TW200848448A - Photo-curable composition - Google Patents

Abstract

The invention provides a photo-curable composition which exhibits superior overall performance including photo-curable, adhesion, mold release property, residual film property, pattern shape, coating performance (I), coating performance (II) and etching suitability. The said photo-curable composition comprises (a) cationically polymerizable monomer, (b) photo-cationic polymerization initiator, and (c) 0.001 to 5 mass% of at least one surfactant selected from a fluorine-based surfactant, a silicone-based surfactant and a fluorine-silicone- based surfactant, and also (d) the content of an organic solvent is less than 1 mass%, (e) the content of a coloring material is less than 0.5 mass%, and more than 10 mass% of the said (a) cationically polymerizable monomer is a compound having oxetane ring.

Description

200848448 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a photocurable composition. [Prior Art] The nanoimprint method is a mold original that is developed in the field of optical disc manufacturing, and which utilizes a pattern of irregularities (generally called a mold). A technique in which a mold, a stamper, and a temperate are pressed against a photoresist to be mechanically deformed to precisely transfer a fine pattern. Because it is a kind of nano-processing technology that can be easily re-formed into a nano-structure to make it economical and at the same time reduce harmful wastes and emissions, it has been used in various fields in recent years. I look forward to it. The nanoimprint method mainly includes the case where the material to be processed is a thermoplastic resin (S. Chou et al.: Appl. Phys. Lett. Vol. 67, 114, 3 3 1 4 (1959)) And two methods using a photocurable composition (M. Colbun et al.: Proc. SPIE, Vol. 676, 7 8 (1999)). The thermal nanoimprint is a method in which a mold core is pressurized to a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is removed to transfer the fine structure to the resin on the substrate. This method is expected to be applied to various applications since it can be applied to various resin materials or glass materials. In addition, in the publication of U.S. Patent No. 5,7,72,90, and U.S. Patent No. 5,95,2,166, a nano-pressure using a thermoplastic resin to form a nano pattern at low cost has been disclosed. The method of printing. 200848448 On the other hand, when using a photonanoimprint method in which light is irradiated through a transparent mold to photoharden the photocurable composition, imprinting at room temperature can be achieved. . Recently, there have also been reports on a new development of a nano-casting method or a reverse imprinting method for manufacturing a three-dimensional laminated structure in which the advantages of the two are combined. There are roughly three application stages for this type of nanoimprinting. The first stage is a case where the formed shape itself has a function and can be applied as an element member or a structural member of various nano technologies, including various micro/nano optical elements or high-density recording media, optical films. The second stage is to integrally form the microstructure and the nanostructure, or to construct a laminated structure by simple inter-layer position alignment for supply in an A-TAS (Micro Total Analysis Systems) or biochip. The manufacturer. The third stage is suitable for the manufacture of high-density semiconductor integrated circuits or the manufacture of transistors for liquid crystal displays by replacing conventional lithography with high-precision position alignment and high integration. And concentrate on practical use has been very active. An example of application for manufacturing a high-density semiconductor integrated circuit is exemplified as a suitable example of the nanoimprint method. In recent years, progress has been made in the miniaturization and integration of semiconductor integrated circuit systems, and the pattern transfer technology required for microfabrication has been highly accurate in the development of photolithography devices. However, the processing method is close to the wavelength of the light source that is exposed to light, and the lithography technique is also close to its limit. Therefore, in order to further advance the miniaturization and high precision, it has evolved into an electron emission 200848448 line drawing device which uses a charged particle beam device instead of the photolithography technique. The use of pattern formation of electron rays has the disadvantage that it is different from the pattern-shaped exposure method using a light source such as an i-ray or a excimer laser, and the pattern is drawn successively. The more patterns are drawn, the more exposure is required (depicted Time to become more time-consuming. Therefore, with the degree of integration such as 256 trillion | Megahertz, 1 GHz (Gigahertz), and 4 GHz, the patterning time has also increased relatively, resulting in concerns about production degradation. Therefore, in order to speed up the electron beam drawing device, a mask of various shapes is combined and an electron beam is collectively irradiated, and a hybrid pattern irradiation method of a miscellaneous shape is developed. However, this method has a fine pattern, but in addition to having to enlarge the electron beam, it also causes a disadvantage that the position of the mask needs to be controlled with higher precision, resulting in an increase in the cost of the apparatus. In view of this, proposals have been made to disclose a nanoimprint lithography which is proposed as a technique for forming a pattern at a low cost. For example, Japanese Patent Publication No. 5,772,905, and U.S. Patent No. 5 discloses a nanoimprint technique in which a tantalum wafer is used as a stamper and has a fine structure of E or less. Further, a composition using a nano-composite which is applicable to the field of semiconductor microlithography is disclosed in Japanese Laid-Open Patent Publication No. 2005-527110. On the other hand, the manufacturing technology or durability of the micro-molecule, the manufacturing cost of the mold core, the peelability of the mold from the resin, the accuracy of alignment or alignment, the inspection technique, etc., are applied to the manufacture of semiconductor integrated circuits. The need for discussion, because of its summary, it is necessary to describe the pattern shape $ (MHz; the ground jump growth rate will be significantly extended to form a complex although the device can be deduced to equipment, etc., implemented in the United States, 5,259,926 P Forming the 25 bulletin, the embossed embossed uniform embossed light has begun to live in 200848448. However, the photoresist used in nanoimprint lithography, although also used in previous semiconductor microfabrication The photoresist needs to be compatible with the etching suitability of various substrates or the peeling suitability after uranium engraving, but it has not been sufficiently reviewed so far. Secondly, for liquid crystal displays (LCD: Liquid Crystal Display) or plasma display panels ( An application example of nanoimprint lithography for flat panel displays such as PDP: Plasma Display Panel) is described. As LCD or PDP substrates are large or tall The trend of refinement, in recent years, there is a kind of photo-nanoimprint lithography (photo-nanoimprint lithography) is a special attention. It is an inexpensive lithography that can be used to replace the film in the manufacture of thin film Conventional photolithography used in crystals (TFTs) or electrode plates. Therefore, it has evolved to develop a photocurable photoresist that can replace the etching photoresist used in conventional photolithography. The etching resist used is required to have high sensitivity, uniformity of coating film, and light-resistance, and it is required to have adhesion to various substrates, etching resistance, heat resistance, and the like. The uniformity of the coating film is also required to have the same characteristics as the uniformity of the coating film, the uniformity of the coating film thickness at the center portion and the peripheral portion of the substrate, or the uniformity of the size due to high resolution due to the enlargement of the substrate. The requirements for various parts such as film thickness and shape tend to be more stringent. So far, in the field of manufacturing liquid crystal display elements using small glass substrates, the photoresist coating method has been used to rotate after being dripped in the center. Method (Electronic Journal, No. 8, pp. 121-123 (2002) 200848448). A coating method in which the center is dripped and rotated, although excellent coating uniformity can be obtained, for example, a large substrate of 1 meter square. In this case, the amount of photoresist that is thrown away during the rotation (during spin coating) is increased, and the crack of the substrate caused by the high-speed rotation or the problem of ensuring the production interval time is caused. The coating performance of the method of rotating after centrifugation in the center is dependent on the rotation speed at the time of rotation and the amount of photoresist coating. If it is to be further applied to a large-scale fifth-generation substrate, it will not be sufficient on the market. A universal motor with the necessary acceleration, and if such a special motor is specifically ordered, it will cause a problem of an increase in component cost. Further, even if the substrate size or the device size has been increased in size, for example, the coating uniformity is ± 3%, the production interval is 60 to 70 seconds/piece, and the performance required in the coating step is hardly changed. It is difficult to respond to the requirements other than uniformity of coating by the method of rotating after the center is dripped and rotated. In view of such problems, a new photoresist coating method which can be applied to a fourth-generation substrate, particularly a large-sized substrate after the fifth-generation substrate, has been proposed to be a photoresist coating method by a nozzle type. The method for applying a photoresist by a discharge nozzle is a method in which a photoresist composition is applied to all coated surfaces of a substrate by relative movement of a discharge nozzle and a substrate. For example, it has been proposed to use a plurality of nozzle holes in a row. A method of discharging the photoresist composition into a strip-shaped discharge nozzle, such as a spout or a slit-shaped discharge port. Further, there has been proposed a method in which a photoresist composition is applied to all coated surfaces of a substrate by a spouting nozzle, and the substrate is rotated to adjust the film thickness. Therefore, if it is desired to replace the conventional photolithography resist with a nanoimprint composition for use in the field of liquid crystal display device manufacturing, it is important to apply uniformity to the substrate of 200848448. A positive-type photoresist used in the manufacture of a semiconductor integrated circuit or a liquid crystal display, or a photoresist for pigment dispersion used for manufacturing a color filter, fluorine-based and/or polyfluorene In the case of an oxygen-based (si 1 ic ο ne - based) surfactant, it is possible to solve the coating trace or the scaly pattern (drying unevenness of the photoresist film) which is generated when coating on a substrate. The method of the problem of poor coating is well known (Japanese Patent Laid-Open No. 7-23 0 1 65, Japanese Patent Laid-Open No. 2000-181 1 05 5, Japanese Invention Patent Open the 2nd 004-9424 1 bulletin). Further, in order to improve the abrasion resistance or coating property of a protective film such as a magnetic disk or a magnetic optical disk, a fluorine-based surfactant or a polyoxyn-based surfactant is added to a solvent-free photocurable composition. Japanese Patent Application Publication No. 2004-9424 No. 1, Japanese Patent Application Laid-Open No. Hei 4- No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. 9 3 1 Bulletin 92). In the same manner, a method of adding a nonionic fluorine-based surfactant to improve the ink discharge stability of the composition for inkjet is disclosed in Japanese Laid-Open Patent Publication No. 2005-8575. Further, Japanese Laid-Open Patent Publication No. 2000-166-103 discloses a hologram of a coating composition which is applied as a thick film by a brush, a pen, a bar coater or the like. When the embossing process is applied to the mold (h ο 1 〇gram), a surfactant containing at least 1% of the polymerizable unsaturated double bond is added, preferably 3% or more is added to improve the water of the cured film. An example of swelling. As described above, a technique of adding a surfactant to a protective film such as a positive-type resist, a color-dispersing photoresist for color filter manufacturing, or a magneto-optical disk to improve coatability is a well-known technique. Further, as shown in the above examples of the ink-jet or coating composition, the addition of a surfactant to a solvent-free photocurable resin, or a technique of adding a surfactant for improvement in characteristics for each application is also public. Everyone knows. However, a method for improving the substrate coating property of a low-viscosity photocurable nanoimprint resist composition which is not a coloring material such as a pigment or a dye, an organic solvent, and an essential component is not substantially contained, It has not been known to date. On the other hand, in the case of photon imprinting, it is necessary to improve the fluidity of the composition in the cavity of the mold recess, and to improve the mold release property of the mold and to improve the separation between the mold and the photoresist. Modularity, improving the adhesion between the photoresist and the substrate. However, it is difficult to improve fluidity, mold release, and adhesion as a whole. Further, if a photon imprinting photoresist containing an organic solvent is used, the solvent must be volatilized after coating. Therefore, in the case of using the composition containing the organic solvent, the safety of the worker or the like which is caused by the inhalation of the solvent or the like is disadvantageous. Therefore, development of a composition substantially free of organic solvents is strongly demanded. Further details on the technology of photon imprinting are given below. Photonic imprint lithography, generally taking a liquid photocurable composition on a substrate of germanium wafer, quartz, glass, film or other material such as ceramic material, metal, or polymer, and Coating with a film thickness of about several tens of nm to several m/m, and then pressing and pressing the mold having fine unevenness of a pattern size of about several tens of nm to several tens/zm from above, and being pressurized -11- 200848448 A method in which the light is irradiated to harden the composition, and the mold is removed from the coating film to obtain a transferred pattern. Therefore, in the case of photonographic lithography, at least one of the substrate or the mold is required to be transparent in order to facilitate the application of light irradiation. Usually, light is applied from the mold core side. Therefore, a large amount of the mold core material is an inorganic material such as quartz or sapphire which can transmit UV (ultraviolet) light or a light transmissive resin. The photo-nanoimprint method has the following advantages with respect to the thermal nanoimprint method: (1) no heating/cooling step is required, so that high yield can be expected, and (2) liquid composition is used. The material can be embossed under low pressure, (3) there is no dimensional change due to thermal expansion, (4) the mold core is transparent, so it is easy to align, and (5) after hardening, it can be obtained firmly. The main advantages of three-dimensional crosslinked bodies and the like. In particular, it is suitable for semiconductor microfabrication applications such as semiconductor fine processing applications requiring alignment accuracy or semiconductor microfabrication applications in the field of flat panel displays. In addition, the other characteristics of the photon imprinting method are: since the resolution is not dependent on the wavelength of the light source compared with the conventional photolithography, the stepper is not required in the microfabrication of the nanometer (stepper) Or an expensive device such as an electron beam drawing device. On the other hand, the photon imprinting method has a problem that the mold core and the resin are in contact because of the need to double the mold core, and there is concern about the durability or cost of the mold core. Also, in the photonic embossing lithography process, residual film is easily caused (the convex portion of the mold core is held down at the photocurable composition). The thinner the remaining layer, the more compact the structure can be formed by nanoimprinting, and therefore it is preferred. In addition, once the residual film is increased, it will affect the line width control during etching, -12-200848448 or easily cause etching residue. As described above, if the thermal and/or photon imprinting method is to be applied to imprint a nanometer-sized pattern on a large area, it is not only required to pressurize the uniformity of the pressure or the original (mold). Flatness also requires measures to control the photoresist that is pressed out. In the prior art of semiconductor technology, a small original plate can be used and a photoresist outflow portion can be provided outside the embossed portion because the field can be arbitrarily set to be used as an element. In addition, in the case of semiconductors, the embossed defective portion may be classified as a defective component and may not be used. However, for example, when applied to a hard disk or the like, it is used as a device in an all-round manner, and therefore it is necessary to take no As for special measures that cause embossing defects. The mold core used in photonic lithography can be manufactured from various materials such as metal, semiconductor, ceramic, SOG (Spin On Glass), or some plastics. For example, there has been proposed a soft polydimethyl siloxane mold having a fine structure as desired, which is disclosed in the pamphlet of WO 99/22849. In order to form a three-dimensional structure on one surface of the mold, various lithography methods can be used depending on the size of the structure and the measures for its decomposition energy. Electron beam and X-ray ray are commonly used for structural sizes of less than 300 nm. Direct laser exposure and UV lithography are used for large structures. Regarding the photon imprinting method, the peeling property of the mold core and the photocurable composition is an important factor, and therefore, regarding the surface treatment of the mold core or the mold core, specifically, until now, it has been attempted to use the hydrogenation halve A silsesquioxane hydride or a fluorinated B-acrylonitrile co-polymer is used to solve the adhesion problem. -13- 200848448 The photocurable resin for photon imprint lithography plus a photocurable resin suitable for nanoimprinting' is roughly classified into a radical polymerization type and an ion polymerization type by a reaction mechanism, or . Although any composition can also be used as an imprinting application, the material is selected in a wide range of radical polymerization types (F· SPIE Microlithography Conference » 5 3 74, 2 3 2 ). As the radical polymerization type, a monomer having a radically polymerizable or (meth)acryl group or an oligomer-containing polymer and a photopolymerizable product are generally used. Therefore, when the light is irradiated, the photopolymerization initiator is subjected to chain polymerization by attacking the vinyl group to form a difunctional or higher polyfunctional monomer or oligomer as a crosslinkable structure. In DJ Resnick et al.: Technol. B, vol. 21, No. 6, pp. 2, 624 (there is a composition that can be imprinted at low pressure and room temperature by using low viscosity UV hardenability). The characteristics of the materials used in photo-imprint lithography are as follows. Although the required characteristics of the materials are different depending on the application, the requirements of the different step characteristics are common. For example, the latest photoresist material manual The main requirements of the first, first, third, and fourth pages (published by the newspaper) are coating properties, low viscosity (< 5 mPa·s), mold release, low hardening shrinkage, etc. Especially for Low-pressure imprinting is required to reduce the residual film rate. It is known that a low-viscosity material is strongly required. On the other hand, if the root example specifies the required characteristics, for example, the optical member is described. It is generally used in the group of vinyl initiators produced by Xu et al.: (2004). If it is a component, then the monomer in J. Vac. S ci. 2003) As follows, but for, revealed in "2005 , feeling: plate adhesion, ф rate, speed hardening: the use: according to the use of the refractive index, light-14-200848448 transmission, etc., for etching photoresist resistance to etching or reduce residual film thickness How to control these required characteristics to maintain the flatness of each characteristic is the key to the design. At least for process materials and permanent films, the characteristics are very different, so the material must be made according to the process or use. A material suitable for use in photon nanoimprint lithography as described above, "Handbook of Latest Photoresist Materials", pages 1, 103 to 104 (published by the Intelligence Agency, 2005), has disclosed a type having about 60 mPa s °C) Viscosity photohardenable material, and is well known. The same in CMC Publishing: "Development and Application of Nanoimprint", page 159 to (2006), reveals a mold release property based on monomethacrylate with a viscosity of 14.4 mPa · s. Fluorine-containing sensibility 〇 As described above, regarding the composition used for anodic embossing, although the viscosity-related requirements are shown, there have been no report design guidelines for materials suitable for various uses until now. . An example of a photohardenable tree that has hitherto been suitable for photon imprint lithography is explained below. In Japanese Laid-Open Patent Publication No. 2004-59820, Japanese Laid-Open Patent Publication No. 2004-5 9822, a isocyanate-based polymer curable resin for producing a full-image or diffraction grating is disclosed. An example of grain processing. Further, in Japanese Patent Publication No. WO 04/1 1 0 8 5, a photocurable composition for imprinting containing a polymer, a photopolymerizer, and a viscosity adjuster is disclosed. In the Japanese Patent Laid-Open Publication No. 2000-119-82, it is disclosed that in order to improve the mold release property of the mold core, a material such as a fluorine-containing curable material is used. Year, (25 ground, 160 component resin has been revealed that the publication of the bullet of the grease makes the light of the first case -15- 200848448 into a method. In N. Sakai et al.: J. Photopolymer Sci· Technol·, In Volume 18, No. 4, 5 3 1 (2005), it is revealed that (1) the δ-type acrylic acid monomer (acry 1 m ο η 〇mer ), ( 2 ) A photocurable radical polymerizable composition of a functional acrylic monomer, (3) a functional acrylic monomer, and a photopolymerization initiator. Further, in N. Sakai et al.: J. Photopolymer Sci. Technol., In Volume 18, page 4, page 1 (r: 2005), it is revealed that it will contain an alicyclic photocurable alicyclic epoxy compound, a novolak epoxy compound, an inorganic/organic hybrid compound, and a photoacid generator. (photo-acid generator) photocationic polymerizable composition, etc., suitable for nanoimprint lithography, and Examples of heat stability or mold stripping properties. In M. Stew Art et al.: MRS Bulletin, Vol. 30, No. 12, page 947 (205), one reveals a (1) functional group. An acrylic monomer, (2) a functional acrylic acid-like monomer, and a photocurable composition containing a polysiloxane (siiicone) (a monofunctional acrylic monomer and a photopolymerization initiator) as an optical curing resin and Measures such as the peelability of the mold core, the film shrinkage after hardening, and the low sensitivity caused by the photopolymerization in the presence of oxygen. In T. Beiley et al.: J. Vac. Sci. Technol., B18 (6), 3, 5 72 (2000), discloses that a photocurable composition containing a monofunctional acrylic monomer, a fluorene-containing monofunctional monomer, and a photopolymerization initiator is formed on a sand substrate (silicon) On the substrate, and using a surface-treated mold, it can reduce defects after molding by photo-imprint lithography. • 16- 200848448 in B. Vratzov et al. J. Vac. Sci. Technol , B21 (6), 2, 760 (2003), reveals that one will contain polyoxyl A photocurable composition of a body, a trifunctional acrylic monomer, and a photopolymerization initiator, which is formed on a ruthenium substrate and has a superior high resolution and uniformity of coating prepared by a SiO 2 mold. . In EKKim et al.: J. Vac. Sci. Technol, B22(l), p. 131 (2004), a cationically polymerizable composition comprising a combination of a specific vinyl ether compound and a photoacid generator is disclosed. An example of a 50 nm pattern size is formed. Although it is characterized by low viscosity and fast hardening speed, it is noted that the tearing property of the template is the technical problem. However, as in N. Sakai et al.: J. Photopolymer Sci. Technol., Vol. 18, No. 4, p. 4, 531 (2005); M. Stewart et al.: MRS Bulletin, Volume 30, Issue 12 , p. 947 (2005); T. Beiley et al.: J. Vac. Sci. Technol., B18 (6), p. 3, 572 (2000)

