JP2008189821A - Photocurable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition which is comprehensively excellent in photocurable properties, adhesion, a mold release property, a membrane-leaving property, a pattern shape, a coating property (I), a coating property (II) and suitability for etching. <P>SOLUTION: The photocurable composition comprises (a) a cation-polymerizable monomer, (b) a cationic photopolymerization initiator and (c) 0.001-5 mass% at least one of fluorine-based surfactant, silicone-based surfactant and fluorine-silicone-based surfactant and the composition has (d) ≤1 mass% content of an organic solvent and (e) ≤0.5 mass% content of coloring matter and contains a compound having an oxetane ring in an amount of at least ≥10 mass% as the cation-polymerizable monomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photocurable composition.

  The nanoimprint method is a development of embossing technology that is well-known in optical disc production. A mold prototype (generally called a mold, stamper, template, etc.) with an uneven pattern is pressed onto a resist, It is a technology that precisely deforms and finely transfers a fine pattern. Once a mold is made, it is economical because nanostructures can be easily and repeatedly molded, and it is a nano-processing technology that has few harmful wastes and emissions, so in recent years it has been expected to be applied in various fields. Yes.

 There are two main types of nanoimprint methods: a case where a thermoplastic resin is used as a material to be processed (Non-Patent Document 1) and a case where a photocurable composition is used (Non-Patent Document 2). Thermal nanoimprinting is a method in which a mold is pressed onto a polymer resin heated to a glass transition temperature or higher, and the mold is released after cooling to transfer the microstructure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, it is expected to be applied to various fields. Patent Documents 1 and 2 disclose a nanoimprint method for forming a nanopattern at low cost using a thermoplastic resin.

  On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold and the photocurable composition is photocured, imprinting at room temperature becomes possible. Recently, new developments such as a nanocasting method combining the advantages of both and a reversal imprint method for producing a three-dimensional laminated structure have been reported. In such a nanoimprint method, there are roughly three stages of application. The first stage is when the molded shape itself has a function and can be applied as various nanotechnology element parts, and various micro / nano optical elements, high-density recording media, and optical films can be mentioned. As the second stage, a laminated structure is constructed by simultaneous integral molding of a micro structure and a nano structure, or simple interlayer alignment, and is intended to be applied to the production of μ-TAS and biochips. As a third stage, high-precision alignment and high integration can be used to fabricate high-density semiconductor integrated circuits in place of conventional lithography, and to create transistors for liquid crystal displays. , Efforts toward commercialization are becoming active.

As an application example of the nanoimprint method, an application example to the production of a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. However, the processing method has approached the wavelength of the light source for light exposure, and the lithography technology has also approached its limit. Therefore, in order to advance further miniaturization and higher accuracy, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, has been used in place of lithography technology. Unlike the batch exposure method in pattern formation using a light source such as i-line or excimer laser, pattern formation using an electron beam takes a method of drawing a mask pattern. The exposure (drawing) takes time and the pattern formation takes time. For this reason, as the degree of integration increases dramatically, such as 256 mega, 1 giga, and 4 giga, the pattern formation time is also greatly increased, and there is a concern that the throughput is significantly inferior. Therefore, in order to increase the speed of the electron beam lithography system, development of a collective figure irradiation method that combines various shapes of masks and irradiates them collectively with an electron beam to form an electron beam of a complicated shape is underway. Yes. However, in this method, pattern miniaturization is advanced, but the electron beam drawing apparatus must be enlarged, and a mechanism for controlling the mask position with higher accuracy is required. There was a drawback.
In contrast, nanoimprint lithography has been proposed as a technique for performing fine pattern formation at low cost. For example, Patent Documents 1 and 3 disclose a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nm or less is formed by transfer.
Patent Document 4 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography. On the other hand, studies to apply nanoimprint lithography to semiconductor integrated circuit fabrication such as micro mold fabrication technology, mold durability, mold fabrication cost, mold releasability from resin, imprint uniformity and alignment accuracy, inspection technology, etc. It started to become active.
However, resists used in nanoimprint lithography have not been sufficiently studied in spite of the necessity for etching suitability for various substrates and stripping suitability after etching as in the case of conventional photoresists for semiconductor microfabrication.

  Next, an application example of nanoimprint lithography to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described. In recent years, optical nanoimprint lithography has attracted particular attention as an inexpensive lithography that replaces conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates as LCDs and PDP substrates increase in size and definition. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method. Etching photoresists used in conventional photolithographic methods are required to have high adhesion, uniformity of coating film, resist saving, adhesion to various substrates, etching resistance, heat resistance, etc. Similar characteristics are required for alternative optical nanoimprint resists.

  With respect to the uniformity of the coating film, demands for various parts such as the coating film thickness uniformity and the dimensional uniformity, film thickness, and shape due to higher resolution are increasing as the substrate size increases. Conventionally, in the field of manufacturing liquid crystal display devices using a small glass substrate, a method of spinning after dropping at the center has been used as a resist coating method (Non-patent Document 3). Although the coating method that spins after dropping in the center can provide good coating uniformity, for example, in the case of a large substrate of 1 m square class, the amount of resist that is shaken off during spinning (during spinning) and discarded becomes considerably large. In addition, problems such as cracking of the substrate due to high-speed rotation and securing of tact time occur. Furthermore, since the coating performance in the method of spinning after dropping in the center depends on the rotational speed at the time of spinning and the amount of resist applied, a general-purpose motor that can obtain the required acceleration when it is applied to a fifth-generation substrate that is further enlarged. However, when such a motor is specially ordered, there is a problem that the cost of parts increases. In addition, even if the substrate size and the apparatus size are increased, the required performance in the coating process, such as coating uniformity ± 3%, tact time 60 to 70 seconds / sheet, etc., is not substantially changed. It has become difficult to meet demands other than coating uniformity. Under such circumstances, a resist coating method using a discharge nozzle method has been proposed as a new resist coating method applicable to large substrates after the fourth generation substrate, particularly the fifth generation substrate and beyond. The discharge nozzle type resist coating method is a method in which a photoresist composition is applied to the entire coated surface of a substrate by relatively moving the discharge nozzle and the substrate. For example, a plurality of nozzle holes are arranged in a row. A method of using a discharge nozzle having a discharge port and a slit-like discharge port and capable of discharging a photoresist composition in a band shape has been proposed. There has also been proposed a method of adjusting the film thickness by applying a photoresist composition to the entire surface of a substrate applied by a discharge nozzle method and then spinning the substrate. Therefore, in order to replace the conventional photolithography resist with the nanoimprint composition and apply it to the field of manufacturing these liquid crystal display elements, the coating uniformity on the substrate is important.

  When a fluorine-based and / or silicone-based surfactant is added to a pigment-dispersed photoresist used for manufacturing positive-type photoresists and color filters used in semiconductor integrated circuit manufacturing and liquid crystal display manufacturing, It is known that problems of poor coating such as striations and scale-like patterns (unevenness of drying of resist film) are solved (Patent Documents 5 to 7). Also disclosed is the addition of fluorine-based surfactants and silicone-based surfactants to solventless photocurable compositions to improve the wear and coating properties of protective films such as compact disks and magneto-optical disks. (Patent Documents 7 to 10). Similarly, Patent Document 11 discloses that a nonionic fluorosurfactant is added in order to improve the ink ejection stability of the inkjet composition. Furthermore, in Patent Document 12, when embossing a painting composition coated with a thick film with a brush, a brush, a bar coater or the like with a hologram processing mold, a polymerizable double bond-containing surfactant is 1% or more, An example in which 3% or more is preferably added to improve the water swellability of the cured film is disclosed. As described above, a technique for adding a surfactant to a protective film such as a positive photoresist, a pigment-dispersed photoresist for producing a color filter, or a magneto-optical disk to improve the coating property is a known technique. In addition, as seen in the above examples of inkjet and painting compositions, there is also a technique for adding a surfactant to a solventless photocurable resin and adding the surfactant to improve the properties in each application. It is known. However, this is a method for improving the substrate coatability of a low-viscosity photo-curable nanoimprint resist composition that does not contain coloring materials such as pigments and dyes and organic solvents, and that does not substantially contain these components. It was not known until.

  On the other hand, in the optical nanoimprint, it is necessary to improve the fluidity of the composition into the cavity of the mold recess, further improve the mold releasability, improve the mold releasability between the mold and the resist, It is necessary to improve the adhesion between the substrates. However, it has been difficult to improve the fluidity, releasability and adhesion.

  Moreover, when the optical nanoimprint resist containing an organic solvent is applied, it is necessary to volatilize the solvent after coating. Therefore, when a composition containing an organic solvent is used, it is disadvantageous in terms of worker safety and simplification of process man-hours due to suction of the volatilized solvent. Therefore, development of a composition containing substantially no organic solvent is strongly desired.

The technology related to optical nanoimprint will be described in more detail. Photo-nanoimprint lithography involves dropping a liquid photocurable composition onto a substrate such as a silicone wafer, quartz, glass, film or other material such as a ceramic material, a metal, or a polymer. After coating with a film thickness, pressing and pressing a mold having fine irregularities with a pattern size of about several tens of nm to several tens of μm, and curing the composition by light irradiation in the pressurized state, A method of releasing the mold and obtaining a transferred pattern is common. For this reason, in the case of optical nanoimprint lithography, at least one of the substrate and the mold needs to be transparent for the convenience of light irradiation. Usually, light is irradiated from the mold side, and an inorganic material such as quartz or sapphire, a light-transmitting resin, or the like is often used as the mold material.
The optical nanoimprint method is (1) no heating / cooling process is required and high throughput is expected compared to the thermal nanoimprint method. (2) Since the liquid composition is used, imprinting at low pressure is possible. Major advantages include (3) no dimensional change due to thermal expansion, (4) the mold is transparent and easy to align, and (5) a robust three-dimensional crosslinked body is obtained after curing. It is done. It is particularly suitable for semiconductor micromachining applications where alignment accuracy is required and for micromachining applications in the field of flat panel displays.

  Another feature of the optical nanoimprint method is that the resolution does not depend on the light source wavelength as compared with ordinary optical lithography. Therefore, expensive devices such as a stepper and an electron beam drawing device are also used for fine processing on the nanometer order. The feature is not required. On the other hand, the optical nanoimprint method requires an equal-magnification mold, and since the mold and the resin are in contact, there are concerns about the durability and cost of the mold. Furthermore, in the optical nanoimprint lithography process, a residual film (a portion where the mold convex portion is pressed against the photocurable composition) is likely to occur. The thinner the remaining film layer, the more preferable is a structure that can be formed using nanoimprint. Further, if there is a large amount of residual film, it tends to be a line width controllability during etching or etching residue.

 In this way, applying the thermal and / or optical nanoimprint method and imprinting nanometer-sized patterns over a large area requires only uniform pressing pressure and flatness of the master (mold). In addition, it is necessary to control the behavior of the resist that is pushed out and flows out. In the conventional semiconductor technology, a region not used as an element can be arbitrarily set on the wafer, so that a resist outflow portion can be provided outside the imprint portion using a small master. In semiconductors, imprint defects should not be used as defective elements. For example, the entire surface functions as a device in applications such as hard disks, so special measures are required to prevent imprint defects. It is.

Molds used in optical nanoimprint lithography can be manufactured from various materials such as metals, semiconductors, ceramics, SOG (Spin On Glass), or certain plastics. For example, a flexible polydimethylsiloxane mold having a desired microstructure described in Patent Document 13 has been proposed. 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 specifications for its resolution. Electron beam and x-ray lithography are typically used for structure dimensions below 300 nm. Direct laser exposure and UV lithography are used for larger structures.
For the photo-nanoimprint method, the releasability between the mold and the photocurable composition is important, and the surface treatment of the mold and mold, specifically, hydrogenated silsesquioxane or fluorinated ethylene propylene copolymer mold is used. Attempts have been made to solve the adhesion problem.

  Here, the photocurable resin used for optical nanoimprint lithography will be described. Photocurable resins applied to nanoimprints are roughly classified into radical polymerization types and ionic polymerization types, or their hybrid types, depending on the reaction mechanism. Although any composition can be imprinted, a radical polymerization type having a wide selection range of materials is generally used (Non-Patent Document 4). As the radical polymerization type, a composition containing a monomer or oligomer having a radically polymerizable vinyl group or (meth) acryl group and a photopolymerization initiator is generally used. When irradiated with light, radicals generated by the photopolymerization initiator attack the vinyl group, and chain polymerization proceeds to form a polymer. When a bifunctional or higher polyfunctional group monomer or oligomer is used as a component, a crosslinked structure is obtained. Non-Patent Document 5 discloses a composition that can be imprinted at low pressure and room temperature by using a low-viscosity UV curable monomer.

