate, the strength and the like increase, and it is used as various pattern forming bodies. Because it becomes possible.

  In addition, the wettability changing layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above. preferable. If the photocatalyst is not contained in the wettability changing layer as described above, the pattern formed body can be used without any problem for a long period of time without worrying about being affected by the passage of time.

b. Decomposition and removal layer Next, the decomposition and removal layer will be described. When the electron beam is irradiated, the decomposition removal layer used in the present invention decomposes and removes the portion of the decomposition removal layer irradiated with the electron beam by the action of the photocatalyst in the photocatalyst containing layer or the action of the electron beam itself. The layer is not particularly limited.

  When the electron beam is irradiated, such a decomposition / removal layer is, for example, both the action of the electron beam itself having high energy transmitted through the photocatalyst containing layer and the action of the photocatalyst in the photocatalyst containing layer excited by the electron beam. As a result, the molecular chain in the decomposition / removal layer is cleaved and decomposed and removed as water, carbon dioxide, etc. The pattern which becomes, ie, the pattern which has an unevenness | corrugation, can be formed.

  This decomposition / removal layer is oxidatively decomposed and vaporized by the action of a photocatalyst by electron beam irradiation, and is therefore removed without any special post-treatment such as a development / washing process. Depending on the material, a cleaning process or the like may be performed.

Moreover, it is preferable that the decomposition removal layer used for this invention not only forms an unevenness | corrugation, but this decomposition removal layer has a high contact angle with a liquid compared with the base material mentioned later.
As a result, the decomposition / removal layer is decomposed and removed, and the region where the base material is exposed can be made a lyophilic region, and the region where the decomposition / removal layer remains can be made a liquid-repellent region, thereby forming various patterns. This is because it becomes possible.

  Here, the lyophilic region is a region having a small contact angle with the liquid, for example, a region having good wettability with respect to the functional part composition when the functional part is formed on the pattern forming body. I will do it. Further, the liquid repellent region is a region having a large contact angle with the liquid, and refers to a region having poor wettability with respect to the functional part composition.

  The contact angle with the liquid on the surface of the decomposition removal layer of the present invention is 10 ° or more, preferably 10 ° or more with a liquid with a surface tension of 40 mN / m, preferably 10 ° or more with a liquid with a surface tension of 30 mN / m. In particular, the contact angle with a liquid having a surface tension of 20 mN / m preferably exhibits a value of 10 ° or more.

  In the present invention, when the characteristic change layer is a decomposition removal layer, the base material described later is preferably lyophilic, specifically, as a contact angle with a liquid having a surface tension of 40 mN / m. The contact angle with a liquid having a surface tension of 40 mN / m is more preferably 5 ° or less, and particularly preferably 1 ° or less.

  Since the wettability of the decomposition removal layer and the substrate is within the above range, the region where the substrate is exposed can be made lyophilic and the region where the decomposition removal layer remains can be made a liquid repellent region. This is because it becomes easy to form a high-definition pattern. Here, the contact angle with the liquid is a value measured by the method described above.

  In this case, the substrate described later may be surface-treated so that the surface becomes lyophilic. Examples of the surface treatment so that the surface of the material is lyophilic include lyophilic surface treatment by plasma treatment using argon or water, and the lyophilic layer formed on the substrate is Examples thereof include a silica film obtained by a sol-gel method of tetraethoxysilane.

  Specific examples of the film that can be used for the above-described decomposition removal layer include a film made of a fluorine-based or hydrocarbon-based resin having liquid repellency. These fluorine-based and hydrocarbon-based resins are not particularly limited as long as they have liquid repellency, and these resins are dissolved in a solvent, for example, a general composition such as a spin coating method. It can be formed by a film method.

  In the present invention, since a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternating adsorption film can be used, a film having no defect can be formed. It can be said that it is more preferable to use such a film forming method.

  Here, the self-assembled monolayer film, the Langmuir-Blodgett film, and the alternating adsorption film used in the present invention will be specifically described.

(I) Self-assembled monolayer The inventors do not know the existence of an official definition of a self-assembled monolayer, but explanation of what is generally recognized as a self-assembled monolayer As a sentence, for example, a review by Abraham Ulman “Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) is excellent. Referring to this review article, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorbing and binding (self-organizing) appropriate molecules to the appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. And organic phosphoric acid molecules. The common commonality of the molecular structure is that there is a functional group that has a relatively long alkyl chain and that interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present invention, these are also included in the self-assembled monolayer.