Sci. Technol., B21 (6), 2, 7 6 0 (2003); Ε·K. Kim et al.: J. Vac. Sci. Technol·, B22(l), p. 131 (2004), various photohardenable resins which have been coated with different functional acrylic monomers, acrylic polymers, and vinyl ether compounds for photon imprint lithography have been disclosed. The material design of the preferred type of composition, the optimum monomer type, the combination of monomers, the optimum viscosity of the monomer or photoresist, the solution properties of the preferred photoresist, and the improvement of the coating properties of the photoresist The teaching guidelines are not revealed at all. Therefore, in order to make the composition widely applicable to the preferred composition required for photonic lithography, it is still unclear until now, so the current situation is absolutely There is no proposal for a satisfactory photonic embossed photoresist composition. The application of the etching photoresist for substrate processing is described in detail below. Etching photoresist is not an element that has to be left as it is to maintain its original state, but merely a simple copy of a semiconductor or transistor circuit pattern. Therefore, if a circuit pattern is to be produced, it is necessary to transfer the photoresist patterns on the respective layers including the elements. The method of transferring the pattern is carried out by an uranium engraving step of selectively removing the uncovered portion of the photoresist. For example, in the manufacture of an electrode plate of a TFT array substrate or a PDP, an etching resist is applied onto a conductive substrate or an insulating substrate sputtered on a glass or a transparent plastic substrate, and the film of each layer is dried, The steps of pattern exposure, development, etching, and photoresist stripping are performed. Most of the previous etch photoresists used a positive photoresist. In particular, an alkali-soluble phenol novolac resin and a 1,2-quinonediazide compound are used as the main component of the photoresist or (poly)hydroxybenzene. Ethylene is a chemically amplified photoresist of a polymer, has high etching resistance, and is easily peeled off, and thus has been widely used for etching photoresist of a semiconductor or a TFT transistor, and has accumulated a lot of knowledge. The etching method can be divided into a wet etching method using various liquid engraving agents, and an ion or a radical (active species) generated by decomposing a gas in a decompressing device to vaporize the film on the substrate. In addition to the dry etching method. The etching process is an important step that greatly affects the design accuracy of the component, the transistor characteristics, the production yield, and the cost. The etching photoresist must be a material that can be applied to any of dry etching and wet etching. - 200848448 Process suitability. If the composition used in photo-imprint lithography is to be applied to the field of photoresist used in such prior lithography, although the same etching resistance as the previous photoresist is required, it is not fully reviewed. Therefore, various problems are often caused in the etching step. The main technical problems of etching photoresist include improving the dimensional accuracy of the pattern, improving the taper processing control (improving the undercut shape), improving the etching uniformity on large substrates, and improving The uranium engraving selectivity of the underlayer, the improvement of the etching treatment speed, the etchability of the multilayer film, the safety of the waste liquid, the exhaust gas, and the like, and the improvement of many defects in the film (particles, residues) after etching, and the like. When the photocurable composition for photon nanoimprinting is used as a etch resist, it is important to be the same as the previous positive photoresist:

(1) The suitability of the etchant and the etching gas selected according to the film type I (2 ) is such that the undercut is not imparted with the adhesion of the pattern and the etched substrate; (3) to improve the pattern before and after etching The dimensional controllability imparts wettability to the etchant and photoresist. However, the nanoimprinted photocurable composition is derived from items (1) to (3) as described above, plus the following (4), (5), and (6) items. Considering that its technical difficulty will become higher. (4) If the photoresist film is hydrophobic when it is improved in peeling property from the mold core, it will cause deterioration of the wettability of the etching liquid and the photoresist, making it easy to produce etching residues; (5) Photocuring property The composition is difficult to peel off because it uses a three-dimensional network structure ' -19- 200848448 compared with the positive type photoresist. Moreover, if the mesh structure is firmer, although the etching resistance is improved, the etching resistance is improved. Peeling will be a more difficult problem; (6) Compared with the previous photolithography, the photon imprinting lithography is easy to remove the residue after being peeled off, and it is easy to generate residue after etching. Problems, etc. Regarding the photocurable composition for nanoimprinting, although various materials have been disclosed, it has not been disclosed so far that any step in the photolithography step, the uranium engraving step, and the stripping step of the nanoimprinting is also suitable for use. Design guidelines for the design of embossed materials or materials. Further, the photocurable composition of the composition for inkjet or the protective film for magneto-optical disc has hitherto been known, and although the photolithography step has a common part in terms of materials, there is no engraving step or The stripping step, which is quite different from the etching photoresist. Therefore, when the photocurable resin to be used for such applications is used as an etching resist as it is, the etching step or the peeling step is likely to cause a problem. Next, a description will be given of a permanent film to which photolithography is applied. The permanent film system can be directly left on a member such as a semiconductor element, a recording medium, or a flat panel display panel, unlike the etching resist as described above. For example, a transparent protective film material for a color filter used for a liquid crystal panel has hitherto used light such as a bismuth oxysulfide molecule, a polyoxyl ray, an epoxy resin, or an acrylic acid resin. A step of forming a protective film by a step of a curable resin or a thermosetting resin (Japanese Laid-Open Patent Publication No. Hei 3 - 1 2 6 9 0). In the formation of a protective film using photolithography, the uniformity of the coating film, the substrate adhesion, the heat resistance, and the like are required in the same manner as the etching resist. In addition, it is required to have high light transmittance, flattening characteristics, solvent resistance, chemical resistance, light resistance, heat and humidity resistance, pressure resistance, and toughness different from the etching resistance of -20-200848448 as described above. The permanent film of sex should have a wide range of characteristics. However, to date, nothing has been disclosed for the preferred composition of the photohardenable composition required to form the transparent protective film used in the nanoimprint method. A gap control material for a liquid crystal color filter is also a permanent film. Conventionally, a photocurable composition composed of a resin, a photopolymerizable monomer, and an initiator has been widely used (Japanese Patent Laid-Open No. 2006) -25 8 8 Communiqué No. 69). The gap control material is required to have high mechanical properties, high hardenability, developability, pattern accuracy, adhesion, and the like for external pressure, but it has heretofore been used for forming a nanoimprint method. The preferred composition of the photohardenable composition required for the gap control material has not been disclosed. SUMMARY OF THE INVENTION [Technical Problem to be Solved by the Invention] The present invention has been made in view of the above-described circumstances to provide a novel photocurable composition having excellent photocurability. In particular, it is intended to provide a curable composition for photon imprint lithography. In particular, it is an object of providing a composition having excellent photocurability, adhesion, mold release property, residual film property, pattern shape, coating property (I), coating property (II), and etching suitability as a whole. Further, when a permanent film such as a protective film or a gap control material is provided, the composition having a superior residual film ratio, light transmittance, and solvent resistance as a whole is intended for the purpose of the composition. [Technical method for solving the problem] Under the technical problems as described above, the inventors of the present invention have focused on the results of the begging and found that the technical problems can be solved by the following methods. (1) A photocurable composition comprising (a) a cationically polymerizable monomer, (b) a photocationic polymerization initiator, and (c) from 0.001 to 5% by mass of a fluorine-based surfactant, and a poly At least one of a rhodium-based surfactant and a fluorine/polyoxyn surfactant; (d) the content of the organic solvent is 1% by mass or less, and (e) the content of the color material is 〇·5% by mass or less, 1% by mass or more of the (a) cationically polymerizable monomer is a compound having an oxetane ring. (2) The photocurable composition according to Item (1), which contains the (a) cationically polymerizable monomer in a range of from 50 to 99% by mass. (3) The photocurable composition according to Item (1) or (2), wherein the (a) cationically polymerizable monomer is a vinyl ether compound. (4) The photocurable composition according to any one of (1) to (3) wherein the (a) cationically polymerizable monomer is a compound containing an oxirane ring . (5) The photocurable composition according to any one of (1) to (4) further comprising an antioxidant. (6) The photocurable composition according to any one of (1) to (5), wherein the photocurable composition is used to: a step of coating a photocurable composition; and a light transmissive mold is imprinted on a photoresist layer on the substrate to deform the photo-curable composition of the -22-200848448; the light is irradiated by the back surface of the mold core or the back surface of the substrate to form a pattern that can be fitted into the desired pattern. And a pattern forming method of the step of desorbing the light transmissive mold core by the coating film. (7) The photocurable composition according to any one of (1) to (5), wherein the photocurable composition is applied to: a step of coating a photocurable composition, and embossing the light transmissive mold a step of deforming the photocurable composition on the substrate, and a step of deforming the photocurable composition from the back surface of the mold or the back surface of the substrate to form a photoresist pattern capable of being fitted into a desired pattern. a step of desorbing the light-transmissive mold core from the coating film; a step of etching the substrate as the mask with the photocurable composition; and a photoresist pattern forming method of the step of etching the photocurable composition and then peeling off. [Effect of the Invention] According to the present invention, when used as an etching resist, it is possible to obtain excellent photocurability, adhesion, mold release property, residual film property, pattern shape, and coating property as a whole (I). ), coating (II) and composition of etching suitability. Further, when it is used as a permanent film, it is possible to obtain a composition having excellent residual film ratio, light transmittance, and solvent resistance as a whole. [Embodiment] [Best Embodiment of the Invention] Hereinafter, the contents of the present invention will be described in detail. In addition, in the case of this case, the meaning of "to" in the range of numbers means that the number listed above and below is used as the lower limit and the upper limit. -23- 200848448 The present invention will be described in detail below. The monomer of the present invention is distinguished from an oligomer (oligomer) or a polymer, and means a compound having a weight average molecular weight of 1, 〇〇〇 or less. In the present specification, a functional group means a group which participates in polymerization. Further, the term "nanoimprint" as used in the present invention means a pattern transfer of a size from about / / m to several tens of nm. The photocurable composition of the present invention can be widely used for production, for example, before light curing, high light transmittance, excellent formation of fine concavo-convex patterns, coating suitability, and other processing suitability, and at the same time, after hardening , sensitivity (speed hardenability), resolution, line-edge roughness, film strength, peelability with mold core, residual film properties, etching resistance, low hardening shrinkage, substrate adhesion or Other items are light nanoimprint lithography which has superior coating properties as a whole. That is, when the photocurable composition of the present invention is used in photonic lithography, it is: (1) the photocurable composition can be easily obtained because of excellent solution fluidity at room temperature. The ground flows into the cavity of the mold cavity, so that the atmosphere is not easily entrained, so that the bubble defects are not caused, and the residue is not easily left in any of the convex portion and the concave portion of the mold after photohardening; (2) due to hardening The cured film has superior mechanical properties, superior adhesion between the coating film and the substrate, and superior release property of the coating film and the mold core. When the mold core is removed, the pattern is not collapsed or coated. The surface of the film is drawn to cause the surface to become rough. Therefore, the excellent pattern can be formed from -24 to 200848448. In addition, it is also suitable as a permanent film because of its superior mechanical properties. (3) The volume shrinkage after photohardening is small. It has excellent transfer characteristics of the mold, so that the correct patterning property of the fine pattern can be achieved; (4) It is suitable for coating of large substrates due to superior coating uniformity. (5) High productivity due to high photohardening speed of the film; (6) It is suitable for use as a semiconductor device or a transistor due to its excellent etching processing accuracy and excellent etching resistance. Etching photoresist for substrate processing; (7) It can be used as an etching photoresist because it has superior photoresist peeling resistance after etching, and therefore can be used as an etching photoresist; and (8) It is suitable as a permanent film because of high light transmittance. The point of view of the ; is the overall superior characteristics. For example, the composition of the present invention is suitable for use in microfabrication of a thin film transistor such as a semiconducting bulk circuit or a liquid crystal display, a protective film for a liquid crystal color filter, and a gap control material. In addition, it can also be widely applied to manufacturing magnetic recording media such as partition walls for plasma display panels, flat screens, MEMS (Micro Electro Mechanical Systems), sensor components, optical disks, high-density storage disks, and the like. An optical member such as a diffraction grating or a relief hologram, a nano device, an optical device, an optical film or a polarizing element, an organic transistor, a microlens array, an immunoassay wafer, a DNA separation wafer, Microreactor, nano-biological device, light wave -25-200848448 lead, optical filter, photonic liquid crystal, etc. (a) Cationic polymerizable monomer The cationically polymerizable monomer used in the present invention will be described. The photocurable composition of the present invention contains a cationically polymerizable monomer, preferably containing a ratio of 50 to 99% by mass of the photocurable composition, more preferably 80 to 96% by mass. Further, the photocurable composition of the present invention is among the (a) cationically polymerizable f monomers, and 10% by mass thereof is a compound having an oxetane ring, preferably from 1 〇 to 1 0 0 The mass% is a compound having an oxetane ring, more preferably having a mass of 15 to 95. / oxirane ring compound. The reason why the photocationic polymerizable monomer has excellent photocurability is because the polymerization reaction is characterized by cation polymerization which is not inhibited by oxygen in the air. In the case of radical polymerization, the active species of the polymerization reaction are carbon radicals, which have the disadvantage of being easily reacted with oxygen to inactivate the loss of polymerization activity. Therefore, when the reaction is carried out in the atmosphere, there is a possibility that the sensitivity is greatly lowered. In order to suppress this problem, it is necessary to take measures such as circulating nitrogen gas to suppress the contact with oxygen as much as possible, but it is difficult to completely eliminate it technically. On the other hand, in the case of cationic polymerization, the cation is responsible for the polymerization activity, and since it is inactive for oxygen, high photopolymerization sensitivity can be obtained. In the photocurable composition of the present invention, the cationically polymerizable monomer is a compound having an oxetane ring of 1% by mass or more. If the photocationic polymerizable monomer is a compound having an oxetane ring, it is known that when used in photonic lithography, it is printed on a mold core, and the photohardening is performed. In terms of properties and adhesion, it is a particularly advantageous compound having an oxetane ring and thus has excellent moldability, photocurability, and adhesion because it has a polymerization reaction. The reason is that the volume change is small and the reactivity is high. That is, in the case of radical polymerization, when a polymerization reaction is carried out, a new carbon-carbon bond is formed in the fraction to narrow the intermolecular distance, and the density of the entire molecule is reduced. On the other hand, in the case of cationic ring-opening polymerization, the bond cleavage (molecular expansion into a chain) in the ring-opening reaction is simultaneously performed at the molecular %, : new bond formation (intermolecular distance reduction), and thus The overall density of the molecules before and after should hardly change. As a result, the mold transfer property and the photocurability are excellent, and the fine pattern can be accurately formed. The adhesion to the substrate is also the same because the volume change after the polymerization is small and the deformation is not caused after the curing, by using a compound having an oxetane ring, thereby A composition having excellent photocurability and adhesion. Further, (it is understood that since the compound having an oxetane ring as a whole has superior light transmittance, heat resistance, and mechanical properties, it is also suitable for use as a permanent film. A compound of a butane ring is suitable, for example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2001-220526, Japanese Patent Publication No. 2001-310937, Japanese Invention Japanese Patent Laid-Open No. 341217, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. On the contrary, it is the case of the case. If it is the case, it can be obtained as a result of the ί, 曰i Lit 2003 - 丨 [ [Ming -27-200848448 Li Tekai No. 200 5 - 1 943 79 a compound having an oxetane ring. The compound having an oxetane ring which can be used in the present invention is preferably a compound having 1 to 4 oxetane rings in its structure, wherein , the viscosity of the photohardenable composition In view of the above, it is preferred to use a compound having one or two oxetane rings. By using the compound 'described above, the viscosity of the photocurable composition can be easily maintained in operation. In the range of good performance, and when used in photo-imprint lithography, the uniformity of coating to the substrate, high adhesion to the mold, and good transfer characteristics of the mold can be obtained. Preferred examples of the compound having two oxetane rings include: a compound represented by the following formulas (1) to (3).

General formula (2) general formula (3)

(3) In the general formula (1) g (3) to 6 substituted or not, 'Ral is a hydrogen atom, and the number of carbon atoms is substituted alkyl (if there is a substituent, then -28- 1 200848448 The substituted or unsubstituted fluoroalkyl group, allyl group, aryl group, furyl group or thienyl group having the carbon atom number of the substituent, the same applies hereinafter. If there are 2 Ral in them, then they may be identical or different. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group and the like, and a preferred fluoroalkyl group is one in which one or more of the hydrogen atoms of the alkyl group are substituted by a fluorine atom. (. ' In the general formulae (1) to (3), Ra2 represents a substituted or unsubstituted alkyl group having from 1 to 6 carbon atoms, and a substituted or unsubstituted carbon number of 7 to 15 a substituted aralkyl group, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, an aryl group, a substituted or unsubstituted aryl group having 2 to 6 carbon atoms, and 2 carbon atoms a substituted or unsubstituted fluorenyloxycarbonyl group having 6 or a substituted or unsubstituted amino carbyl group having 2 to 9 carbon atoms. Examples of the "alkyl group" include methyl group and ethyl group. , propyl, butyl, pentyl, 2-ethylhexyl, cyclohexyl, phenoxyethyl; ί - examples of "aralkyl" include: benzyl, alpha-methylbenzyl, 1 -naphthylmethyl, 2-naphthylmethyl, 1-mercaptomethyl, 9-fluorenylmethyl, 4-fluorobenzyl, 2-methoxybenzyl, phenethyl; "alkenyl" Examples include: vinyl, b propylene, 2-methyl-1-propenyl, benzyl-1-propenyl, 1-butenyl, 2-phenylvinyl; examples of "aryl" include: Phenyl, 1-naphthyl, 2-enyl, 9-phenanthryl. An example of "mercapto" is Examples include acetamino group, propyl fluorenyl group, butyl fluorenyl group, pentamidine group, and cyclohexylcarbonyl group; examples of "alkoxycarbonyl group" include: methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxy group Examples of "amines" include: Ν·ethylamine methyl thiol, N -29- 200848448 propylamine methyl sulfhydryl, N-butylamine carbhydryl, N-pentylamine A Mercapto, N,N-dimethylaminecarbamyl. In the general formulae (1) to (3), Ra3 represents a chain or branched alkyl, chain or branched poly(alkylene) An oxy) group, a chain or a branched hydrocarbon group, a carbonyl group or a carbonyl group-containing alkyl group, a carboxyl group-containing alkyl group, an amine group containing an indenyl group, or a group represented by the following formula:

Ra6 R37 Ra6

Ra6 f^a7 ; a6 Examples of the "alkylene group" include, for example, an extended ethyl group, a propyl group, and a butyl group; and examples of the "poly(alkyloxy) group" include: An oxy) group, a poly(propoxy) group, and the like. Examples of the "hydrocarbyl group" include a propyl group, a methyl group, a propyl group, and a butyl group. When Ra3 is a polybasic group as described above, then Ra4 is a substituted or unsubstituted alkyl group representing a hydrogen atom, having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number of 1 to 4. An alkoxy group, a halogen atom, a nitro group, a cyano group, a thiol group, a lower alkylcarboxy group (for example, a carbon number of 1 to 4), a carboxyl group, or an amine carbenyl group.