The characteristics of the material used for optical nanoimprint lithography will be described in detail. The required characteristics of materials vary depending on the application to be applied, but the demands for process characteristics are common regardless of the application. For example, main requirements shown in Non-Patent Document 6 are applicability, substrate adhesion, low viscosity (<5 mPa · s), releasability, low cure shrinkage, fast curability, and the like. It is known that there is a strong demand for low-viscosity materials especially in applications that require low-pressure imprinting and reduction of the residual film ratio. On the other hand, when the required characteristics are listed for each application, there are, for example, a refractive index and light transmittance for an optical member, and an etching resistance and a remaining film thickness reduction for an etching resist. The key to material design is how to control these required properties and balance them. At least the process material and the permanent film have different required characteristics, so the material must be developed according to the process and application. As a material applied to such optical nanoimprint lithography, Non-Patent Document 6 discloses a photocurable material having a viscosity of about 60 mPa · s (25 ° C.). Similarly, Non-Patent Document 7 discloses a fluorine-containing photosensitive resin with improved releasability having a viscosity of 14.4 mPa · s mainly composed of monomethacrylate.
As described above, regarding the composition used in optical nanoimprinting, although there is a description of a demand for viscosity, there has been no report on a material design guideline for adapting to each application.

  An example of a photocurable resin that has been applied to optical nanoimprint lithography will be described. Patent Documents 14 and 15 disclose examples of embossing using a photocurable resin containing a polymer having an isocyanate group for producing a relief hologram or a diffraction grating. Patent Document 16 discloses a photocurable composition for imprints containing a polymer, a photopolymerization initiator, and a viscosity modifier.

 Patent Document 17 discloses a pattern forming method using a fluorine-containing curable material in order to improve releasability from a mold.

  Non-Patent Document 8 includes (1) a functional acrylic monomer, (2) a functional acrylic monomer, and (3) a photocurable radical polymerizability combining a functional acrylic monomer and a photopolymerization initiator. A composition is disclosed. In Non-Patent Document 8, an alicyclic photocurable alicyclic epoxy compound, a novolac epoxy compound, a photocationic polymerizable composition containing an inorganic / organic hybrid compound and a photoacid generator, etc. are applied to nanoimprint lithography, The example which investigated the mechanical stability and mold peelability is disclosed.

  In Non-Patent Document 9, as a device for improving problems such as peelability between a photocurable resin and a mold, film shrinkage after curing, and low sensitivity due to inhibition of photopolymerization in the presence of oxygen, (1 A photocurable composition comprising a) a functional acrylic monomer, (2) a functional acrylic monomer, a silicone-containing monofunctional acrylic monomer, and a photopolymerization initiator is disclosed.

  In Non-Patent Document 10, a photocurable composition containing a monofunctional acrylic monomer, a silicone-containing monofunctional monomer, and a photopolymerization initiator is formed on a silicone substrate, and light is emitted using a surface-treated mold. It is disclosed that defects after molding in nanoimprint lithography are reduced.

In Non-Patent Document 11, a photocurable composition containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is formed on a silicone substrate, and high resolution and coating can be achieved using a SiO ₂ mold. A composition having excellent uniformity is disclosed.

  Non-Patent Document 12 discloses an example in which a 50 nm pattern size is formed by a cationic polymerizable composition in which a specific vinyl ether compound and a photoacid generator are combined. Although it is characterized by a low viscosity and a high curing rate, it is stated that template peelability is an issue.

  However, as shown in Non-Patent Documents 8 to 12, although various photocurable resins in which an acrylic monomer, an acrylic polymer, a vinyl ether compound, and an epoxy compound having different functional groups are applied to optical nanoimprint lithography are disclosed. Guidelines for designing materials such as preferred types of compositions, optimal monomer types, monomer combinations, optimal viscosities of monomers or resists, preferable resist solution properties, and improved resist coatability Is not disclosed at all. Therefore, a preferable composition for widely applying the composition to optical nanoimprint lithography applications is not known, and a satisfactory optical nanoimprint resist composition has never been proposed so far.

  The application to an etching resist for substrate processing will be described in detail. The etching resist is not an element left as it is, but merely a copy of a semiconductor or transistor circuit pattern. In order to create a circuit pattern, it is necessary to transfer these resist patterns to various layers including devices. The method of transferring the pattern is performed by an etching process that selectively removes the uncovered portion of the resist. For example, TFT array substrates and PDP electrode plates are manufactured by applying an etching resist on a conductive base or insulating base sputtered on a glass or transparent plastic substrate, drying, pattern exposure, development, and etching. The resist peeling process is performed on the thin film of each layer. Conventionally, a positive type photoresist has been often used as an etching resist. In particular, resists containing alkali-soluble phenol novolac resin and 1,2-quinonediazide compound as main components and chemically amplified resists containing (poly) hydroxystyrene as a polymer have high etching resistance and are easy to peel off. So far, etching photoresists for semiconductors and TFT transistors have been widely used, and much knowledge has been accumulated. For etching, there are wet etching methods using various liquid etchants and dry etching methods that vaporize and remove the film on the substrate using ions and radicals (active species) generated by decomposing gas with plasma in a decompression device. is there. Etching is an important process that greatly affects device design accuracy, transistor characteristics, yield, and cost. Etching resist has material and process compatibility that can be applied to both dry etching and wet etching. is necessary. In order to apply the composition used for optical nanoimprint lithography to the resist field used in these conventional photolithography, etching properties similar to those of conventional photoresists are necessary, but etching has not been sufficiently studied. Various problems occurred in the process.

The main technical issues for etching resists are improvement of pattern processing dimensional accuracy, improvement of taper processing control (improvement of undercut shape), improvement of etching uniformity on large substrates, improvement of etching selectivity with the substrate, etching speed There are many problems such as improvement of the multi-layered film, ensuring safety of waste liquid, waste gas, etc., and improving defects on the film (particles, residues) after etching. When applying a photocurable composition for photonanoimprint as an etching resist, like a conventional positive photoresist,
(1) etchant selected according to film type, suitability for etching gas,
(2) imparting adhesion between the pattern and the etched substrate so as not to cause an undercut;
(3) In order to bathe the dimensional controllability of the pattern before and after etching, it is important to impart wettability between the etchant and the resist.

However, in addition to the points (1) to (3) above, the nanoimprint photocurable composition has a higher technical difficulty in terms of the following (4), (5), and (6).
(4) In order to enhance the releasability from the mold, if the resist film is made hydrophobic, the wettability of the etchant and the resist is further deteriorated, and etching residue is likely to occur.
(5) Since the photocurable composition has a three-dimensional network structure, it is difficult to peel off compared to a positive resist. Further, although a stronger network structure improves etching resistance, it is more difficult to peel off. The point that
(6) Compared with conventional photolithography, optical nanoimprint lithography has a tendency that a residue is likely to be generated after etching because a residue is likely to be generated in a portion to be etched away after the mold is peeled off.
Although various materials have been disclosed for photo-curable compositions for nanoimprinting, disclosure of nanoimprinting materials and design of materials for use in any of the photolithographic process, etching process, and peeling process of nanoimprinting are possible. There has never been a guideline. In addition, photocurable compositions that have been known so far for ink-jet compositions and magneto-optical disk protective films may not have an etching process or a peeling process, although the photolithographic process has a common part in the material. It is very different from etching resist. Therefore, when the photocurable resin applied in these uses is applied as an etching resist as it is, problems often occur in the etching process and the peeling process.

 Next, a permanent film to which photolithography is applied will be described. Unlike the etching resist, the permanent film is an element that is left as it is on a semiconductor element, a recording medium, a flat display panel, or the like. For example, as a transparent protective film material for color filters used in liquid crystal panels, a protective film is conventionally formed by a process using a photocurable resin or thermosetting resin such as siloxane polymer, silicone polyimide, epoxy resin, acrylic resin, etc. (Patent Document 18). In the formation of the protective film by photolithography, the uniformity of the coating film, the substrate adhesion, the heat resistance, and the like are required as in the etching resist. In addition, a wide range of properties as a permanent film different from the above etching resists such as high light transmittance, flattening properties, solvent resistance, chemical resistance, light resistance, moist heat resistance, scratch resistance, pressure resistance, and toughness are also required. The However, no preferred composition of a photocurable composition for forming a transparent protective film used in the nanoimprint method has been disclosed so far.

 A spacer for a liquid crystal color filter is also a kind of permanent film, and so far, a photocurable composition comprising a resin, a photopolymerizable monomer and an initiator has been widely used (Patent Document 19). Spacers are required to have a wide range of high mechanical properties against external pressure, high curability, developability, pattern accuracy, adhesion, etc., but photocurable compositions for forming spacers used in nanoimprint methods so far No preferred composition of was disclosed.

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The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a novel photocurable composition excellent in photocurability, particularly, a curable composition for optical nanoimprint lithography.
In particular, an object is to provide a composition that is comprehensively excellent in terms of photocurability, adhesion, releasability, remaining film properties, pattern shape, coatability (I), coatability (II), and etching suitability. .
Another object of the present invention is to provide a composition that is generally excellent in residual film ratio, light transmittance, and solvent resistance when used as a permanent film such as a protective film or a spacer.

As a result of intensive studies by the inventors based on the above problems, it has been found that the above problems can be solved by the following means.
(1) at least one of (a) a cationic polymerizable monomer, (b) a photocationic polymerization initiator, (c) a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant 0.001 to 5% by mass, (d) the content of the organic solvent is 1% by mass or less, (e) the content of the coloring material is 0.5% by mass or less, and the (a) cation A photocurable composition in which 10% by mass or more of the polymerizable monomer is a compound having an oxetane ring.
(2) The photocurable composition according to (1), which contains the cationic polymerizable monomer (a) in a range of 50 to 99% by mass.
(3) The photocurable composition according to (1) or (2), which contains a vinyl ether compound as the cationic polymerizable monomer (a).
(4) The photocurable composition according to any one of (1) to (3), which contains a compound having an oxirane ring as the cationic polymerizable monomer (a).
(5) The photocurable composition according to any one of (1) to (4), further comprising an antioxidant.
(6) A step of applying a photocurable composition, a step of pressurizing a light transmissive mold onto a resist layer on a substrate and deforming the photocurable composition, irradiating light from the back of the mold or the back of the substrate, The method according to any one of (1) to (5), which is used in a pattern forming method including a step of curing a film and forming a pattern that fits in a desired pattern, and a step of removing a light-transmitting mold from a coating film. Photocurable composition.
(7) A step of applying a photocurable composition, a step of pressurizing a light transmissive mold onto a resist layer on a substrate and deforming the photocurable composition, irradiating light from the back of the mold or the back of the substrate, A step of curing a film to form a resist pattern that fits in a desired pattern, a step of removing a light-transmitting mold from a coating film, a step of etching a substrate using the photocurable composition as a mask, and a photocurable composition The photocurable composition according to any one of (1) to (5), which is used in a resist pattern forming method including a step of peeling after etching.

  According to the present invention, when used as an etching resist, a composition that is comprehensively excellent in photocurability, adhesion, releasability, remaining film properties, pattern shape, coatability (I), coatability (II), and etching suitability. Became possible to get. Further, when used as a permanent film, it has become possible to obtain a composition that is comprehensively excellent in the remaining film rate, light transmittance, and solvent resistance.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The present invention is described in detail below. The monomer in the present invention is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers. In the present specification, the functional group refers to a group involved in polymerization.
The nanoimprint referred to in the present invention refers to pattern transfer having a size of about several μm to several tens of nm.

 The photocurable composition of the present invention has, for example, a high light transmittance before curing, excellent in the ability to form a fine concavo-convex pattern, applicability and other processability, and sensitivity (fast curability) after curing. ), Resolution, line edge roughness, coating strength, releasability from mold, residual film properties, etching resistance, low curing shrinkage, substrate adhesion or other light that can provide excellent coating properties It can be widely used for nanoimprint lithography.