(Ii) Langmuir-Blodgett Film If the Langmuir-Blodgett film used in the present invention is formed on a substrate, the major difference from the self-assembled monomolecular film described above is Absent. It can be said that the Langmuir-Blodgett film is characterized by its formation method and the advanced two-dimensional molecular packing properties (high orientation and high order). That is, in general, Langmuir-Blodgett film-forming molecules are first developed on the gas-liquid interface, and the developed film is condensed by the trough to change into a highly packed condensed film. In practice, this is transferred to a suitable substrate for use. It is possible to form a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Further, not only low molecules but also polymers and colloidal particles can be used as the film material. Recent examples of the application of various materials are described in detail in the review by Tokuharu Miyashita et al. “Prospects for Nanotechnology for the Creation of Soft Nanodevices” Polymer Vol. 50, September, 644-647 (2001).

(Iii) Alternating Adsorption Film In general, an alternating adsorption film (Layer-by-Layer Self-Assembled Film) is formed by sequentially applying a material having a functional group having at least two positive or negative charges onto a substrate. It is a film formed by adsorbing and bonding and laminating. Since a material having a large number of functional groups has many advantages such as increased strength and durability of the membrane, recently, an ionic polymer (polymer electrolyte) is often used as a material. Further, particles having surface charges such as proteins, metals and oxides, so-called “colloid particles” are also frequently used as film-forming substances. More recently, membranes that actively utilize weaker interactions than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have been reported. A relatively recent example of alternating adsorption films is slightly biased toward materials with electrostatic interaction as the driving force, but a review by Paula T. Hammond “Recent Explorations in Electrostatic Multilayer Thin Film Assembly” Current Opinion in Colloid & Interface Science, 4, 430-442 (2000). The alternate adsorption film can be described by taking the simplest process as an example, by repeating the adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge a predetermined number of times. It is a film to be formed. As with Langmuir-Blodgett membranes, no development-condensation-transfer operations are required. Further, as apparent from the difference in these production methods, the alternate adsorption film generally does not have a two-dimensional high orientation / high order like the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film formation methods, such as the ability to easily form a dense film without defects and the ability to form even fine irregular surfaces, tube inner surfaces, and spherical surfaces. Have many.

  In addition, the thickness of the decomposition removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by the electron beam irradiated in the characteristic change pattern forming step described later. The specific film thickness varies greatly depending on the type of electron beam to be irradiated, the material of the decomposition removal layer, etc., but is generally within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0 μm. It is preferable to be within the range of 1 μm.

c. Adhesion Change Layer Next, the adhesion change layer used in the present invention will be described. The adhesion changing layer used in the present invention is not particularly limited as long as the adhesion changes by the action of the photocatalyst accompanying the irradiation of the electron beam or the action of the electron beam itself. It is preferably a layer in which the adhesiveness is changed so that the adhesiveness with the object on the surface of the adhesiveness-changing layer is improved by the action of the photocatalyst accompanying the irradiation of the line.

  Thus, by using an adhesive change layer in which the adhesiveness is changed so that the adhesiveness to an object is improved by electron beam irradiation, the region irradiated with the electron beam is irradiated with an excellent adhesion region and an electron beam. This makes it possible to make a non-adherent part as an adhesion inhibition region. Utilizing this difference in adhesion, for example, when a functional part composition is deposited on forming a functional part on a pattern-forming body, the functional part composition is applied only to a region having good adhesion. Since the functional part composition does not adhere to the adhesion inhibition region, the functional part composition in the adhesion inhibition region can be easily removed.

  Here, the region having good adhesion is a region having good adhesion to an object, and means a region having good adhesion to the functional part composition when the functional part is formed on the pattern forming body. I will do it. In addition, the adhesion-inhibiting region is a region having poor adhesion to an object, and refers to a region having poor adhesion to the functional part composition.