Ra5 represents an oxygen atom, a sulfur atom, a methylene group, -NH-, - s〇-, -S02-, a C(CF3)2-, or -c(CH3)2-.

Ra is a hospital or aryl group having 1 to 4 carbon atoms, and η is an integer of 〇 to 2,000 (preferably an integer of 〇 to 500), and each of Ra6 is -30-200848448 is completely the same Or different. Ra7 is a valence group having a carbon number of 1 to an alkyl group, an aryl group or a structure represented by the following formula, and each of $ Ra7 may be identical or different. A8 na8 {and-〇)^如一 Ra8

Ra8 Ra8 In the above formula, Ra8 is an alkyl group having 1 to 4 carbon atoms, or an aryl group, and the same may be the same or different, and m is an integer of 0 to 100. The compound having 3 to 4 oxetane rings is a compound represented by the formula (4) as shown by $ /1 . General formula (4)

In the formula (4), Ral is synonymous with the one in the formula (1) as described above. The preferred range is also synonymous. Further, examples of the Ra9 of the multivalent linking group include, for example, a branched alkyl group having a carbon atom number of 1 to 12 represented by a group represented by A to C below, as represented by D below. A branched poly(alkyleneoxy) group such as a group or a branched polydecyloxy group such as a group represented by the following E. j is 3 or 4. Each Ral can be identical or different. -31- 200848448 ch2— A Ra10-C-CH2— , CH 2 — > n 2 B —CHf C-CH 2 — , CH 2 —

CH2~{〇CH2CH2) 十-ch2ch3 C H2~^OC h2c h2) ch3 ch3 ch3 E-CH2—Cj;H—CH2—Ping Yi Yi Yining i-CH2-〒 H-CH2-~CH2 ch3 CH3 CH2- In A as described above, RalG represents a methyl group, an ethyl group or a propyl group. Further, in D as described above, p is an integer from 1 to 10, and the number of three p's may be identical or different. Further, the other mode of the compound having an oxetane ring which is suitable for use in the present invention is a compound represented by the formula (5) which has an oxetane ring in a side chain as shown below. General formula (5 ) —Ο—Si-0—Ra11 (CH2)3

In the general formula (5), Ral and Ra8 are the same as those in the above formula, and when two or more are present, respectively, they may be identical or different. Ra 11 is a substituted or unsubstituted alkyl or trialkylsulfanyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, and is an integer of 1 to 4. -32- 200848448 "Compound having one oxetane ring in the molecule" includes, for example, 3-ethyl-3-hydroxymethyloxetane, 3-(methallyloxy) Methyl-3-ethyloxetane, (3-ethyl-3-oxocyclomethoxy)methylbenzene, 4-fluoro-[b (3-ethyloxetine) Methyl]benzene, 4-methoxy-[Bu(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [Bu (3-ethyl-3-oxetane) Alkyl phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanyl) ether, isobornyloxyethyl (3-ethyl-3-oxetane) Ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, hexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl Diglycol 3-ethyl-3-oxetanylmethyl)ether, dicyclopentadiene (3-ethoxycyclobutanemethyl)ether, dicyclopentenyloxyethyl ( 3-ethoxybutanylmethyl)ether, dicyclopentenyl (3-ethyl-3-oxaxymethyl)ether, tetrahydrofuranyl (3-ethyl-3-oxetane) Alkyl)ether, tetrabromobenzene (3-ethyl-3-oxetanylmethyl)ether, bromophenoxyethyl (3-ethyl-3-oxetanylmethyl)ether, tribasic (3-B) 3-oxobutanylmethyl)ether, 2-tribromophenoxy(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl (3-3 -oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxobutanylmethyl)ether, butoxyethyl (3-ethyl-3-oxocycle) Dingshen), ether, pentachlorophenyl (3-ethyl-3-oxetanyl) methyl bromide (3-ethyl-3-oxetanylmethyl) ether, Borneyl (yl-3-oxetanylmethyl)ether, 3-(4-bromobutoxymethyl)oxybutane, benzoic acid (3-methyloxetane- 3-yl) a case is a group) butane alkylmethyl alkoxy group methyl 2-ethanol (yl-3-yl-3: cyclobutylmethyl 2 · tetrabromophenethyl ethyl - heterocyclic A, five Examples of the "compound having two or more oxetane rings in the molecule" include, for example, 3,7-bis(3-oxetane) Base-5-oxa-decane 3,3,-(1,3-(2-methylene)propanediylbis(oxymethylene))bis(3-ethyloxetane), :l,4-bis[( 3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl] Benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl], 1,3-bis[(3-ethyl-3-oxocyclobutane) Mercaptomethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxo Heterocyclic butanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetan) Methyl)ether, tricyclic ketone dikis dimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane ginseng (3-ethyl-3-oxo Heterocyclic butanemethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxyl) Heterocyclic butane methoxy) hexane, neopentyl alcohol ginseng (3-ethyl-3-oxetanylmethyl) ether, Ethyl pentaerythritol (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dioxane Tetraol (3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol (3-ethyl-3-oxetanylmethyl)ether, dioxane Tetrapropanol (3_ethyl-3-oxetanylmethyl)ether, caprolactone modified dipentaerythritol tert (3_ethyl-3-oxetanylmethyl) Ether, caprolactone modified dipentaerythritol (3-ethyl-3-oxetanylmethyl) ether, bistrimethyl methacrylate (3-ethyl-3- Oxetanemethyl)ether, EO (ethylene oxide) modified -34- 200848448 ^ bisphenol A bis (3_ethyl _ 3 - oxetane) methyl ether, 1 & quot 〇(propylene oxide) modified bisphenol A bis(3_ethyl-3-oxetanyl methyl)ether, EO (ethylene oxide) modified hydrogenated bisphenol A double (3 _Ethyl_3-oxetanylmethyl)ether 'PO (epoxypropylamine) modified hydrogenated biguanide A bis(3-ethyl-3-oxetanylmethyl)ether , EO (epoxy EB) modified bisphenol F (3-ethyl-3-oxygen) Cyclobutanemethyl)ether, poly(3-(4-bromobutoxymethyl)-3-methyloxetane), N-oxetan-2-ylmethoxymethyl Acrylamide, 3,5-bis(3-ethyl-3-oxetanyl methoxy)benzoic acid, 3,5-bis(3-ethyl-3-octobutane Methyl methoxy)benzoic acid methyl ester, 5-(3-ethyl-3-oxetanyl)isophthalic acid, 1,1,1-parax [4(3-ethyl-3-oxo) Heterocyclic butane methoxy)phenyl]ethane and the like. These methods may be used alone or in combination of two or more thereof. The method for producing each compound having an oxetane ring as described above is not particularly limited, and can be carried out according to a conventionally known method. , for example, benzoate ring synthesis from diols as disclosed by Pattison (DB Pattison, J. Am. Chem. Soc. 5 3 4 5 5, ί 79 (1977)) Further, in addition to these, a compound having i to 4 oxetane rings having a molecular weight of about 1, 〇〇〇 to 5, 〇〇〇 is also included. A commercially available product of "a compound having an oxetane ring" can be used: for example, OXT101 (3-ethyl-3-pyridinyl) manufactured by Toagosei Co., Ltd. ); ΟΧΤ221 (bis[1-ethyl(3-oxetanyl)methyl ether)]-35- 200848448 manufactured by East Asia Synthetic Co., Ltd.; 1,4-double [(3-B) manufactured by East Asia Synthesis Co., Ltd. Benzyl-3-oxetanyl)methoxymethyl]benzene; OXT211 (3-ethyl-3-(phenoxymethyl)oxetane) manufactured by Toagosei Co., Ltd.; East Asia Synthetic Company Manufactured MPO (3,3-dimethyl-2-(p-methoxyphenyl)oxetane); ETERNACOLL OXBP manufactured by UBE INDUSTRIES, LTD., used in the present invention The compound having an oxetane ring is preferably a compound represented by the formulae (1) to (3), Ral is preferably a methyl group or an ethyl group, and particularly preferably a methyl group; and Ra2 is preferably carbon. An alkyl group or a phenyl group having 1 to 6 atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms; and Ra3 is preferably a chain or branched alkyl group, a chain or a branched polymer. (alkyloxy) group And particularly preferably a (CH2) S -, - CH2CH2 (OCHCH) t-; s represent an integer of 1-8, t is an integer of 0 to 3. Representative. By selecting such substituents, the viscosity of the polymerizable composition can be lowered, so that in the case of photonographic lithography, good coating uniformity to the substrate can be obtained. The high density of the benevolent, good transfer characteristics of the mold. The photocationic polymerizable compound used in the present invention may have both an oxirane ring and an oxetane ring in the molecule, and it is possible to use, for example, Japanese Laid-Open Patent Publication No. 20 2-235-66 The compound disclosed in Japanese Laid-Open Patent Publication No. 2 0 0 2 - 2 1 2 5 2 7 . The "compound having both an oxirane ring and an oxetane ring" is preferably a compound represented by the formula (6) shown below. By using these compounds', the polymerization rate can be increased, and as a result, a highly rigid sensitivity polymerizable composition can be obtained. -36- 200848448

In the formula (6), Ral is each synonymous with Ral in the formulae (1) to (3), and the preferred range is also the same. The (a) cationically polymerizable monomer other than the compound having an oxetane ring in the photocurable composition of the present invention is preferably a compound having an ethylene oxide f ring and/or a vinyl ether compound. . (Compound having an oxirane ring) The compound having an oxirane ring suitable for use as the above-mentioned photopolymerizable compound having an oxetane ring is described in the present invention. Examples of the "compound having an oxirane ring" include, for example, an alicyclic polyepoxide, a polyglycidyl ester of a polybasic acid, a polyglycidyl ether of a polyhydric alcohol, a polyoxyalkylene glycol. Polyglycidyl ethers, polyglycidyl ethers of aromatic polyols, polycondensed waters of aromatic polyols, hydrogenated compounds of glyceryl ethers, urethane polyepoxides, and epoxidized poly Butadiene and the like. These compounds may be used alone or in combination of two or more. The compound having an oxirane ring which can be used in the present invention is preferably a compound containing an epoxycycloalkyl group and/or a glycidyl group. These compounds have superior cationic polymerizability. The epoxycycloalkyl group-containing compound is preferred because it has a low viscosity and a fast curing rate, and among them, a compound containing an epoxycyclohexyl group is preferred. The glycidyl group-containing compound imparts flexibility to the polymer, increases the migration property of the polymerization system, and further improves the hardenability from -37 to 200848448. Examples of the "epoxycyclohexyl group-containing compound" include, for example, 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, 2-(3,4-ring) Oxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, adipic acid (3,4-epoxy-6-methylcyclohexylmethyl)ester, 3,4-epoxy-6-methylcyclohexyl-3,,4,-epoxy-6'-methyl Cyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether, exoethyl bis (3,4 -epoxycyclohexane carboxylate), ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylhexene Ester-modified 3, epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexyl Base-3', 4'-epoxycyclohexyl phthalate, 1.2:8,9 digoxynene and the like. Among the "epoxycyclohexyl group-containing compounds", preferred is 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, adipic acid bis (3, 4) -Epoxycyclohexylmethyl)ester, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone Modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexyl Methyl 3', 4'-epoxycyclohexane carboxylate, 1.2:8,9 diepoxide. Examples of commercially available "epoxycyclohexyl-containing compounds" suitable for use include: 1^11-6100, 1; ¥11-6105, 1; ¥11-6110, 1; ¥11-6128, UVR- 6200, UVR-6216 (above is manufactured by Union Carbide Corp.); CELLOXIDE 202 1, CELLOXIDE 202 1 P > -38- 200848448 CELLOXIDE 20 8 1, CELLOXIDE 20 8 3, CELLOXIDE 20 8 5, CELLOXIDE 3 000, EPOLEAD GT -3 00, EPOLEAD GT-301, EPOLEAD GT-3 02, EPOLEAD GT-400, EPOLEAD 401, EPOLEAD 403 (above manufactured by Daicel Chemical Industries, Ltd.); KRM-2100, KRM-2 1 10, KRM-2 199 (The above is manufactured by Asahi Denka Kogyo Co., Ltd. (ADEKA; Asahi Denka Kogyo Κ·Κ.)). The components as described above may be used singly or in combination of two or more kinds thereof. Examples of the "glycidyl group-containing compound" suitable for use include, for example, bisphenol hydrazine diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A Diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenation double Phenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl Ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, one or two or more alkylene oxides added to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin The polyglycidyl ethers of the obtained polyether polyols: diglycidyl esters of aliphatic long-chain dibasic acids; glycidyl ethers which are one of aliphatic higher alcohols; benzoic acid, formic acid, butyl benzoic acid or One of the polyether alcohols obtained by adding the alkylene oxide is shrunk Oil ether; glycidyl esters of higher fatty acids and the like.

Among these components, preferred are bisphenol A diglycidyl ether, bisphenol F-39-200848448 diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether 1,4·Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol Glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether. Examples of commercially available "glycidyl-containing compounds" suitable for use include, for example, UVR-6216 (manufactured by Union Carbide Corp.); GLYCIDOL, AOEX24, CYCLOMER A200 (above

Daicel Chemical Industry Co., Ltd.; Epikote 828, Epikote 812, Epikote 1031, Epikote 872, Epikote CT508 (above manufactured by Yuka Shell Co., L td); KRM - 2 4 0 0, KRM- 241 0, KRM-2408, KRM-2490, KRM-2720, KRM-27 5 0 (above is manufactured by Asahi Denki Kogyo Co., Ltd.). These may be used alone or in combination of two or more thereof. In addition, the compounds having an oxirane ring are not limited to the preparation method thereof, but can be referred to, for example, Jiushan KK Publishing, Fourth Edition Experimental Chemistry Lecture 20 Organic Synthesis II, page 213, Heisei 4 years (1992); "The Chemistry of Heterocyclic Compounds-Small Ring Heterocycles" edited by Alfred Hasfner, Volume 3, Exiranes ) , John & Wiley and Sons, An Interscience