That is, when the photocurable composition of the present invention is used for optical nanoimprint lithography,
(1) Since the solution fluidity at room temperature is excellent, the photocurable composition can easily flow into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Even after photocuring, residues are unlikely to remain,
(2) The cured film after curing has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent mold release properties between the coating film and the mold. Since stringing does not cause surface roughness, a good pattern can be formed, and because it has excellent mechanical properties, it is suitable for permanent films.
(3) The volume shrinkage after photocuring is small and the mold transfer characteristics are excellent, so that an accurate moldability of a fine pattern is possible.
(4) Because of excellent coating uniformity, it is suitable for the field of coating and micromachining on large substrates.
(5) Since the photocuring speed of the film is high, the productivity is high.
(6) Since it is excellent in etching processing accuracy, etching resistance, etc., it can be suitably used as an etching resist for substrate processing of semiconductor devices and transistors,
(7) It is excellent in resist releasability after etching and does not produce a residue, so that it can be suitably used as an etching resist.
(8) Since the light transmittance is high, it can be suitably used as a permanent film.
From the viewpoint of, it is excellent overall.

 For example, the composition of the present invention can be suitably applied to fine processing applications such as semiconductor integrated circuits and liquid crystal display thin film transistors, protective films for liquid crystal color filters, and spacers, which have heretofore been difficult to develop. In addition, partition materials for plasma display panels, flat screens, micro electro mechanical systems (MEMS), sensor elements, optical recording media such as optical disks and high-density memory disks, optical parts such as diffraction grating relief holograms, nano devices, optical devices It can also be widely applied to the production of optical films, polarizing elements, organic transistors, microlens arrays, immunoassay chips, DNA separation chips, microreactors, nanobiodevices, optical waveguides, optical filters, photonic liquid crystals, and the like.

(A) Cationic polymerizable monomer The cationic polymerizable monomer used in the present invention will be described. The photocurable composition of the present invention contains a cationically polymerizable monomer, preferably 50 to 99% by mass of the photocurable composition, and more preferably 80 to 96% by mass. Include in percentage.
Furthermore, the photocurable composition of the present invention is (a) a compound having 10% by mass of a cationic polymerizable monomer having an oxetane ring, and preferably 10% to 100% by mass of a compound having an oxetane ring. And more preferably a compound having a 15 to 95% by mass oxetane ring.
The reason why the photocationically polymerizable monomer is excellent in photocurability is due to the characteristic of cationic polymerization that the polymerization reaction is not inhibited by oxygen in the air. In the case of radical polymerization, the active species in the polymerization reaction is a carbon radical, which has the disadvantage that it easily reacts with oxygen to deactivate and loses the polymerization activity. For this reason, when the reaction is carried out in the atmosphere, the sensitivity may be greatly reduced. In order to suppress this, it is necessary to devise a technique for suppressing contact with oxygen as much as possible by circulating nitrogen, but it is technically difficult to eliminate it at all. On the other hand, in the case of cationic polymerization, it is the cation that is responsible for the polymerization activity, which is inert to oxygen, so that high photopolymerization sensitivity can be obtained. The photocurable composition of the present invention contains 10% by mass or more of a compound having an oxetane ring as the cationic polymerizable monomer.

 It was found that the use of a compound having an oxetane ring as the photocationically polymerizable monomer is particularly excellent in terms of mold transfer characteristics, photocurability, and adhesion when used in photonanoimprint lithography. The reason why the compound having an oxetane ring is excellent in mold transfer property, photocurability and adhesion is due to the feature that the volume change is small before and after the polymerization reaction and the reactivity is high. In the case of normal radical polymerization, a new carbon-carbon bond is formed between the molecules during the polymerization reaction, which reduces the intermolecular distance and reduces the bulk of the whole molecule. On the other hand, in the case of cationic ring-opening polymerization, the bond cleavage by the ring-opening reaction (molecules spread in a chain) and the formation of new bonds between molecules (the distance between molecules decreases) occur at the same time. The overall bulkiness hardly changes. As a result, it is excellent in mold transfer characteristics and photocurability, and it is possible to accurately form a fine pattern. Similarly, the adhesiveness to the substrate is also such that the volume change is small before and after the polymerization reaction, and no distortion occurs after curing. Thus, it became possible to obtain a composition excellent in photocurability and adhesion by using a compound having an oxetane ring. Further, it has been found that a compound having an oxetane ring is preferable as a permanent film because it is comprehensively excellent in light transmittance after curing, heat resistance and mechanical properties.

Examples of the compound having an oxetane ring that can be used in the present invention include, for example, JP-A-8-143806, JP-A-2001-220526, JP-A-2001-310937, JP-A-2003-341217, The compounds having an oxetane ring described in JP-A-2004-91557, JP-A-2004-143137, and JP-A-2005-194379 can be suitably used.
The compound having an oxetane ring that can be used in the present invention is preferably a compound having 1 to 4 oxetane rings in its structure, and in particular, has one or two oxetane rings from the viewpoint of the viscosity of the photocurable composition. Preference is given to using compounds. By using such a compound, it becomes easy to maintain the viscosity of the photocurable composition within a favorable range of handling properties, and when used in optical nanoimprint lithography, the coating uniformity on the substrate, the mold High adhesion and good mold transfer characteristics can be obtained.

  Preferable examples of the compound having 1 to 2 oxetane rings in the molecule include compounds represented by the following general formulas (1) to (3).

General formula (1)

General formula (2)

General formula (3)

In the general formulas (1) to (3), R ^a1 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (in the case where it has a substituent, including the carbon number of the substituent, the same shall apply hereinafter) ), A substituted or unsubstituted fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any one or more hydrogen atoms of these alkyl groups are substituted with fluorine atoms. .

In the general formulas (1) to (3), R ^a2 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, and a substituted group having 2 to 6 carbon atoms. Or an unsubstituted alkenyl group, an aryl group, a substituted or unsubstituted acyl group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, a substituted or unsubstituted group having 2 to 9 carbon atoms Represents a carbamoyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, amyl group, 2-ethylhexyl group, cyclohexyl group, and phenoxyethyl group. Aralkyl groups include benzyl group, α-methylbenzyl group, 1 -Naphthylmethyl group, 2-naphthylmethyl group, 1-anthracenylmethyl group, 9-anthracenylmethyl group, 4-fluorobenzyl group, 2-methoxybenzyl group, phenethyl group, and the alkenyl group includes Examples thereof include a vinyl group, 1-propenyl group, 2-methyl-1-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group and 2-phenylvinyl group. As the aryl group, a phenyl group, 1-propenyl group, Examples include a naphthyl group, a 2-anthracenyl group, and a 9-phenanthrenyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, and a cyclohexylcarbonyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Examples of the carbamoyl group include an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, an N-amylcarbamoyl group, and an N, N-dimethylcarbamoyl group.

In the general formulas (1) to (3), R ^a3 represents a chain or branched alkylene group, a chain or branched poly (alkyleneoxy) group, a chain or branched hydrocarbon group, a carbonyl group or An alkylene group containing a carbonyl group, an alkylene group containing a carboxyl group, an alkylene group containing a carbamoyl group, or a group shown below is represented.

 Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

When R ^a3 is the above polyvalent group, R ^a4 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, a halogen atom, nitro A group, a cyano group, a mercapto group, a lower alkyl carboxyl group (for example, having 1 to 4 carbon atoms), a carboxyl group, or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, —NH—, —SO—, —SO ₂ —, —C (CF ₃ ) ₂ —, or —C (CH ₃ ) ₂ —.
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, n is an integer of 0 to 2000 (preferably an integer of (0 to 500)), and each R ^a6 is the same or different. It may be. R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure, and each R ^a7 may be the same or different.

上式中、Ｒ^a8は、炭素数１〜４のアルキル基、またはアリール基であり、それぞれ同一であっても異なっていてもよく、ｍは０〜１００の整数である。

In the above formula, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, which may be the same or different, and m is an integer of 0 to 100.

  Examples of the compound having 3 to 4 oxetane rings include compounds represented by the following general formula (4).

General formula (4)

In general formula (4), R ^a1 has the same meaning as in general formula (1), and the preferred range is also the same. In addition, as R ^a9 which is a polyvalent linking group, for example, a branched polyalkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly ( An alkyleneoxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4. Each R ^a1 may be the same or different.

In the above A, R ^a10 represents a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10, The numerical value of three p may be the same or may differ.

  Another embodiment of the compound having an oxetane ring that can be suitably used in the present invention includes a compound represented by the following general formula (5) having an oxetane ring in the side chain.

General formula (5)

In the general formula (5), R ^a1 and R ^a8 each have the same meaning as in the above formula, and when two or more exist, they may be the same or different. R ^a11 is a substituted or unsubstituted alkyl group or trialkylsilyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, and r is an integer of 1 to 4.

  Examples of the compound having one oxetane ring in the molecule include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, and (3-ethyl-3-oxetanylmethoxy) methyl. Benzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3- Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl- 3-Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl) 3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ) Ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2- Tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanyl) Til) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3- (4-bromobutoxymethyl) ) -3-methyloxetane, (3-methyloxetane-3-yl) methylbenzoate, and the like.

  Examples of compounds having two or more oxetane rings in the molecule include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanedii Rubis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] biphenyl, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3 Ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3- Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl) -3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl- -Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl) -3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3 -Ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl) -3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, poly (3- (4- Bromobutoxymethyl) -3-methyloxetane), N-oxetan-2-ylmethoxymethylacrylamide, 3,5-bis (3-ethyl-3-oxetanylmethoxy) benzoic acid, 3,5-bis (3-ethyl- Examples include 3-oxetanylmethoxy) benzoic acid methyl ester, 5- (3-ethyl-3-oxetanyl) isophthalic acid, 1,1,1-tris [4 (3-ethyl-3-oxetanylmethoxy) phenyl] ethane, and the like. These can be used alone or in combination of two or more.

The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method. For example, Pattyson (DBPattison, J. Am. Chem. Soc., 3455, 79 (1957)) Discloses an oxetane ring synthesis method from a diol.
In addition to these, compounds having 1 to 4 oxetane rings of a polymer having a molecular weight of about 1000 to 5000 are also included.

  As a commercial item of the compound having an oxetane ring, for example, OXT101 manufactured by Toa Gosei Co., Ltd. (3-ethyl-3-hydroxyoxetane, OXT221 manufactured by Toa Gosei Co., Ltd., di [1-ethyl (3-oxacenyl) methyl ether], Toa Gosei Co., Ltd. 1,4-bis {[(3-ethyl-3-octacel) methoxymethyl] benzene, OXT211 (3-ethyl-3- (phenoxymethyl) octacene) manufactured by Toa Gosei Co., Ltd., MPO (3, 3-dimethyl-2- (p-methoxyphenyl) oxetane) and Ube Industries ETERNACOLL OXBP can be used.

The compound having an oxetane ring used in the present invention is preferably a compound represented by the general formulas (1) to (3), and R ^a1 is preferably a methyl group or an ethyl group, particularly a methyl group. R ^a2 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms, and R ^a3 is a chain or branched alkylene It is preferably a group, a chain or branched poly (alkyleneoxy) group, particularly preferably — (CH ₂ ) _s —, —CH ₂ CH ₂ (OCHCH) _t —, and s is an integer of 1 to 8, t represents an integer of 0 to 3. By selecting these substituents, the viscosity of the polymerizable composition can be kept low, and when used in optical nanoimprint lithography, it has good coating uniformity on the substrate, high adhesion to the mold, and good mold transfer. Characteristics can be obtained.

The photocationically polymerizable compound used in the present invention may have both an oxirane ring and an oxetane ring in the molecule, and are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2002-235066 and 2002-212527. Compounds can be used.
The compound having both an oxirane ring and an oxetane ring is preferably a compound represented by the following general formula (6). By using these compounds, the polymerization rate can be increased, and as a result, a polymerizable composition having high curing sensitivity can be obtained.

General formula (6)

In the general formula (1), R ^a1 has the same meaning as R ^{1a in} the general formulas (1) to (3), and the preferred range is also the same.

 As the cationic polymerizable monomer (a) other than the compound having an oxetane ring in the photocurable composition of the present invention, a compound having an oxirane ring and / or a vinyl ether compound is preferable.

Compound having an oxirane ring In the present invention, a compound having an oxirane ring that is preferably used in combination with the photopolymerizable compound having an oxetane ring will be described. Examples of compounds having an oxirane ring include, for example, alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, aromatic polyols Examples include polyglycidyl ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  The compound having an oxirane ring that can be used in the present invention is preferably a compound containing an epoxycycloalkyl group and / or a glycidyl group. These compounds are excellent in cationic polymerizability. A compound containing an epoxycycloalkyl group is preferred because it has a low viscosity and a high curing rate, and a compound containing an epoxycyclohexyl group is particularly preferred. A compound containing a glycidyl group imparts flexibility to the polymer, increases the mobility of the polymerization system, and further improves the curability.