  The adhesion changing layer in the present invention contains an adhesion inhibiting substance and is a layer from which the adhesion inhibiting substance is removed by electron beam irradiation (first aspect), and on the adhesion changing layer by electron beam irradiation. In some cases, irregularities are formed on the surface, and the adhesion is physically improved (second embodiment).

  First, the first aspect will be described. The adhesion changing layer of this embodiment is a case where a substance that inhibits adhesion is contained before irradiation with an electron beam. In this case, the adhesion inhibiting substance can inhibit adhesion of the functional part composition applied by, for example, a vapor deposition method in the adhesion inhibition region where the electron beam is not irradiated. is there. In addition, when irradiated with an electron beam, for example, both the action of an electron beam having high energy transmitted through the photocatalyst-containing layer and the action of the photocatalyst activated by the electron beam cause The molecular chain of the adhesion inhibitor is cleaved. As a result, the adhesion-inhibiting substance is removed, and it is possible to form a good adhesion region with improved adhesion.

  Specifically, as the first aspect of the adhesiveness change layer, the same material as described in the wettability change layer can be used.

  Next, the second aspect will be described. When the electron beam irradiation layer of this embodiment is irradiated with an electron beam, the surface has fine irregularities due to, for example, both the action of an electron beam having high energy and the action of a photocatalyst activated by the electron beam. Is formed. Thereby, a physical anchor effect works and it becomes possible to improve the adhesiveness of the composition for functional parts, for example, when forming a functional part on a pattern formation body. In addition, in the adhesion-inhibiting region that is not irradiated with the electron beam, the fine unevenness is not formed, so it is difficult for the functional part composition to adhere, and this difference in adhesion is utilized. Thus, the characteristic change pattern can be easily formed.

  As the second aspect of the adhesion changing layer, specifically, the same ones as those described for the decomposition removal layer can be used.

(2) Base Material Next, the base material will be described. In the present invention, for example, the base material is used when the above-described property change layer is not self-supporting, is a decomposition removal layer, or when the pattern forming body substrate requires strength. As shown to (a), the characteristic change layer 5 is provided on the base material 4. FIG.

  Such a substrate is appropriately selected according to the intended use of the finally obtained pattern forming body, and even if it has flexibility, it does not have flexibility. It may be transparent or opaque.

  Further, when energy is irradiated from the pattern forming substrate side when forming a characteristic change pattern, which will be described later, it is preferable that the substrate transmits an electron beam.

Here, the material for the substrate used in the present invention is not particularly limited, and various materials can be used as necessary. Specific examples include metals such as glass, aluminum, and alloys thereof, plastics, woven fabrics, nonwoven fabrics, and the like. (3) Others The pattern-forming substrate in the present invention has a finally obtained pattern. A light shielding portion or the like may be provided depending on the use of the formed body.

  The shape and formation position of the light-shielding portion are not particularly limited. For example, the light-shielding portion may be formed between the base material and the characteristic change layer, or may be formed on the characteristic change layer. Good. Furthermore, it may be formed on the characteristic change layer on the side opposite to the side on which the characteristic change pattern is formed on the substrate for pattern formation, or on the substrate.

  Such a light shielding part may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.

The light shielding part used in the present invention is not particularly limited as long as it shields an electron beam to be described later. Specifically, carbon fine particles, metal oxides, It may be a layer containing light-shielding particles such as inorganic pigments and organic pigments. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.

(Photocatalyst containing layer side substrate)
Next, the photocatalyst containing layer side substrate used in the present invention will be described. The photocatalyst-containing layer side substrate used in the present invention has at least a photocatalyst-containing layer and a substrate, and is usually formed by forming a thin-film photocatalyst-containing layer formed by a predetermined method on the substrate. is there. In addition, as the photocatalyst-containing layer side substrate, a substrate in which a photocatalyst-containing layer side light-shielding portion or primer layer formed in a pattern is formed can be used. Hereinafter, each structure of this photocatalyst containing layer side board | substrate is demonstrated.