Publication, New York, 1985; Yoshimura, then, Vol. 29, No. 12, p. 32, 1985; Yoshimura, then, Vol. 30, No. 5, p. 42, 1986; Yoshimura, then, No. 30 Book No. 7, pp. 42-40-200848448, 1986; Japanese Patent Application Laid-Open No. PCT-100378; Invention Patent No. 2,906,245; and Patent No. 2,926,262. The content of the compound having an oxirane ring used in the present invention in (a) the cationically polymerizable monomer is preferably from 5 to 90% by mass, more preferably from 1 to 80% by mass, further preferably It is 15 to 70% by mass. (Vinyl ether compound) The vinyl ether compound which can be used in the present invention together with the photopolymerizable compound having an oxetane ring as described above will be described. Examples of the "vinyl ether compound" used in the present invention include, for example, 'methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl Ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl decyl vinyl Ether, benzylidene ether, dicyclopentyl b.; (3⁄4 ether, 2 -dicyclopentenyloxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl Vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, tetrahydrofuranyl Vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4·hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl Ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenyl ethyl vinyl Ether, polyphenoxyethylene glycol vinyl ether, etc. "monofunctional vinyl ethers": ethylene glycol divinyl ether, diethylene glycol divinyl ether, poly-41 - 200848448 ethylene glycol divinyl Ethyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide diethyl ether ether, biguanide F alkylene oxide divinyl ether, etc." Divinyl ethers; dimethyl ether trivinyl ether, trimethylolpropane trivinyl ether, ditrimethyl methyl propane tetravinyl ether, glycerol trivinyl ether, neopentyl alcohol Ethyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, epoxy propylene compound addition Methylpropane trivinyl ether, ethylene oxide addition of ditrimethylolpropane tetravinyl ether, propylene oxide addition of ditrimethylolpropane tetraethyl ether ether, ethylene oxide plus Neopentyl alcohol tetravinyl ether, propylene oxide addition neopentyl alcohol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether, ring "Polyfunctional vinyl ethers" such as propane-added pentaerythritol hexavinyl ether, etc. These vinyl ether compounds are characterized by low viscosity, low odor, and low skin irritation. The ethinyl ether compound is a method which can be as disclosed, for example, in Stephen. C. Lapin, Polymers Paint Colour Journal. 1 79 (4,237), 32 1 (1988), that is, a polyol or a polyhydric phenol and The reaction of acetylene, or the reaction of a polyhydric alcohol or a polyhydric phenol with a halogenated alkyl vinyl ether, and these may be used alone or in combination of two or more thereof for use in the vinyl ether compound of the present invention. The content of the (a) cationically polymerizable monomer is preferably from 5 to 90% by mass, more preferably from 10 to 8% by mass, still more preferably from 20 to 70% by mass. -42- 200848448 (Other polymerizable compound) In the other cationically polymerizable compound used in the present invention, a compound having several functional groups in the same molecule can also be used. For example, a compound containing an ethyl aryl group and an epoxy group in the same * molecule or a reactive compound having a propenyl ether group and an epoxy group is suitably used. In addition, "polymerizable compound having photocationic polymerizability and photoradical polymerizability" is also possible to use 3-methyl-3-oxetanylmethyl acrylate/Osaka Organic Chemical Co., Ltd. (Osaka Organic Chemical Co., Ltd.) Industry, Ltd.), ΟΧΕ-10); 3-methyl-3-oxetanyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., ΟΧΕ-30); vinylcyclohexene oxide 1, 2·Epoxy-4-vinylcyclohexane (manufactured by Daicel Chemical Industry Co., Ltd., CELLOXIDE 2000); (meth) acrylate compound having an oxetane ring (ETERNACOLL OXMA, manufactured by Ube Industries, Ltd.) Compounds such as. Further, the preferred blending form of the polymerizable monomer in the photocurable composition of the present invention is described, but the blending range of the polymerizable monomer is not limited thereto. In the present invention, a cationically polymerizable monomer having one cationically polymerizable functional group is generally used as a reactive diluent which is effective for lowering the viscosity of the photocurable composition of the present invention in the total polymerizable compound. The amount to be added is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less. When the ratio of the monomer having one cationically polymerizable group is 95% by mass or less, the mechanical strength, etching resistance, and heat resistance of the cured film can be more favorably maintained -43 to 200848448, In the case where an organic polymer is used as the mold core material which is embossed by light nanon, it is preferable to suppress swelling of the mold core and to reduce deterioration of the mold core. On the other hand, a monomer having one or two cationically polymerizable groups is generally used as a photocurable composition of the present invention because it is used as a reactive diluent, and thus is mixed. The ratio is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more of the total polymerizable compound. In the present invention, the photocationic polymerizable compound f " as described above is mainly used, but the radical polymerizable compound may be used within the range which does not impair the efficacy of the present invention. The content of the radically polymerizable compound is preferably from 1 to 30% by mass, and more preferably from 3 to 20% by mass, based on the total polymerizable compound. A specific example of the photo radical polymerizable monomer which can be used in the present invention is a group which is preferably a group containing an ethylenic bond. Examples of the monomer of the "ethyl group having an ethylenic bond" include, for example, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, and ethoxylated I(meth)acrylic acid. Phenyl ester, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, N-vinyl-2-pyrrolidone, N-propylene Mercaptomorpholine, phenoxy diglycol acrylate, ethoxy diglycol acrylate, N-vinyl caprolactam, hydroxytrimethylacetate neopentyl glycol diacrylate, polyethylene diacrylate Alcohol ester, tripropylene glycol diacrylate, ethylene oxide modified trimethyl methacrylate modified by propylene oxide, trimethylolpropane triacrylate modified by propylene oxide, neopentyl alcohol ethoxylate tetraacrylate Ester, dineopentaerythritol hexaacrylate, ethylene oxide modified dimethyl acrylate, ethylene oxide modified bis-44- 200848448 neopentyl glycol acrylate, tetrahydrofuran acrylate, triacrylate Trimethylolpropane ester, 1,6·hexanediol diacrylate, modified ethylene oxide Bisphenol A acrylate, neopentyl glycol diacrylate, urethane acrylate, epoxy acrylate, N-hydroxyethyl acrylamide, ethylene oxide modified bisphenol A diacrylate, Various acrylate oligomers or polymers such as polyester acrylate, polyurethane acrylate, polyether acrylate, polyepoxy acrylate, and the like. Further, in the present invention, it is preferred that the total amount of the polymerizable compound is from 40 f, to 90% by mass based on (a) a cationically polymerizable monomer. (b) Photocationic polymerization initiator Next, the photocationic polymerization initiator used in the present invention will be described. In the photocurable composition of the present invention, a photocationic polymerization initiator is used, and it is preferably contained in the photocurable composition in an amount of from 0.1 to 15% by mass, more preferably from 0.2 to 12% by mass, and Further preferably, it contains 〇.3 to 10% by mass. By setting the ratio of the photocationic polymerization initiator to 0.1% by mass or more, the sensitivity (speed hardenability), the resolution, the edge roughness, and the coating film strength can be further improved. On the other hand, by setting the ratio of the photo-cationic polymerization initiator to 15% by mass or less, light transmittance, coloring property, workability, and the like are not easily deteriorated, which is preferable. In the inkjet composition containing a color material such as a dye and/or a pigment, or a liquid crystal display color filter composition, various evaluations of the amount of a preferred photopolymerization initiator have been carried out in the past. There is no report on the addition amount of the photocationic poly-45-200848448 initiator which is a photocurable composition for nanoimprinting or the like. Therefore, a system which substantially contains a color material such as a dye and/or a pigment affects the photocurability. Therefore, in such applications, the amount of photopolymerization initiator added is optimized under the measurement of this problem. On the other hand, in the photocurable composition of the present invention, the color material of the dye and/or the pigment is not an essential component, and therefore the optimum range of the photopolymerization initiator may be different from the composition for inkjet or liquid crystal. The case of a person who is in the field of a composition such as a color light film for a display. The photocationic polymerization initiator used in the present invention is one in which the mixing is active for the wavelength of the light source used, and the use can produce an appropriate active species. Further, the photocationic polymerization initiator may be used alone or in combination of two or more. The photocationic polymerization initiator which can be used in the photocurable composition of the present invention is not particularly limited as long as it is a compound capable of generating a photocationic polymerization by receiving an energy ray such as ultraviolet rays. Onium salt), more preferably an aromatic iron salt, further preferably an aryl sulfonium salt and an aryl i〇donium salt ° "key salt" specific examples include: Phenyl iodine, 4-methoxydiphenyl iodine, bis(4-methylphenyl) iodine, bis(4·terino-butylphenyl) inscription, double (twelve yard benzene) Iodine, triphenylsulfonium, diphenyl-4-thiophenoxyphenylhydrazine, bis[4-(diphenylfluorenyl)-phenyl] sulfide, bis[4-(di(4) - (2-hydroxyethyl)phenyl)indolyl)-phenyl]sulfide, 7?5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-7 ?]-(methylethyl)-benzene]-iron (1 + ) and the like. -46- 200848448 Specific examples of "anion" include, for example, tetrafluoroborate (BF〆), hexafluorophosphate (PF6_), hexafluoroantimonate (SbF6·), hexafluoroarsenate (AsF0_) , hexachloroantimonate (SbCl6·), perchlorate ion (C104_), trifluoromethanesulfonate ion (CF3s〇3·), fluorosulfonate ion (FS〇r), toluenesulfonate ion, trinitro An benzenesulfonic acid anion, a trinitrotoluenesulfonic acid anion, and the like In particular, the specific examples of the "aromatic key salt" include those disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 50-158680. Aromatic halogen-salt; Japanese Patent Publication No. 5 0 - 1 5 1 9 9 7 , Japanese Invention Patent Laid-Open No. 52_3 0 8 99, Japanese Invention Patent No. 56- The V IA group aromatic key salt disclosed in Japanese Laid-Open Patent Publication No. 5-501-2, Japanese Laid-Open Patent Publication No. Hei No. 5-5 - 1 2 5 1 0 5, and the Japanese Patent Laid-Open No. 5 ο-ΐ 5 The v A group aromatic key salt disclosed in the Japanese Patent Publication No. 8 6-9, Japanese Patent Laid-Open No. 5-6-8428, Japanese Patent Laid-Open No. 5-6-149402, Japan The oxosulfoxonium salt disclosed in the Japanese Patent Laid-Open Publication No. SHO-57-A No. 49-291, and the like. A diazonium salt; a thiopyranium salt as disclosed in the specification of U.S. Patent No. 4,1,3,65,5 Thiopyry Hum salt ), iron/allene complex, aluminum complex/photodecomposition ruthenium compound initiator, halogenated halide of light, ortho-nitrobenzyl An ester compound, a quinone imide sulfonate compound, a bissulfonyldiazomethane compound, an oxime sulfonate compound-47-200848448. The photocationic polymerization initiator which can be used in the present invention is a compound which can be widely used, for example, for chemically amplified photoresist or photocationic polymerization (see "Organic Materials for Imaging (IMAGING)" edited by the Organic ELECTRONICS Materials Research Institute. Text extended (1993), pages 187 to 192). These compounds are in the "The Organic Materials for Imaging (IMAGING)" edited by the Chemical Society of Japan (THE CHEMICAL SOCIETY OF JAPAN), Volume 71, No. 11, 1998, Organic ELECTRONICS Materials Research Association. The photocationic polymerization initiator disclosed in 99 3) can be easily synthesized by a well-known method. Examples of commercially available products of "photocationic polymerization initiator" include, for example, UVI-695 0, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (the above is U ni ο n C arbide C 〇 Rp.manufacturing); Adekaoptomer SP-150, SP-151, SP-170, SP-171, SP-172 (above is manufactured by Asahi Denki Kogyo Co., Ltd.); Irgacure 261, IRGACURE OXEOl, IRGACURE CGI- 1 3 97, CGI-1325, CGI- 1 3 8 0, CGI-1311, CGI-263, CGI-268, CGI- 1 3 97, CGI- 1 3 2 5, CGI- 1 3 8 0, CGI-1311 (above is steam Manufactured by Ciba Specialty Chemicals Inc.; CI-248 1, CI-2624, CI-263 9, CI-2064 (The above is manufactured by Nippon Soda Co.? Ltd.) ); CD-1010, CD-1011, CD-1012 (above is manufactured by SARTOMER); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103 -48 - 200848448, BBI-103 (above is manufactured by Midori Kagaku Co., Ltd.); PCI-061T, PCI-062T, PCI-020T, PCI-022T (The above is limited by Nippon Chemical Co., Ltd.) Manufactured by Nippon Kayaku Co., Ltd.; PHOTOINITIATOR 2074 (manufactured by Rhodia Co., Ltd.); UR-1104, UR-1105, UR-1106, UR-1107' UR-1113, UR-1114, UR-1115, UR -1118, UR-1200

SAIT15, UR-SAIT16, UR-SAIT22, U R - S AIT 3 0 (above is manufactured by URAY Corporation). Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-171, SP-172, CD-1012, Μ PI -

, UR-1201, UR-1 202, UR- 1 203, UR- 1 204, UR- 1 205, UR- 1 207, UR-1401, UR- 1 402, UR- 1 403, UR-M1010, UR- M101 1 , UR-M10112 , UR-SAIT01 , UR-SAIT02 > UR- SAIT03 , UR-S AIT04 , UR-SAIT05 , UR-SAIT06 , UR- SAIT07 , UR-SAIT08 , UR-SAIT09 , UR-SAIT1 0 , UR-SAIT11, UR-SAIT12, UR-SAIT1 3, UR-SAIT14, and UR-l 03 are high-light hardening sensitivities that can be exhibited by the inclusion of such compositions. The photocationic polymerization initiator as described above may be used singly or in combination of two or more kinds thereof. In the present invention, in addition to the photocationic polymerization initiator, a photoradical polymerization initiator may be used insofar as it does not impair the effects of the present invention. The radical photopolymerization initiator which can be used in the present invention is contained in the range of from 1 to 8 mass%, preferably from 0.2 to 7 mass%, and more preferably in the total composition. • A range of 3 to 6 mass%. The photo-radical polymerization initiator which can be used in the present invention is active in the wavelength of the light source used in the use of -49-200848448, and may be used alone or in combination of two or more. As the photoradical photopolymerization initiator used in the present invention, for example, a commercially available photoradical polymerization initiator can be used. Examples of such include include, for example, Irgacure (registered trademark) 2959 (1_[4-(2-hydroxyethoxy)phenyl)-2, available from Ciba Specialty Chemicals Inc. _hydroxy-2-methyl-1-propan-1-one), Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered by f, standard) 5 00 (1-hydroxycyclohexyl) Phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2·dimethoxy-1,2·diphenylethane-1-one), Irgacure (registered trademark) 369 (2- Benzyl-2-dimethylamino-1(4-morpholinylphenyl)butanone-1), Irgacure (registered trademark) 907 (2-methyl-1-[4-methylphenylsulfuric acid 〕]-2-morpholinylpropan-1-one), Irgacure (registered trademark) 819 (bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide), Irgacure (registered trademark) 1800 (bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-one) I, Irgacure (registered Trademark) 1 80 0 (bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl -1-phenyl-1-propan-1-one), Irgacure (registered trademark) OXE01 ( 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-( 0- Benzopyridinium), Darocur (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1 3 9 8, 1174 And 1 020, CGI 242 (ethone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(0-ethenyl)肟)); available from BASF Corporation Lucirin -50- 200848448 ΤΡΟ (2,4,6-trimethylbenzhydryldiphenylphosphine oxide), Lu TPO-L (2,4,6-trimethyl) Benzobenzylphenylethoxyphosphine oxide); ESACURE 1001M ((4-Benzylmercaptophenylsulfanyl)phenyl]-2-methyl-2-- 4- from Nihon Siber Hegner KK Methylsulfonyl)propan-1-one); available from Asahi Kasei A Adekaoptomer (registered trademark) Ν-1414 (Taste D-benzophenone Adekaoptomer (registered trademark) N-1717 (Π丫H定系)