  Examples of the compound containing an epoxycyclohexyl group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4. -Epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4′-epoxy-6′-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate) , Ε-caprolactone modification 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone Examples thereof include modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1.2: 8,9 diepoxy limonene, and the like.

  Among compounds containing an epoxycyclohexyl group, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1.2: 8,9 diepoxy limonene is preferred.

  Examples of commercially available products that can be suitably used as the compound containing an epoxycyclohexyl group include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), and ceroxide. 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403 (Daicel Chemical Industries, Ltd.) )), KRM-2100, KRM-2110, KRM-2199 (manufactured by Asahi Denka Kogyo Co., Ltd.). The said component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the compound containing a glycidyl group that can be preferably used include bisphenol A 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, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; long aliphatic chains Diglycidyl esters of dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids Etc. can be illustrated.

  Among these components, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the compound containing a glycidyl group include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka) Kogyo Co., Ltd.). These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

  The content of the compound having an oxirane ring used in the present invention and (a) the cationic polymerizable monomer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and (15 to 70)% by mass. Further preferred.

Vinyl ether compound The vinyl ether compound which can be preferably used in combination with the photopolymerizable compound having an oxetane ring in the present invention will be described.
Examples of the vinyl ether compound used in the present invention include 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 methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene G Coal vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, Monofunctional vinyl ethers such as chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene Divinyl ethers such as coal divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether; trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, Pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl Polyfunctional vinyl ethers such as ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, propylene oxide-added dipentaerythritol hexavinyl ether Etc.
These vinyl ether compounds are characterized by low viscosity, low odor, and low skin irritation.

  These vinyl ether compounds are prepared by the method described in, for example, Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, reaction of polyhydric alcohol or polyhydric phenol with acetylene, They can be synthesized by a reaction of a monohydric alcohol or a polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used alone or in combination of two or more.

  The content of the vinyl ether compound used in the present invention in the (a) cationic polymerizable monomer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass.

Other polymerizable compounds As other cationic polymerizable compounds used in the present invention, compounds having a plurality of types of functional groups in the same molecule can also be applied.
For example, a compound containing a vinyl ether group and an epoxy group in the same molecule or a reactive compound having a propenyl ether group and an epoxy group can be preferably used.
In addition, as a polymerizable compound having photocationic polymerization property and photoradical polymerization property, 3-methyl-3-oxetanylmethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., OXE-10), 3-methyl-3-oxetanylmethyl acrylate ( Osaka Organic Chemical Industry, OXE-30), vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (manufactured by Daicel Chemical Industries, Celoxide 2000), (meth) acrylate compounds having an oxetane ring (Ube Industries, ETERNACOLL OXMA) Etc.) can also be used.

Furthermore, although the preferable blend form of the polymerizable monomer in the photocurable composition of this invention is described, the range of the blend of a polymerizable monomer is not specifically limited to these.
In the present invention, a cationically polymerizable monomer having one cationically polymerizable functional group is usually used as a reactive diluent and is effective in reducing the viscosity of the photocurable composition of the present invention. Preferably it is 95 mass% or less of a polymeric compound, More preferably, it is 90 mass% or less, Most preferably, it is added in 85 mass% or less. By setting the ratio of the monomer having one cationic polymerizable group to 95% by mass or less, it is preferable because the mechanical strength, etching resistance, and heat resistance of the cured film tend to be kept better, Further, when an organic polymer is used as a mold material for optical nanoimprint, there is a tendency that swelling of the mold can be suppressed and deterioration of the mold can be reduced. On the other hand, a monomer having one or two cationically polymerizable groups is usually essential for the photocurable composition of the present invention because it is used as a reactive diluent, and preferably a fully polymerizable compound. 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

In this invention, although the said photocationic polymerizable compound is mainly used, a radically polymerizable compound can also be used together in the range which does not impair the effect of this invention. 1-30 mass% is preferable with respect to all the polymeric compounds, and, as for the content rate of a radically polymerizable compound, 3-20 mass% is more preferable.
As a specific example of the photoradical polymerizable monomer that can be used in the present invention, a monomer having an ethylenic bond-containing group is preferably used.

 Examples of monomers having an ethylenic bond-containing group include 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, Phenoxytetraethylene glycol (meth) acrylate, N-vinyl-2-pyrrolidone, N-acryloylmorpholine, phenoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, N-vinylcaprolactam, hydroxypivalate neopentyl glycol diacrylate, polyethylene glycol diacrylate, Tripropylene glycol diacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylo Propanetriacrylate, pentaerythritol ethoxytetraacrylate, dipentaerythritol hexaacrylate, ethylene oxide modified phosphoric dimethacrylate, ethylene oxide modified neopentyl glycol diacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, 1,6-hexane Diol diacrylate, ethylene oxide modified bisphenol A diacrylate, neopentyl glycol diacrylate, urethane acrylate, epoxy acrylate, N-hydroxyethyl acrylamide, ethylene oxide modified bisphenol A diacrylate, polyester acrylate, polyurethane acrylate, polyether acrylate, poly Epoxy acrylate It includes various acrylate oligomers or polymers.

  Furthermore, in this invention, it is preferable that 40-90 mass% is (a) cation polymerizable monomer in all the polymeric compounds.

(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. The photocurable composition preferably contains 0.1 to 15% by mass, and preferably contains 0.2 to 12% by mass. More preferably, it is more preferably 0.3 to 10% by mass.
By setting the proportion of the cationic photopolymerization initiator to 0.1% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating film strength can be further improved. On the other hand, it is preferable that the ratio of the cationic photopolymerization initiator is 15% by mass or less because light transmittance, coloring property, handling property and the like are hardly deteriorated.
So far, in ink-jet compositions and color filter color filter compositions containing coloring materials such as dyes and / or pigments, various addition amounts of preferred photocationic polymerization initiators have been studied. There is no report on the preferred addition amount of the cationic photopolymerization initiator for the photocurable composition. Therefore, in a system substantially containing a coloring material such as a dye and / or a pigment, the photocurability is affected. Considering this point, the amount of photopolymerization initiator added is optimized in these applications. On the other hand, in the photocurable composition of the present invention, coloring materials such as dyes and / or pigments are not essential components, and the optimal range of the photopolymerization initiator is such as an inkjet composition or a liquid crystal display color filter composition. It may be different from the field.

  As the cationic photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used. Further, only one kind of the cationic photopolymerization initiator may be used, or two or more kinds thereof may be used.

  The cationic photopolymerization initiator applicable to the photocurable composition of the present invention may be a compound that generates a substance that initiates cationic photopolymerization by receiving energy rays such as ultraviolet rays, and is preferably an onium salt, an aromatic onium. Salts are more preferred, and arylsulfonium salts and aryliodonium salts are more preferred.

Specific examples of the onium salt include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl- 4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η ⁵ -2, 4- (cyclopentadienyl) [1,2,3,4,5,6-η]-(methylethyl) -benzene] ^-iron ( ¹⁺ ) and the like.
Specific examples of the anion include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl). ₆ ^-), perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion (CF ₃ SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene Examples include sulfonate anions.

  In particular, specific examples of the aromatic onium salt include aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP Group VIA aromatic onium salts described in JP-A-52-30899, JP-A-56-55420, JP-A-55-125105, etc., Group VA-aromatics described in JP-A-50-158698, etc. Onium salts, oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., described in JP-A-49-17040, etc. Aromatic diazonium salts, thiobililium salts, iron / allene complexes, aluminum complexes / photolytic silicon compound systems described in US Pat. No. 4,139,655 Agents, halides that photogenerate a hydrogen halide, o- nitrobenzyl ester compounds, imide sulfonate compound, bissulfonyldiazomethane compounds, mention may be made of an oxime sulfonate compound.

  As the photocationic polymerization initiator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely used (edited by Organic Electronics Materials Research Group, “Organization for Imaging”). Materials, "Bunshin Publishing (1993), pages 187-192). These compounds are photocationic polymerization initiators described in THE CHEMICAL SOCIETY OF JAPAN Voi.71 No.11, 1998, edited by Organic Electronics Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing (1993). Similarly to the above, it can be easily synthesized by a known method.

  Commercially available photocationic polymerization initiators include UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide), Adekaoptomer SP-150, SP-151. , SP-170, SP-171, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261, IRGACURE OXE01, IRGACURE CGI-1397, CGI-1325, CGI-1380, CGI-1311, CGI-263 , CGI-268, CGI-1397, CGI-1325, CGI-1380, CGI-1311 (above, manufactured by Ciba Specialty Chemicals), CI-2481, CI-2624, CI-2639, CI-2064 (above, Japan) Soda Co., Ltd.), CD-10 10, CD-1011, CD-1012 (manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (and above) , Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (Nippon Kayaku Co., Ltd.), PHOTOINITIATOR 2074 (Rhodia Co., Ltd.), UR-1104, UR- 1105, UR-1106, UR-1107, UR-1113, UR-1114, UR-1115, UR-1118, UR-1200, UR-1201, UR-1202, UR-1203, UR-1204, UR-1205, UR-1207, UR-1401, UR-1402, UR-1403, UR M1010, UR-M1011, UR-M10112, UR-SAIT01, UR-SAIT02, UR-SAIT03, UR-SAIT04, UR-SAIT05, UR-SAIT06, UR-SAIT07, UR-SAIT08, UR-SAIT09, UR-SAIT10, UR-SAIT11, UR-SAIT12, UR-SAIT13, UR-SAIT14, UR-SAIT15, UR-SAIT16, UR-SAIT22, UR-SAIT30 (above, manufactured by URAY). Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-171, SP-172, CD-1012 and MPI-103 have higher photocuring sensitivity due to the composition containing them. Can be expressed. Said photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

In the present invention, in addition to the cationic photopolymerization initiator, a radical photopolymerization initiator may be used in combination as long as the effects of the present invention are not impaired.
The radical photopolymerization initiator that can be used in combination with the present invention can be contained in the range of 0.1 to 8% by mass, preferably in the range of 0.2 to 7% by mass in the total composition. More preferably, it can contain in 0.3-6 mass%.

  As the radical photopolymerization initiator that can be used in combination with the present invention, those having activity with respect to the wavelength of the light source to be used are blended, and only one kind or two or more kinds may be used.

  As the radical photopolymerization initiator used in the present invention, for example, a commercially available radical photopolymerization initiator can be used. Examples of these include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (available from Ciba). (Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane- 1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinop Lopan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide) 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), Darocur (registered) Standard) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (R) 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO available from BASF -L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methyl), available from ESACUR Nippon Siebel Hegner Phenyls Phonyl) propan-1-one, N-1414 Adeka optomer (registered trademark) N-1414 (carbazole phenone) available from Asahi Denka Co., Adeka optomer (registered trademark) N-1717 (acridine), Adekaoptomer (registered trademark) N-1606 (triazine type), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1 manufactured by Sanwa Chemical Co., Ltd.) , 3,5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5, manufactured by Sanwa Chemical Co., Ltd.) -Triazine), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, Midori Chemical TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3 , 4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxa Nton ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone , Methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl Examples include -4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate.

(C) Fluorosurfactant, Silicone Surfactant, and Fluorine / Silicone Surfactant Next, the surfactant used in the present invention will be described. The photocurable composition of the present invention contains 0.001 to 5% by mass and 0.002 to 4% by mass of at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. It is preferable to contain, and it is more preferable to contain 0.005-3 mass%.
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
If the fluorine-based surfactant, silicone-based surfactant, and fluorine-silicone-based surfactant are less than 0.001% by mass in the photocurable composition of the present invention, the effect of coating uniformity is insufficient, On the other hand, if it exceeds 5% by mass, the mold transfer characteristics are deteriorated, which is not preferable. The fluorine-based surfactant, silicone-based surfactant and fluorine-silicone-based surfactant used in the present invention may be used alone or in combination of two or more. In the present invention, it is preferable to include both a fluorine-based surfactant and a silicone-based surfactant, or a fluorine / silicone-based surfactant. In particular, it is most preferable to contain a fluorine / silicone surfactant.

 By using such a surfactant, the photocurable composition of the present invention can be applied to a silicon wafer for manufacturing a semiconductor element, a glass square substrate for manufacturing a liquid crystal element, a chromium film, a molybdenum film, a molybdenum alloy film, or tantalum. Striations and scales that occur during coating, such as various films, such as films, tantalum alloy films, silicon nitride films, amorphous silicone films, tin oxide-doped indium oxide (ITO) films and tin oxide films The purpose of solving poor coating problems such as the pattern of the resist (unevenness of drying of the resist film), the fluidity of the composition into the cavity of the mold recess, and the mold releasability between the mold and the resist are improved. It is possible to improve the adhesion between the substrate and the substrate, to lower the viscosity of the composition, and the like. In particular, in the photocurable composition of the present invention, by adding the above-mentioned surfactant, the coating uniformity can be greatly improved, and in coating using a spin coater or slit scan coater, it is good regardless of the substrate size. Application suitability is obtained.