(1) Photocatalyst-containing layer The photocatalyst-containing layer used in the present invention is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the characteristic change layer. Or a film formed of a single photocatalyst. The surface characteristics may be particularly lyophilic or lyophobic. In addition, when forming a characteristic change pattern on the characteristic change layer described later, when energy is irradiated from the photocatalyst containing layer side substrate side, the photocatalyst containing layer is a layer capable of transmitting an electron beam. It is preferable that

  In such a photocatalyst-containing layer, the action mechanism of a photocatalyst represented by titanium dioxide as described later is not necessarily clear, but a carrier generated by electron beam irradiation reacts directly with a nearby compound, Alternatively, it is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of the organic matter. In the present invention, this carrier is considered to act on the compound in the property change layer on the photocatalyst-containing layer.

Examples of the photocatalyst used in the present invention include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), which are known as photo semiconductors. Bismuth oxide (Bi ₂ O ₃ ) and iron oxide (Fe ₂ O ₃ ) can be mentioned, 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 more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst having a particle size of 20 nm or less.

  The photocatalyst-containing layer in the present invention may be formed by a photocatalyst alone as described above, or may be formed by mixing with a binder. In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.

  Examples of other methods for forming the photocatalyst-containing layer composed only of the photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum vapor 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, which can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.

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

  In the case of using a binder, it is preferable that the binder main skeleton has a high binding energy that is not decomposed by photoexcitation of the photocatalyst. For example, in the description of the wettability changing layer in the characteristic changing layer described later. Examples thereof include organopolysiloxanes described in detail.

  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. The coating solution can be formed by coating on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating 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, hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.

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

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

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

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

  At this time, the material constituting the substrate to be used is appropriately selected depending on the irradiation direction of the electron beam in the characteristic change pattern forming step to be described later, whether the obtained pattern forming body transmits the electron beam, and the like.

  That is, for example, in the case where a substrate that does not transmit an electron beam is used as the pattern forming body, the electron beam irradiation direction is necessarily from the photocatalyst containing layer side substrate side, and as shown in FIG. Must be disposed on the photocatalyst-containing layer side substrate 3 side and irradiated with an electron beam. As will be described later, the photocatalyst-containing layer side light-shielding portion is formed in a predetermined pattern on the photocatalyst-containing layer side substrate in advance, and the photocatalyst containing layer-side light-shielding portion is used to form the characteristic change pattern. It is necessary to irradiate an electron beam from the containing layer side substrate side. In such a case, it is necessary for the substrate to transmit an electron beam.

  On the other hand, if the substrate of the pattern forming body is, for example, a transparent resin film, it can be irradiated with an electron beam by placing a photomask on the pattern forming substrate side. is there. Further, as described above, when the light shielding portion is formed in the pattern forming body substrate, it is necessary to irradiate an electron beam from the pattern forming body substrate side. In such a case, the electron beam transparency of the substrate is not particularly required.

  The substrate used in the present invention may be a flexible substrate such as a resin film, or may be a non-flexible substrate such as a glass substrate. This is appropriately selected depending on the electron beam irradiation method in the characteristic change pattern forming step described later.

  Thus, the substrate used for the photocatalyst-containing layer side substrate in the present invention is not particularly limited in material, but in the present invention, the photocatalyst-containing layer side substrate is used repeatedly. A material having a predetermined strength and having a surface having good adhesion to the photocatalyst containing layer is preferably used.

  Specific examples include glass, ceramic, metal, and plastic.

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

(3) Photocatalyst containing layer side light-shielding part As the photocatalyst containing layer side light shielding part used for this invention, you may use what the photocatalyst containing layer side light shielding part formed in pattern shape was formed. By using the photocatalyst containing layer side substrate having the photocatalyst containing layer side light-shielding portion in this way, it is not necessary to use a photomask or perform drawing irradiation with a laser beam at the time of electron beam irradiation. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.

  Such a photocatalyst containing layer side light-shielding part having such a photocatalyst containing layer side light shielding part can be made into the following two embodiments depending on the formation position of the photocatalyst containing layer side light shielding part.

  For example, as shown in FIG. 2, a photocatalyst-containing layer side light-shielding portion 10 is formed on a substrate 1, and a photocatalyst-containing layer 2 is formed on the photocatalyst-containing layer side light-shielding portion 10 to form a photocatalyst-containing layer side substrate. It is an embodiment. The other is an embodiment in which, for example, as shown in FIG. 3, a photocatalyst containing layer 2 is formed on a substrate 1, and a photocatalyst containing layer side light shielding portion 10 is formed thereon to form a photocatalyst containing layer side substrate. .