Adekaoptomer (registered trademark) N-1606 (triazo trap); TFE-trinitro 2-[2-(furan-2-yl)vinyl]-4 manufactured by Sanwa Chemical Co., Ltd. , 6-bis(trichloromethyl)-1 trinitrogen tillage, TME-trinitrogen (2-[2-methylfuran-2-yl)vinyl]-4,6- manufactured by Sanwa Chemical Co., Ltd. Bis(trichloromethyl)-1,3,5-cultivation, MP-triazine trap (2-(4-methoxy)-4,6-bis(trichloromethyl)) manufactured by Sanwa Chemical Co., Ltd. -1,3,5-triazinium); TAZ-1 1 3 (2-[2-(3, methoxyphenyl)vinyl]_4,6-bis (Midori Chemicals) manufactured by Midori Chemicals Trichloromethyl)-1,3,5-tri), Ding-8-108 (2-(3,4-dimethylphenyl)-4,6-bis(trichloromethyl)-) manufactured by Midori Chemical Co., Ltd. 1,3,5-triazine trap), diphenyl 4,4'·bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-phenyl-4'-methyl Diphenyl sulfide, 4-phenylbenzophenone, ethyl ketone, 2-chlorooxosulfanthene, 2-methyloxysulfide _ sing, 2-isopropyloxysulfur, 4-isopropyl Oxythioxanthine, 2,4-diethyloxysulfide-卩, 1-chloro-4·yloxy Sulfuric acid bismuth, 2-methyl oxysulfonium [li喔, oxysulfonium sulphate, benzoin 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl The ether cirin can obtain 1-[phenyl phenyl]>, and the chemical trap (3,5-(5-triazophenyl)- 4-diazepine oxy ketone, formazan Oxygen, benzene-51- 200848448 acetonyl isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxybenzene Ethyl ketone, and dibenzoxyl ketone, methyl o-benzhydryl benzoate, 2-benzylidene naphthalene, 4-benzylidene biphenyl, 4-benzylidene diphenyl ether, 1 , 4-benzylidene benzene, diphenylethylenedione (benzil), 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane, 2-B Base, 2,2-bis(2-chlorophenyl)4,5,4',5,-fluorene (3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2 , 2-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole, ginseng (4-dimethylamine V'phenyl)methane, Ethyl 4-(dimethylamino) benzoate, 2-benzoic acid Methylamino)ethyl ester, butyloxyethyl benzoate _4_(dimethylamino) ester, etc. (c) Fluorine-based surfactant, polyfluorene-based surfactant, and fluorine-polyoxyl system The surfactant is next described in the surfactant used in the present invention. The photocurable composition of the present invention contains at least one of a fluorine-based surfactant, a polyfluorene-based surfactant, and a fluorine-polyoxyn surfactant in an amount of from 0.1 to 5% by mass. It is contained in an amount of 0.002 to 4% by mass, and more preferably in a range of 0.005 to 3% by mass. The "fluorine-polyoxyl surfactant" as used herein means two components having a fluorine-based surfactant and a polyoxyn-based surfactant. When the fluorine-based surfactant, the polyfluorene-based surfactant, and the fluorine-polyoxyn surfactant are less than 0.001% by mass in the photocurable composition of the present invention, coating uniformity is applied. The effect is not sufficient. On the other hand, if it exceeds 5% by mass, the transfer characteristics of the mold are deteriorated, so that it is not preferable to -52-200848448. The fluorine-based surfactant, the polyoxymethylene-based interface agent, and the fluorine-polyoxynene-based surfactant used in the present invention may be used singly or in combination of two or more. In the present invention, it is preferred to contain both a fluorine-based interface active and a polyfluorene-based surfactant, or a fluorine-polyoxyl-based active agent. In particular, it is most preferable to contain a fluorine/polyoxyn surfactant. By using the above-mentioned surfactant, it is possible to solve the problem of forming a ruthenium wafer for manufacturing a conductor element or a glass substrate for manufacturing a liquid crystal element, and to form a chromium film, a molybdenum film, a molybdenum alloy film, a giant film, and a giant a line or scale caused by coating a photohardenable product of the present invention on a substrate by using various films such as a tantalum nitride film, an amorphous tantalum film, or a tin oxide-doped indium oxide (ITO) tin oxide film. The purpose of the coating problem such as the pattern (drying unevenness of the photoresist film), the improvement of the fluidity of the composition in the cavity of the mold portion, the improvement of the mold release property between the mold and the photoresist, the good light resistance and the substrate The adhesion between the components is reduced, the viscosity of the composition is lowered, etc. In the photocurable composition of the present invention, the above-mentioned active agent is added, whereby the coating uniformity can be greatly improved, and In the application of the rotary coater or the slit coater, good coating suitability can be obtained without depending on the substrate size. The "nonionic fluorine-based surfactant" used in the present invention includes, for example, a trade name. Florard FC-43 0, FC-43 1 (manufactured by Sumitomo 3 M Co., Ltd.); SURFLON "S-382" (manufactured by As ah i Glass Co., Ltd.); EFTOP "EF-122A, 122B, 122C > EF-121, 126, EF-127, MF-100" (Tochem Products Co., Ltd. active agent with a sexual agent interface in the semi-finished membrane, membrane or sexual group uniformity, concave, especially the interface is limited For example, 3M Product Name Ltd. EF-manufacturing-53-200848448); trade names PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA); trade names FTERGENT FT25 0, FT251, DFX18 ( All manufactured by NEOS Co., Ltd.; trade names Unidain DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.); Trade names Megafac 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink and Chemicals, Inc.) Examples of "nonionic lanthanide surfactants" include: For example, Trade name SI-1 0 series (Takemoto Oil & Fat Co·, Lt d)) Manufacture); Megafac Paintad 31 (manufactured by Dainippon Oil Chemical Industries, Ltd.); KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the "fluoro-polyoxyn surfactant" used in the present invention include, for example, trade names X-7 0-090, X-7 0-09 1, X-70-092, X-70- 093 (all manufactured by Shin-Etsu Chemical Co., Ltd.); trade name Megafac R-0 8, XRB-4 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.). In the photocurable composition of the present invention, in addition to the above, other nonionic surfactants may be used for the purpose of improving the flexibility of the photocurable composition and the like. Examples of the commercially available product of the "nonionic surfactant" include, for example, D-3110, D-3120, D-3412, D-3440, D-3510, D of the Paionin series manufactured by Takemoto Oil Co., Ltd. -3 605 and other polyoxyethylene alkylamines; Paionin series manufactured by Takemoto Oil Co., Ltd. -1305, 0-1315, 〇-1405, 0-1420, D-150 4, D-1508, D-1518 Polyoxyethylene alkyl ether, etc.; -54- 200848448 Polyethylene oxide monoester of D-2112-A, D-2 1 12-C, D-2 123-C, etc. of Paionin series manufactured by Takemoto Oil Co., Ltd. Acid ester; polyethylene oxide difatty acid ester of D-2405-A, D-2410·D, D _ 2 1 1 0 - D, etc. of Paioniri series manufactured by Takemoto Oil Co., Ltd.; manufactured by Takemoto Oil Co., Ltd. Polyethylene oxide alkyl phenyl ether of D-406, D-410, D-414, D-418, etc. of Paionin series; SURF YNOL manufactured by Nissin Chemical Industry Co., Ltd. It is a polyoxyethylene tetramethyl decyne glycol diether such as 104S, 420, 440, 465, and 4 8 5 of J. Further, a reactive surfactant having a polymerizable group can also be used in combination with the surfactant used in the present invention. For example, polyallyloxyethylene glycol methacrylate (Nippon Oil & Fats Co., Ltd. trade name: Blemmer PKE series); poly(meth) methacrylate Ethylene glycol ester (Japan Oil & Fats Co., Ltd. trade name: Blemmer PNE series); poly(meth)phenoxy propylene glycol methacrylate (Japanese Oils and Fats Co., Ltd. trade name: Blemmer PNP series): polymethyl methacrylate Sodium decyl phenoxy (ethylene glycol-propylene glycol) ester (Japanese Oils and Fats Co., Ltd. trade name: Blemmer PNEP-600); AQUAL Ο N RN -1 0, RN - 2 0, RN-30, RN-50 RN-202 5, HS-05, HS 1 0, HS - 2 0 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like. The content of the other nonionic surfactant is preferably in the range of from 1 to 5 mass% of the photohardenable composition of the present invention. (d) Organic solvent -55-200848448 The organic solvent contained in the curable composition of the present invention is in a range of 2% by mass or less, more preferably 5% by mass or less, and particularly preferably not contained. The photocurable composition of the present invention preferably contains an organic solvent which dissolves the components of the photocurable composition of the present invention because it preferably contains a specific monofunctional and/or difunctional monomer as a reactive diluent. It does not need to be non-existent. Further, if the organic solvent is not contained, there is no need for a baking step for the purpose of volatilizing the solvent, which contributes to a simplification of the process and the like. Therefore, the photocurable composition of the present invention does not need to contain an organic solvent, but when a compound which cannot be dissolved by a reactive diluent is used as a component of the photocurable composition of the present invention, it is dissolved. Or if you want to adjust the viscosity slightly, you can add it as you like. The type of the organic solvent to be used in the photocurable composition of the present invention, as long as it is a solvent generally used for a photocurable composition or a photoresist, and is soluble in each of the photocurable compositions of the present invention. There are no special restrictions on the principal component and its ability to disperse the average sentence 'without reacting with those ingredients. Specifically, it includes, for example, "alcohols" such as methanol and ethanol, "brewed" of the four gas 咲 寺 temple, B _ * alcohol - methyl ether, ethylene glycol dimethyl ether, B "Glycol ethers" such as diol methyl ethyl ether, ethylene glycol monoethyl ether, etc.: "ethyl acetate", ethyl celecoxib acetate, etc. Acidic vinegar", monoglycol-methyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, digan "diethylene glycol" such as alcohol monobutyl ether; "propylene glycol alkyl ether acetate-56-200848448" such as propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate; toluene, xylene, etc. "Aromatic hydrocarbons"; "ketones" such as acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, etc.; 2-hydroxypropionic acid Ester, methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate , methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 - "Ethyl lactate" such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate or ethyl lactate, and may also be added: N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N_methyl shame D-butanone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone 1, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, acetic acid a high boiling point solvent such as benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or phenyl racelus acetate. These may be used alone or in combination of two or more of them. Among the temples, 'preferably methoxy propylene glycol acetate, 2-ethyl propyl acrylate, 3-methoxy propylene Methyl ester, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone, etc. (e) color material The photocurable composition of the present invention, Content of pigments and/or dyes 0 · 5 mass % or less, preferably 0 · 3 mass % or less, particularly preferably not contained. The color material usable in the present invention is included in the composition of the UV ink jet composition, color filter -57-200848448 A color material such as a pigment used for a composition for a CCD image sensor or the like. Specifically, various inorganic pigments or organic pigments which have hitherto been known can be used. The inorganic pigment is a metal oxide or a metal oxide. A metal compound represented by a salt or the like, specifically, a metal oxide or a metal composite oxide of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum or the like. The organic pigment" is, for example, CI Pigment Yellow (Pigment Y e 11 ow ) 1 1 , 2 4 , 3 1 , 5 3 , 8 3 , 9 9 , 1 0 8 , 1 0 9 , 110 , 138 , 139 , 151 , 154, 167; C·I · Pigment Orange 36, 38, 43; CI·Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 20 9 ; CI Pigment Violet 19, 23, 32, 39; Pigment Blue 1, 2, 15, 16, 22, 60, 66; CI Feeding green (Pigment Green) 7,36,37; C.I. Pigment Brown (Pigment Brown) 25,28; C.I. pigment black (Pigment Black) 1,7; and carbon black. The photocurable composition of the present invention preferably has a viscosity at 25 ° C of 20 mPa·s or less, more preferably a polymerizable monomer of 19 mPa·s or less. When the viscosity is set to 20 mPa·s or less, it is not easy to cause bubble defects due to being trapped in the atmosphere of the mold recess, so that the residue does not easily remain in the mold convex portion after photohardening. If a large amount of residue is present, the etching of the substrate is hindered, so that it is preferable that the residue is not left. The lower limit of the viscosity is, although not particularly limited, usually 3 mPa · s or more. Further, the photocurable composition of the present invention has a moisture content at the time of preparation of 2.0% by mass or less, more preferably 1.5% by mass, still more preferably 1% by mass or less. The moisture content was set to 2.0% by mass at -58 to 200848448 at the time of preparation, whereby the storage of the photocurable composition of the present invention was stabilized more stably. Further, in the photocurable composition of the present invention, in addition to the photocationic initiator, a photosensitizer may be added to the wavelength of the entire UV domain. A typical sensitizer which can be used in the present invention is disclosed in Cleopatra [J. V. Crivello, Adv. in Polymer Sci,: page 1 (1 904)], in particular, Its lines: You, Philippine, Π丫D Ding orange, thioxanthone, 2-chloro D hawthorn, benzoflavin, N-vinylcarbazole, 9,10-dibutoxy fluorene , coumarin, ketocoumarin, phenanthrene, camphorquinone, morpholin derivative, etc. < The content of the photosensitizer in the photocurable composition of the present invention is preferably 30 The mass% or less is more preferably 20% by mass or less and is 10% by mass or less. The lower limit of the content of the photosensitizer is not particularly limited, but when the effect is to be exhibited, the lower limit of the content of the photosensitizer is about 0.1. The light used in the polymerization of the present invention is not only ultraviolet light or low beam. Optical electromagnetic waves of wavelengths in the regions of far ultraviolet light, visible light, infrared light, etc., also include radiation, and the radiation includes, for example, microwave, radiation, EUV (Extreme Ultraviolet), X. In addition, laser light such as 248 nm excimer laser, 193 nm quasi-split, 172 nm excimer laser can be used. These lights may use monochromatic light (single-wavelength light) of an optical filter, or may be a plurality of different lengths of light (composite light). The exposure may be formed by patterning for the purpose of multiple exposure, film strength, etching resistance, etc., and then qualitatively polymerizing to include the 62th including oxysulfonium in a group, and the amount of ultraviolet, or electrons. The ray is thundered by a wave or by -59-200848448 full exposure. In the composition of the present invention, in addition to the components as described above, a mold release agent, a decane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aging agent, and a plasticization may be added as needed. Agent, adhesion promoter, thermal polymerization initiator, inorganic fine particles, elastomer fine particles, photoacid proliferation agent, photobase generator, basic compound, flow regulator, antifoaming agent, dispersant, and the like. For the purpose of further improving the release property, the release agent can be optionally mixed in the photocurable composition of the present invention. Specifically, it is added so that the mold core pressed against the layer of the photocurable composition of the present invention can be peeled off without causing the surface of the resin layer to become rough or peeled off. The release agent is a conventionally known release agent, such as a polyoxymethylene release agent, a polyethylene wax, a guanamine wax, a Teflon powder (a Teflon is a registered trademark), and the like. Solid wax, fluorine-based, phosphate-based compounds and the like can be used. Further, the release agents may be attached to the mold in advance. When it is used in combination with the photocurable resin as described above for use in the present invention, it is particularly preferable from the viewpoint of mold release property of the mold, and it is not easy to cause peeling of the plate. . The polyoxo-type release agent is a release agent having a basic structure of an organic polyoxymethane, for example, an unmodified or modified polyoxygenated oil, and a polytrimide containing trimethyldecyloxy phthalic acid The polysiloxane, the polyoxynene-based acrylic resin, etc. are in accordance with the conditions. The "modified polyoxo-oxygen oil" is modified by adding -60-200848448 to the side chain and/or the end of the polyoxyalkylene oxide. The quality is obtained, and can be divided into reactive polyphthalic acid oil and non-reactive polypyridyl oil. "Reactive polyoxalate oil" includes: amine-based modification, epoxy modification, carboxy modification, methanol modification, methacrylic modification, thiol modification, phenol modification, and single-end reaction. Sexual, heterologous functional group modification. "Non-reactive polyoxo-oxygen oil" includes: polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, advanced hospital oxygen modification, bureau Grade fatty acid upgrading, fluorine modification, etc. It is also possible to apply two or more of the above-mentioned modified methods in one polyoxyalkylene molecule. The modified polyoxygenated oil preferably has a moderate compatibility with the composition of the composition. In particular, in the case of using a reactive polyoxyxene oil which is reactive with other coating film forming components which are optionally mixed in the composition, the photocurable composition of the present invention is fixed to the cured hardened film by a chemical bond. Therefore, the problem of adhesion, contamination, deterioration, and the like of the cured film is not easily caused. In particular, it is effective for improving the adhesion to the vapor deposition layer during the vapor deposition step. Further, in the case of (meth)acrylonitrile-modified polyfluorene oxide, ethylene-based modified polyfluorene, or the like, which is modified by a photocurable functional group, it will be The photocurable composition of the present invention is crosslinked, and thus has excellent properties after hardening. Polyoxane containing trimethylsulfonyloxy phthalic acid is easy to seep out of the surface and has excellent mold release property, and has superior adhesion even if it penetrates the surface, and has excellent metal evaporation or external protection. The adhesion of the film layer is therefore preferred. The release agent as described above may be added in only one type or a combination of two or more. -61 · 200848448 When a release agent is added to the photocurable composition of the present invention, it is preferably in the total amount of the composition. The ratio is 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. When the ratio of the mold release agent is 0.001% by mass or more, the mold release property of the mold core and the photocurable composition layer tends to be more excellent. On the other hand, by setting the ratio of the release agent as described above to 10% by mass, it is not easy to cause the coating film surface to become rough due to repulsion when the composition is applied. There is a problem in that it is not easy to hinder the adhesion of the substrate itself of the product and the adjacent layer such as the vapor deposition layer, the film breakage at the time of transfer, etc. (the film strength is too weak). In the composition of the present invention, the organic metal coupling agent may be mixed in order to improve the heat resistance, the strength, or the adhesion to the metal deposition layer of the surface structure having the fine uneven pattern. Further, since the organometallic coupling agent has an effect of promoting a heat hardening reaction, it is effective. The "organic metal coupling agent" y can be any of various coupling agents such as a decane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent. Examples of the "decane coupling agent" used in the photocurable composition of the present invention include, for example, vinyl trichlorodecane, vinyl stilbene (β-methoxyethoxy) decane, vinyl triethoxy group. Vinyl decane such as decane or vinyltrimethoxydecane; acrylic acid such as 7-methacryloxypropyltrimethoxydecane or γ-methylpropenyloxypropylmethyldimethoxydecane Decane; β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, r-glycidylpropyltrimethoxydecane, γ-glycidylpropylmethyldiethoxyfluorene- 62- 200848448 alkane; Ν-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, Ν-β-(aminoethyl)-γ-aminopropylmethyldimethoxy Amino decane such as decane, γ-aminopropyltrimethoxydecane, fluorenyl-phenyl-γ-aminopropyltrimethoxydecane; and γ-hydrothiopropyltrimethoxy of other decane coupling agents Base decane, γ-chloropropylmethyldimethoxydecane, γ-chloropropylmethyldiethoxy oxane, and the like.