Examples of nonionic fluorosurfactants used in the present invention include trade names Florard FC-430 and FC-431 (manufactured by Sumitomo 3M), trade names Surflon “S-382” (manufactured by Asahi Glass), EFTOP “EF” -122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 (any OMNOVA), product names aftergent FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), product names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), product Name megafuak 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.) Examples of silicon-based surfactants include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink & Chemicals), and KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned.
Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

In addition to the above, other nonionic surfactants may be used in combination with the photocurable composition of the present invention for the purpose of improving the flexibility of the photocurable composition. Examples of commercially available nonionic surfactants include polyoxy, such as D-3110, D-3120, D-3412, D-3440, D-3510, and D-3605 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene alkyl ethers such as ethylene alkylamine, D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, and D-1518 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene monofatty acid esters such as D-2112-A, D-2112-C and D-2123-C of the Pionein series manufactured by Takemoto Yushi Co., Ltd. D- of the Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene difatty acid esters such as 2405-A, D-2410-D, D-2110-D, etc., manufactured by Takemoto Yushi Co., Ltd. Onin series D-406, D-410, D-414, D-418 and other polyoxyethylene alkyl phenyl ethers, Nissin Chemical Industry's Surfinol series 104S, 420, 440, 465, 485, etc. And polyoxyethylenetetramethyldecynediol diether. Moreover, the reactive surfactant which has a polymeric group can also be used together with the surfactant used by this invention. For example, allyloxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNE series), nonylphenoxy polypropylene glycol monometa. Acrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNP series), Nonylphenoxy poly (ethylene glycol-propylene glycol) monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNEP-600), Aqualon RN-10, RN- 20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (Daiichi Kogyo Seiyaku Co., Ltd.) and the like.
The content of the other nonionic surfactant is preferably in the range of 0.001 to 5% by mass of the photocurable composition of the present invention.

(D) Organic solvent The organic solvent contained in the curable composition of this invention is 2 mass% or less, More preferably, it is 0.5 mass% or less, and it is especially preferable not to contain.
Since the photocurable composition of the present invention preferably contains a specific monofunctional or bifunctional monomer as a reactive diluent, an organic solvent for dissolving the components of the photocurable composition of the present invention Need not be contained. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, the photocurable composition of the present invention does not necessarily contain an organic solvent, but in a reactive diluent, a compound that does not dissolve is dissolved as a component of the photocurable composition of the present invention or viscosity. When fine-tuning, etc., it may be added arbitrarily. The organic solvent that can be preferably used in the photocurable composition of the present invention is a solvent that is generally used in a photocurable composition or a photoresist, and is included in the photocurable composition of the present invention. There is no particular limitation as long as each main component is dissolved, uniformly dispersed, and does not react with these components.

Specifically, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve acetate Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol methyl Propylene glycol alkyl ether acetates such as ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, etc. Ketones; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, Such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc. And esters such as acid esters.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.
Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.

(E) Coloring material In the photocurable composition of the present invention, the content of a coloring material such as a pigment and / or dye is 0.5% by mass or less, preferably 0.3% by mass or less and not contained. Is particularly preferred.
Examples of the coloring material used in the present invention include coloring materials such as pigments used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like. Specifically, various conventionally known inorganic pigments or organic pigments can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And metal complex oxides. Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150 , 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36, 37, CIPigment Brown 25 28, CIPigment Black 1, 7 and carbon black.

 The viscosity at 25 ° C. of the photocurable composition of the present invention is preferably 20 mPa · s or less. More preferably, a polymerizable monomer having a viscosity of 19 mPa · s or less is used. By setting the viscosity to 20 mPa · s or less, bubble defects are less likely to be generated by the air taken into the mold recesses, and residues are less likely to remain on the mold projections after photocuring. If a large amount of residue remains, the etching process of the substrate is hindered, and it is preferable that the residue does not remain. The lower limit of the viscosity is not particularly defined, but is usually 3 mPa · s or more.

  In addition, the water content at the time of preparation of the photocurable composition of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, and further preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the photocurable composition of the present invention can be made more stable.

  Furthermore, in addition to the photocationic polymerization initiator, a photosensitizer may be added to the photocurable composition of the present invention to adjust the wavelength in the UV region. Typical sensitizers that can be used in the present invention include those disclosed in Krivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically, pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

  The content ratio of the photosensitizer in the photocurable composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less in the composition. Although the minimum of a photosensitizer content rate is not specifically limited, In order to express an effect, the minimum of a photosensitizer content rate is about 0.1 mass%.

  The light for initiating polymerization of the present invention includes not only light having a wavelength in the region of ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light, or electromagnetic waves, but also radiation. For example, microwave, electron beam, EUV, and X-ray are included. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light with a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and after the pattern is formed for the purpose of increasing the film strength and etching resistance, the entire surface can be further exposed.

  In addition to the above components, the photocurable composition of the present invention may include a release agent, a silane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiaging agent, and a plasticizer as necessary. Adhesion promoters, thermal polymerization initiators, inorganic particles, elastomer particles, photoacid multipliers, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants, and the like may be added.

  For the purpose of further improving the releasability, a release agent can be arbitrarily blended in the photocurable composition of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the photocurable composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used. Moreover, these mold release agents can be adhered to the mold.

  Silicone release agents have particularly good release properties from the mold when combined with the above-mentioned photocurable resin used in the present invention, and the phenomenon of taking a plate hardly occurs. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, and silicone acrylic resin.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more of the above-described modification methods can be performed on one polysiloxane molecule.

  The modified silicone oil is preferably compatible with the composition components. In particular, in the case of using a reactive silicone oil that is reactive with other coating-forming components blended as necessary in the composition, in the cured film obtained by curing the photocurable composition of the present invention. Since these are fixed by chemical bonding, problems such as adhesion inhibition, contamination, and deterioration of the cured film hardly occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it crosslinks with the photocurable composition of the present invention, and thus has excellent properties after curing. .

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeding out on the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
The said mold release agent can be added only 1 type or in combination of 2 or more types.

  When a release agent is added to the photocurable composition of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass in the total amount of the composition, and is added in a range of 0.01 to 5% by mass. It is more preferable. When the ratio of the release agent is 0.001% by mass or more, the effect of improving the mold release between the mold and the photocurable composition layer tends to be improved. On the other hand, when the ratio of the release agent is within the above range of 10% by mass, the problem of surface roughness of the coating film due to repelling during coating of the composition hardly occurs, and the substrate itself and the adjacent layer in the product For example, it is preferable in that the adhesion of the vapor deposition layer is hardly hindered and the film is not easily broken during transfer (the film strength is too weak).

  In the photocurable composition of the present invention, an organic metal coupling agent may be blended in order to increase the heat resistance, strength, or adhesion of the surface structure having a fine uneven pattern to the metal deposition layer. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

  Examples of the silane coupling agent used in the photocurable composition of the present invention include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyl Acrylic silanes such as trimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldi Epoxy silanes such as ethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N -Phenyl -Aminosilane such as γ-aminopropyltrimethoxysilane; and other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and the like. .

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

  The said organometallic coupling agent can be mix | blended in the ratio of 0.001-10 mass% in solid content whole quantity of a photocurable composition, for example. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective in improving heat resistance, strength, and adhesion with the vapor deposition layer. On the other hand, it is preferable that the ratio of the organometallic coupling agent is 10% by mass or less because the stability of the composition and the deficiency in film formability can be suppressed.

  The photocurable composition of the present invention may contain a polymerization inhibitor in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like. It is preferable to mix | blend a polymerization inhibitor in the ratio of 0.001-10 mass% with respect to the whole quantity of a photocurable composition, for example.

Furthermore, a known antioxidant can be included in the composition of the present invention.
The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). In particular, in the present invention, the addition of an antioxidant has an advantage that the cured film can be prevented from being colored or the decrease in film thickness due to decomposition can be reduced. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness.

  As commercially available products of antioxidants, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB AO70, AO80, AO503 (made by ADEKA Co., Ltd.), etc. are mentioned, These may be used independently and may be mixed and used. It is preferable to mix | blend antioxidant in the ratio of 0.01-10 mass% with respect to the whole quantity of the composition of this invention, and it is further more preferable to mix | blend in the ratio of 0.2-5 mass%.

  Examples of commercially available antioxidants include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Sumilyzer S (manufactured by Sumitomo Chemical Co., Ltd.), and the like. It is preferable to mix | blend antioxidant in the ratio of 0.01-10 mass% with respect to the whole quantity of a composition, and it is more preferable to mix | blend in the ratio of 0.1-5 mass%.

  As a commercial item of an ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350 400 (above, manufactured by Sumitomo Chemical Co., Ltd.). It is preferable to mix | blend a ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of a photocurable composition.

  Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) Etc. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the photocurable composition.

The photocurable composition of the present invention can contain a known antioxidant. The antioxidant suppresses fading caused by light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.
Examples of commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the photocurable composition.

  A plasticizer can be added to the photocurable composition of the present invention in order to adjust adhesion to the substrate, flexibility of the film, hardness, and the like. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate , Di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.

  An adhesion promoter may be added to the photocurable composition of the present invention in order to adjust adhesion to the substrate. Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2'-bipyridine derivatives, benzotriazoles, organic phosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used. The adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain the effect.

  When hardening the photocurable composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  The photocurable composition of the present invention may contain a photobase generator as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitro Benzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5- Diacetyl-4 Preferred examples include (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. It is done.

  For the purpose of improving the heat resistance, mechanical strength, tackiness, etc. of the coating film, a filler may be added as an optional component to the photocurable composition of the present invention. As the inorganic fine particles, those having an ultra fine particle size are used. Here, “ultrafine particle” means a particle of submicron order, and generally means a particle having a particle size smaller than a particle having a particle size of several μm to several 100 μm, which is generally called “fine particle”. ing. The specific size of the inorganic fine particles used in the present invention varies depending on the use and grade of the optical article to which the photocurable composition is applied, but generally the primary particle size is in the range of 1 nm to 300 nm. Is preferably used. If the primary particle size is 1 nm or more, the moldability, shape maintaining property and releasability of the photocurable composition can be sufficiently improved, while if the primary particle size is 300 nm or less, it is necessary for curing the resin. It is preferable in terms of transparency.

Specific examples of the inorganic fine particles include metal oxide fine particles such as SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , and Al ₂ O ₃ , among which colloidal dispersion is possible as described above. In addition, it is preferable to select and use a particle having a particle size on the order of submicron, and particularly, it is preferable to use colloidal silica (SiO ₂ ) fine particles.

  The inorganic fine particles are preferably blended in a proportion of 1 to 70% by mass and particularly preferably in a proportion of 1 to 50% by mass in the total solid content of the photocurable composition. By setting the proportion of the inorganic fine particles to 1% by mass or more, the moldability, shape maintaining property and releasability of the photocurable composition of the present invention can be sufficiently improved, and the proportion of the inorganic fine particles is set to 70% by mass. % Or less is preferable in terms of strength and surface hardness after exposure and curing.

In the photocurable composition of the present invention, elastomer particles may be added as an optional component for the purpose of improving mechanical strength, flexibility, and the like.
The elastomer particles that can be added as an optional component to the photocurable composition of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 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 / Particles of elastomer such as polyene copolymer, acrylic rubber, butadiene / (meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

  Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resinas Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.

  These elastomer particles can be used alone or in combination of two or more. The content of the elastomer component in the photocurable composition of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

The photocurable composition of the present invention can contain a known antioxidant. The antioxidant suppresses fading caused by light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.

  A basic compound may be optionally added to the photocurable composition of the present invention for the purpose of suppressing curing shrinkage, improving thermal stability, and improving storage stability. Examples of the basic compound include amines and nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine. , Trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine and triethanolamine.