  In any of the embodiments, the photocatalyst-containing layer-side light-shielding portion is arranged in the vicinity of the arrangement portion of the photocatalyst-containing layer and the characteristic change layer as compared with the case where a photomask is used. Therefore, it is possible to reduce the influence of scattering of the electron beam in, so that the pattern irradiation of the electron beam can be performed very accurately.

  Furthermore, in the embodiment in which the photocatalyst containing layer side light shielding part is formed on the photocatalyst containing layer, the film thickness of the photocatalyst containing layer side light shielding part is set when the photocatalyst containing layer and the characteristic change layer are arranged at predetermined positions. By keeping the width equal to the width of the gap, there is an advantage that the photocatalyst containing layer side light-shielding portion can be used as a spacer for making the gap constant.

  That is, when the photocatalyst containing layer and the characteristic change layer are arranged facing each other with a predetermined gap therebetween, the photocatalyst containing layer side light-shielding portion and the characteristic change layer are arranged in close contact with each other. The predetermined gap can be made accurate, and in this state, the characteristic change pattern can be accurately formed on the characteristic change layer by irradiating the photocatalyst-containing layer side substrate with an electron beam. It is.

  The method for forming such a photocatalyst-containing layer side light-shielding part is not particularly limited, and is appropriately selected according to the characteristics of the surface on which the photocatalyst-containing layer side light-shielding part is formed, the required shielding properties against electron beams, and the like. Used.

  For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.

  Alternatively, a method may be used in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder is formed in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.

  In the above description, the two positions of the photocatalyst containing layer side light shielding portion between the substrate and the photocatalyst containing layer and the surface of the photocatalyst containing layer have been described as the formation position of the photocatalyst containing layer side. It is also possible to adopt a mode in which the photocatalyst-containing layer side light shielding portion is formed on the surface that is not provided. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be preferably used when the characteristic change pattern is changed in a small lot.

(4) Primer layer Next, the primer layer used for the photocatalyst containing layer side substrate of the present invention is explained. In the present invention, when the photocatalyst-containing layer side light-shielding portion is formed in a pattern on the substrate as described above, and the photocatalyst-containing layer is formed on the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side substrate is used. A primer layer may be formed between the side light shielding part and the photocatalyst containing layer.

  The function and function of this primer layer are not always clear, but by forming a primer layer between the photocatalyst-containing layer side light-shielding part and the photocatalyst-containing layer, the primer layer is characterized by the characteristics of the layer that changes the characteristics of the photocatalyst. Impurities from the openings existing between the photocatalyst containing layer side light shielding part and the photocatalyst containing layer side light shielding part, which are factors that hinder the change, in particular, residues generated when patterning the photocatalyst containing layer side light shielding part, metal, metal It is considered that it has a function of preventing diffusion of impurities such as ions. Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.

  In the present invention, the primer layer prevents impurities existing in not only the photocatalyst containing layer side light shielding part but also the opening formed between the photocatalyst containing layer side light shielding parts from affecting the action of the photocatalyst. The primer layer is preferably formed over the entire surface of the photocatalyst containing layer side light shielding portion including the opening.

  FIG. 4 shows an example of the photocatalyst containing layer side substrate on which such a primer layer is formed. A primer layer 11 is formed on the surface of the substrate 1 on which the photocatalyst containing layer side light shielding portion 10 of the substrate 1 on which the photocatalyst containing layer side light shielding portion 10 is formed, and this primer layer 11. The photocatalyst containing layer 2 is formed on the surface of the film.

  The primer layer in the present invention is not particularly limited as long as the primer layer is formed so that the photocatalyst containing layer side light-shielding portion of the photocatalyst containing layer side substrate is not in contact with the photocatalyst containing layer.

The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of the amorphous silica is represented by the general formula SiX ₄ and X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, Silanol which is a hydrolyzate thereof or polysiloxane having an average molecular weight of 3000 or less is preferable.

  The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.

(Characteristic change pattern formation)
Next, formation of the characteristic change pattern will be described. In the formation of the characteristic change pattern of the present invention, the pattern is formed on the surface of the characteristic change layer by irradiating an electron beam from a predetermined direction after arranging the photocatalyst-containing layer and the characteristic change layer at a predetermined position. The process to perform is performed. Hereinafter, the formation of the characteristic change pattern will be described.

(1) Arrangement of Photocatalyst Containing Layer and Characteristic Change Layer In the characteristic change pattern forming step of the present invention, first, at a predetermined interval so that the photocatalyst acts between the photocatalyst containing layer and the characteristic change layer during electron beam irradiation. In the present invention, the photocatalyst-containing layer and the characteristic change layer are disposed with a gap of 200 μm or less, and then irradiated with an electron beam from a predetermined direction. At this time, the photocatalyst-containing layer and the characteristic change layer may be adhered to each other.

  In the present invention, the gap has a very good pattern accuracy, a high photocatalyst sensitivity, and therefore a good property change efficiency of the property change layer, 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 range of the gap is particularly effective for a substrate for a pattern forming body having a small area in which the gap can be controlled with high accuracy.

  On the other hand, when processing is performed on a substrate for a pattern forming body having a large area of, for example, 300 mm × 300 mm, the photocatalyst-containing layer side substrate and the pattern forming body substrate are not contacted and the fine gap as described above is formed between It is extremely difficult to form between the two. Therefore, when the pattern forming body 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 photocatalyst sensitivity and deterioration of efficiency of characteristic change. This is because there is an effect that unevenness does not occur in the characteristic change on the layer.

  Thus, when irradiating an electron beam to a relatively large area pattern formation substrate, the setting of the gap in the positioning device between the photocatalyst containing layer side substrate and the pattern formation substrate in the electron beam irradiation device is set, It is preferable to set within a range of 10 μm to 200 μm, particularly within a range of 25 μm to 75 μm. By setting the set value within such a range, the pattern accuracy is not significantly reduced and the sensitivity of the photocatalyst is not greatly deteriorated, and the photocatalyst-containing layer side substrate and the pattern forming body substrate are not in contact with each other. This is because they can be arranged.

  Thus, by disposing the photocatalyst-containing layer and the property change layer surface at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, when the interval between the photocatalyst containing layer and the characteristic change layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, there is a possibility that the characteristic change rate may be slowed. Absent. In addition, it is not preferable that the active oxygen species generated are difficult to reach the characteristic change layer, and in this case as well, the speed of the characteristic change may be reduced.

  In the present invention, such an arrangement state only needs to be maintained at least during the electron beam irradiation.

  An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst-containing layer and the characteristic change layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the property change layer. By having a pattern similar to the change pattern, a predetermined characteristic change pattern can be formed on the characteristic change layer.

  In the present invention, such a spacer may be formed as one member. However, for simplification of the process, as described in the column of the photocatalyst containing layer side substrate, the photocatalyst of the photocatalyst containing layer side substrate is used. It is preferable to form on the surface of the containing layer. In the above description of the photocatalyst-containing layer side substrate, the photocatalyst-containing layer side light shielding portion has been described. However, in the present invention, such a spacer protects the surface so that the photocatalytic action does not reach the surface of the property change layer. Therefore, it may be formed of a material that does not have a function of shielding the irradiated energy.

(2) Electron Beam Irradiation Next, the electron beam irradiation is performed on the facing portions while maintaining the above-described arrangement. In addition, the electron beam irradiation (exposure) in the present invention can change the characteristics of the surface of the property change layer by the photocatalyst-containing layer, and can change the properties of the surface of the property change layer by the action of the electron beam. It is a concept that includes irradiation of any electron beam that is possible.

  In general, such electron beam irradiation is performed by heating a cathode made of a tungsten filament in a high vacuum and accelerating the generated thermoelectrons at high speed by charging.

  Such an electron beam has a high energy, and by irradiating the above-described property change layer, it is possible to increase physical properties in a short time and to cut surface molecular chains. It is possible to carry out with efficiency.

  In addition, the electron beam can excite the photocatalyst contained in the above-described photocatalyst-containing layer, and the characteristics of the property change layer can be changed also by the action of the photocatalyst.

  Here, the electron beam irradiation direction in the present invention is a photocatalyst containing layer side light shielding part or a method for forming a characteristic change pattern such as whether a light shielding part is formed on the pattern forming substrate side, or a photocatalyst containing layer side substrate. Alternatively, it is determined depending on whether or not the pattern forming substrate can pass through the electron beam.

  That is, when the photocatalyst containing layer side light-shielding part is formed, it is necessary to irradiate the electron beam from the photocatalyst containing layer side substrate side, and in this case, the photocatalyst containing layer side substrate transmits the electron beam irradiated. It is necessary to let In this case, when the photocatalyst-containing layer side light-shielding part is formed on the photocatalyst-containing layer and this photocatalyst-containing layer side light-shielding part is used so as to function as a spacer as described above, the energy irradiation direction May be from the photocatalyst containing layer side substrate side or from the pattern forming body substrate side.

  On the other hand, when the light shielding part is formed on the pattern forming substrate side, it is necessary to irradiate energy from the pattern forming substrate side, and in this case, the electrons irradiated on the pattern forming substrate substrate The line needs to be transparent. In this case as well, when a light-shielding portion is formed on the characteristic change layer, and this light-shielding portion is used so as to function as a spacer as described above, the energy irradiation direction is also from the photocatalyst containing layer side substrate side. It may be from the pattern forming body substrate side.

  In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on which the photomask is arranged, that is, either the photocatalyst containing layer side substrate or the pattern forming body substrate needs to be transparent.

(3) Removal of photocatalyst containing layer side substrate When the energy irradiation as described above is completed, the photocatalyst containing layer side substrate is moved away from the arrangement position with the characteristic change layer, thereby changing the characteristic as shown in FIG. A characteristic change pattern 9 in which the characteristics of the layer 5 are changed is formed.

  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.

  Hereinafter, this embodiment will be described in more detail through examples.

<Example 1>
A photocatalyst inorganic coating solution (ST-K03 manufactured by Ishihara Sangyo Co., Ltd.) was applied on a mask having a chromium pattern formed on synthetic quartz glass, and then dried at 150 ° C. to form a photocatalyst-containing layer having a thickness of 0.01 μm.

  Next, the glass substrate was immersed in a composition in which 5 g of fluoroalkylsilane (TSL8233GE manufactured by Toshiba Silicone) and 1.5 g of 0.1N hydrochloric acid water were mixed, washed with IPA, dried at 150 ° C., and glass A wettability changing layer was obtained on the substrate. The contact angle of water on this surface was 105 °.

  Next, the photocatalyst-containing layer and the wettability changing layer are opposed to each other with a gap of 10 μm, and using an electron beam irradiation apparatus (manufactured by Nisshin High Voltage), an acceleration voltage of 175 KeV is applied from the photocatalyst-containing layer side substrate side. Dose 5 Mrad. The electron beam was irradiated under the conditions of

  As a result, the surface of the wettability changing layer irradiated with the electron beam by the photocatalytic action had a contact angle with water of 10 ° or less.

<Example 2>
A photocatalyst inorganic coating solution (ST-K03 manufactured by Ishihara Sangyo Co., Ltd.) was applied on a mask having a chromium pattern formed on synthetic quartz glass, and then dried at 150 ° C. to form a photocatalyst-containing layer having a thickness of 0.01 μm.

  Subsequently, 2 g of Iupilon Z400 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) mainly composed of polycarbonate was dissolved in 30 g of dichloromethane and 70 g of 112 trichloroethane to obtain a composition for a decomposition removal layer. This composition was applied onto a glass substrate with a spin coater and dried at 100 ° C. for 60 minutes to obtain a decomposition removal layer (thickness: 0.1 μm). The contact angle of water on this surface was 71 °.

  Next, the photocatalyst-containing layer and the decomposition removal layer are opposed to each other with a gap of 10 μm, and using an electron beam irradiation apparatus (manufactured by Nissin High Voltage), an acceleration voltage of 175 KeV and an irradiation dose from the photocatalyst-containing layer side substrate side. 5Mrad. The electron beam was irradiated under the conditions of

  As a result, the decomposition removal layer irradiated with the electron beam was decomposed and removed by the photocatalytic action to expose the glass substrate, and the contact angle with water became 10 ° or less.

DESCRIPTION OF SYMBOLS 1 ... Base | substrate 2 ... Photocatalyst containing layer 3 ... Photocatalyst containing layer side board | substrate 4 ... Base material 5 ... Characteristic change layer 6 ... Pattern formation body substrate 7 ... Photomask 8 ... Electron beam 9 ... Characteristic change pattern 10 ... Photocatalyst containing layer side Light shielding part 11… Primer layer

Claims (21)

  By the action of the photocatalyst-containing layer side substrate having the base, the photocatalyst-containing layer containing the photocatalyst formed on the base, the photocatalyst-containing layer side light-shielding portion formed on the photocatalyst-containing layer, and the photocatalyst in the photocatalyst-containing layer A pattern forming body substrate having a characteristic changing layer whose characteristics change is arranged with a gap so that the photocatalyst-containing layer and the characteristic changing layer are 200 μm or less, and then irradiated with an electron beam from a predetermined direction. Thereby, the characteristic change pattern in which the characteristic changed on the surface of the characteristic change layer is formed.   2. The method for producing a pattern forming body according to claim 1, wherein the photocatalyst containing layer side substrate side is irradiated with an electron beam.   The method for producing a pattern forming body according to claim 1, wherein the substrate for pattern forming body includes a base material and a characteristic change layer formed on the base material.   The said photocatalyst containing layer is a layer which consists of photocatalysts, The manufacturing method of the pattern formation body in any one of Claim 1 to 3 characterized by the above-mentioned.   The method for producing a pattern forming body according to claim 4, wherein the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method.   The said photocatalyst containing layer is a layer which has a photocatalyst and a binder, The manufacturing method of the pattern formation body in any one of Claim 1- Claim 3 characterized by the above-mentioned. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxide. The method for producing a pattern forming body according to any one of claims 1 to 6, wherein the pattern forming body is one or more substances selected from iron (Fe ₂ O ₃ ). Method for manufacturing a patterned member according to claim 7, wherein the photocatalyst is titanium oxide (TiO _2).   The distance between the photocatalyst-containing layer and the surface of the property change layer when the surface of the property change layer is irradiated with an electron beam is in a range of 0.2 μm to 10 μm. The manufacturing method of the pattern formation body in any one of Claims 8-8.   The method for producing a pattern forming body according to any one of claims 1 to 9, wherein the characteristic change layer is a layer not containing a photocatalyst.   11. The wettability changing layer according to claim 1, wherein the property changing layer is a wettability changing layer whose wettability is changed so that a contact angle with a liquid is lowered by an action of a photocatalyst accompanying irradiation of an electron beam. The manufacturing method of the pattern formation body in any one of the preceding claims.   The contact angle with the liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in the portion not irradiated with the electron beam and 9 ° or less in the portion irradiated with the electron beam. The manufacturing method of the pattern formation body of Claim 11 characterized by the above-mentioned.   The method for producing a pattern forming body according to claim 11, wherein the wettability changing layer is a layer containing an organopolysiloxane.   The method for producing a pattern forming body according to claim 13, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. 14. n is an integer from 0 to 3.) It is an organopolysiloxane which is one or more of the hydrolytic condensates or cohydrolytic condensates of the silicon compound represented by (13). Or the manufacturing method of the pattern formation body of Claim 14.   The method for producing a pattern forming body according to any one of claims 11 to 15, wherein the wettability changing layer has a self-supporting property.   The pattern formation according to any one of claims 1 to 10, wherein the characteristic change layer is a decomposition removal layer that is decomposed and removed by the action of a photocatalyst accompanying irradiation of an electron beam. Body manufacturing method.   18. The pattern forming body according to claim 17, wherein a contact angle of the liquid with respect to the decomposition / removal layer is different from a contact angle of the liquid with respect to the base material exposed when the decomposition / removal layer is decomposed and removed. Manufacturing method.   The method for producing a pattern forming body according to claim 17 or 18, wherein the decomposition / removal layer is any one of a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternating adsorption film.   The contact angle with the 40 mN / m liquid of the decomposition / removal layer is 10 ° or more, and 9 ° or less on the base material. The manufacturing method of the pattern formation body of description.   The said characteristic change layer is an adhesiveness change layer from which adhesiveness changes by the effect | action of the photocatalyst accompanying irradiation of an electron beam, The claim in any one of Claim 1-10 characterized by the above-mentioned. A manufacturing method of a pattern formation object.

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