Examples of "Qin coupling agent" include, for example, triisostearyl hydrazine, isopropyl ester, isopropyl dodecyl benzene sulfonyl isopropyl titanate, ginseng (_ __ _ octyl ester) titanium Isopropyl acrylate, bis(dioctyl phosphite) tetramethylene propyl titanate, bis (ditridecyl phosphite) tetraoctyl titanate, bisphosphite, _ Q ditridecyl) titanate Tetrakis(2,2-diallyloxymethyl) ester, bis( _code dioctyl phosphate) hydroxyacetate titanate, bis(dioctyl pyrophosphate) 鈥^ A-ethylene diester, trioctyl decyl titanium Isopropyl isopropylate, isopropyl isopropyl isostearyl isopropyl citrate, isopropyl isostearyl bis propyl octanoate, isopropyl tris(dibenzoate) Ester, isopropyl triisopropylphenyl phenyl titanate, amide, ethyl ethanoethyl phthalate, phenoxyacetic acid ~ a cumene ester, diisostearyl Methyl phthalate titanate and the like. Examples of the "zirconium coupling agent" include, for example, a tetra-n-co-base pin, a tetra-butoxy fluorene, a tetrakis-acetic acid zirconium ketone, and a dibutoxy bis( 2 acid keto acid). Zirconium, tributoxyethylacetonitrile acetate cone, butoxy iyi keto acid bis(ethylacetamidoacetate) chromium, and the like. Examples of "Ming Coupling Agents" include, for example, isopropyl sulphate, p, diisopropylaluminum mono-butoxy aluminum, secondary-butyric acid aluminum, acetonitrile, = isopropyl acid ethyl Acetyl aluminum acetate, ginseng (ethyl ethyl decyl acetate) aluminum, = isopropyl acid - 63 - 200848448 alkyl acetoxy aluminum acetate, monoethyl acetoacetic acid bis ( ) aluminum, ginseng (ethyl hydrazino) Ethyl acetonitrile) aluminum and the like. The organometallic coupling agent as described above may have a ratio of the organic metal coupling agent to 0.001 1 in a ratio of 〇·〇〇1 to 10% by mass in the total amount of the photosolid content, and improve heat resistance, strength, and impartance. The tendency of the vapor-deposited layer to be dense is effective. On the other hand, when the organic gold is set to 10% by mass or less, there is a tendency for the film forming property of the composition to be impaired, which is preferable. In the photocurable composition of the present invention, a polymerization inhibitor may be mixed. The "polymerization inhibitor" may be a quinone such as a diphenyl hydrazine such as a butyl hydrazine, a catechol or a hydroquinone monomethyl ether; a thiophene thief; a copper or the like for a photocurable composition. The total amount is preferably mixed, for example, at a ratio of %. Further, in the composition of the present invention, it may be made to contain an oxidizing agent. The antioxidant is used to suppress fading caused by ozone, active oxygen, NOx, SOx (X is an integer) or the like due to heat or light irradiation. In particular, in the present invention, the oxidizing agent has an advantage of preventing the coloration of the cured film or reducing the film thickness. As described above, the rate of the antioxidant group-containing amine, the sterically hindered amine-based antioxidant, the nitrogen-containing impurity, the thioether-based antioxidant, and the sterically hindered phenol-based antioxidant ethyl acetoacetate hardening composition When the amount is more than or equal to 5% by weight, the stability is more stable than the ratio of the coupling agent, and the storage stability is suppressed, for example, hydroquinone or triphenyl hydrazine; benzene SI, polymerization inhibitor The 0.001 to 10 masses are well known for their resistance to fading and the various oxidizing gases which have been added with less resistance due to decomposition. The inclusions include: anthracycline hydrogen sulfide-based compounding agent, ascorbic acid-64 - 200848448, zinc sulfate, thiocyanate, thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, etc. Among them, a sterically hindered phenol-based antioxidant or a thioether-based antioxidant is particularly preferable from the viewpoint of coloring and film thickness reduction of the hardened film. Examples of commercially available products of "antioxidants" include: Irganox 1010, 1 03 5, 1 076, 1 222 (above is manufactured by Ciba Specialty Chemicals Co., Ltd.); Antigene P ' 3C ' FR ' Sumilizer S ' Sumilizer GA -80 (manufactured by Sumitomo Chemical Co., Ltd.); Adekasutabu AO70, AO80, AO503 (manufactured by AD EKA), etc., which can be used alone or mixed. use. The total amount of the antioxidant relative to the composition of the present invention is preferably mixed at a ratio of from 1 to 1% by mass, more preferably from 2 to 5% by mass. Examples of commercially available products of "antioxidants" include: Irganox 1010, 1035, 1076, 1222 (above is manufactured by Ciba Specialty Chemicals Co., Ltd.); Antigene P, 3C, FR, Sumilizer S (manufactured by Sumitomo Chemical Industries, Ltd.) Wait. The antioxidant is preferably mixed in a ratio of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total amount of the composition. Examples of commercially available products of "ultraviolet absorber" include: Tinuvin P, 234, 320, 326, 327, 328, 213 (above is manufactured by Ciba Specialty Chemicals Co., Ltd.); Sumisorb 110, 130, 140, 220, 250, 3 00, 3 20, 3 4 0, 3 5 0, 400 (above is manufactured by Sumitomo Chemical Industries Co., Ltd.). The total amount of the ultraviolet absorber is preferably 0.02 to 10% by mass based on the total amount of -65 to 200848448 of the photocurable composition. Examples of commercially available products of "light stabilizers" include: Tinnvin 292, 144, 622LD (above is manufactured by Ciba Specialty Chemicals Co., Ltd.); Sanol LS-770, 765, 292, 2626, 1114, 744 (above Sankyo Chemical Industries Co., Ltd.) and the like. The total amount of the light stabilizer relative to the photocurable composition is preferably mixed at a ratio of from 0.11 to 10% by mass. The photocurable composition of the present invention may contain a well-known antioxidant. The antioxidant is used to suppress fading due to light irradiation and fading due to various oxidizing gases such as ozone, active oxygen, NOx, SOx (X is an integer), and the like. Examples of the "antioxidant" as described above include: mercapto amides, sterically hindered amine-based antioxidants, nitrogen-containing heterocyclic thiol-based compounds, thioether-based antioxidants, and sterically hindered phenol-based antioxidants. Ascorbic acid, zinc sulfate, thiocyanate, thiourea derivative, saccharide, nitrite, sulfite, thiosulfate, hydroxylamine derivative, and the like. Examples of commercially available products of "anti-aging agent" include: Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, manufactured by Sumitomo Chemical Industries Co., Ltd.). The total amount of the anti-aging agent relative to the photocurable composition is preferably mixed at a ratio of 〇·〇 1 to 1% by mass. In the photocurable composition of the present invention, a plasticizer may be added to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like. Specific examples of preferred "plasticizers" include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dioctanoate, dimethylethylene phthalate Alcohol ester, tricresyl phosphate, dioctyl adipate, dibutyl sebacate-66 - 200848448, triethylene glyceryl, dimethyl adipate, diethyl adipate, adipic acid (n-butyl) ester, dimethyl suberate, diethyl suberate, di(n-butyl) suberate, and the like. The plasticizer may be arbitrarily added in an amount of 30% by mass or less in the composition. It is preferably 20% by mass or less, more preferably 10% by mass or less. When the effect of adding the plasticizer is to be obtained, it is preferably 0.1% by mass or more. In the photocurable composition of the present invention, an adhesion promoter may be added to adjust the adhesion to the substrate or the like. "Adhesion promoter" can be used: benzimidazoles or polybenzimidazoles, pyridine derivatives substituted with lower hydroxyalkyl groups, nitrogen-containing heterocyclic compounds, urea or thiourea, organic phosphorus Compound, 8-oxyquinoline, 4-hydroxyacridine, 1,10-morpholine, 2,2'-bipyridine derivative, benzotriazole, organophosphorus compound and phenyldiamine compound , 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and derivatives, benzothiazole derivatives, and the like. The adhesion promoter is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less in the composition I. When the effect of adding the adhesion promoter is to be obtained, it is preferably 0.1% by mass or more. When the photocurable composition of the present invention is to be cured, a polymerization initiator may be added as needed. Preferred "thermal polymerization initiators" include, for example, peroxides and azo compounds. Specific examples thereof include a benzamidine peroxide, a tertiary butyl peroxybenzoate, azobisisobutyronitrile, and the like. In the photocurable composition of the present invention, a photobase generator (photo-base-67-200848448 generator) may be added as needed to adjust the shape and sensitivity of the pattern. Preferred examples thereof include, for example, 2-nitrobenzylcyclohexylamine amide, triphenylmethanol, 0-amine-methylhydrazine hydroxy decylamine, hydrazine-aminomethyl hydrazide, [[(2) ,6-dinitrophenylhydrazino)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane n-diamine, 4-(methylthiophenyl) Mercapto)-1 -methyl-1 -morpholinylethane, (4 _morpholinylbenzylidene)-1-benzyl-1-dimethylaminopropane, N- (2-nitrate Benzomethyloxycarbonyl)pyrrolidine, hexaammine cobalt (111) gin (triphenylmethyl borate), 2-benzyl-2,dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2,6-dimethyl-3,5-diethylindol-4-(2,-nitrophenyl)-1,4·dihydropyridine, 2,6-di Methyl-3,5-diethylindol-4-(2',4,-dinitrophenyl)-1,4-dihydroindole is more than D. In the photocurable composition of the present invention, a coating of any component can be added for the purpose of improving heat resistance, mechanical strength, adhesion, and the like of the coating film. Inorganic particles are those that use ultra-fine particles. The so-called "ultrafine particles" are submicron-sized particles whose particle size is smaller than a particle having a particle size of from //m to a number of 1.00 m as generally referred to as "microparticles". The specific size of the inorganic fine particles used in the present invention is not the same as the use and grade of the optical article to which the photocurable composition is applied, but it is generally preferred to use a primary particle size ranging from 1 nm to 300 nm. By. When the primary particle size is 1 nm or more, the formability, shape retention, and mold release property of the photocurable composition can be sufficiently improved. On the other hand, when the primary particle size is 300 nm or less, Since the transparency required for hardening the resin is maintained, it is preferable in terms of transparency. Specific examples of the inorganic fine particles are metal oxide fine particles including SiO 2 , TiO 2 , ZrO 2 , SnO 2 , -68-200848448 A12 Ο 3 or the like, and it is preferred to select from among these to apply colloidal dispersion as described above and have a secondary Micron-sized particle size 'especially preferably using colloidal cerium oxide (SiO 2 ) particles. The inorganic fine particles are preferably a ratio of 1 to 7 % by mass in the total solid content of the photocurable composition, and particularly preferably a ratio of 1 to 50 % by mass. By setting the ratio of the inorganic fine particles to 1% by mass or more, the formability, shape retention, and mold release property of the composition of the present invention can be sufficiently improved, and the ratio of the inorganic fine particles can be set to 70% by mass or less. , sufficient strength or surface hardness can be obtained after exposure hardening. Further, in the photocurable composition of the present invention, elastomer particles of any composition may be added for the purpose of improving mechanical strength, flexibility, and the like. The elastomer particles which may be added as an optional component in the photocurable composition of the present invention have an average particle diameter of preferably from 10 nm to 700 nm, more preferably from 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/isoprene copolymer, ethylene/propylene copolymer , ethylene/α-olefin copolymer, ethylene/α-olefin/polyene copolymer, acrylic rubber, butadiene/(meth)acrylate copolymer, styrene/butadiene block Microparticles of elastomers such as polymers, styrene/isoprene block copolymers, and the like. Further, core-shell type fine particles in which the elastomer fine particles are covered with a methyl methacrylate polymer, a methyl methacrylate/glycidyl methacrylate copolymer or the like can be used. Elastomeric particles can also be used in a crosslinked structure. These elastomer fine particles may be used singly or in combination of two or more. In the composition of the invention of the present invention, the content of the elastomer component is preferably from 1 to 35 mass%, more preferably from 2 to 30 mass%, particularly preferably from 3 to 20 mass%. In the composition of the present invention, a well-known antioxidant can be contained. The antioxidant is used for suppressing fading caused by light irradiation, and fading caused by various oxidizing gases such as ozone, active oxygen, NOx, and SOx (X is an integer). Examples of such "antioxidants" include: mercapto amides, sterically hindered amine-based antioxidants, nitrogen-containing heterocyclic thiol-based compounds, thioether-based antioxidants, sterically hindered phenolic antioxidants, ascorbic acid. Classes, zinc sulfate, thiocyanates, thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. In the photocurable composition of the present invention, a basic compound can be arbitrarily added for the purpose of suppressing curing shrinkage, improving thermal stability, storage stability, and the like. Examples of the "basic compound" include a nitrogen-containing heterocyclic compound such as an amine, quinoline or quinolizine, a basic alkali metal compound, a basic alkaline earth metal compound, and the like. Among these, from the viewpoint of compatibility with a photopolymerizable monomer, an amine such as octylamine, naphthylamine, xylene diamine, benzhydrylamine or diphenylamine is preferable. Dibutylamine, dioctylamine, dimethylaniline, qiiinuclidine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine , hexamethylenetetramine and triethanolamine. In the present invention, a cationic polymerization initiator which generates an acid due to energy rays combines a substance which spontaneously and catalytically generates an acid due to the action of an acid generated (hereinafter referred to as "acid proliferator" (acid amplifier )"), can also increase the hardening speed. In the case of the Japanese Patent Application Laid-Open No. Hei 08-248 5 6 1 and the Japanese Patent Application Laid-Open No. Hei. The compound of Patent No. 3 1 02640, specifically, includes, for example, 1,4-bis(p-toluenesulfonyloxy)cyclohexane, cis-3-(p-toluenesulfonate) Base)-2 - pine sterol, cis-3 -(p-octanesulfonyloxy)-2_sonol. Examples of the commercially available compound include, for example, Acpress 11M (manufactured by Nippon CHEMIX Co., Ltd.) and the like. Next, a method of forming a pattern (especially a fine concavo-convex pattern) of the photocurable composition of the present invention will be described. In the present invention, the curable composition of the present invention is applied and cured to form a pattern. Specifically, at least a pattern forming layer composed of the photocurable composition of the present invention is applied onto a substrate or a support, and dried as necessary to form a layer (pattern forming layer) composed of a photocurable composition. To form a pattern acceptor, the mold core is then crimped onto the surface of the pattern forming layer of the pattern receptor to perform processing of the transfer mold pattern, and the fine uneven pattern forming layer is exposed to be hardened. The photo-imprint lithography using the pattern forming method of the present invention can also be carried out by lamination or multiple patterning, or can be used in combination with usual hot stamping. Further, the pattern formation can be continuously performed by the package loading and unloading method. Further, the composition of the present invention may be applied to the substrate or the support by applying the composition of the present invention, and then the layer composed of the composition may be exposed, hardened, and dried (baked) as needed. A permanent film such as a cover layer or an insulating film is produced. -71 - 200848448 Hereinafter, a pattern forming method and a pattern transfer method using the photocurable composition of the present invention will be described. The photocurable composition of the present invention may be a conventional coating method, for example, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, and rotation. It can be formed by coating by a coating method, a slit scanning method, or the like. The film thickness of the layer composed of the photocurable composition of the present invention may vary depending on the use, but may be f:· 0 · 0 5 # m to 3 0 // m. Further, the composition of the present invention can also be applied with multiple coatings. The substrate or support for coating the photocurable composition of the present invention is not particularly limited, and quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film, Ni, Cu, Cr may be used. Electrode substrate such as metal substrate, paper, SOG (spin-coated glass), polyester film, polycarbonate film, polyimide film, etc., TFT array substrate, and electrode plate of p DP (plasma display) , glass or transparent plastic substrate, ITO (oxygen (indium tin) or metal) conductive substrate, insulating substrate, silicon, silicon nitride, polysilicon, A substrate made of a semiconductor such as silicon oxide or amorphous silicon, etc. The shape of the substrate may be a plate shape or a roll-like shape. Light for hardening the composition of the present invention Although there are no special restrictions, it can be light or radiation of wavelengths in areas of high-energy ionizing radiation, near-ultraviolet rays, far ultraviolet rays, visible rays, infrared rays, etc. "High-energy ionizing radiation sources", although in the industry For the most convenient and cost-effective -72- 200848448 is most commonly used, for example, by Cockcroft type accelerator, Van de Graaff type accelerator, linear accelerator, magnetic It induces "electron rays" accelerated by accelerators such as betatrons and cyclotrons, but other radioactive isotopes or 7-rays, X-rays, alpha rays, and neutrals emitted by atomic furnaces can also be used. Examples of "radiation" such as Neutron beam and Proton beam. Examples of "ultraviolet source" include, for example, ultraviolet fluorescent lamps, low-pressure mercury lamps#, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, and carbon arcs. Lights, solar lights, etc. Examples of "radiation" include, for example, microwave, EUV (Extreme Ultraviolet). In addition, in LED (Light Emitting Diode), semiconductor laser, or Laser light used for microfabrication of semiconductors such as 248 nm KrF excimer laser light or 193 nm ArF excimer laser is also suitable It is used in the present invention. The light of the present invention can be used in the present invention by using monochromatic light or by using several different wavelengths of light (mixed light). Photonic imprint lithography, at least one of the mold material and/or the substrate must select a light transmissive material. For photoimprint lithography of the present invention, a photocurable composition is coated on the substrate. Then, the light transmissive mold core is pressed and the back surface of the mold is irradiated with light to harden the photocurable composition. Further, a method of applying a photocurable composition to a light-transmitting substrate, pressing the mold, and irradiating light from the back side of the mold to harden the photocurable composition may be employed. -73- 200848448 Although the light irradiation can be carried out in a state in which the mold core is still attached, it can be carried out after peeling off the mold core, but in the present invention, it is preferred to carry out the state in which the mold core is still adhered. The mold used in the present invention is a mold having a pattern to be transferred. Although the mold core can be patterned by, for example, photolithography or electron beam drawing, and according to the precision of the processing, the mold pattern forming method is not particularly limited in the present invention. The light-transmitting mold core material used in the present invention is not particularly limited as long as it has specific strength and durability. Specifically, for example, a light-transparent resin such as glass, quartz, PMMA (polymethyl methacrylate) or polycarbonate resin, a transparent metal vapor-deposited film, a soft film such as polydimethyl siloxane, or a photo-cured film. , metal film, etc. When the transparent substrate of the present invention is used, the non-light transmitting type core material used is not particularly limited, but may have a specific strength. Specifically, for example, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, a substrate such as SiC, tantalum, tantalum nitride, polycrystalline germanium, germanium oxide, or amorphous germanium, or the like. , but there are no special restrictions. The shape may be any one of a plate-shaped mold core and a roll-shaped mold core. The roll-shaped mold core is suitable for the case where continuous transfer productivity is particularly required. The mold core used in the present invention as described above may also be subjected to a mold release treatment for improving the peelability of the photocurable composition from the mold core. It is also suitable for use by a processor to which a decane coupling agent such as a polyfluorene-based or fluorine-based compound is applied, for example, manufactured by Daikin Industries Co., Ltd. under the trade name OPTOOL DSX or manufactured by Sumitomo 3M Co., Ltd., and the product name is Novec EGC- 1720, etc. - 74- 200848448 commercially available release agent. When photoimprint lithography is carried out using the present invention, it is usually preferred to carry out the pressure at a pressure of 1 Torr or less. When the pressure of the mold core is set to be 10 or less, the mold or the substrate is not easily deformed, the pattern accuracy tends to be improved, and the pressure is low, so that the scale of the apparatus can be reduced, which is preferable. The pressure of the mold core is preferably within a range in which the residual film of the photocurable composition of the convex portion of the mold is reduced, and the range in which the uniformity of the transfer of the mold is ensured is selected. In the present invention, the photoimprint light is applied. The light irradiation at the time of engraving may be sufficient to be larger than the amount of irradiation required for hardening. The amount of irradiation required for hardening is determined by investigating the amount of bonding of the photocurable composition or the adhesion of the cured film. Further, in the photoimprint lithography which is applied to the present invention, the substrate temperature at the time of light irradiation is usually carried out at room temperature, but in order to improve the reactivity, light irradiation may be performed while heating. When the vacuum state is formed in advance before the light irradiation, it is effective in preventing the bubble from being mixed, suppressing the decrease in reactivity due to the incorporation of oxygen, and improving the adhesion between the mold and the photocurable composition. Light irradiation is performed under vacuum. In the present invention, the preferred degree of vacuum is carried out in the range from lfT1 Pa to normal pressure. The composition of the present invention can be prepared by mixing the components as described above, for example, by a sieve having a pore diameter of 〇 · 〇 5 / m to 5 · 0 / m to prepare a solution. The mixing and dissolving of the photocurable composition is usually carried out in the range of 〇 ° C to 100 ° C. Filtration can be divided into multiple stages, or repeated -75- 200848448 multiple times. Alternatively, the filtered liquid can be filtered again. The material used for the filtration may be a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin or the like, but is not particularly limited. The case where the photocurable composition of the present invention is applied to etching photoresist will be described. The etching step can be carried out by a method suitably selected from the well-known etching treatment methods for performing removal of the portion of the substrate not covered by the photoresist pattern to obtain a pattern of the film. This can be carried out by any of the methods of treating the etching solution (wet uranium engraving) or discharging the reactive gas by plasma to activate (dry uranium engraving) under reduced pressure. In the "etching liquid" for the wet etching as described above, many uranium engravings, such as ferric chloride/hydrochloric acid, hydrochloric acid/nitric acid, hydrobromic acid, etc., have been developed and have been put into practice. Practical application. That is, for Cr (chromium), a mixture of ammonium cerium nitrate solution or cerium nitrate/hydrogen peroxide solution is used; for Ti (titanium), a mixed solution of hydrofluoric acid, hydrofluoric acid and nitric acid is used; For Ta (large), a mixture of ammonium solution and hydrogen peroxide solution is used; for Mo (molybdenum), a mixture of hydrogen peroxide solution, ammonia water and hydrogen peroxide solution, and a mixture of phosphoric acid and nitric acid are used; For MoW (molybdenum tungsten) and A1 (aluminum), a mixture of phosphoric acid and nitric acid, a mixture of hydrofluoric acid and nitric acid, a mixture of phosphoric acid, nitric acid and acetic acid, and for IT Ο (indium tin oxide) are used. Dilute aquaregia, ferric chloride solution, hydrogen iodide solution; for SiNx or SiO 2, use buffered hydrofluoric acid, hydrofluoric acid / ammonium fluoride mixture; for Si, polycrystalline cesium, use hydrofluoric acid • nitric acid • a mixture of acetic acid; for W (tungsten), a mixture of ammonia water and hydrogen peroxide solution; for PSG (phosphorus glass: -76-200848448 phosphosi 1 icateg 1 ass), a mixture of nitric acid and hydrofluoric acid is used. ,Correct BSG (borosilicate glass: boro silicate glass), using a mixture of hydrofluoric acid-ammonium fluoride and the like. The wet etching adopts a shower method or an immersion method. However, since the etching rate, in-plane uniformity, and wiring width accuracy are determined depending on the processing temperature, the processing conditions must be determined according to the substrate type, use, and line width. Optimum. Further, when the wet uranium engraving as described above is carried out, it is preferable to carry out a post-baking treatment to prevent undercut due to the penetration of the etching liquid. Usually, the post-baking treatment is carried out at about 90 ° C to 140 ° C, but is not limited thereto. The dry etching is basically a parallel plate type dry etching apparatus in which a pair of parallel electrodes are provided in a vacuum apparatus and a substrate is provided on one of the electrodes. Depending on the difference between the electrode used to generate the plasma and the electrode connected to one side of the substrate or the electrode connected to the opposite electrode, it can be classified into a reactive ion etching (RIE) mode mainly involving ions, and mainly A plasma etching (PE) mode in which free radicals are involved. The etching gas used in the dry etching as described above is an etching gas suitable for each film type. That is, for a-Si/n + or s-Si, carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine) is used; for a-SiNx, Then use carbon tetrafluoride + oxygen; for a-SiOx, use carbon tetrafluoride + oxygen, carbon trifluoride + oxygen; for Ta (giant), use carbon tetrafluoride (sulfur hexafluoride) + oxygen; for M〇Ta/M〇W (molybdenum giant/molybdenum tungsten), carbon tetrafluoride + oxygen is used; for Cr (chromium), chlorine + oxygen is used; for A1 (aluminum), Use boron trichloride + chlorine, hydrogen bromide -77 - 200848448, hydrogen bromide + chlorine, hydrogen iodide and the like. In the dry etching step, there is a possibility that the structure of the photoresist is greatly deteriorated due to ion rushing or heat, and the peeling property is also affected. The method for peeling off the photoresist used for transferring the pattern to the underlying substrate after etching is explained below. Peeling can be removed by liquid removal (wet stripping) or by plasma discharge of oxygen under reduced pressure to form a gas (dry strip/ashing), or ozone and UV light. The stripping is removed by oxidizing it into a gas to remove (dry strip/UV ashing) or the like to remove the photoresist. A stripper is generally known as an aqueous solution of an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of ozone dissolved water, and a mixture of an amine and dimethyl hydrazine or N-methylpyrrolidone. . A conventional example of the latter is a mixture of monoethanolamine/dimethyl hydrazine (mass mixing ratio = 7/3). The photoresist peeling rate is greatly affected by temperature, liquid amount, time, pressure, etc., but can be optimized depending on the type and use of the substrate. In the present invention, it is preferred to impregnate the substrate (minutes to several tens of minutes) at a temperature ranging from room temperature to about 1 〇 C ° C, and then wash and wash with a solvent such as butyl acetate. From the viewpoint of improving the washing property, the particle removability, and the corrosion resistance of the peeling liquid itself, it is also possible to wash only water. A preferred example of water washing is pure water spraying, and a preferred example of drying is air knife drying. When the amorphous germanium is exposed on the substrate, the oxide film is formed by the presence of water and air, so that it is preferable to block the air. In addition, it is also suitable for ashing and peeling by liquid medicine. Ashing systems include plasma ashing, downflow ashing, ozone ashing, UV/ozone ashing. For example, -78- 200848448 When dry-etching an A1 substrate, it is common to use chlorine-based aluminum chloride, which is a product of chlorine and A1, which may corrode A1. To prevent such problems, preservatives may also be used. The stripping liquid is not particularly limited except for the etching step, the stripping step, and the washing step as described above, and may be appropriately selected from the steps formed in the case. For example, hardening or the like can be selected. These may be used alone or in combination of two or more groups. There is no particular limitation, and although it may be selected according to the purpose, it is suitable to use, for example, full heat treatment or full exposure as described above. The method of treatment" includes a method of heating the prepared pattern in its entirety. The surface film strength of the pattern as described above can be improved by comprehensively. In general, the temperature is preferably 80 to 20 (TC, more preferably 90 to 180 ° C. The heating temperature is set to 8 (TC or more, whereby there is a tendency to further increase the strength of the film treated with heat, and It is set to 2 0 0 t: This can more effectively suppress the components in the photocurable composition and make the film quality weak. It can be used to perform the device heated as before, without special restrictions, depending on the purpose. Appropriately selected from the conventional device, for example, a drying box, a hot plate, a wire heater, etc. In addition, if a hot plate is used, the substrate should be floated on the plate for heating to obtain uniform heating. As described above, the "method of comprehensive exposure processing" includes a method of comprehensively exposing a pattern which is formed by a comprehensive gas, but in the case of a full-scale gas, it is known that the processing steps of the water-washing method are combined. Appropriate light treatment, etc., such as heating, that is, heating, by raising the ground below, by the well-known IR of the decomposition (infrared forming pattern, such as the shape of the exposure, ie -79-200848448 Can promote The hardening in the composition for forming the photosensitive layer as described above causes the surface of the pattern to be hardened, thereby improving the etching resistance. The apparatus for the full exposure is not particularly limited, but may be used according to the purpose. Although it is suitably selected, it is preferable to use, for example, a UV exposure machine such as an ultrahigh pressure mercury lamp. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. The materials, usage amounts, and ratios shown in the following examples are shown. The scope of the present invention is not limited to the specific examples described below, and the contents of the present invention are not limited to the specific examples described below. The code of each monomer used in the examples is as follows: <monomer> C-1: 3-ethyl-3-(phenoxymethyl)oxetane (OXT21 1 : manufactured by Toagosei Co., Ltd.) [ C- 2: 3-ethyl-3-hydroxyethyl oxetane (OXT101: manufactured by Toagosei Co., Ltd.) C-3: bis[1-ethyl(3-oxetanyl)methyl ether] OXT221: manufactured by Toagosei Co., Ltd.) C-4: Main ingredient 1 4. Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (OXT-121: manufactured by Toagosei Co., Ltd.) C-5: 3·ethyl-3- ( 2- Ethylhexyloxymethyl)oxetane (OXT212: manufactured by Toagosei Co., Ltd.) -80-200848448 C-6 : The following oxetane synthesized by the method disclosed in Synthesis Example 1 Compound C-7 of the alkane ring: Compound C-8 having the oxetane ring shown below synthesized by the method disclosed in Synthesis Example 2: synthesized by the method disclosed in Synthesis Example 3. Compound C-9 of oxetane ring as shown below: (3-methyl-3-oxetanyl)methyl acrylate (OXE-10: Osaka Organic Chemical Industry Ltd. )) C-10 : 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (manufactured by Cyracure-6105·· Union Carbide Corp.) Cl 1 : 1·2 ···8,9 Diepoxide (CELLOXIDE 3000:

Made from Daicel Chemical Industry Co., Ltd. C-12 : Vinylcyclohexene oxide 1,2-epoxy-4-vinylcyclohexene (CELLOXIDE 2000 : Daicel Chemical Industry Co., Ltd.) C-13 : Epoxidized fatty acid glycerin Ester (CELLOXIDE 202 1 P: manufactured by Daicel Chemical Industry Co., Ltd.) C-14 : Hydroxybutyl vinyl ether (HBVE: manufactured by Maruzen Petrochemical Co., Ltd.) C-15: Sangan Alcohol divinyl ether (RAPI-CURE D VE-3 : ISP · JAPAN) -81- 200848448 C-16 : Trimethylolpropane triacrylate (ARONIX M-309: manufactured by Toagosei Co., Ltd.)