  In the present invention, the cationic polymerization initiator that generates acid by energy rays is combined with a substance (hereinafter referred to as an acid proliferation agent) that newly generates an acid by the action of the generated acid to improve the curing rate. It can also be made. Examples of the acid proliferating agent include Japanese Patent Application Laid-Open No. 08-248561, HYPERLINK "http://www.ekouhou.net/disp-A,H10-1508.html" Japanese Patent Application Laid-Open No. 10-1508, HYPERLINK "http: //www.ekouhou.net/disp-A,H10-1508.html "Japanese Patent Laid-Open No. 10-1508, HYPERLINK" http://www.ekouhou.net/disp-B,3102640.html "Japanese Patent No. 3106640 Compounds disclosed in the publication, specifically 1,4-bis (p-toluenesulfonyloxy) cyclohexane, 1,4-bis (p-toluenesulfonyloxy) cyclohexane, cis-3- (p-toluenesulfonyloxy) -2-pinanol and cis-3- (p-octanesulfonyloxy) -2-pinanol. Examples of commercially available compounds include ACPRESS 11M (manufactured by Nippon Chemix Co., Ltd.).

  Next, the formation method of the pattern (especially fine concavo-convex pattern) using the photocurable composition of this invention is demonstrated. In the present invention, a curable composition is applied and cured to form a pattern. Specifically, a layer (pattern forming layer) made of a photocurable composition is applied on a substrate or a support by applying at least a pattern forming layer made of the photocurable composition of the present invention and drying as necessary. To form a pattern receiver, press the mold against the surface of the pattern receiving layer of the pattern receiver, perform a process of transferring the mold pattern, and expose and harden the fine concavo-convex pattern forming layer. The optical imprint lithography according to the pattern forming method of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint. Alternatively, the pattern may be formed continuously by roll-to-roll.

  In addition, as an application of the photocurable composition of the present invention, the photocurable composition of the present invention is applied on a substrate or a support, and a layer comprising the composition is exposed, cured, and dried as necessary ( By baking, a permanent film such as an overcoat layer, a spacer, or an insulating film can be produced.

  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 is generally applied to coating methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, and spin coating. It can be formed by coating by a slit scanning method or the like. The film thickness of the layer made of the photocurable composition of the present invention is 0.05 μm to 30 μm, although it varies depending on the intended use. In addition, the photocurable composition of the present invention may be applied multiple times.

  The substrate or support for applying the photocurable composition of the present invention is quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate such as Ni, Cu, Cr, Fe, Polymer substrate such as paper, SOG, polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass or transparent plastic substrate, conductive substrate such as ITO or metal, insulating substrate, silicone, nitriding There are no particular restrictions on semiconductor fabrication substrates such as silicone, polysilicon, silicone oxide, and amorphous silicone. The shape of the substrate may be a plate shape or a roll shape.

  The light for curing the photocurable composition of the present invention is not particularly limited, and examples thereof include high energy ionizing radiation, light having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared, or radiation. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The radiation includes, for example, microwaves and EUV. Also, laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic light, or may be a plurality of lights having different wavelengths (mixed light).

Next, the molding material that can be used in the present invention will be described. In optical nanoimprint lithography using the photocurable composition of the present invention, it is necessary to select a light transmissive material for at least one of the mold material and / or the substrate. In the photoimprint lithography applied to the present invention, a photocurable composition is applied onto a substrate, a light transmissive mold is pressed, light is irradiated from the back surface of the mold, and the photocurable composition is cured. . Moreover, a photocurable composition is apply | coated on a transparent substrate, a mold is pressed, light can be irradiated from the back surface of a mold, and a photocurable composition can also be hardened.
The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered.

As the mold that can be used in the present invention, a mold having a pattern to be transferred is used. The mold can form a pattern according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
The light-transmitting mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, examples thereof include glass, quartz, PMMA (Polymethylmethaclylate), a light transparent resin such as polycarbonate resin, a transparent metal vapor deposition film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film.

  The non-light transmissive mold material used when the transparent substrate of the present invention is used is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. The shape may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.

  The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the peelability between the photocurable composition and the mold. Suitable for treatment with a silane coupling agent such as silicone or fluorine, such as Daikin Industries, trade name: OPTOOL DSX, Sumitomo 3M, trade name: Novec EGC-1720 Can be used.

  When performing photoimprint lithography using the present invention, it is usually preferred that the mold pressure be 10 atmospheres or less. It is preferable that the mold pressure is 10 atm or less because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and the apparatus can be reduced because the pressure is low. The mold pressure is preferably selected in a region where the uniformity of mold transfer can be ensured within a range in which the residual film of the photocurable composition on the mold convex portion is reduced.

In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The irradiation amount necessary for curing is determined by examining the consumption of bonding of the photocurable composition and the tackiness of the cured film.
In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the photocurable composition. May be. In the present invention, the preferable degree of vacuum is 10 ⁻¹ Pa to normal pressure.

  The photocurable composition of the present invention can be prepared as a solution by mixing the above components and then filtering with a filter having a pore size of 0.05 μm to 5.0 μm, for example. Mixing and dissolution of the photocurable composition is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for the filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

The case where the photocurable composition of the present invention is applied to an etching resist will be described. The etching step can be performed by a method appropriately selected from known etching methods, and is performed to remove the underlying portion not covered with the resist pattern, thereby obtaining a thin film pattern. Either a treatment with an etching solution (wet etching) or a treatment in which a reactive gas is activated by plasma discharge under reduced pressure (dry etching) is performed.
The etching process may be a batch system in which an appropriate number of sheets are processed together, or a single wafer process in which each sheet is processed.

As etching solutions for performing the wet etching, many etching solutions have been developed and used, typically ferric chloride / hydrochloric acid, hydrochloric acid / nitric acid, hydrobromic acid, and the like. For Cr, mixed solution of cerium ammonium nitrate or cerium nitrate / hydrogen peroxide solution, for Ti, diluted hydrofluoric acid, hydrofluoric acid / nitric acid solution, for Ta, mixed solution of ammonium solution and hydrogen peroxide solution For Mo, hydrogen peroxide solution, a mixture of ammonia water and hydrogen peroxide solution, a mixture solution of phosphoric acid and nitric acid, and MoW and Al, a mixture solution of phosphoric acid and nitric acid, a mixture solution of hydrofluoric acid and nitric acid, phosphoric acid Nitric acid / acetic acid mixed solution For ITO, diluted aqua regia, ferric chloride solution, hydrogen iodide water, SiNx and SiO ₂ are buffered hydrofluoric acid, hydrofluoric acid / ammonium fluoride mixed solution, Si, poly Si Is a mixture of hydrofluoric acid, nitric acid and acetic acid, W is a mixture of ammonia water and hydrogen peroxide, PSG is a mixture of nitric acid and hydrofluoric acid, and BSG is a mixture of hydrofluoric acid and ammonium fluoride. used.
Wet etching may be either a shower method or a dip method, but the etching rate, in-plane uniformity, and wiring width accuracy largely depend on the processing temperature, so the conditions are optimal according to the substrate type, application, and line width. It is necessary to make it. Further, when performing the wet etching, it is desirable to perform post-baking in order to prevent undercut due to the penetration of the etching solution. Usually, these post-baking is performed at about 90 ° C. to 140 ° C., but is not necessarily limited thereto.

The dry etching basically uses a parallel plate type dry etching apparatus having a pair of electrodes arranged in parallel in a vacuum apparatus and setting a substrate on one of the electrodes. Reactive ion etching (RIE) mode in which ions are mainly involved and radicals are mainly involved depending on whether the high-frequency power source for generating plasma is connected to the electrode on the side where the substrate is installed or to the opposite electrode The plasma etching (PE) mode is classified.
As an etchant gas used in the dry etching, an etchant gas suitable for each film type is used. For a-Si / n ⁺ and s-Si, carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine), for a-SiN _x tetrafluoride carbon + oxygen, is for a-SiO _x carbon tetrafluoride + oxygen trifluoride carbon + oxygen, is for Ta carbon tetrafluoride (sulfur hexafluoride) + oxygen tetrafluoride is for MoTa / MoW Examples include carbon fluoride + oxygen, Cr + oxygen for Cr, and boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, etc. for Al. In the dry etching process, the resist structure may be greatly altered by ion bombardment or heat, which also affects the peelability.

  A method for removing the resist used for pattern transfer to the lower substrate after etching will be described. Peeling can be removed with a liquid (wet peeling), or oxidized by plasma discharge of oxygen gas under reduced pressure and removed in a gaseous state (dry peeling / ashing), or oxidized with ozone and UV light. The resist can be removed by several stripping methods such as removing it in a gaseous state (dry stripping / UV ashing). As the stripping solution, an aqueous solution system such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and ozone-dissolved water and an organic solvent system such as a mixture of an amine and dimethyl sulfoxide or N-methylpyrrolidone are generally known. As an example of the latter, a monoethanolamine / dimethyl sulfoxide mixture (mass mixing ratio = 7/3) is well known.

 The resist stripping rate is greatly related to temperature, liquid amount, time, pressure, etc., and can be appropriately determined depending on the substrate type and application. In the present invention, it is preferable to immerse the substrate (from several minutes to several tens of minutes) in the temperature range of room temperature to 100 ° C., and rinse with water such as butyl acetate and then rinse with water. From the viewpoint of improving the rinsing properties, particle removability, and corrosion resistance of the stripping solution itself, only water rinsing may be used. A preferable example is a pure water shower for washing and an air knife drying for drying. When the amorphous silicone is exposed on the substrate, an oxide film is formed in the presence of water and air. Therefore, it is preferable to block air. Moreover, you may apply the method of using together ashing (ashing) and peeling by a chemical | medical solution. Examples of ashing include plasma ashing, downflow ashing, ashing using ozone, and UV / ozone ashing. For example, when an Al substrate is processed by dry etching, a chlorine-based gas is generally used, but aluminum chloride, which is a product of chlorine and Al, may corrode Al. In order to prevent these, a stripping solution containing a preservative may be used.

  There is no restriction | limiting in particular as other processes other than the said etching process, peeling process, rinse process, and water washing, It can mention selecting from the process in well-known pattern formation suitably. For example, a hardening process process etc. are mentioned. These may be used alone or in combination of two or more. There is no restriction | limiting in particular as a hardening process, Although it can select suitably according to the objective, For example, a whole surface heat processing, a whole surface exposure process, etc. are mentioned suitably.

 Examples of the method for the entire surface heat treatment include a method for heating the formed pattern. By heating the entire surface, the film strength on the surface of the pattern is increased. As heating temperature in whole surface heating, 80-200 degreeC is preferable and 90-180 degreeC is more preferable. When the heating temperature is 80 ° C. or higher, the film strength by heat treatment tends to be further improved, and when it is 200 ° C. or lower, the components in the photocurable composition are decomposed and the film quality is weak and brittle. Can be more effectively deterred. There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned. Moreover, when using a hot plate, in order to heat uniformly, it is desirable to carry out by lifting the substrate on which the pattern is formed from the plate.

 Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed pattern. The entire surface exposure accelerates the curing in the composition forming the photosensitive layer and the surface of the pattern is cured, so that the etching resistance can be increased. There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Abbreviations of the monomers used in the examples and comparative examples of the present invention are as follows.
<Monomer>
C-1: 3-ethyl-3- (phenoxymethyl) octacene (OXT211: manufactured by Toa Gosei Co., Ltd.)
C-2: 3-ethyl-3-hydroxyethyloxetane (OXT101: manufactured by Toagosei Co., Ltd.)
C-3: Di [1-ethyl (3-octacenyl) methyl ether] (OXT221: manufactured by Toagosei Co., Ltd.)
C-4: Main component 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.)
C-6: Compound C-7 having the following oxetane ring synthesized by the method described in Synthesis Example 1: Compound C-8 having the following oxetane ring synthesized by the method described in Synthesis Example 2: Compound C-9 having the following oxetane ring synthesized by the method described below: (3-methyl-3-oxetanyl) methyl acrylate (OXE-10: manufactured by Osaka Organic Industrial Co., Ltd.)
C-10: 3,4-epoxycyclohexylmethyl-3 ′, 4 ′ epoxycyclohexanecarboxylate (Cyracure-6105: manufactured by Union Carbide)
C-11: 1.2: 8,9 diepoxy limonene (Celoxide 3000: manufactured by Daicel Chemical Industries)
C-12: Vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexene (Celoxide 2000: manufactured by Daicel Chemical Industries)
C-13: Epoxidized fatty acid glyceride (Celoxide 2021P: manufactured by Daicel Chemical Industries)
C-14: Hydroxybutyl vinyl ether (HBVE: manufactured by Maruzen Petrochemical Co., Ltd.)
C-15: Triethylene glycol divinyl ether (RAPI-CURE DVE-3: manufactured by ISB Japan)
C-16: Trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.)

 The abbreviations of the radical photopolymerization initiator used in the examples and comparative examples of the present invention are as follows.

<Photocationic polymerization initiator>
U-1: Sulfonium photoacid generator (manufactured by Union Carbide: UVI6990)
U-2: triallylsulfonium hexafluorophosphate salt (manufactured by Midori Chemical Co., Ltd .: DTS-102)
U-3: Triallylsulfonium hexafluorophosphate salt mixture (manufactured by Dow Chemical Company: Syracure UVI6992)
U-4: Tri-p-chlorophenylsulfonium hexafluorophosphate U-5: 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)] manufactured by Ciba Geigy: OXE-01

Abbreviations for the surfactants and additives used in the examples and comparative examples of the present invention are as follows.
<Surfactant>
W-1: Fluorosurfactant (manufactured by Tochem Products: Fluorosurfactant)
W-2: Silicone-based surfactant (Dainippon Ink & Chemicals, Inc .: Megafuck Paintad 31)
W-3: Fluorine / silicone surfactant (manufactured by Dainippon Ink & Chemicals, Inc .: Megafuk R-08)
W-4: Fluorine / silicone surfactant (Dainippon Ink Chemical Industries, Ltd .: Megafuak XRB-4)
W-5: Acetylene glycol nonionic surfactant (Shin-Etsu Chemical Co., Ltd .: Surfynol 465)
W-6: Polyoxyethylene polyoxypropylene condensate (Takemoto Yushi Co., Ltd .: Pionine P-1525)
W-7: Fluorosurfactant (Dainippon Ink Chemical Co., Ltd .: MegaFuck F470)
W-8: Fluorosurfactant (Dainippon Ink Chemical Co., Ltd .: MegaFax EXP.TF907)
W-9: Fluorosurfactant (Dainippon Ink & Chemicals, Inc .: MegaFuck F1405)

<Additives>
A-1: 2-chlorothioxanthone A-2: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
A-3: 4,4′-diethylaminobenzophenone A-4: 1,9-dibutoxyanthracene A-5: N-ethyldiethanolamine A-6: tributylamine A-7: silane coupling agent (vinyltriethoxysilane) (Shin-Etsu Silicone)
A-8: CI Pigment Black 7 (manufactured by Clariant Japan)
A-9: CI Pigment Blue 15: 3 (manufactured by Gokoku Dye)
A-10: Dispersant (Ajinomoto Fine Techno Co., Ltd .: PB822)
A-11: Rosin-modified maleic resin (Halitak R-100, Harima Chemical)
A-12: Propylene carbonate (manufactured by Kanto Chemical)

<Evaluation of Photocurable Composition-I>
About each of the composition obtained by Examples 1-10 and Comparative Examples 1-10, it measured and evaluated in accordance with the following evaluation method.
Table 1 shows the polymerizable monomers (Examples and Comparative Examples) used in the compositions.
Table 2 shows the compounding ratios (Examples and Comparative Examples) of the polymerizable monomers contained in the composition.
Table 3 shows the compounding ratios (Examples and Comparative Examples) of the polymerizable monomer, photopolymerization initiator, surfactant, and additive used in the composition.
Table 4 shows the results (Examples and Comparative Examples) of the present invention. In addition, the comprehensive evaluation in Table 4 is performed according to the following criteria, and it can be used at A rank.
A: B rank is within 2 items.
B: B rank is 3 or more items.
C: B rank is 4 items or more, or C rank is 1 item.

<Viscosity measurement>
The viscosity was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd. The rotational speed during the measurement is 100 rpm for 0.5 mPa · s to less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for less than 30 mPa · s for 10 mPa · s, and 60 mPa · s for 30 mPa · s to 60 mPa · s. Less than 10 rpm, 60 mPa · s or more and less than 120 mPa · s was 5 rpm, and 120 mPa · s or more was 1 rpm or 0.5 rpm, respectively.

<Measurement of photocurability>
Photocurability is measured using a high-pressure mercury lamp as a light source, and the change in the absorption of the monomer at 810 cm ⁻¹ is measured using a Fourier transform infrared spectrometer (FT-IR). Rate) in real time. In Table 4, A represents the case where the curing reaction rate is 0.2 / second or more, and B represents the case where the curing reaction rate is less than 0.2 / second.

<Adhesion>
Adhesion is determined by visual observation of whether or not the photocured photocurable resist pattern is attached to the tape side when the tape is attached to the surface of the photocured photocurable resist pattern and peeled off. It was evaluated as follows.
A: No pattern adherence on the tape side B: Very thin pattern adherence to the tape side, but C: Adherence of pattern clearly recognized on the tape side

<Peelability>
The peelability was evaluated by observing with an optical microscope whether or not an uncured product remained in the mold when the mold was peeled off after photocuring.
A: No residue on mold surface B: Residue on part of mold surface C: Residue on entire mold surface

<Observation of residual film properties and pattern shape>
The shape of the transferred pattern and the residue of the transferred pattern were observed with a scanning electron microscope, and the remaining film property and the pattern shape were evaluated as follows.
(Residual film properties)
A: No residue is observed B: A little residue is observed C: Many residues are observed (pattern shape)
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partially different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 20%). C: The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.

<Spin coating suitability>
Applicability (I)
After spin-coating the photocurable composition of the present invention on a 4-inch 0.7 mm-thick glass substrate on which an aluminum (Al) film having a thickness of 4000 angstroms was formed, to a thickness of 6.0 μm, The glass substrate was allowed to stand for 1 minute, surface observation was performed, and evaluation was performed as follows.
A: No repelling and coating streaks (striation) observed B: Some coating streaks observed C: Repelling or coating streaks were observed strongly

<Slit application suitability>
Applicability (II)
The photocurable composition of the present invention was formed into a 4-inch aluminum (Al) film having a film thickness of 4000 angstroms using a slit coater resist coating apparatus (head coater system manufactured by Hirata Kiko Co., Ltd.) for coating a large substrate. A 0.7 mm thick glass substrate (550 mm × 650 mm) was applied to form a resist film with a thickness of 2.0 μm, and the presence or absence of streaky irregularities appearing vertically and horizontally was observed and evaluated as follows. .
A: Streaky unevenness was not observed B: Streaky unevenness was observed to be weak C: Streaky unevenness was observed strongly or repellency was observed on the resist film

<Etching property>
The photocurable composition of the present invention is formed in a pattern on the aluminum (Al) formed on the glass substrate, and after curing, the aluminum thin film is etched with a phosphoric nitrate etchant, and a 10 μm line / space is visually and microscopically observed. And evaluated as follows.
A: An aluminum line having a line width of 10 ± 2.0 μm was obtained. B: Variation in line width of the line became a line exceeding ± 2.0 μm. C: A defective portion of the line existed or the space between the lines was Connected

(Synthesis Example 1)
Sodium hydride (5.2 g) was suspended in 100 mL of dimethylformamide under ice-cooling, and 10.2 g of 3-methyl-3-oxetanemethanol was added dropwise. After stirring for 30 minutes, 20.3 g of 1-bromo-2-ethylhexane was added dropwise. After stirring for 30 minutes, the mixture was warmed to room temperature and stirred for 6 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, washed with saturated brine, and dried over magnesium sulfate. Ethyl acetate was distilled off and the residue was purified by column chromatography to obtain 4,9 g of compound C-6.
¹ H-NMR (300 MHz, CDCl ₃ , δ): 4.52 (dd, 2H), 4.37 (dd, 2H), 3.40 (s, 2H), 3.35 (d, 2H), 1 .52 (m, 1H), 1.40-1.22 (m, 11H), 0.95-0.84 (m, 6H).
It was 2.4 mPa * s when the viscosity at 25 degrees C of compound C-6 was measured using RE80 type viscometer (brand name, Toki Sangyo Co., Ltd. make).

(Synthesis Example 2)
204.3 g of 3-methyl-3-oxetanemethanol and 500 mL of pyridine were stirred in an ice bath, and 419.4 g of p-toluenesulfonyl chloride was added thereto in small portions. After stirring in an ice bath for 3 hours, 2 L of water was added to the reaction solution for crystallization. The white solid was filtered, washed with water until the smell of pyridine disappeared, and then dried. Yield 471.9 g (92%).
90 g of sodium hydride was suspended in 1 L of N, N-dimethylformamide under ice cooling, and a solution of dimethylformamide (500 mL) of 153.2 g of 3-methyl-3-oxetanemethanol was added dropwise. After stirring for 30 minutes, 384.5 g of the tosyl white solid obtained earlier was added in small portions. After stirring for 30 minutes, the mixture was warmed to room temperature and stirred for 6 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, washed with saturated brine, and dried over magnesium sulfate. Ethyl acetate was distilled off and the residue was purified by vacuum distillation. 210.0 g of compound C-7 was obtained as a fraction at 94 ° C. to 98 ° C. at about 4 mmHg. The yield was 75%.
¹ H-NMR (300 MHz, CDCl ₃ , δ): 4.52 (dd, 4H), 4.38 (dd, 4H), 3.56 (s, 4H), 1.34 (s, 6H).
It was 5.2 mPa * s when the viscosity at 25 degrees C of compound C-7 was measured using RE80 type | mold viscosity meter (brand name, the Toki Sangyo company make).

(Synthesis Example 3)
A 48% aqueous sodium hydroxide solution (150 mL), epichlorohydrin (100 mL), and tetrabutylammonium hydrogen sulfate (3.7 g) were stirred at room temperature, and 25 g of 3-ethyl-3-hydroxymethyloxetane was slowly added dropwise thereto over 30 minutes. The mixture was further stirred at room temperature for 7 hours, and the reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water, washed with saturated brine, and dried over magnesium sulfate. Ethyl acetate was distilled off and the residue was purified by chromatography to obtain 32.4 g of compound C-8.
¹ H-NMR (300 MHz, CDCl ₃ , δ): 4.48 (dd, 2H), 4.40 (d, 2H), 3.64-3.58 (m, 3H), 3.41 (d, 1H), 2.75 (dd, 1H), 2.61 (dd, 1H), 1.77 (q, 2H), 1.38 (s, 3H), 0.95 (t, 3H).
It was 5.9 mPa * s when the viscosity at 25 degrees C of compound C-8 was measured using RE80 type | mold viscosity meter (brand name, Toki Sangyo Co., Ltd. make).

Example 1
As a polymerizable monomer, 14.07 g of 3-ethyl-3- (phenoxymethyl) octacene monomer (C-1), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (C-5) 65.66 g, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (C-4) 14.07 g, sulfonium salt UVI 6990 (manufactured by Dow Chemical Company) as a photopolymerization initiator 5.5 g, 0.1 g of Megafuak XRB-4 (W-4: manufactured by Dainippon Ink & Chemicals, Inc.) as a fluorine / silicone surfactant, and 9,10-dibutoxyanthracene (Kawasaki Chemical) as a sensitizer 0.60 g (manufactured by Kogyo Co., Ltd.) was precisely weighed and mixed at room temperature for 24 hours to obtain a uniform solution. It was 18 mPa * s when the viscosity of the composition was measured. This prepared composition was spin-coated on a 4-inch silicone substrate so as to have a thickness of 6.0 μm. The spin-coated coated base film was set in a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source, the mold pressure was 50 kN / cm ² , and the degree of vacuum during exposure was 0.2 Torr. 170 mJ / cm ² from the back surface of a mold made of polydimethylsiloxane having a line pattern of 10 μm and a groove depth of 5.0 μm (SILPOT 184 manufactured by Toray Dow Corning Co., Ltd. cured at 80 ° C. for 60 minutes). After exposure, the mold was released, and the characteristics of the composition were examined in the same manner as in Example 1. As a result, it was confirmed that the photocurability, adhesion, mold release property, residual film property, pattern shape, coatability (spin coatability, slit coatability), and etchability were comprehensively satisfied.

Examples 2-10
In the same manner as in Example 1, the polymerizable monomers shown in Table 1 were mixed at the ratio shown in Table 2 to prepare the compositions shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. All the compositions of Examples 2 to 10 are generally satisfied with respect to photocurability, adhesion, mold release, residual film, pattern shape, coatability (spin coatability, slit coatability), and etchability. It was recognized that it was possible.

Comparative Example 1
The composition was prepared by removing only the surfactant from the composition without changing the monomer, photopolymerization initiator, additive type, and blending ratio used in Example 1. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. Compared to the composition of Example 1, the composition of Comparative Example 1 was deteriorated in releasability, remaining film property, coating property (spin coating property, slit coating property), and etching property, and was totally satisfied. It was not possible.

Comparative Example 2
The monomer, photopolymerization initiator, additive type, and blending ratio used in Example 2 were not changed, and the surfactant type was changed from that of the present invention to a nonionic surfactant different from the present invention ( The composition was adjusted in place of W-5). The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. Compared to the composition of Example 2, the composition of Comparative Example 2 was not completely satisfactory due to deterioration in mold release properties, coating properties (spin coating properties, slit coating properties), and etching properties. It was.

Comparative Example 3
The monomer, photopolymerization initiator, additive type, and blending ratio used in Example 3 were not changed, and the surfactant type of the nonionic surfactant different from that of the present invention was selected from the composition ( The composition was adjusted in place of W-6). The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. Compared to the composition of Example 3, the composition of Comparative Example 3 was not completely satisfactory because of its release properties, coating properties (spin coating properties, slit coating properties), and etching properties. It was.

Comparative Example 4
Without changing the monomer, photopolymerization initiator, surfactant type and blending ratio used in Example 4, 2.5% by mass of solvent (A-12: propylene carbonate) was added to the composition. The composition was adjusted. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. Compared with the composition of Example 4, the composition of Comparative Example 4 deteriorated the remaining film property, the pattern shape, and the etching property, and was not totally satisfactory.

Comparative Example 5
The monomer (A-9: CI Pigment Blue 15: 3) in the composition was changed to 3.0 without changing the monomer, photopolymerization initiator, surfactant type, and blending ratio used in Example 5. Mass% was added to adjust the composition. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. Compared with the composition of Example 5, the composition of Comparative Example 5 was deteriorated in photocurability, pattern shape, and etching property, and was not totally satisfactory.

Comparative Example 6
In the same manner as in Example 1 of the present invention, the compositions described in Examples (ink composition 3) of the ink jet composition disclosed in JP-A-2005-8759 were used. The monomer was mixed at a ratio 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 the characteristics of the composition were examined. The results are shown in Table 4. The composition of Comparative Example 6 was inferior to the composition of the present invention in terms of photocurability, releasability and etching, and was not totally satisfactory.

Comparative Example 7
In the composition of Comparative Example 6, the pigment (A-8: CI Pigment Black 7) and the dispersant A-10: Dispersant (manufactured by Ajinomoto Fine Techno Co., Ltd .: PB822) were excluded from the composition, and the other components were Comparative Example 6. Using the same components as in Example 1, the polymerizable monomers shown in Table 1 were mixed in the proportions shown in Table 2 to prepare compositions having the compositions shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. From the results of Table 4, the composition of Comparative Example 7 was inferior to the composition of the present invention in terms of photocurability, releasability, pattern shape, and etching, and was not totally satisfactory.

Comparative Example 8
The composition described in Comparative Example (Curing Composition No. 5) of the photocurable composition disclosed in JP-A-2005-194379 is polymerized as shown in Table 1 in the same manner as in Example 1 of the present invention. Monomers were mixed at a ratio 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 the characteristics of the composition were examined. The results are shown in Table 4. The composition of Comparative Example 8 had poor photocurability, releasability, and remaining film property, and was not satisfactory in pattern shape, coatability (spin coatability, slit coatability), and etchability.

Comparative Example 9
The composition described in the comparative example (cured composition No. 5) of the photocurable composition for inkjet disclosed in JP-A-2005-194379 is shown in Table 1 in the same manner as in Example 1 of the present invention. A polymerizable monomer was mixed at a ratio shown in Table 2 to prepare a composition having a composition shown in Table 3. The prepared composition was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 4. The composition of Comparative Example 8 was not satisfactory in all of photocurability, mold release property, residual film property, pattern shape, coatability (spin coatability, slit coatability), and etchability.

Comparative Example 10
In the same manner as in Example 1 of the present invention, the composition described in Comparative Example (Ink Composition 1 Curing Composition No. 5) of the photocurable composition for inkjet disclosed in JP-A-2005-41893 is used. The polymerizable monomers shown in Table 1 were mixed at the ratio 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 the characteristics of the composition were examined. The results are shown in Table 4. The composition of Comparative Example 8 was not satisfactory in all of photocurability, mold release property, residual film property, pattern shape, coatability (spin coatability, slit coatability), and etchability.

<Evaluation of Photocurable Composition-II>
The photocurable composition of the present invention was evaluated as a permanent film (protective film).
<Residual film ratio>
The photocurable composition of the present invention is spin-coated on a glass substrate to a thickness of 4 μm, set in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and exposed from the back surface of the mold under conditions of 500 mJ / cm ^2. After the exposure, the mold was released and heated in an oven at 230 ° C. for 150 minutes. The film thickness of the pattern part of the photocurable resin before and after heating was measured with a profiler P11 manufactured by Tenkor, and the remaining film ratio after heating was determined and evaluated as follows.
A: Remaining film ratio exceeding 90% B: Remaining film ratio 85-90%
C: Remaining film ratio less than 85

<Transmissivity>
The photocurable composition of the present invention is spin-coated on a glass substrate to a thickness of 4 μm, set in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and exposed from the back surface of the mold under conditions of 500 mJ / cm ^2. After the exposure, the mold was released and heated in an oven at 230 ° C. for 150 minutes. The light transmittance of the pattern portion of the photocurable resin after heating was measured with a spectrophotometer UV2100 manufactured by Shimadzu, and the transmittance after heating was evaluated as follows.
A: Transmittance exceeding 90% B: Transmittance 85-90%
C: Transmittance less than 85

<Solvent resistance>
The photocurable composition of the present invention is spin-coated on a glass substrate to a thickness of 4 μm, set in a nanoimprint apparatus using a high-pressure mercury lamp as a light source, and exposed from the back surface of the mold under conditions of 500 mJ / cm ^2. After the exposure, the mold was released and heated in an oven at 230 ° C. for 150 minutes. After heating, it was immersed in each solution of N-methylpyrrolidone (NMP), 5% sodium hydroxide, and 5% hydrochloric acid for 30 minutes, and the change in film thickness before and after immersion was determined and evaluated as follows.
A: Almost no change in film thickness is observed (less than 1%)
B: Some change in film thickness is observed (less than 1 to 5%)
C: Change in film thickness is slightly observed (5% or more)

Example 11
The monomer, photopolymerization initiator, surfactant, type of sensitizer and mixing ratio used in Example 1 were not changed, and 2 antioxidants (Sumitomo Chemical Industries: Sumilizer GA80) were added to the composition. A photocurable composition was prepared in the same manner as in Example 1 except for adding mass%. This adjusted photocurable composition was spin-coated on a glass substrate so as to have a film thickness of 4 μm, and the spin-coated coating base film was used as a light source from a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC. Set in a nanoimprint apparatus, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (Toray Dow Corning: SILPOT 184 cured at 80 ° C. for 60 minutes The film was exposed under the condition of 500 mJ / cm ² from the back surface of the mold made of the material. After the exposure, the mold was released, and the remaining film rate and transmittance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 5. The composition of Example 11 was comprehensively excellent in the remaining film ratio, light transmittance, and solvent resistance, and also excellent in properties as a permanent film.

Example 12
The monomer, photopolymerization initiator, surfactant type and blending ratio used in Example 5 were not changed, and 2% by mass of an antioxidant (ADEKA: ADK STAB AO503) was added to the composition. 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 thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (Toray Dow Corning: SILPOT 184 cured at 80 ° C. for 60 minutes) ) Was exposed from the back surface of the mold made of) under the condition of 500 mJ / cm ² , and after the exposure, the mold was released, and the remaining film rate and transmittance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 5. The composition of Example 12 was comprehensively excellent in the remaining film rate, light transmittance, and solvent resistance, and also excellent in properties as a permanent film.

Example 13
The monomer, photopolymerization initiator, surfactant, and mixing ratio used in Example 8 were not changed, and 2% by mass of an antioxidant (made by ADEKA: ADK STAB AO503) was added to the composition. 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 thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (Toray Dow Corning: SILPOT 184 cured at 80 ° C. for 60 minutes) ) Was exposed from the back surface of the mold made of) under the condition of 500 mJ / cm ² , and after the exposure, the mold was released, and the remaining film rate and transmittance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 5. The composition of Example 13 was comprehensively excellent in the remaining film rate, light transmittance, and solvent resistance, and also excellent in properties as a permanent film.

Example 14
The monomer, photopolymerization initiator, surfactant type, and blending ratio used in Example 8 were not changed, and the antioxidant (Sumitomo Chemical Industries: Sumilizer GA80) was added in an amount of 3.0% by mass in the composition. In addition, 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 thickness of 4 μm, and the spin-coated base film was applied to a nanoimprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. Set, mold pressure is 10 kN / cm ² , vacuum degree during exposure is 0.2 Torr, polydimethylsiloxane having a 5 mm square pattern (Toray Dow Corning: SILPOT 184 cured at 80 ° C. for 60 minutes) ) Was exposed from the back surface of the mold made of) under the condition of 500 mJ / cm ² , and after the exposure, the mold was released, and the remaining film rate and transmittance of the pattern part of the photocurable resin before and after heating were measured. Thereafter, the solvent resistance of the photocured film was examined. The results are shown in Table 5. The composition of Example 14 was comprehensively excellent in the remaining film ratio, light transmittance, and solvent resistance, and also excellent in properties as a permanent film.

Comparative Example 11
The composition used in Comparative Example 8 was patterned in the same manner as in Example 11, and the characteristics of the composition were examined. The results are shown in Table 5. The composition of Comparative Example 11 was inferior in the remaining film ratio and solvent resistance.
Comparative Example 12
The prepared composition used in Comparative Example 9 was patterned in the same manner as in Example 11, and the characteristics of the composition were examined. The results are shown in Table 5. The composition of Comparative Example 12 was not at a level that could satisfy any of light transmittance, residual film rate, and solvent resistance.
Comparative Example 12
The prepared composition used in Comparative Example 9 was patterned in the same manner as in Example 11, and the characteristics of the composition were examined. The results are shown in Table 5. The composition of Comparative Example 12 was not at a level that could satisfy any of light transmittance, residual film rate, and solvent resistance.
Comparative Example 13
The prepared composition used in Comparative Example 10 was patterned in the same manner as in Example 11, and the characteristics of the composition were examined. The results are shown in Table 5. The composition of Comparative Example 13 was not at a level that could satisfy all of the light transmittance, the remaining film rate, and the solvent resistance.

 The photocurable composition of the present invention includes a semiconductor integrated circuit, a flat screen, a microelectromechanical system (MEMS), a sensor element, an optical disk, a magnetic recording medium such as a high-density memory disk, an optical component such as a diffraction grating relief hologram, Nano devices, optical devices, optical films and polarizing elements for flat panel display fabrication, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunity It can be used as an optical nanoimprint resist composition for forming a fine pattern when producing an analysis chip, DNA separation chip, microreactor, nanobiodevice, optical waveguide, optical filter, photonic liquid crystal and the like.

Claims (7)

(A) a cationically polymerizable monomer, (b) a photocationic polymerization initiator, (c) at least one of fluorine-based surfactant, silicone-based surfactant, and fluorine-silicone-based surfactant 0.001 And (d) the content of the organic solvent is 1% by mass or less, (e) the content of the coloring material is 0.5% by mass or less, and (a) the cationic polymerizable monomer A photocurable composition in which 10% by mass or more of the monomer is a compound having an oxetane ring. The photocurable composition of Claim 1 which contains the said (a) cation polymerizable monomer in 50-99 mass%. The photocurable composition according to claim 1 or 2, comprising a vinyl ether compound as the cationic polymerizable monomer (a). The photocurable composition according to any one of claims 1 to 3, comprising a compound having an oxirane ring as the (a) cationic polymerizable monomer. Furthermore, the photocurable composition of any one of Claims 1-4 containing antioxidant. The step of applying the photocurable composition, the step of pressurizing the light transmissive mold onto the resist layer on the substrate and deforming the photocurable composition, irradiating light from the back of the mold or the back of the substrate, and curing the coating film And the photocurable property of any one of Claims 1-5 used for the pattern formation method including the process of forming the pattern fitted to a desired pattern, and the process of removing | desorbing a light-transmitting mold from a coating film. Composition. The step of applying the photocurable composition, the step of pressurizing the light transmissive mold onto the resist layer on the substrate and deforming the photocurable composition, irradiating light from the back of the mold or the back of the substrate, and curing the coating film A step of forming a resist pattern that fits into a desired pattern, a step of removing the light-transmitting mold from the coating film, a step of etching the substrate using the photocurable composition as a mask, and the photocurable composition after etching The photocurable composition of any one of Claims 1-5 used for the resist pattern formation method including the process to peel.