C-6 C-7 C-8 The photoradical polymerization initiator used in the examples and comparative examples of the present invention was encoded as follows. <Photocationic polymerization initiator> Ul: Hydrazine photoacid generator (manufactured by Union Carbide Corp.: UVI6990) U-2: Triallyl hexafluorophosphate (manufactured by Midori Chemical Co., Ltd.: DTS-102) U-3 : Triallyl hexafluorophosphate mixture (manufactured by Dow Chemical Co.: Cyracure UVI6992) u-4: Tris-chlorophenyl sulfonium hexafluorophosphate U-5: 1,2- Octanedione, 1-[4-(phenylthio)-2-(o-benzhydrylhydrazine)] (manufactured by Ciba Specialty Chemicals Co., Ltd.: OXE-01) In the examples and comparative examples of the present invention The coding of the surfactants and additives used is as follows. <Surfactant> -82- 200848448 W-l : Fluorine-based surfactant (Tochem Products Co.,

Ltd. Manufactured by: Fluorine-based surfactant) W-2: Polyoxo-based surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: Megafac Paintad 31) W-3 : Fluorine-polyfluorene-based surfactant (Greater Japan) Ink Chemical Industry Co., Ltd.: Megafac R-08) W-4: Fluorine-polyfluorene-based surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: Megafac XRB-4) W-5 : Acetylene glycol-based nonionic interfacial activity Agent (manufactured by Shin-Etsu Chemical Co., Ltd.: SURFYNOL 465) W-6 : Polyoxyethylene-polyoxypropylene condensate (manufactured by Takemoto Oil Co., Ltd.: Paionin P- 1 5 2 5 ) W-7 : Fluorine-based surfactant (Great Japan Ink Chemical Industry Co., Ltd.: Megafac F470) W-8: Fluorine-based surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd.: Megafac EXP. TF907) W-9: Fluorine-based surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd.: Megafac F 1 405 ) <Additives> A - 1 : 2-Chlorooxysulfide η Hawthorn-2: 9,10-Dibutoxypurine (Kawasaki Chemical Industry Co., Ltd. (

Kawasaki Kasei Chemicals, Ltd.) A-3 : 4,4'-diethylaminobenzophenone-83- 200848448 A-4: 1,9-dibutoxyanthracene A-5 : N- Ethyldiethanolamine A-6: Tributylamine A-7 : decane coupling agent (vinyl triethoxy decane) (Shin-Etsu Silicone Co., Ltd.) A-8: CI Pigment Black ( Pigment Black) 7 (Clariant

Made by Japan) A- 9 : CI Pigment Blue 15:3 (Mikuni Color Ltd.) A -1 0 : Dispersant (Ajinomoto F ine - T ech η o Manufactured by Ajinomoto Fine-Techno Co., Inc.: PB 822 ) Al 1 : rosin-modified maleic acid resin (HARITAC R-100: Harima Chemicals,

Inc.) Manufacturing A-12: Propylene carbonate (Kanto Chemical Co., Ltd.

(manufactured by Chemical Co., Inc.) <Evaluation of Photocurable Composition-I> Each of the compositions prepared according to Examples 1 to 1 and Comparative Examples 1 to 1 was evaluated by the following evaluation method. Determination and evaluation. Table 1 shows the polymerizable monomers (Examples, Comparative Examples) used for the composition, respectively. Table 2 shows the mixing ratios (Examples, Comparative Examples) of the polymerizable monomers contained in the composition, respectively. -84- 200848448 Table 3 shows the mixing ratio of the polymerizable monomer, photopolymerization initiator, surfactant, and additive used for the composition, respectively (Examples, Comparative Examples) Table 4 shows the results of the present invention ( Examples and comparative examples). In addition, the aggregate assessments in Table 4 were performed on the following basis. If it is above the A grade, it is practical. A: B grade has 2 or less; B: B grade has 3 or more; C: B grade has 4 or more, or even if c grade has 1 item. <Viscometry>

The viscosity was measured using a RE_80L type rotational viscometer manufactured by Toki Sangyo Co., Ltd., and measured at 25 ± 0.2 ° C. When the rotation speed at the time of measurement is 0.5 mPa·s or more and less than 5 Pa·s, it is 100 rpm: when it is 5 mPa·s or more and less than 10 Pa·s, it is 50 rpm; 10 mPa · s or more, less than 30 Pa·s, 20 rpm; above 30 mPa · s, less than 60 Pa·s ' is 10 rpm; above 60 mP a · s, less than 120 For Pa·s, it is: 5 rpm; at 120 mPa · s or more, it is 1 rpm or 0.5 rpm. <Measurement of Photocurability> The photocurability was measured by using a local pressure mercury lamp as a light source, and the change of 810 cm_1 absorption was performed using a Fourier transform (Fourier transform) type infrared spectroscopic device (ft-IR) in real time. -85- 200848448 Determine the rate of hardening reaction (unit consumption rate). In Table 4, A represents a case where the curing reaction rate is 0.2/sec or more, and B represents a case where the curing reaction rate is less than 0.2 / sec. <Adhesion> Adhesion is to attach a photo-cured photocurable photocuring tape to the surface of the photocurable photocurable photoresist pattern and to remove it by visual inspection. The photoresist pattern was attached and evaluated on the following basis: A: no pattern adhesion on the adhesive side; B: although extremely thin on the adhesive side, pattern adhesion was observed; C: on the adhesive side Obviously observed pattern attachment. <Peelability> The peeling property is to observe whether or not there is an unhardened material residue after the mold is peeled off after photohardening, and then evaluated by the following criteria: A: no residue on the surface of the mold; B: surface of the mold core Some of them have residues; C: There is a residue on the surface of the mold. <Observation of residual film property and pattern shape> The pattern shape after transfer and the residue of the transfer pattern were observed by a scanning electron microscope, and the residual film property and pattern shape were evaluated by the following criteria: (residual film property) A : Unobserved To the residue; B: A small amount of residue can be observed; C: Many residues can be observed. -86- 200848448 (Pattern shape) A: The original pattern is roughly the same as the pattern shape source of the mold core; B: The original pattern shape which is different from the pattern shape source of the mold core (the difference from the original pattern is less than 20%) Scope); C: The original pattern of the pattern shape source of the mold kernel is significantly different, or the difference between the film thickness of the pattern and the original pattern is 20% or more. <Rotary coating suitability> Coating property (I) The photocurable composition of the present invention was rotated on a 4-inch glass substrate having a thickness of 0.7 mm formed into a film thickness of 4000 angstroms (A1). After spin coating to a thickness of 6.0 // m, the glass substrate was allowed to stand for 1 minute, and the surface state was observed, and then evaluated on the following basis: A: no cracking and coating streaks were observed (coating line marks); B: A few coating streaks were observed; C: Severe cracking or coating streaks were observed. <Slit coating suitability> Coating property (11) The composition of the present invention was applied to a slit type photoresist coating apparatus (Head Coater System manufactured by Hirata Corp.) for coating a large substrate. A 4 inch glass substrate (550×x-87-200848448 650 mm) having a thickness of 0.7 mm and a thickness of 4,000 angstroms (A1) was formed to form a photoresist film having a film thickness of 2.0/m. And whether or not there is streaky unevenness in the warp and weft direction, and then evaluated as follows: A: no streaky unevenness is observed; B: streaky unevenness is observed slightly; C: severe streaky shape is observed Uniformity, or cracking observed in the photoresist. <Uranium engraving> The aluminum photo film is formed into a pattern on the aluminum (A1) formed on the glass substrate as described above, and after hardening, the aluminum film is etched with a phosphorous etchant, and The line width/pitch was visually observed and observed under a microscope, and then evaluated on the following basis: Α: An aluminum wire having a line width of 10±2·0/zm was produced; B: The line width unevenness of the obtained line was more than ± 2.0 // m line C: The defective part of the wire exists or the lines are connected. [Synthesis Example 1] 5 · 2 g of sodium hydride was suspended in 100 ml of dimethyl hydrazine in an ice bath, and 10.2 g of 3-methyl-3-oxetane methanol was added dropwise for 30 minutes. , 20.3 g of 1-bromo-2-ethylhexane was added dropwise. After stirring for 4 minutes, the temperature was raised to room temperature and stirred for 6 hours. The reaction solution was diluted with water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, washed with saturatedness, and dried over magnesium sulfate. Then, ethyl acetate was distilled off and purified by column chromatography to obtain 4·9 g of Compound C-6. h-NMR (3 00 MHz, CDC13, 5): 4.52 (dd, 2Η), observation of the reference film, the original acid etching) / / m base armor. Stir ^ 3 0 , then brine and 4.37 -88- 200848448

(dd, 2H), 3.40 (s, 2H), 3.35 (d, 2H), 1.52 (m, lH), 1.40-1.22 (m, llH), 0.95-0.84 (m, 6H) 使用 by using RE 80 Viscosity meter (trade name, manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity of compound C-6 at 25 ° C. The result was 2.4 mPa · s ° [Synthesis Example 2] 204.3 g of 3-A in an ice bath The base 3-oxetane methanol was stirred with 500 ml of pyridine, and 4 1 9 · 4 g of p-toluenesulfonyl chloride was added thereto in small portions. After stirring for 3 hours in an ice bath, 2 liters of water was added to the reaction liquid to cause crystallization. Then, the white solid was filtered and washed with water until the odor of pyridine disappeared, and then dried. The yield was 471.9 g (92%). 90 g of sodium hydride was suspended in 1 liter of N,N-dimethylformamide under ice bath, and 153.2 g of 3-methyl-3-oxocyclohexane was added dropwise. Butane methanol in dimethylformamide solution (500 ml). After stirring for 30 minutes, a white solid of 3 84.5 g of toluenesulfonate base which was just prepared was added in small portions. After stirring for 30 minutes, the mixture was warmed to room temperature and stirred for 6 hours. The reaction solution was diluted with water and then extracted with ethyl acetate. The ethyl acetate layer was washed with water, washed with saturated brine, and dried over magnesium sulfate. Then, ethyl acetate was distilled off and purified by column chromatography. As a result, 210.0 g of a distillate of Compound C-7 was obtained at about 4 mmHg, 94 ° C to 98 ° C. Its yield is 75%. W-NMR (3 00 MHz, CDC13, 5): 4.52 (dd, 4H), 4.38 (dd, 4H), 3.56 (s, 4H), 1.34 (s, 6H). -89- 200848448 By using a RE80 type viscometer (trade name, manufactured by Toki Sangyo Co., Ltd., the viscosity of the compound C-7 at 25 ° C was measured, and the result was 5.2 mP a · s [Synthesis Example 3] at room temperature. Stir 150 ml of 48% aqueous sodium hydroxide solution, 1 表 of epichlorohydrin, 3.7 g of tetrabutylammonium hydrogen sulfate, and then slowly drop 25 g of 3-ethyl-3-hydroxymethyl group for B minutes. The oxetane was stirred at room temperature for further 7 hours, and the reaction mixture was diluted with water and then extracted with ethyl acetate. The ethyl acetate layer was washed with water and then brine, and then dried over magnesium sulfate. Ethyl acetate was purified by chromatography. As a result, 32.4 g of Compound C-8 was obtained. W-NMR (3 00 MHz, CDC13, 5): 4.48 ( dd, 2H ), (d, 2H), 3.64 -3.58 (m, 3H), 3.41 (d, lH) &gt; 2. dd, 1H), 2.61 (dd, 1H), 1.77 (q5 2H), 1.38 (5), 0.95 (t, 3H). The viscosity of the compound C-8 at 25 ° C was measured by using a RE 8 0 viscometer (trade name, manufactured by Toki Sangyo Co., Ltd.), and the result was m P a · s ° [Example 1] 14·07 g of 3-ethyl-3-(phenoxymethyl)oxyalkylene monomer (C-1), 6 5.66 g of 3-ethyl-3-(2-ethylhexyloxy)oxalate Cyclobutane (C-5), 14.07 g of 1,4 bis[(3-ethylheterocyclobutane methoxy)methyl]benzene (C-4) as a polymerizable single 5.5 g bismuth salt UVI6990 (manufactured by Dow Chemical Co., Ltd.) as a polymerization initiator, 1 g of Megafac XRB-4 (W-4: manufactured by Dainippon), ml of f 30 alkane. After that, it was washed with a column type of 4.40 75 (3H male cyclobutane 3-oxide, manufactured by Photo Ink-90-200848448 Chemical Industry Co., Ltd.) as a fluorine-polyfluorene-based surfactant, and 〇·60 g of 9, 10-Dibutoxy oxime (manufactured by Kawasaki Chemical Industry Co., Ltd.) was used as a sensitizer and mixed at room temperature for 24 hours to prepare a homogeneous solution. The viscosity of the composition was determined to be 1 8 mPa·s. The prepared composition was spin-coated to a thickness of 6.0 / z m on a 4 inch tantalum substrate. The spin-coated coated base film is mounted on a nano-imprinting device manufactured by ORC Corporation with a partial pressure mercury lamp (lamp power of 2,0 0 m W / cm 2 ) as a light source, and a pressure of 50 is applied to the mold core. kN/cm2, vacuum in exposure is 0.2 Torr, from the line pattern with l〇#m, the depth of the groove is 5.0 //m, the polydimethyl oxime (Toray-Dow Corning) The SILPOT 184 manufactured by the company is cured at 80 ° C for 60 minutes. The back side of the mold is exposed to a temperature of 170 mm J / cm 2 , and after exposure, the mold is removed, and then with the example 1 Investigate the characteristics of the composition in the same way. As a result, it was confirmed that it has satisfactory photocurability, adhesion, mold release property, residual film property, pattern shape, applicability (spin coating property, slit coating property), and etching as a whole. Sex. [Examples 2 to 10] In the same manner as in Example 1, the polymerizable monomers shown in Table 1 were mixed at a ratio as shown in Table 2 to prepare a composition as shown in Table 3. . The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. It is also confirmed that any of the compositions of Examples 2 to 10 has satisfactory photocurability, adhesion, mold release property, residual film property, pattern shape, and coating property (rotation coating property) as a whole. , slit coating properties) and f insects -91- 200848448 Sex. [Comparative Example 1] The composition was prepared by removing only the surfactant from the composition without changing the type of the monomer, the photopolymerization initiator, and the additive used in Example 1, and the mixing ratio. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. The composition of Comparative Example 1 was compared with the composition of Example 1 in terms of mold release property, residual film property, and coatability (spin coating property, slit coating C' property). The uranium engraving has deteriorated, and the producers are not omnipresent. [Comparative Example 2] The type of the surfactant was changed from the composition to the non-ionic system different from the present invention, without changing the type of the monomer, the photopolymerization initiator, and the additive used in Example 2, and the mixing ratio. The surfactant (W-5) is used to prepare the composition. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were investigated. The results are shown in Table 4. In the composition of Comparative Example 2, the mold release property, the coatability (spin coating property, the slit coating property), and the etching property were deteriorated compared with the composition of Example 2, and the obtained one was not as a whole. Satisfactory. [Comparative Example 3] The type of the surfactant was changed from the composition to the non-ionic system different from the present invention, without changing the type of the monomer, the photopolymerization initiator, and the additive used in Example 3, and the mixing ratio. The surfactant (W-6) is used to prepare the composition. The prepared composition was patterned in the same manner as in Example 1 from -92 to 200848448, and then the characteristics of the composition were investigated. The results are shown in Table 4. In the composition of Comparative Example 3, the mold release property, the coatability (spin coating property, the slit coating property), and the etching property were deteriorated compared with the composition of Example 3, and the obtained one was not as a whole. Satisfactory. [Comparative Example 4] 2.5% by mass of a solvent (A-1 2 :carbonic acid) was added to the composition without changing the type of the monomer, the photopolymerization initiator, and the surfactant used in Example 4 and the mixing ratio. Propylene ester) to prepare the composition. The composition thus obtained was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. In the composition of Comparative Example 4, the residual film property, pattern shape, and etching property were deteriorated as compared with the composition of Example 4, and the obtained one was not satisfactory as a whole [Comparative Example 5] The pigment (A-9: CI Pigment Blue (Pigment Blue) was added to the composition without changing the type of the monomer, the photopolymerization initiator, and the surfactant used in Example 5 and the mixing ratio. ) 15:3) to modulate the composition. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. In the composition of Comparative Example 5, the photocurability, pattern shape and engraving property were deteriorated as compared with the composition of Example 5, and the obtained one was not satisfactory as a whole. [Comparative Example 6] The composition disclosed in the Example (Ink Composition 3) of the composition of Inkjet-93-200848448, which is disclosed in Japanese Laid-Open Patent Publication No. 2005-8759, In the same manner as in the first embodiment of the invention, the polymerizable monomers as shown in Table 2 were mixed at a ratio as shown in Table 2 to prepare a composition having the composition shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. The composition of Comparative Example 6 had poor photocurability, mold release property and etchability as compared with the composition of the present invention, and the obtained one was not satisfactory as a whole. [Comparative Example 7] In the composition of Comparative Example 6, a pigment (A-8: CI Pigment Black 7), a dispersant A-10: a dispersant (manufactured by Ajinomoto Fine-Techno Co., Ltd.) : PB822) Except for the composition, the other components were the same as those of Comparative Example 6, and in the same manner as in Example 1 of the present invention, the polymerization shown in Table 1 was mixed in the ratio shown in Table 2. The monomer was prepared to have a composition as shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. As is apparent from the results of Table 4, the composition of Comparative Example 7 was inferior to the composition of the present invention in photocurability, mold release property, pattern shape and etching property, and the obtained one was not a whole. Can be satisfactory. [Comparative Example 8] A composition disclosed in a comparative example (hardened composition No. 5) of a photocurable composition, which is disclosed in Japanese Laid-Open Patent Publication No. 2005- 1943, In the same manner as in Example 1, the polymerizable monomers shown in Table 1 - 94 to 200848448 were mixed at a ratio as shown in Table 2 to prepare a composition having the composition shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. The composition of Comparative Example 8 was not satisfactory in photocurability, mold release property, and residual film property, and was also satisfactory in pattern shape, coatability (spin coating property, slit coating property), and etching property. [Comparative Example 9] The composition disclosed in the comparative example (cured composition No. 5) of the photocurable composition for inkjet is disclosed in Japanese Laid-Open Patent Publication No. 2005-194379. In the same manner as in the first embodiment of the invention, the polymerizable monomers shown in Table 1 were mixed at a ratio as shown in Table 2 to prepare a composition having the composition shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. The composition of Comparative Example 9 was not satisfactory in any of photocurability, mold release property, residual film property, pattern shape, coatability (spin coating property, slit coatability), and etching property. . [Comparative Example 1 〇] It is disclosed in Japanese Laid-Open Patent Publication No. 2005-4-1868, which is incorporated in a comparative example of the photocurable composition for inkjet (ink composition 1 hardening composition N 〇. 5 ) In the same manner as in Example 1 of the present invention, the polymerizable monomers shown in Table 1 were mixed in a ratio as shown in Table 2 to prepare a composition as shown in Table 3. Things. The prepared composition was patterned in the same manner as in Example 1, and then the characteristics of the composition were investigated. The results are shown in Table 4. Comparative Example 1 Composition of ruthenium-95·200848448, which is neither photocurability, mold release property, residual film property, pattern shape, coatability (spin coating property, slit coating property), and uranium engraving property For those who are satisfied. Table 1

Polymerizable monomer functional group number viscosity (25 ° C) (mPa · s ) C-1 1 13.8 C-2 2 10.0 C-3 1 13.8 C-4 1 22.4 C-5 2 12.8 C-6 1 2.4 C-7 2 5.2 C-8 2 5.9 C-9 3 or more 80.0 C-10 2 150.0 C-11 1 5.0 C-12 1 1.5 C-13 - 252.0 C-14 1 5.4 C-15 2 2.7 C-16 3 80.0 -96 - 200848448 Table 2 Polymerizable monomer Example 1 C-1 (15) / C-5 (70) / C-4 (15) Example 2 C-5 (55) / C-2 (45) Example 3 C-5 (27) / C-6 (19) C-7 (27) / C-8 (27) Example 4 C-6 (30) / C-7 (40) / C-8 (30) Implementation Example 5 C-1 (30) / C-2 (35) / C-11 (35) Example 6 C-2 (27) / C-5 (27) / C-11 (19) / C-8 ( 27) Example 7 C-1 (20) / C-5 (60) / C-15 (20) Example 8 C-1 (10) / C-5 (60) / C-14 (30) Example 9 C-12 (40) /C-5 (40) /C-15 (20) Example 10 C-3 (50) /C-10 (20) /C-15 (30) Comparative Example 1 C-1 (15) /C-5 (70) /C-4 (15) Comparative Example 2 C-5 (55) /C-2 (45) Comparative Example 3 C-5 (27) /C-6 (19) C -7 (27) / C-8 (27) Comparative Example 4 C-6 (30) / C-7 (40) / C-8 (30) Comparative Example 5 C-1 (30) /02 (35) / C-11 (35) Comparative Example C-9 (18.1) / C-2 (45.7) / C-3 (24.1) / C-16 (12.1) Comparative Example 7 C- 9 (18.1) /C-2 (45.7) /C-3 (24.1) /C-16 (12.1) Comparative Example 8 C-1 (68.8) /C-13 (31.2) Comparative Example 9 C-1 (70.3) /C-5 (29.7) Comparative Example 10 C-3 (58.1) /C-11 (41.9)

-97- 200848448 Table 3 Polymerizable Monomer (*) Photopolymerization Initiator Surfactant, Additive Example 1 (93.80) U-1 (5.5) W-4 (0.10) A-2 (0.60) Example 2 ( 94.90) U-1 (4.5) W-2 (0.30) A-3 (0.30) Example 3 (93.70) U-4 (5.5) W-2 (0.30) A-4 .(0.50) Example 4 (94.30 U-5 (5.5) W-1 (0.20) Example 5 (94.40) U-1 (3.5) U-2 (2.0) W-4 (0.10) Example 6 (95.80) U-3 (2.0) / U-5 (2.0) W-3 (0.20) Example 7 (94.30) U-5 (5.0) W-3 (0.20) A-1 (0.50) Example 8 (92.49) U-1 (5.0) /U -3 (2.0) W-3 (0.5) A-5 (0.01) Example 9 (95.60) U-1 (4.0) W-1 (0.10) A-2 (0.30) Example 10 (95.47) U-1 (3.5) /U-2 (1.0) W-2 (0.01) A-7 (0.02) Comparative Example 1 (93.90) U-1 (5.5) A-2 (0.60) Comparative Example 2 (94.90) U-1 ( 4.5) W-5 (0.30) A-3 (0.30) Comparative Example 3 (93.70) U-4 (5.5) W-6 (0.30) A-4 (0.50) Comparative Example 4 (91.8) U-5 (5.5) W-1 (0.20) A-12 (2.5) Comparative Example 5 (91.40) U-1 (3.5) U-2 (2.0) W-4 (0.10) A-9 (3.0) Comparative Example 6 (82.9) U- 2 (3.0) W-7 (0.02) / W-8 (0.02) / A-8 (4.0) / A-5 (0.1) / A-12 (5.0) / A-10 (5.0) Comparative Example 7 (91.9 U- 2 (3.0) A-5 (0.1) / A-12 (5.0) Comparative Example 8 (94.5) U-3 (2.5) A-6 (0.5) / A-12 (2.5) Comparative Example 9 (75.3) U- 3 (2.5) W-9 (0.1) / A-11 (5.0) / A-10 (1.0) / A-9 (3.0) / A-12 (2.5) Comparative Example 10 (86.0) U-3 (2.5) A-10 (5.0) / A-8 (4.0) / A-12 (2.5) (* ) Use the polymerizable monomer described in Table 2 - 98- 200848448 Table 4

Viscosity light hard adhesion peeling residual film pattern coating application coating etching total (25〇C) mPa · s qualitative shape (I) (II) Evaluation Example 1 18 AABBAAAAA Example 2 11 AABBAAAAA Example 3 7 AAAAAAAAA Example 4 6 AAAAAAAAA Example 5 17 AABBAAAAA Example 6 8 AAAAAAAAA Example 7 18 AABBAAAAA Example 8 14 AABBAAAAA Example 9 4 AABBAAAAA Example 10 16 AABB A_ AAAA Comparative Example 1 18 AACCBBB^ C Comparative Example 2 11 AACBABBB — C Comparative Example 3 7 AABAABBBB Comparative Example 4 5 AAABBAABB Comparative Example 5 29 BABBBAABB Comparative Example B 15 BABABAABB Comparative Example 7 6 BABABAABB Comparative Example 8 20 AACCBBBBC Comparative Example 9 25 AABCCBBBC Comparative Example 10 20 AABCCBBBC <Photohardenable Composition Evaluation - Π The photocurable composition of the present invention was evaluated as a permanent film (protective film). <residual film rate>

The photocurable composition of the present invention was spin-coated on a glass substrate to a film thickness of 4 // m, and then mounted on a nanoimprinting device using a high-pressure mercury lamp as a light source, and 500 00 mJ/ from the back of the mold core. The conditions of cm2 were exposed, and after exposure, the mold was removed and heated in an oven at 23 ° C for 150 minutes. The film thickness of the pattern portion of the photocurable resin before and after heating was measured with PROFILER P11 manufactured by Tennol Co., Ltd., and the residual film ratio after heating was measured, and then evaluated based on the following criteria: A ·· residual film ratio exceeded 90%; B: The residual film rate is 85 to 90% -99- 200848448 C : The residual film rate is less than 8 5 . <Transmittance> The photocurable composition of the present invention was spin-coated on a glass substrate to a film thickness of 4 // m, and then mounted on a nanoimprinting device using a high-pressure mercury lamp as a light source, and from the back of the mold core The conditions were exposed at 500 mJ/cm2, and after exposure, the mold was removed and heated in an oven at 23 ° C for 150 minutes. The light transmittance of the pattern portion of the photocurable resin after heating was measured by a spectrophotometer UV2100 manufactured by Shimadzu Corp., and the transmittance after heating was evaluated by the following criteria: A: transmittance exceeding 90%; B : Transmittance is 85 to 90%; C : Transmittance is less than 8 5 . <Solvent resistance> The photocurable composition of the present invention was spin-coated on a glass substrate to a film thickness of 4 // m, and then mounted on a nanoimprinting device using a high-pressure mercury lamp as a light source, and from the back of the mold core Exposure was carried out under conditions of 500 mJ/cm2, and after exposure, the mold was removed and heated in an oven at 230 ° C for 150 minutes. After heating, each solution of N-methylpyrrolidone (NMP), 5% sodium hydroxide, and 5% hydrochloric acid was immersed for 30 minutes, and then the film thickness change before and after the immersion was measured and evaluated as follows: : Almost no change in film thickness (less than 1%); B: slight change in film thickness (less than 1 to 5%); C: slight change in film thickness (5% or more). [Example 1 1] -100-200848448 2% by mass of the composition was added without changing the type and mixing ratio of the monomer, photopolymerization initiator, surfactant, and sensitizer used in Example 1. An antioxidant (manufactured by Sumitomo Chemical Co., Ltd.: Sumilizer GA8®) was prepared in the same manner as in Example 1 to prepare a photocurable composition. The prepared photocurable composition was spin-coated on a glass substrate to a film thickness of 4 μm, and the spin-coated coated base film was mounted on a high-pressure mercury lamp manufactured by ORC (lamp power was 2,000 mW/ Cm2) as a light source nanoimprinting device, and applying a pressure of 1〇kN/cm2 in the mold core, and exposing the ft &quot; vacuum in the light to 〇·2 Tori*, from a square pattern with 5 mm The back side of the mold is made of polydimethyl siloxane (the SILPOT 184 manufactured by Toray-Dow Corning Co., Ltd. is cured at 80 ° C for 60 minutes), exposed at 500 mJ/cm2, and then exposed after exposure. The mold was opened, and the residual film ratio and transmittance of the pattern portion of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 5. The composition of Example 1 has a superior residual film ratio, light transmittance, solvent resistance as a whole, and also has excellent characteristics as a permanent film. [Example 1 2] The embodiment is not changed. In the case of the type of the monomer, the photopolymerization initiator, and the surfactant to be used, and the mixing ratio, 2% by mass of an antioxidant (ADEKA manufactured by Adekasutabu AO503) was added to the composition, and the same as in Example 1. The photocurable composition is prepared in a manner. The prepared composition was spin-coated on a glass substrate to a film thickness of 4 // m, and the spin-coated coated base film was mounted on a high-pressure mercury lamp manufactured by 0RC Corporation - 101-200848448 (lamp power was 2,000) mW/cm2) as a light source nanoimprinting device, and applying a pressure of 10 kN/cm2 in the mold core, a vacuum of 0.2 T〇rr in the exposure, and a polydimethyl group having a square pattern of 5 mm The back side of the arsenic (the hardened by SILPOT 184 manufactured by Toray-Dow Corning Co., Ltd. at 80 ° C for 60 minutes) is exposed to a condition of 500 mJ/cm 2 , and the mold is removed after exposure. The kernel was then measured for the residual film ratio and transmittance of the pattern portion of the photocurable resin before and after heating. Thereafter, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 5. The composition of Example 1 2, which has a superior residual film ratio, light transmittance, solvent resistance as a whole, and also has excellent properties as a permanent film. [Example 1 3] 2% by mass of an antioxidant (made by ADEKA: Adekasutabu AO5) was added to the composition without changing the type of the monomer, the photopolymerization initiator, the surfactant, and the mixing ratio used in Example 8. 03), and a photocurable composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a film thickness of 4/m, and the spin-coated coated base film was mounted on a high-pressure mercury lamp manufactured by ORC (lamp power: 2,000 mW/cm2) As a light source nanoimprinting device, and applying a pressure of 10 kN/cm2 in the mold core and a vacuum degree of 0.2 Torr in the exposure, the polydimethyl methoxyoxane having a square pattern of 5 mm (to the east) The back side of the mold core made of SILPOT 184 manufactured by Li-Dong Corning Co., Ltd. at 80 ° C for 60 minutes is exposed to 500 00 mJ/cm 2 , and after exposure, the mold is removed, and then the temperature is measured before and after heating. The residual film ratio and transmittance of the pattern portion of the photocurable resin. Thereafter, the photocuring film was investigated for solvent resistance of -102-200848448. The results are shown in Table 5. The composition of Example 1 3 had a superior residual film ratio, light transmittance, solvent resistance as a whole, and also had excellent properties as a permanent film. [Example 1 4] 3.0% by mass of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd.) was added to the composition without changing the type of the monomer, the photopolymerization initiator, and the surfactant used in the embodiment 8 and the mixing ratio. : Sumilizer GA80), and a photocurable composition was prepared in the same manner as in Example 1. The prepared composition was spin-coated on a glass substrate to a film thickness of 4 // m, and the spin-coated coated base film was mounted on a high-pressure mercury lamp manufactured by ORC (lamp power: 2,000 mW/cm 2 ) a nanoimprinting device as a light source, and applying a pressure of 10 kN/cm 2 in the mold core, and a vacuum of 0.2 To rr in the exposure, from a polytetramethyl decane having a square pattern of 5 mm (will The back side of the mold of the SILPOT 184 manufactured by Toray Dow Corning, which is hardened at 80 ° C for 60 minutes, is exposed at 5,000 mJ/cm 2 , and after exposure, the mold is removed and the heating is measured. The residual film ratio and transmittance of the pattern portion of the photocurable resin before and after. Thereafter, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 5. The composition of Example 1 4 had excellent residual film ratio, light transmittance, solvent resistance as a whole, and also had superior properties as a permanent film. [Comparative Example 1 1] The composition which was previously prepared in Comparative Example 8 was patterned in the same manner as in Example 11, and then the characteristics of the composition were investigated. The results are shown in Table 5. The composition of Comparative Example 1 1 was inferior in residual film ratio and solvent resistance -103 - 200848448. [Comparative Example 1 2] The composition previously prepared in Comparative Example 9 was patterned in the same manner as in Example 11, and then the characteristics of the composition were investigated. The results are shown in Table 5. In the composition of Comparative Example 1 2, either of the light transmittance, the residual film ratio, and the solvent resistance was not a satisfactory level. [Comparative Example 1 3] The composition previously prepared in Comparative Example 1 was patterned in the same manner as in Example 11, and then the characteristics of the composition were investigated. The results are shown in Table 5. In the composition of Comparative Example 1 3, either of the light transmittance, the residual film ratio, and the solvent resistance was not a satisfactory level. table 5

Residual Film Rate Light Transmissive Solvent Resistance NMP NaOH HC1 Example 11 AAAAA Example 12 AAAAA Example 13 AAAAA Comparative Example 11 BB ~ BB* A Comparative Example 12 C ] CCCB Comparative Example 13 CCCBC [Industrial Applicability] The composition of the invention is a magnetic recording medium, a diffraction grating or a plate making system for manufacturing a semiconductor integrated circuit, a flat screen, a MEMS (Micro Electro Mechanical Systems), a sensor element, a compact disc, a high-density storage disc, or the like. Optical members such as photo films, nano devices, optical devices, optical films or polarizing elements required for manufacturing flat panel displays, thin film transistors for liquid crystal displays, organic transistors, color filters, outer protective layers, pillars , rib material for liquid crystal alignment, microlens array, immuno-104 - 200848448 analysis wafer, dna separation wafer, microreactor, nano biodevice, optical waveguide, optical filter, photonic liquid crystal, etc., can be used as A photon-imprinted photoresist composition formed in a fine pattern. [Simple description of the diagram] None. [Main component symbol description] Μ . -105-

Claims (1)

200848448 X. Patent application scope: 1 - A photocurable composition containing (a) a cationically polymerizable monomer, (b) a photocationic polymerization initiator, and (c) a 0.001 to 5% by mass of a fluorine-based interface At least one of an active agent, a polyfluorene-based surfactant, and a fluorine/polyoxy-based surfactant, and (d) the content of the organic solvent is 1% by mass or less, and (e) the content of the color material is 0.5% by mass. % or less of the (a) cationically polymerizable monomer is a compound having an oxetane or a ring. The photocurable composition according to claim 1, wherein the (a) cationically polymerizable monomer is contained in the range of 50 to 99% by mass. The photocurable composition according to claim 1, wherein the (a) cationically polymerizable monomer is a vinyl ether compound. 4. The photocurable composition according to claim 1, wherein the (a) cationically polymerizable monomer is a compound comprising an oxirane ring [5. The photohardenable composition according to the invention, wherein the (a) cationically polymerizable monomer is at least one of the compounds represented by the general formulae (1) to (3) shown below: Formula (1) General formula (2) •106- 200848448 General formula (3) [In the general formulae (1) to (3), Ral is a substituted or unsubstituted alkyl group representing a hydrogen atom, having 1 to 6 carbon atoms, or a substituted or unsubstituted carbon number of 1 to ό Substituted fluoroalkyl, allyl, aryl, furyl or thienyl, if two Ral are present therein, then they may be identical or different; R represents a number of carbon atoms of 1 to 6 Substituted or unsubstituted aryl, substituted or unsubstituted aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted alkenyl, aryl having 2 to 6 carbon atoms a substituted or unsubstituted fluorenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, a substituted carbon number of 2 to 9 or Unsubstituted aminyl group; Ra3 represents a chain or branched alkyl, chain or branched poly(alkyloxy) group, a chain or branched hydrocarbon group, a carbonyl group or a carbonyl group. a base group, a carboxyl group-containing alkyl group, an amine group containing an alkyl group, or a group represented by the following formula: Wherein the "alkylene group" includes an exoethyl group, a propyl group, and a butyl group; -107-200848448 "poly(alkyloxy) group" includes a poly(ethyleneoxy) group, and a poly(extension) The oxy) group and the like, the "hydrocarbyl group" includes a propenyl group, a methyl propylene group, a butenyl group, etc.; if Ra3 is a polybasic group as described above, Ra4 represents a hydrogen atom and has 1 carbon atom. a substituted or unsubstituted alkyl group to 4, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, an amino group, a thiol group, a lower alkylcarboxy group (carbon) The number of atoms is 1 to 4), a carboxyl group, or an amine carbenyl group; R is an oxygen atom, a sulfur atom, a methylene group, -NH-, a SO-, -s〇2-, -c(cf3)2- Or —C(CH3)2—; Ra6 represents an alkyl or aryl group having 1 to 4 carbon atoms, and n is an integer from ο to 2,000 (preferably an integer of 0 to 500), each of which Ra6 may be identical or different; Ra7 is a fluorenyl group having 1 to 4 carbon atoms, an aryl group or a valence group having a structure represented by the following formula, each of which may be identical or Different: Ra8 Ra8 Ra8 Ra8 In the above formula, Ra8 is an alkyl group having 1 to 4 carbon atoms, or an aryl group, each of which may be identical or different, and m is an integer from 〇 to 100. 〇6 · The photocurable composition according to claim 1, which further contains an antioxidant. 7. The photocurable composition of claim 1, wherein the photocurable composition is used to include: a step of coating a photocurable composition; and a light transmissive mold - 108 - 200848448 is imprinted on a substrate a photoresist layer for deforming the photocurable composition; a step of irradiating light from the back surface of the mold core or the back surface of the substrate to harden the coating film to form a pattern that can be fitted into a desired pattern; and coating A pattern forming method of a step of desorbing a light transmissive mold core. 8. The photocurable composition according to claim 1, wherein the photocurable layer is applied to: a step of coating a photocurable composition, and a photoresist layer imprinted on the substrate by a light transmissive mold. a step of deforming the photocurable composition; irradiating light from the back surface of the mold core or the back surface of the substrate to harden the coating film to form a photoresist pattern capable of being fitted in a desired pattern; desorbing light transmission from the coating film Step of the mold core, a step of etching the substrate as a mask with a photocurable composition, and a method of forming a photoresist pattern by a step of etching the photocurable composition and then peeling off. -109- 200848448 VII. Designation of Representative Representatives (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention.