TW200846824A - Curing composition for photonano-imprinting lithography and pattern forming method by using the same - Google Patents

Curing composition for photonano-imprinting lithography and pattern forming method by using the same Download PDF

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TW200846824A
TW200846824A TW97102134A TW97102134A TW200846824A TW 200846824 A TW200846824 A TW 200846824A TW 97102134 A TW97102134 A TW 97102134A TW 97102134 A TW97102134 A TW 97102134A TW 200846824 A TW200846824 A TW 200846824A
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composition
group
mass
example
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TW97102134A
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Takashi Takayanagi
Yasumasa Kawabe
Hiroki Sasaki
Kyohei Sakita
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Fujifilm Corp
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Priority to JP2007242717A priority patent/JP2008202022A/en
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Abstract

Provided is a novel curing composition for photonano-imprinting lithography with excellent photocuring property. The said curing composition for photonano-imprinting lithography comprises 35 to 99 mass% of polymeric unsaturated monomer; 0.1 to 15 mass% of photo-polymerization initiator; 0.001 to 5 mass% of at least one of fluorine-based surfactant, silicon-based surfactant, and fluorine, silicon surfactant; and 0.1 to 50 mass% of inorganic oxide microparticle.

Description

[Brief Description of the Invention] [Technical Field] The present invention relates to a curable composition for photonic printing and a pattern forming method using the same. [Prior Art]

The nano printing method is a embossing technique well known in the development of optical discs, and a metal mold prototype in which a photoresist is formed by pressing a photoresist (generally called a mold (m ο I d ), a stamp (stamper) ), template 〇6〇^1316)) The technique of mechanically deforming and precisely transferring fine patterns. In the case of the production of a mold, it is expected to be applied to various fields in recent years in order to make the nanostructures more economically simple and reproducible, and at the same time, harmful nano-processing techniques with less waste and emissions. The nano printing system has proposed the case of thermoplastic resin as the material to be processed (S. Chou et a I. : A pp I. P hys . L e 11 · Vo I · 6 7, 3114 (1 995)) And the case of using a hardening composition for photolithographic printing lithography (MC ο I bun et al, : Proc. SPIE, Vol. 3676, 379 (1999)). In the case of thermal nano-printing, a resin which is heated to a glass transition temperature or higher is pressed into a mold, and a mold is released after cooling to transfer the fine structure to the resin on the substrate. . Since it can be applied to various resin materials and glass materials, applications in various aspects are expected. A nano-printing method in which a nano pattern is inexpensively formed using a thermoplastic resin is disclosed in U.S. Patent No. 5,772,905 and U.S. Patent No. 5,956,216. On the other hand, a light-colored nano-printing method in which a light-curable composition for photonic printing lithography is light-cured by a transparent mold is irradiated with light, and the pattern 200846824 can be printed at room temperature. Recently, a new development has been reported on the combination of the nano-casting method of the two advantages or the reverse printing method of producing a three-dimensional laminated structure. The nano printing method like this is considered to have the following applications. The shape formed by the first one is functional, and can be applied as a variety of nano-technical component parts or structural members, such as various micro-nano optical elements or local density records. Media, optical films, structural members in flat panel displays, and the like. The second one is applied to the μ-TAS or the biochip maker by constructing a laminated structure by micro-structuring and nano-fabrication, or by simply positioning between layers. The third method is suitable for producing a high-density semiconductor integrated circuit or a transistor in a liquid crystal display, instead of conventional lithography, by high-precision positioning and high integration. In recent years, the practical combination of the nano printing method related to such applications has been alive. An application example of the nanoprinting method will first be described as an application example for the fabrication of a high-density semiconductor integrated circuit. In recent years, the semiconductor integrated circuit has been moving toward miniaturization and integration, and the high Φ precision system of the photolithography (P h 01 ο I ith 〇graphy) device has made it possible to achieve its fine processing. Pattern transfer technology. However, the processing method is close to the wavelength of the light exposure source, and the lithography technique is close to the limit. For this reason, in order to be able to move toward further miniaturization and gastricization, an electron beam drawing device of a charged particle beam device is used instead of the photolithography technique. An overall exposure method in which a pattern forming system using an electron beam and a light source using a j-ray laser or the like is formed is not a stomach's approach to forming a mask pattern, and the pattern is drawn as the stomach is more Multiple exposures (drawing) time, but have the disadvantage of requiring time in pattern formation. For this reason, with the 256 Mega, 1 Giga, 4 Giga, and the integrated body 200846824, the pattern formation time has also increased dramatically, and the productivity has been significantly deteriorated. For this reason, development of an overall pattern irradiation method in which an electron beam drawing device is combined with various shapes to form an integral electron beam and an electron beam is formed to form a complicated shape. However, in addition to the miniaturization of the pattern on the one hand, the electron beam drawing device has to be enlarged, and on the other hand, the mechanism for controlling the position of the mask with higher precision becomes necessary, and so-called device is produced. The disadvantage of increased cost. On the other hand, nano-printing lithography proposed by the technique of forming a fine pattern at a low cost has been proposed. For example, U.S. Patent No. 5,772,905 and U.S. Patent No. 5,259,926 disclose a nano-printing technique in which a twin crystal is used as a film and a fine structure of 25 nm or less is transferred. Further, Japanese Laid-Open Patent Publication No. 2005-5271 No. 0 discloses a composite composition suitable for use in nano-printing in the field of semiconductor microlithography. On the other hand, the durability of the micro-molding mold making technique or the mold, the production cost of the mold, the peelability from the mold resin, the printing uniformity or the alignment φ precision, inspection In the fabrication of semiconductor integrated circuits such as technology, the review system for nano-printing lithography has begun to be enthusiastic. Next, an application example of a nanodisplay lithography for a flat panel display such as a liquid crystal display (LCD) or a plasma display (PDP) will be described. With the large-scale or high-definition movement of LC D or PDP substrates, replacing the conventional photolithography used in the manufacture of thin film transistors (TFTs) or electrode plates, inexpensive photolithographic photolithography The system has received attention in recent years. Therefore, development of a photocurable photoresist which replaces the etching photoresist used in the conventional photolithography method has become necessary. In the case of the transparent protective film material described in JP-A-2005-30199, JP-A-2005-301289, or JP-A-2005-301289, JP-A-2005-301289 The application of the spacers contained in the bulletin* has also been reviewed. The photoresist for such a structural member is different from the above-described etching photoresist, and is eventually referred to as a permanent photoresist or a permanent film because it eventually remains in the display. A description will be given of a permanent film suitable for use in conventional photolithography. The permanent film system is different from the above-described etching photoresist, and its elements can be left as it is on a semiconductor φ element, a recording medium, a flat display panel or the like. For example, it can be used as a transparent protective film material for a color filter used for a liquid crystal panel, and conventionally, a photocurable resin such as a siloxane polymer, a phthalocyanine, an epoxy resin, or an acrylic resin is used. A transparent protective film is formed in the process of the thermosetting resin (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 6-43643). In the aspect of forming a protective film by photolithography, uniformity of a coating film, substrate adhesion, high light transmittance after heat treatment exceeding at least 200 ° C, planarization characteristics, solvent resistance, and the like are also required. Characteristics such as scratch resistance.

The spacer which defines the cell gap in the liquid crystal display is also a kind of permanent film. In the conventional photolithography, the photohardenability of the resin, the photopolymerizable monomer and the initiator is generally widely used. (Special opening 2 0 0 4 - 2 4 0 2 4 1 bulletin). The spacer system also requires high mechanical properties, hardness, developability, pattern accuracy, adhesion, and the like for external pressure. However, the transparent protective film used in the nano printing method or the preferred composition of the photocurable composition for forming the spacer has not been disclosed. In addition, the uniformity of the coating film is on the enlargement of the substrate and the substrate

200846824 Various types of parts such as dimensional uniformity, film thickness, and shape caused by coating film thickness uniformity or high resolution in the center and peripheral parts are strictly required. Conventionally, in the field of manufacturing liquid crystal display devices using small glass substrates, a method of applying a central drip and then rotating is used as a photoresist coating method (Electronic Journal, 121-123 Νο. 8 (2002)). Although the coating method in which the center is dripped and rotated can obtain good coating uniformity, for example, in the case of a large substrate of 1 m square class, there is a considerable amount of photoresist which is shaken off during rotation (during rotation), and A problem arises in that the φ substrate is broken due to high-speed rotation or that the tact time is ensured. In addition, the coating performance of the method of rotating after dropping in the center is related to the rotation speed at the time of rotation and the coating amount of the photoresist, and is not necessary in order to be applied to the fifth generation of the large-scale plate. A universal motor with acceleration, and when customizing a motor like this, there is a problem of increasing the cost of parts. Further, since the substrate size or the device size is increased in size, the required performance in a coating step such as coating uniformity ± 3% and production interval time of 60 to 70 seconds per sheet is substantially constant, so after the center is dropped The method of spinning φ is difficult to correspond to requirements other than coating uniformity. In view of the current state of the art, a new photoresist coating method which is applicable to a large substrate from the fourth generation substrate, particularly the fifth generation substrate, has been proposed to have a nozzle type coating method. The nozzle-type photoresist coating method is a method in which a photoresist composition is entirely applied to a coated surface of a substrate by moving a discharge nozzle and a substrate, and it is proposed to use, for example, a plurality of nozzle holes. A method of discharging the discharge nozzle of the photoresist composition in a strip shape, or a method of discharging the discharge nozzle of the photoresist composition in a row. Further, there has been proposed a method in which the photoresist composition is applied to the coated surface of the substrate 200846824 by a discharge nozzle type, and the substrate is rotated to adjust the film thickness. Therefore, in order to replace the nano-printing composition with a conventional photolithography photoresist, and to apply it to the field of liquid crystal display device manufacturing, it is important to coat the substrate uniformity. * In the case of a positive-type photoresist used in the production of a semiconductor integrated circuit or a liquid crystal display, or a pigment-dispersed photoresist for color filter production, a fluorine-based and/or a lanthanoid surfactant can be added to solve the coating property. Specifically, the problem of coating defects such as a striped or scaly pattern (the Φ drying unevenness of the photoresist film) caused by coating on a substrate is known (Japanese Patent Laid-Open No. 7 2 3 0 1 6) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2000-94241. Further, in order to improve the abrasion resistance or coating property of a protective film such as a compact disc or a magnetic optical disc, a fluorine-based surfactant or a lanthanum surfactant is added to the solvent-free photocurable composition. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the same manner, in order to improve the ink discharge stability of the ink jet set φ, a nonionic fluorine-based surfactant is added. In addition, Japanese Laid-Open Patent Publication No. 2003-1 65930 discloses the use of a embossing process for embossing a hologram to form a paint composition coated with a thick film such as a bristles, a pen, or a bar coater, and adds 1% or more. An example of a surfactant containing a polymerizable unsaturated double bond, preferably 3% or more, to improve the water swelling property of the cured film. As described above, a technique of adding a surfactant to a protective film such as a positive photoresist or a pigment dispersion resist for color filter production or a magnetic optical disk to improve coatability is a conventional technique. Further, as observed in the above-described examples of the ink-jet or coating composition, in order to improve the property improvement in the respective applications in order to improve the property improvement in the respective use of the solvent-free photocuring 10-200846824 resin, the interfacial activity is added. The technology of the agent is also well known. Japanese Laid-Open Patent Publication No. H07-84625 discloses an example in which a photocurable resin using a fluorine-containing surfactant is used as a photoresist for photonic printing in the production of a semiconductor integrated circuit. However, there has been no known method for improving the substrate coating property of a photocurable nano-printing resist composition which is an optional component of a pigment, a dye or an organic solvent used in a permanent film.

Further, in the photonic printing, the fluidity of the composition in the pores of the mold cavity is good, and the mold release property is good, and the peeling property between the mold and the photoresist is good. The adhesion between the photoresist and the substrate is good. It is difficult to have both fluidity, peelability, and adhesion. The prior art relating to photon printing in the scope of application of the present invention will be described in more detail. Photonic printing lithography generally consists of a hardening composition of liquid nano-printing lithography on a substrate of germanium wafer, quartz, glass, film or other material such as ceramic material, metal or polymer. a film having a thickness of a few tens of nanometers to a number of φ is applied, and a mold having a fine unevenness of a pattern size of a few tens of nm to several tens/m. is pressed and pressed under pressure. A method of removing a film from a coating film to obtain a transferred pattern after illuminating the composition to harden the composition. For this reason, at least one of the substrate or the mold is necessary to be transparent in the case where the light is printed. Usually, the case where the illuminating is performed from the side of the mold is a general one, and the mold material is usually made of an inorganic material such as quartz or sapphire which can penetrate U V light or a light transmissive resin. Compared with the thermal nano printing method, the photonic printing method can be exemplified by -11-200846824, such as: (1) no heating/cooling process is required, and high productivity is expected, and (2) due to the use of the liquid composition Low pressurization for printing, (3) no dimensional change due to thermal expansion, (4) mold mold is transparent and easy to align, (5) ^ hardened three-dimensional crosslinked body after hardening The main advantage. In particular, it is suitable for semiconductor micromachining applications requiring alignment accuracy or for microfabrication applications in the field of flat panel displays. Moreover, another feature of the photon printing method is that the resolution is independent of the wavelength of the light source, so that the stepper is stepped or even at the nano level. A high-priced device such as an electron beam drawing device is an unnecessary feature. On the other hand, the photon printing method is necessary for a double-molding mold, and since the mold is in contact with the resin, there is a concern about the durability or cost of the mold. Therefore, for the application of thermal and/or photon printing, large-area printing of micron, or nano-sized patterns, not only the uniformity of the pressing pressure or the flatness of the master (casting mold) is required, but also It is also necessary to control the flow of the above-mentioned composition into the pores of the mold cavity or the spring action of the composition which flows out. The mold mold used in the photonic lithography can be manufactured from a wide variety of materials such as metal, semiconductor, ceramic, SOG (Spin On Glass), or a certain plastic. For example, a mold having a soft polydimethyl oxane having a desired fine structure is described in the International Publication WO 9 9/2 2 84 9 . 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 of the decomposition ability. Electron beam and X-ray lithography are typically used for structure sizes below 300 nm. Direct laser exposure and U V lithography make 200846824 for larger structures. Regarding the photon printing method, the releasability of the mold and the hardenable composition for photonic printing lithography is important, and attempts have been made to bury the surface of the mold or the mold, specifically The ytterbium hydroxide sesquioxide beta or fluorinated ethylene propylene copolymer mold is used to solve the adhesion problem and the like. Here, the photocurable resin used in the photolithographic printing lithography will be described. The photocurable resin suitable for nano-printing is roughly classified into a radical polymerization type, an ion polymerization type, or a mixed type of φ or the like according to the difference of the reaction mechanism. Any composition can be printed, but the range of materials is generally selected from a wide range of free radical polymerization types (F. Xu et al.: SPIE Microlith〇graphy Conference, 5374, 232 (2004)). The radical polymerization type is generally carried out by using a monomer having a radically polymerizable vinyl group or a (meth) propionate group (monomer) or a composition containing an oligomer and a photopolymerization initiator. The radical generated by the photopolymerization initiator attacks the vinyl group to carry out chain polymerization to form a polymer. A crosslinked structure can be obtained by using a bifunctional i 2 polyfunctional monomer or oligomer as a component. D"· Re snicketa I ·: J · Va c . S ci · Te ch η ο I · B, Vo I · 2 1 , N 〇 · 6, 2624 (2003) Revealing the use of low-viscosity UV hardening Monomer, a composition that can be imprinted at low pressure and room temperature. The material properties used in photonographic lithography are described in detail. The material @胃求性性 varies according to the application, but there is a common point irrespective of the use of the process. For example, the main requirements for the latest photoresist material handbook, P1, i 034 04 (2005, published by the intelligence agency) are coating properties, substrate adhesion, low viscosity (< 5 m Pa. s), _ M f raw 'low hardening shrinkage rate, quick hardening and the like. It is known that the requirements for low-viscosity materials are strong, especially in low-pressure -13-200846824 printing and reduction of residual film rate. On the other hand, in another characteristic characteristic of the exemplified application, for example, the optical member has a refractive index, a light transmittance, and the like, and the etching resistance is reduced, and the residual film thickness is reduced. How to control the requirements of these characteristics, whether or not each characteristic is balanced, becomes the key to material design. At least the material required for the process material and the permanent film is required to be developed according to the > process and use. Materials suitable for use in photonic lithography are disclosed in the latest photoresist material manual, 'P 1, 103~1 04 (2005, published by the Intelligence Agency) with approximately 6Qmpa • s (2 5 °C) Viscosity photohardenable materials are well known. Similarly, CMC publishes: Development and application of nano-printing P159~160 (in 2006, it revealed that the exfoliation system with monomethacrylate as the main component and viscosity of 14.4 m Pa • s is elevated fluorine Photosensitive Resin The composition used in photon printing as described above has a description of the requirements relating to the viscosity. However, there has been no report on the design guidelines for materials suitable for each application.

An example of a photocurable resin which has hitherto been applied to photonic lithography is described. JP-A-2004-59820, JP-A-2004-59822 discloses the use of a photocurable resin containing a polymer having an isocyanate group for producing a relief type hologram or a diffraction grid, and embossing Processing examples. Japanese Laid-Open Patent Publication No. 2006-1 1 4882 discloses a curable composition for printing nano-printing lithography containing a polymer, a photopolymerization initiator, and a viscosity modifier. Japanese Laid-Open Patent Publication No. 2000-143924 discloses a pattern forming method using a fluorine-containing curable material in order to improve the peelability from a mold. -14- 200846824 N. Sakai et al.: j.photopolymer Sci.Technol.Vol.18, Νο·4,531 (2005) discloses the inclusion of (1) functional acrylic monomers, (2) functional acrylic monomers (3) Photocurable radically polymerizable composition or photocurable epoxidized composition in combination with a functional acrylic monomer and a photopolymerization initiator, and a photocationic polymerizable composition of a photoacid generator For example, it is suitable for nanolithographic lithography, and an example of thermal stability and mold mold peelability is examined. M. Stewart et al.: MRS Buletin, Vo I · 30, No. 1 2, 947 (2005) discloses the inclusion of (1) functional acrylic monomers, (2) functional propylene φ acid monomers, ruthenium containing The curable composition for photonic printing lithography of the monofunctional acrylic monomer and the photopolymerization initiator is used for improving the photocurable resin, the peeling property with the mold, and the film shrinkage after curing. A method in which photopolymerization in the presence of oxygen hinders problems such as low sensitivity caused by the polymerization. T. Beiiey et al.: J. Va c . S c i. Te ch π ο I. B 1 8 (6) Γ 3572 (2000) reveals that ytterbium containing a monofunctional acrylic monomer is formed on the ruthenium substrate. a hardening composition for photonic printing lithography of a monofunctional monomer and a photopolymerization initiator, and using a surface-treated mold to reduce defects in the mold after photolithography . B.Vratzov et al.: J. Va c . S c i. Te ch η ο I. B 2 1 (6), 2760 (2 003) reveals the formation of a ruthenium-containing monomer, a trifunctional acrylic acid on a ruthenium substrate. The curable composition for photonic printing lithography of a body and a photopolymerization initiator is a composition excellent in high resolution and uniformity of coating by a SiO 2 mold. EKKim et a IJ Vac. Sci. Technol, B 2 2 (1 ), 131 (2004) discloses the formation of a 50 nm pattern size by combining a specific vinyl ether compound with a cationic polymerizable composition of a photoacid generator. -1 5 - 200846824 Example. Its characteristics are low in viscosity and fast in hardening speed, but the description of template peelability is a problem. However, such as N. S a k a i e t a I. : J . P h o t ο p o 1 y m e r

Sci.Technol.Vol.18, N o . 4 , 531(2 0 05) , M . S tewartet al. *· MRS Buletin, Vol.30, No.12, 947 (2005) - T.Beiley et al. : J.Vac.Sci.Techno I ·Β18(6), 3572(2000), B.Vratzov et al. : J.Vac.Sci.Technol.B21 (6), 2760(2003) > EKKim et al : J.Vac.Sci.Techno!, B22(1), 1 3 1 (2 0 0 4)

However, acrylic monomers, acrylic polymers, and vinyl ether compounds having different functional groups are suitable for photocurable resins for photolithographic printing. Various types of compositions are preferred, and the most suitable monomers are preferred. The material-design-related pointers, such as the combination of the species, the monomer, or the most suitable viscosity of the photoresist, the preferred solution properties of the photoresist, and the improvement of the coating properties of the photoresist, are not disclosed at all. For this reason, it is not known that a preferred composition which can be widely used for photonic lithography is known, and there has been no known light nano-printing photoresist composition at present. B. Vratzov et al.: J. Vac. Sci. Technol. B21 (6), 2760 (2003), EKKim et al.: J. Vac. Sci. Technol, B22 (1), Although the composition of 131 (2004) is low in viscosity, it can be photohardened to form a pattern, and in the case of continuous heat treatment, the transmittance of the cured film is low (coloring) and the hardness is insufficient. It is not practical for permanent film. The composition is not generally known.

Proc.SPIE Int.Soc.Opt.Eng., Vol.61 51 , No.Pt2, 61512F (2006), Science and Industry, Vol.80, No.7, 322 (2006) Proposed by the use of optical function cross-linking An inorganic/organic hybrid material composed of a mixture of cerium oxide sol, (A-16-200846824 meth) acrylate monomer, and photopolymerization initiator treated with a material, and reported for application to photonic lithography . Proc.SPIE Int.Soc.Opt.Eng., Vol.6 1 51 , No.Pt2, 61512F (2006), Science and Industry, Vo I.80, No.7,322 (2006) Reported with a print 'brush The pattern of the material of 200 nm line length is formed, or the pattern of the mold can be patterned to a line width of 600 nm. However, there is a problem that the peeling property with the mold or the hardness of the cured film is insufficient, and it is not always possible. Also, in Proc. SPIE Int. Soc. Opt. Eng., Vol. 6151, No. Pt2, Φ 615 12F (2006), Science and Industry, Vo I · 80, Ν ο . 7, 3 2 2 (2 Although the composition of 0 0 6 ) is also low in viscosity, it can be photohardened to form a pattern, and in the case of continuous heat treatment, the transmittance of the cured film is low (coloring), and the hardness is also insufficient. In particular, it is not known to be a durable composition which is practical as a permanent film. Japanese Patent Publication No. 2000-1 43924 discloses a hard coating composition containing a surface-treated colloidal cerium oxide, a specific (meth)acrylic monomer, a leveling agent, and a photopolymerization initiator, and reports For applications in which a film hardness φ and a low hardening shrinkage are combined, the composition of the film and the mold release property are insufficient, and it is difficult for photonic lithography. . Further, the transmittance in the case of heat treatment after photohardening is low (coloring), and it is not suitable for use as a permanent film. Therefore, the fact is that a photoresist composition which is practically suitable as a permanent film and which can be applied by a photon printing method has not been proposed. The main technical subjects for permanent film are pattern accuracy, adhesion, transparency after heat treatment at 200 ° C, high mechanical properties (strength for external pressure), scratch resistance, flattening properties, and solvent resistance. Heating section -17- 200846824 Many problems such as low gas permeability reduction. In the case where the curable composition for light nano-printing for photonic printing is used as a permanent film, as in the case of using a photoresist such as a conventional acrylic resin, - (1) uniformity of the coating film _ ( 2) Transparency after heat treatment (3) The scratch resistance is important. At the same time, in the case of the hardening composition for photolithographic printing lithography, in addition to the above points (1) to (3), it is necessary to consider the following points (4) and (5), and the composition is designed. Can improve the difficulty of technology. (4) It is necessary to ensure the fluidity of the photoresist to the concave portion of the mold, and the low viscosity is used in the absence of solvent or a small amount of solvent. (5) After photohardening, it is easily peeled off from the mold and the mold is applied. In the curable composition for nano-printing lithography for nano-printing which does not adhere to the mold, various materials have been disclosed, and the composition of the ink-jet composition or the protective film for magnetic optical disc Φ has been known. The composition or the use of the curable composition for photonic printing lithography as an etch resist, although the curable composition for photonic lithography used in the permanent film has a common portion with the material, However, there are very different differences in heat treatment at high temperatures and mechanical strength. 'The photocurable resin used for inkjet, protective film for magnetic optical discs, and etch resists is directly used as a permanent film. In the case of a photoresist, it is not practically useful in terms of transparency, solvent resistance, and the like. SUMMARY OF THE INVENTION Problems to be Solved by the Invention -1 8 -

Inventor's Specialization 200846824 The present invention provides optical photolithography excellent in photocurability, which is excellent in photocurability, adhesion, peelability, coatability, and uranium engraving. Further, the object of the invention is to provide a composition which has excellent residual film properties, light transmittance, and g resistance and solvent resistance as a protective film. Means for Solving the Problem Prior to the above-mentioned problems, the above problems can be solved by the following means. (1) A polymerizable unsaturated monomer which is cured by photo-nano-printing lithography, which is 35 to 99% by mass, a starting agent, a fluorene-based agent of 1· 〇0 1 to 5 mass%, and fluorine·矽It is at least 1; inorganic oxide fine particles of a surfactant. (2) A composition for hardening φ-loading of a photon printing lithography, wherein at least one of a portion having a group having an ethylenically unsaturated bond in a molecule, and at least one of a sulfur atom is contained in the composition. One of the above-mentioned polymerizable unsaturated monomers and the above polymerizable unsaturated monomer. (3) The composition according to (2), wherein at least one of the compounds of (b) and (c) is a single body. (a) having an ethylenic unsaturated 3 in one molecule, the purpose of which is to provide a novel curable composition. Special residual film properties, pattern shapes, and excellent composition. The permanent film of the spacer or the like; the mechanical properties such as the damage, and the results of the heart review found that the composition contains 0.1 to 15% by mass of the photopolymer active agent, the lanthanum interface dust, and 0.1~ 50% by mass of the three-component composition, wherein the content of (1) is 15% by mass or more, and the content of the polymerizable unsaturated monomer having an oxygen atom or a nitrogen atom is 48 to 99% by mass, which is selected from the following (a) a site of a functional polymerizable unsaturated monounium bond, and a polymerizable unsaturated monomer (b) containing an aliphatic cyclic moiety of a hetero-19-200846824 atom, having a site containing an ethylenic unsaturated bond in one molecule, The polymerizable unsaturated monomer (c) having a = bond and an NR bond (R is a hydrogen atom or a methyl group) has a moiety containing an ethylenically unsaturated bond in one molecule, and an alicyclic moiety having a carbon number of 6 to 12 The polymerizable unsaturated monomer (4), wherein the hetero atom of the monofunctional polymerizable unsaturated monomer of the above (a) is any one of an oxygen atom, a nitrogen atom and a sulfur atom. More than one species. The composition of any one of (2) to (4), wherein the monofunctional polymerizable unsaturated single system is selected from any one of the following formulae (I) to (vm). . General formula (1)

(In the formula (R), R11 represents a hydrogen atom or a methyl group, and r12, r13, r14, and R15 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, or an ethoxy group. N1 represents 1 or 2, and ml is represented by any of 〇, 1, 2. Z11 represents a methylene group, an oxygen atom, or a -NH- group, and two Z11 systems may be different from each other. W11 represents - C( = 〇)- or -S02-. R12 and R13 and R 1 4 and R 1 5 may be bonded to each other to form a ring) -20- 200846824 Formula (丨I)

(In the formula (II), R21 represents a hydrogen atom or a methyl group, and r22, r23, r24 and R25 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, or a An oxygen group, R22 and R23, and 4 and R25 groups may be bonded to each other to form a ring. The Π2 system is represented by any one of 1, 2, and 3, and the m2 system is not 0, 1, or 2. Γ21 represents a methylene group or an oxygen atom) Formula (丨丨1)

(In the formula (m), R^, Rw, R34 and r35 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group. η 3 is represented by In any of 1, 2, and 3, m 3 is represented by any of 〇, 】, and 2. X31 represents -C(=0)...methylene, ethylidene, and two X31 systems may be mutually Different. 丫3 2 series means methylene or oxygen atom) -21 - 200846824 Formula (IV)

(In the formula (IV), R41 represents a hydrogen atom or a methyl group. R4 2 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halomethoxy group or an ethoxy group, respectively. W41 represents a single bond. No bond, or _ n4 means any of 2, 3, and 4. (42 shows _〇(=〇)-= or methylene, and each X42 system may be the same or different. M carbon number It is a hydrocarbon linking group of 1 to 4, an oxygen atom or a nitrogen atom, each of the same or different) and an R43 cyclin atom, C(=0)-. > ~ 0 = 0 · ^ 4 1 is not a M41 system

General formula (V)

(In the formula (V), R51 represents a hydrogen atom or a methyl group. z 52 atom, -CH = N- or methylene. W52 means methylene or oxygen means a single bond or -c (c = 0) Y-Y represents a single bond or _c (c and R55 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a sulfonic acid atom, a methoxy group, or an ethoxy group, and r54 and R55 may be bonded to each other. X51 can be single-bonded or unbonded. (7) ^ 〇, 彳, 2 -22 - is an oxygen atom. Y52 = 〇) - R54 butyl, halogen 〖 knot to form one of either. 200846824 5 2, Z52, R54 At least one of the formula (VI) R contains an oxygen atom or a nitrogen atom) >61

R 62 ./N,

Xi V3 (in the formula (vi), R61 is a hydrogen atom or a methyl group. R62 and rS3 are each a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, and a (CH3)2N-(CH2)m6- group. (m6 is 1, 2 or 3), CH3CO-(CR64R65)p6- (R64 and R65 represent a hydrogen atom or a methyl group, respectively, p6 is a 1, 2 or 3), (CH3)2-N -(CH2)p6-(p6 is any one of 1, 2 or 3). However, in the formula (VI), the moiety of -NR62 (R63) may be -N = C = fluorenyl. R62 and R63 are not hydrogen atoms at the same time, and X6 system, -CO-, -c〇ch2·, -COCH2CH2-, -C〇CH2CH2CH2-, -C〇OCH2CH2-) (VN) R71 〇

3 R7 (in the formula (VII), R71 and R72 are each a hydrogen atom or a methyl group, and R represents a gas atom, a methyl group or an ethyl group).

(In the formula (VIII), 'R81 means a hydrogen atom, a methyl group or a hydroxy group-23-200846824 R8 2. R83, R84 and R85 are each represented by a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group or a hydroxymethyl group. Hydroxyethyl, propyl and butyl, at least two of R8 2, R8 3, R84 and R85 may be bonded to each other to form a ring. W81 is methylene, -NH·, -N(CH3)-, - N(C2H5)-.W82 means a single bond or -C(=0)-. • When W82 is a single bond, R82, R83, R84 and R84 are not hydrogen atoms. n7 is an integer of 〇~8. ). (6) The composition according to any one of (1) to (5), wherein the polymerizable unsaturated monomer further contains 0.1 mass. /. The above-mentioned site having at least one ethylene Φ-unsaturated bond and a second polymerizable unsaturated monomer containing a ruthenium atom and/or a phosphorus atom. (7) The composition according to any one of (1) to (6) wherein the inorganic oxide microparticles are colloidal cerium oxide. (8) The composition according to (7), wherein the colloidal cerium oxide is a surface-treated colloidal cerium oxide. (9) The composition according to (8), wherein the colloidal cerium oxide is a colloidal cerium oxide sand surface-treated with a compound having a reactive (meth) acrylate group. (10) A composition according to any one of (1) to (9) which contains an antioxidant. (11) A composition according to any one of (1) to (10), wherein the viscosity at 25 ° C is 25 mPa 's or less. (12) A method of forming a pattern, comprising: a step of coating a composition according to any one of (1) to (11); and pressing the photoresist layer on the substrate with a light-transmissive mold a step of deforming the coated composition; -24- 200846824 a step of irradiating light from the back surface of the mold or the back surface of the substrate and hardening the coating film to form a photoresist pattern of a desired pattern; The step of detaching the mold from the coating film. EFFECTS OF THE INVENTION According to the present invention, it is possible to provide, as an etch resist, light curability, adhesion, peelability, residual film property, pattern shape, coatability, and etching suitability. A comprehensive composition. In addition, when it is used as a permanent film, it is possible to obtain a composition excellent in comprehensiveness in terms of mechanical properties such as residual film properties, light transmittance, and scratch resistance, and solvent resistance. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the contents of the present invention will be described in detail. Further, in the present specification, "~" is used by including the numerical values described above and below as the lower limit and the upper limit.

The invention is described in detail below. In the present specification, methyl (acrylate) means acrylate and methacrylate, methyl (acrylic acid) means acrylic acid and methacrylic acid, and methyl (acrylic acid) type means acrylonitrile and methyl group. C storage base. Further, in the present specification, the monomer (single amount) is the same as the monomer. The single system in the present invention is classified into an oligomer or a polymer, and is a compound having a mass average molecular weight of 1,0 0 or less. In the present specification, a functional group is a group which is involved in polymerization. Further, the so-called nano printing system in the present invention is transferred from a pattern having a large number of turns #m to tens of nm. That is, of course, it is not limited to printing on a nanometer level. The curable composition for photonic printing lithography of the present invention (hereinafter, referred to as "the composition of the present invention" by {堇-25-200846824), for example, has high light transmittance and fine concavo-convex pattern before curing. Excellent forming ability, coating suitability, and other processing suitability, and after hardening, sensitivity (speed hardenability), resolution, line edge roughness, film strength, and mold mold Peelability, residual film characteristics, uranium engraving resistance, low hardening shrinkage, substrate adhesion, or other points, comprehensive film properties can be obtained. For this reason, the composition of the present invention can be widely used for photonic printing lithography.

That is, the composition of the present invention is used in the case of photonic lithography, and it is considered to have the following characteristics. Generally, it is considered that: (1) Since the fluidity of the solution at room temperature is excellent, the composition easily flows into the pores of the concave portion of the mold mold, and the atmosphere is hard to enter, so that it is less likely to cause bubble defects, regardless of the convex portion of the mold. Among the recesses, it is difficult to leave a residue after light curing. (2) Since the cured film after curing is excellent in mechanical properties, the adhesion between the coating film and the substrate is excellent, and the peeling property between the coating film and the mold is excellent, so that no pattern collapses or is peeled off when the mold is peeled off. The surface of the coating film is not drawn and does not cause surface cracking, and a good pattern can be formed. (3) Since the volume shrinkage after photohardening is small and the transfer characteristics of the mold are excellent, the correct shape of the fine pattern is possible. (4) Because it is excellent in coating uniformity, it is suitable for coating of large substrates, microfabrication, etc. (5) Because the film has a high photohardening speed and high productivity. (6) Since it is excellent in uranium engraving precision and uranium engraving resistance, it can be suitably used as a uranium engraved photoresist for processing a substrate such as a semiconductor device or a transistor, etc. -26-200846824, (7) because of the etched light It is excellent in resist releasability and does not cause residue. Therefore, it can be suitably used as a photoresist. (8) Mechanical properties such as light transmittance, residual film property, and scratch resistance, and high solvent resistance. Therefore, it is suitable for use as a variety of permanent films, and the like. For example, the composition of the present invention can be suitably applied to a fine φ processing use such as a thin film transistor, a protective film for a liquid crystal color filter, a spacer, or the like in a semiconductor integrated circuit or a liquid crystal display which has hitherto been difficult to carry out. Used in other applications, such as partition walls for plasma display panels, flat screens, micro-electrical mechanical systems (ME MS), inductive components, optical discs, high-density storage discs (mem 〇rydisc), etc. An optical component such as a lattice or an embossed hologram, a nanodevice, an optical device, an optical film or a polarizing element, an organic transistor, a color filter, an overcoat layer, a pillar, a liquid crystal alignment rib, Production of microlens arrays, immunoassay wafers, DNA separation wafers, microreactors, nanobiodevices, optical waveguides, optical filters, optical liquid crystals, and the like. The viscosity of the composition of the present invention will be described. The viscosity in the present invention is not specifically stated as a viscosity at 25 ° C. The viscosity of the composition of the present invention at 25 ° C is preferably 2 5 m P a · s or less, preferably 20 μm P a • s or less, more preferably 3 to 18 mPa·s. By forming such a viscosity, the ability to form fine concavo-convex patterns before curing, coating suitability, and other processing suitability can be imparted, and after hardening, resolution, linear edge roughness, residual film characteristics, and substrate adhesion can be imparted after curing. Sexual or excellent film properties at other points. When the viscosity of the composition of the present invention is 3 m P a · s or more, there is a tendency that the coating property of the substrate -27-200846824 is not suitable for coating, or the mechanical strength of the film is less likely to occur. Specifically, by setting the viscosity to 3 mPa*s or more, it is preferable to suppress the occurrence of unevenness on the surface of the coating composition and to cause the composition to flow out from the substrate during coating. On the other hand, when the viscosity of the composition of the present invention is 25 mPa · ε or less, even if the mold having the fine concavo-convex pattern adheres to the composition, the composition flows into the concave cavity of the mold. Since the atmosphere becomes difficult to carry out, it is difficult to cause bubble defects, and it is preferable that it is difficult to generate a residue after photocuring in the convex portion of the mold.

The composition of the present invention contains 3 5 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 15% by mass of a photopolymerization initiator, 0.001 to 5% by mass of a fluorine-based surfactant, and a lanthanide interfacial activity. At least one of a solvent and a fluorine/ruthenium-based surfactant, and 0.1 to 50% by mass of inorganic oxide fine particles. Polymerizable Unsaturated Monomer The composition of the present invention preferably contains a functional group having an ethylenically unsaturated bond in the molecule and a monofunctional polymerizable unsaturated moiety having at least one of an oxygen atom, a nitrogen atom and a sulfur atom. The monomer is a polymerizable unsaturated mono φ body and contains the monofunctional polymerizable unsaturated monomer, and the content of the polymerizable unsaturated monomer is 48 to 99% by mass. More preferably, the monofunctional polymerizable unsaturated monomer is a composition of 15% by mass or more, more preferably 25 to 60% by mass of the composition. The monofunctional polymerizable unsaturated monomer is preferably a monofunctional polymerizable unsaturated monomer selected from the following (a), (b) and (c). (a) a polymerizable unsaturated monomer having a moiety containing an ethylenically unsaturated bond in one molecule and an aliphatic cyclic moiety containing a hetero atom (preferably an oxygen atom, a nitrogen atom and a sulfur atom) -28- 200846824 (b) a polymerizable unsaturated monomer having one molecule containing an ethylenically unsaturated bond and a -c(=0)-bond and an NR bond (R is a hydrogen atom or a methyl group) (c) having one molecule The polymerizable unsaturated monomer having a portion containing an ethylenically unsaturated bond and an alicyclic portion having a carbon number of 6 to 12 is preferably a monofunctional polymerizable unsaturated single system used in the present invention. (I) to a polymerizable unsaturated monomer represented by any one of the formula (VIII). General formula (1)

(In the formula (R), R11 represents a hydrogen atom or a methyl group, and R12, R13, R14 and R15 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group or an ethoxy group. The n1 series is not 1 or 2, and the ml is represented by any one of 〇, 1, 2. Z11 represents a methylene group, an oxygen atom, or a -NH- group, and the two Z11 systems may be different from each other. - C( = 0) - or - S〇2-. R12 and R13 and R1 4 and R15 may be bonded to each other to form a ring. Here, R 1 1 is preferably a hydrogen atom. R 1 2, R 1 3, R 1 4 and R 1 5 are preferably a hydrogen atom or a methyl group, and a hydrogen atom is preferred. The ml system or 彳 is preferred. It is preferred that at least one of Z11 is an oxygen atom. W11 is -C( = 〇)- is preferred. When π 1 is 2 or more, R 1 4 and R 1 5 may be the same or different. Specific examples of the compound represented by the formula (I) include, for example, the following formulae (1-1) to (Bu 19). -29- 200846824

And (1—3)

(1-10) (1-11) tt-6)

(1-14)

-30 - 200846824 Formula (π)

(In the formula (II), R21 represents a hydrogen atom or a methyl group, and R22, R23, R24 and R25 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, or a methoxy group. And ethoxy. R22 and R23 and R24 and R25 may be bonded to each other to form a ring. η 2 is represented by any one of 1, 2, and 3, and m 2 is represented by any of 〇, 1, and 2 Y21 represents a methylene group or an oxygen atom. The R21 hydrogen atom is preferred. R22, R23, R24 and R25 are each preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and preferably a hydrogen atom, a methyl group or an ethyl group. Preferably, η 2 is 1 or 2. The m 2 system 0 or 1 is preferred. Specific examples of the compound represented by the formula (Π) include, for example, the following formulas (11-1) to (1)-9). 200846824

(II-5) (II-3) Ο

(II a 4)

General formula (Ml)

?35 /X

Bisyl 3 5 , methyl, ethyl. The nM system is expressed as any one of 1, 2, and 3, and the heart system is represented by any one of 〇, 1, and 2. Let _C( = 〇)-, methylene, and ethyl, and the two X31 systems be different from each other.丫32 represents a methylene group or an oxygen atom. R 3 2, R 3 3, R 3 4 and R 3 5 are each preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, and a hydrogen atom is preferred. The η 3 series 1 or 2 is preferred. Specific examples of the compound represented by the formula (Π I) include, for example, the following formula (m-ι)~(m-11) -32- 200846824

(ΠΙ—7) (III—8) (III-9)

General formula (iv)

R41

(In the formula (IV), R41 represents a hydrogen atom or a methyl group. R42 and R43 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group. It means a single bond, no bond, or - C( = 0) -. n4 means any of 2'3, 4. X42 means -C( = 〇)-, -C = C-, -33 - 200846824 -C = N-, or methylene, each X42 system may be the same or different. |y|41 is a hydrocarbon linking group having 1 to 4 carbon atoms, an oxygen atom or a nitrogen atom, and each M41 system may be the same or Different) R41 is a hydrogen atom. R42 and R43 are each preferably a hydrogen atom, a methyl group or an ethyl group, and a hydrogen atom is preferred. M41 is preferably any of a methylene group, an ethylidene group, a propyl group and a butyl group. Specific examples of the compound represented by the formula (IV) include the following formulas (I V-1 ) to (IV-1 3).

-34- 200846824

C2h5

(IV-5)

(! V- 1 Ο) ο

General formula (V)

-35 - 200846824

(In the formula (V), R represents no hydrogen atom or methyl group. Z52 represents an oxygen atom, _c Η = N- or a methylene group. W52 represents a methylene group or an oxygen atom. 丫52 represents a single bond. Or a c(c = o)~ R54 and R55 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, an ethoxy group, and a group of R55 and R55, respectively. Bonding to form a ring. X51 can be a single bond or no bond. m 5 is either 〇, 1, or 2.

At least one of W52, Z52, and R'R contains an oxygen atom or a nitrogen atom. Here, where X51 is a non-bonded bond, it is considered to be an exemplary compound (V-7) of the formula (v) 0 described later. , (V-8) mode bonding form. R51 is preferably a hydrogen atom. R54 and R55 are each preferably a hydrogen atom, a methyl group or an ethyl group, and a hydrogen atom or a methyl group is preferred. It is preferred that m 5 is 1 or 2. Specific examples of the compound represented by the formula (V) include the following formulas (V-1) to (V-8).

(V-4) Ο

200846824 Formula (VI) R61 R62 (In the formula (VI), R61 is a hydrogen atom or a methyl group, and R62 and R63 are each a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a propyl group, a (CH3)2N group. -(CH2:)m6_ (m6 is 1, 2 or 3), CH3CO-(CR64R65)p6- (R64 and r65)

It does not mean a hydrogen atom or a methyl group, P6 is one of 1, 2 or 3), (CH3)2-N-(CH2)p6- (p6 is one of 1, 2 or 3). However, in the formula (VI), the moiety of -NR62 (R63) may be -N = C = 0 group, and R62 and R63 are gas atoms when not in question. Further, specific examples of the compound represented by the formula (VI) of the X6-based -CO-, -COCH2-, -COCH2CH2-, -COCH2CH2CH2-, and -COOCH2CH2*· are, for example, the following formula ( v卜1)~(v卜1 〇) 〇

Ch2ch2oh

(v Bu 3) ch2ch3

NCO

ο (VI-6) N-ch2ch3

-37 200846824 Formula (vii) R71 〇l72 R72 (In the formula (VM), R71 and R72 are each a hydrogen atom or a methyl group. 'R73 means a hydrogen atom, a methyl group or an ethyl group.) Specific examples of the compound represented by the following formula (VII-1) Ή 〇Λ CH3 ch3 (VII-2)

(VII-3) General formula (VIM)

R 8 2, R 8 3, R 8 4, and R 8 5 are represented by a hydrogen atom, a hydroxyl group, a methyl ethyl group, a hydroxymethyl group, a hydroxyethyl group, a propyl group, and a butyl group, and R82, R83, F, and R85, respectively. At least two of them may be bonded to each other to form a ring. W81 is a methylene group -NH-, -N(CH3)...-N(C2H5)-. When W82 represents a single bond or _〇(= 〇) W82 is a single bond, R82, R83, r84 and R84 are not hydrogen atoms. It is an integer representing 〇~8). · R81 is preferably a hydrogen atom. Specific examples of the compound represented by the formula (VIII) can be exemplified by the following formula: 38-200846824 Formula (vm-1) to (νιπ-14).

(砸一 2)

(Μ-3)

OH (Μ — 4) 〇1 — 5) (Μ — 6)

(砸一11)

01-14) Second polymerizable unsaturated monomer The present invention may contain a polymerizable unsaturated monomer other than the above polymerizable unsaturated monomer. For example, a site having an ethylenically unsaturated bond and a polymerizable unsaturated monomer containing a ruthenium atom and/or a phosphorus atom may be mentioned. The second polymerizable unsaturated monomer as described above may be a monofunctional polymerizable unsaturated monomer or a poly-39-200846824 functional polymerizable unsaturated monomer. It is preferable that the polymerizable unsaturated single system is contained in the polymerizable unsaturated monomer in an amount of 0.1% by mass or more. The second polymerizable unsaturated single system may employ, for example, the following (I X 1 ) to (I X - 2 3 ) 〇

(IX-1) och3 l/CH3 Si\ och3 och3 I/〇ch3 Si, och3o

(IX — 3) och3 |/〇ch3 si\ och3 (IX-2)

〇 (IX-4)

(IX — 5) 〇 /CH3 Si\ I CHa ch3

CH3 〇V"^CH3 I ch3 ch3 (IX-6) CH3 ch3 (IX-7)

(IX-8)

(IX-10)

〇 (IX-11)

(IX-12) -40 - 200846824

(IX-15) (IX-16)

(IX-17) (IX-18)

0 (IX-19)

0 (IX-22)

(IX-23) The composition of the present invention is intended to improve the hardness of the film, the flexibility, and the like, and further to use a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (1-functional polymerization) Sexually unsaturated monomer). Specifically, for example, 2-propenyloxyethyl phthalate, 2-propenyloxy 2-hydroxyethyl phthalate, 2-propenyloxyethyl hexahydrophthalate, 2 · Propylene methoxypropyl phthalate, 2-ethyl-2-butyl propylene glycol acrylate, 2-ethylhexyl-41 - 200846824 (meth) acrylate, 2-ethylhexyl carbitol (methyl) Acrylate, 2-propenyl (meth) propionate, 2-(methyl) chlorophyllin, 2-hydroxypropyl (meth) acrylate, 2-methoxy Ethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic dimer, aliphatic epoxide (methyl) Propionate, benzyl (meth) acrylate, butane diol mono (meth) acrylate, butoxy ethyl (meth) acrylate, butyl (meth) acrylate, cetyl ( Methyl) acrylate, epoxy oxime (hereinafter referred to as "EO") formazan (meth) acrylate, propylene dipropylene glycol (meth) acrylate, ethoxylated phenyl (methyl) propyl Acid ester, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (methyl) Acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, Methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (methyl ) acrylate, octyl (meth) propylene φ acid ester, p-nonyl phenoxy ethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate , phenoxyethyl (meth) acrylate, phenoxy diglycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (methyl Acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (methyl) Ethyl ester, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (Meth) acrylate, EO modified tribromophenyl (meth) acrylate, tri-dodecyl (meth) acrylate, P-isopropenyl phenol, styrene, -42 - 200846824 α - Methylbenzene storage, acrylic acid, ethylene glycol, isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate η propyl (meth) acrylate, isocyanate isopropyl (meth)propionate, isocyanate η-butyl (meth) acrylate, isocyanate isobutyl (meth) acrylate, isocyanate, second butyl (meth) acrylate, isocyanate Isocyanate alkyl (meth) acrylate such as tert-butyl (meth) acrylate; (meth) propylene decyl methyl isocyanate, (meth) propylene decyl ethyl isocyanate, (meth) propylene oxime N-propyl isocyanate, (methyl)丙 醯 醯 基 isopropyl isocyanate, (meth) acrylonitrile η-butyl isocyanate, (meth) propylene decyl isobutyl isocyanate, (meth) propylene decyl second butyl isocyanate, (A (meth)propyl-nonylalkyl isocyanate such as acrylonitrile-tert-butyl isocyanate. The other polymerizable unsaturated monomer used in the present invention is preferably a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups. In the present invention, an example of a bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bonds and having a 0 group can be preferably used, and examples thereof include diethylene glycol monoethyl ether (meth) acrylate and dihydroxyl. Methyl dicyclopentane di(meth)acrylate, di(meth)acrylated isocyanurate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol Di(meth)acrylate, hydrazine modified 1,6-hexanediol di(meth)acrylate, EC ruthenium modified 1,6-hexanediol di(meth)acrylate, allyloxypoly Ethylene glycol acrylate, 1,9-nonanediol di(meth) acrylate, bismuth bisphenol quinone di(meth) acrylate, ρ 〇 modified bisphenol A di(meth) acrylate, Modified bisphenol A di(meth) acrylate, EO modified bisphenol F di(meth) acrylate, ECH modified hexahydro phosphine benzene di-43- 200846824 formic acid monoacrylate, hydroxytrimethyl acetic acid Pentyl glycol di(meth) propylene 酉 酉 0, neopentyl alcohol mono(methyl) propyl vinegar, 〇 质 modified neopentyl glycol dipropylene, sulphuric acid ester, epoxy propylene (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, caprolactone modified hydroxytrimethyl acetate neopentyl glycol, stearic acid modified pentaerythritol di(meth) acrylate, ECH modified benzene Di(meth) acrylate formic acid, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propanol-butanediol) di(meth)acrylate, polyester ( b) acrylate, poly(ethylene) di(meth) acrylate, polypropylene glycol di(meth) acrylate, 0 ECH modified propylene glycol di(meth) acrylate, bismuth (meth) acrylate, triethyl Diol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, methyl dicyclohexyl di(methyl)propionate, neopentyl glycol modified trimethyl Propane di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerin di(meth)acrylate, dipropylene glycol di(meth)acrylic acid Ester, divinylethylene urea, divinyl propylene urea. Among these, in particular, 1,9-nonanediol di(meth)acrylate, %tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate' hydroxytrimethyl Neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate or the like is suitably used in the present invention. Examples of the polyfunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri(meth)acrylate and EO-modified glycerol tri(meth)acrylate. P〇modified triglyceride (meth) acrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane three (Meth) acrylate, Ο Ο modified trimethylolpropane tri(methyl) -44- 200846824 acrylate, p 〇 modified trimethylolpropane tri (meth) acrylate, ginseng Ethoxyethyl)isocyanate, dipentaerythritol hexa(methyl)propionate, caprolactone modified dipentaerythritol hexa(meth) acrylate, dipentaerythritol hydroxypenta(meth) acrylate, Institute-based modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly(meth) acrylate, alkyl modified dipentaerythritol tri(meth) acrylate, di-trimethylolpropane tetra (methyl) Acrylate, pentaerythritol ethoxy IV Methyl) acrylate, pentaerythritol tetra(meth) acrylate, and the like.

Among these, in particular, E 0 is modified by tris(meth)acrylate, PO modified triglyceride (meth)acrylate, trimethylolpropane tri(meth)acrylate, and hydrazine. Trimethylolpropane tri(meth)acrylate, p 〇-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, pentaerythritol ethoxy tetra(meth)acrylic acid An ester, pentaerythritol tetra(meth)acrylate or the like is suitably used in the present invention. When two or more photopolymerizable functional groups are used in one molecule, since a large amount of photopolymerizable functional groups are introduced into the composition as described above, the crosslink density of the constituent φ material is extremely large, and various types after hardening are obtained. The effect of physical improvement is improved. Among various physical properties after hardening, in particular, heat resistance and durability (wear resistance, chemical resistance, and water resistance) increase upward due to an increase in crosslinking density, even in high heat, friction, or exposure to a solvent, fine The deformation, disappearance, and damage of the concave-convex pattern also become difficult to cause. The composition of the present invention is intended to further increase the crosslinking density. To achieve the object of the present invention, a polyfunctional oligomer or polymer having a molecular weight larger than that of the above polyfunctional polymerizable unsaturated monomer may be blended. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyamine-45-200846824 formate acrylate, polyether acrylate, polyepoxy acrylate, and the like. An oligomer, a polymer, or the like having a large volume structure such as a substance, a phosphazene skeleton, an adamantane skeleton, a bulky plug-in type, a (Ca "do) skeleton, a norbornene skeleton, etc. The compound is a polymerizable unsaturated monomer used in the present invention. Examples of the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, and polyoxyalkylene glycols. Polyglycidyl ethers, polycondensation φ glycerides of aromatic polyols, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxides and epoxidized polybutadiene These compounds may be used singly or in combination of two or more kinds thereof. Examples of the epoxy compound which can be preferably used are exemplified by bisphenol A diglycidyl ether and 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 0 F Diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylol Propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; by oxidation of two or more kinds of aliphatic polyols such as ethylene glycol, propylene glycol or glycerin Polyglycidyl ethers of polyether polyols obtained from olefins; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butyl phenol or A monoglycidyl ether of a polyether alcohol obtained by adding an alkylene oxide; a glycidyl ester of a higher fatty acid, etc. -46- 200846824 A commercially available product which is suitable for use as a glycidyl group-containing compound, for example, UVR-6216 (Union Carbide), Gly Cidol, AOEX24, Cycroma A200, (above 'Dai Sil Chemical Industry Co., Ltd.), Epikote 828, Epikote 812, Epikote 1031, Epikote 872, Epikote CT508 (above, oleochemical shell), KRM-2400 , KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, manufactured by Asahi Denki Kogyo Co., Ltd.), etc. These may be used alone or in combination of two or more.

Further, the compound having such an oxirane ring is not limited to the production method thereof, and can be referred to, for example, Jiushan KK Publishing, Fourth Edition Experimental Chemistry Lecture 20 Organic Synthesis II, 213~, Heisei 4, Ed.by Alfred Hasfner , The chemistry of heterocyclic compounds-Small Ring

Heterocycles pa rt 3 O xiranes , John & Wiley and Sons, An Interscience Publication, New York, 1 985, Yoshimura, Next, vol. 2, No. 12, 32, 1 985, Yoshimura, then, 30, 5, 42, 1986 Japanese, Yoshimura, et al., vol. 30, No. 7, No. 4, No., No., No., No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1,100, s, No. 1, pp. No. 2, 906, 245, and No. 2,962,262. The polymerizable unsaturated single system used in the present invention may also be a vinyl ether compound. The vinyl ether compound may be appropriately selected, and examples thereof include 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, and diethylene glycol monovinyl group. Ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,3-propylene glycol divinyl ether, 1,3-butylene glycol divinyl ether 1,4·butanediol divinyl ether, butyl-47 - 200846824 monool divinyl ether, neopentyl glycol divinyl ether, trivinyl ether, trimethylolethane trivinyl ether , hexanediol tetraethylene glycol diethyl succinyl ether, pentaerythritol divinyl ether vinyl ether, pentaerythritol tetravinyl ether, sorbitol sorbitol penta vinyl ether, ethylene glycol diethylene vinyl alcohol Ethyl vinyl ether, ethylene glycol dipropyl ethene _ diethyl vinyl ether, trimethylolpropane triethylene glycol methyl methacrylate; (: 兀 伸 ethyl ethyl ethene ether, pentaerythritol Ether, pentaerythritol tri-ethyl vinyl ether, pentaerythritol ether, 1,1,1-gin[4-(2-hydroxyethoxy)phenyl]dihydroxyethyl ether, etc. These vinyl ether compounds are those described in Stephen. C. Lapin, Polymers Paint Col 1 79 (4237), 32 1 (1 988), ie, the reaction of a phenol with acetylene, or a polyol or a multivalent The phenol is synthesized by the reaction with a halogen ether, and these may be used singly or in combination. The styrene derivative may also be used as the saturated monomer of the present invention. For example, the styrene derivative may be P-A. Methoxy-/3-methylstyrene, P-hydroxystyrene, etc. Further, it may be a conjugated derivative of the monofunctional polymer of the present invention, and examples thereof include styrene, P-methylphenylene, and olefin. , /3-methylstyrene, p-methylmethylphenylene storage, P_methoxy-β-methylstyrene, P-based phenylethylidene derivative, for example, 1-vinylnaphthalene , α-methyl _ 1 -ethyl methacrylate 2: divinyl ether, pentaerythritol tritetravinyl ether, ether, triethylenediether, triethylenedivinyl ether, diethyl ether Vinyl alcohol tetraethyl ethyl ethane, bisphenol A by, for example, our Journal. Polymeric non-phenylene group of two or more kinds of polyhydric alcohol or polyalkylated alkylene , P-: styrene p-methoxyphenylethyl, α-methylphenylethyl; etc., vinylnaphthyl naphthalene,/5-methyl-48-200846824-based-1-vinylnaphthalene, 4- Methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, etc. Further, in order to improve the peelability or coatability of the mold, it is also possible to use a trifluoroethyl group ( Methyl) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl (meth) acrylate, (perfluoro Fluorine atom of hexyl)ethyl (meth) acrylate, octafluoropentyl (meth) acrylate 'perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Compound.

The polymerizable unsaturated single system used in the present invention may be blended with a propenyl ether and a butenyl ether. Preferably, for example, 1-dodecyl-1 -propenyl ether, 1-dodecyl-1-butenyl ether, 1-butoxymethyl-2-northene, 1- 4-bis(1-butoxy)butane, 1,10-bis(1-butoxy)decane, 14-:(1-butoxymethyl)cyclohexane, diethylene glycol Bis(1-butenyl)ether, 1,2,3-tris(1-butenyloxy)propane, propenyl ether propyl carbonate, and the like. Next, a preferred blending form of the polymerizable unsaturated monomer in the composition of the present invention will be described. The composition of the present invention is preferably a component containing a polymerizable unsaturated monomer having at least one of oxygen, nitrogen, φ or a sulfur atom, and further preferably a polyfunctional polymerizable unsaturated monomer. The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent. The viscosity of the composition of the present invention can be effectively reduced, and it is usually added in an amount of 15% by mass or more based on the total amount of the polymerizable unsaturated monomer. It is preferably in the range of 20 to 80% by mass, more preferably 25 to 70% by mass, particularly preferably 30 to 60% by mass. By setting the ratio of the monofunctional polymerizable unsaturated monomer selected from the above (a), (b) and (c) to 80% by mass or less, the composition of the present invention is subjected to hard-49 - 200846824 The mechanical strength, the etching resistance, and the heat resistance of the cured film tend to be good, and it is preferable to suppress the swelling of the mold and the deterioration of the mold when used as a mold for light nano printing. Further, since the above-mentioned monofunctional polymerizable unsaturated monomer is more preferable as the reactivity, it is preferably added in an amount of 15 mass of the wholly polymerizable unsaturated monomer. The monomer having two unsaturated bond-containing groups (bifunctional polymerizable monomer) is preferably 90 φ, more preferably 80% by mass or less, particularly preferably 70% by mass, based on the total polymerizable unsaturated monomer. Add below. The proportion of the monounsaturated and the bifunctional polymerizable unsaturated monomer in the unsaturated monomer is preferably from 1 to 95% by mass, more preferably from 3% by mass, particularly preferably from 5 to 90% by mass. In the specific polymerizable unsaturated monomer having a polyfunctionally polymerizable unsaturated monomer having a 3-unsaturated bond-containing group, it is preferably added in an amount of 80% by mass or less, mass% or less, and particularly preferably 60% by mass or less. The ratio of the polymerizable φ body having three or more polymerizable unsaturated bond-containing groups is 80% by mass or less, and the viscosity of the composition is preferred. In the composition of the present invention, in particular, the polymerizable unsaturated monomer is 15 to 80% by mass based on the monofunctional polymerizable unsaturated monomer, and the ethylenically unsaturated monomer is 0 to 60% by mass. /. The trifunctional or higher polyunsaturated monomer is preferably a ratio of from 1 to 60% by mass, and the polymerizable unsaturated monomer is from 20 to 70% by mass. /. The bifunctional grouping monomer is 〇50 mass%, and the trifunctional or higher polyfunctional polymer is 2 to 50 mass. /. The ratio of the ratio is preferably. More preferably, it is possible, on the one hand, the diluent system: % or more of the unsaturated mass% in the range of total polymerization. 3 to 95 or more, more preferably 70 in total. The functional component is polymerized by the reduction of the unsaturated monomer. The polymerizable property is monofunctionally unsaturated. Mono-50-200846824 The composition of the present invention is especially blended with at least one ethylenically unsaturated bond. A site and a polymerizable unsaturated monomer containing a ruthenium atom and/or a phosphorus atom are suitable. The site having at least one ethylenically unsaturated bond, ^, and a polymerizable unsaturated monomer containing a ruthenium atom and/or a phosphorus atom are generally used for the purpose of improving the peeling property with the mold or the adhesion to the substrate. In the case of adding a 0.1% by mass to the wholly polymerizable unsaturated monomer. It is preferably added in the range of 0.2 to 10% by mass, more preferably 0.3 to 7% by mass, particularly preferably 5% to 5% by mass. The number of sites having an ethylenically unsaturated bond (the number of functional groups) φ is preferably from 1 to 3. Further, the moisture content at the time of preparation of the composition of the present invention is preferably 2.0% by mass or less, preferably 1.5% by mass, more preferably 1.% by mass or less. When the water content at the time of preparation is 2% by mass or less, the preservability of the composition of the present invention can be made more stable. Further, the content of the organic solvent in the composition of the present invention is preferably 3% by mass or less based on the total composition. That is, since the composition of the present invention preferably contains a specific monofunctional or bifunctional monomer as a reactive diluent, φ, the organic solvent used for dissolving the component in the composition of the present invention is not necessarily contained. necessary. Further, if the organic solvent is not contained, the baking step for the purpose of volatilizing the solvent is not required, and the process is simplified to be effective. Therefore, the content of the organic solvent in the composition of the present invention is preferably 3% by mass or less, more preferably 2% by mass or less, and is particularly preferably contained. Therefore, the composition of the present invention does not necessarily need to contain an organic solvent, and the reactive diluent can be arbitrarily added when the undissolved compound is dissolved as a composition of the present invention or when the viscosity is finely adjusted. The type of the organic solvent which can be suitably used in the composition of the present invention is a solvent used for the conventional photo-light-printing lithography-hardening-51-200846824 composition or a photoresist, as long as it can dissolve and uniformly disperse the present invention. The compound to be used may be used, and is not particularly limited as long as it does not react with these components. The organic solvent may, for example, be an alcohol such as methanol or ethanol; an ether such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether or ethylene glycol methyl ethyl ether; Glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate; diethylene glycol monomethyl Diethylene glycols such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol φ ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether Propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, etc.; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid φ, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate esters such as esters and the like. Further, N-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine-methylformamide, hydrazine-methylacetamide, hydrazine, hydrazine-dimethylacetamide may also be added. Amine, Ν_methylindole, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, caproic acid, octanoic acid, octanol, 1-nonanol, benzyl High in alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. Boiling point solvent. These can be used alone or in combination with -52- 200846824. Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone Methyl isobutyl ketone, 2-heptanone, etc. are particularly preferred. 'Photopolymerization initiator>> A photopolymerization initiator can be used in the composition of the present invention. The photopolymerization initiator used in the present invention contains, for example, 〇. 1 to 15% by mass, preferably 0. 2 to 12% by mass, more preferably 0.3 to 10% by mass, based on the total composition. When two or more kinds of photopolymerization initiators are used in φ, the total amount thereof is in the above range. When the ratio of the photopolymerization initiator is 〇1% by mass or more, the sensitivity (speed hardenability), the resolution, the linear edge roughness, and the coating film strength tend to be improved. On the other hand, when the ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the coloring property, the handleability, and the like tend to be improved. In the past, there have been various reviews on the composition of inkjet compositions containing dyes and/or pigments or liquid crystal display color filters, and the amount of suitable photopolymerization initiators and/or photoacid generators. However, the amount of a suitable photopolymerization initiator and/or photoacid generator added to the curable composition for nano-printing lithography for nano-printing or the like is not reported. That is, in a system containing a dye and/or a pigment, these functions as a radical scavenger without affecting photopolymerization and sensitivity. In view of this, the use of these is to optimize the amount of the photopolymerization initiator to be added. On the other hand, in the composition of the present invention, the dye and/or the pigment are optional components, and the optimum range of the photopolymerization initiator is a composition for inkjet or a composition for a color filter of a liquid crystal display. The domain is different. The photopolymerization initiator used in the present invention is a compound which is active for the wavelength of the light source used and which produces an appropriate active species. Further, the photopolymerization initiator may be used alone or in combination of two or more. As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. Examples thereof include Irgacure (registered trademark) 2959 (1-[4-(2-hydroxyethoxy)phenyl) 2-hydroxy-2-methyl-1-propene available from Ciba Corporation. 1-ketone, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-cyclohexyl phenyl ketone, diphenyl ketone), |叩3〇11 『6 (registered trademark) 651 (2,2-dimethoxy-1,2-@diphenylethan-1-one), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamine) Base-1 - (4 - morpholinophenyl) butanone-1), Irgacure (registered trademark) 907 (2-methyl-1 [4-methylthiophenyl]-2- morpholino-propane- 1-ketone, 1 『93〇11^(registered trademark) 819(bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, Irgacu re (registered trademark) 1800 (double (2, 6-dimethoxybenzimidyl)-2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, Irgacure (registered trademark) 1 800 (double ( 2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanol -1- Ketone), Irgacure (registered trademark) OXE01 (1,2-octanedione, 1-[4-( Phenylthio)phenyl]-2-(0-benzylidenehydrazine), Da ro cur (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one) ), Darocur (registered trademark) 1116, 1398, 1 174 and 1020, CGI242 (ethanol, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl] -1-(0-ethylhydrazine), Luckin TPO (2,4,6-trimethylbenzimidyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4, 6-trimethylbenzimidyl ethoxyethoxyphosphine oxide, available from ESACUR Japan Siber Hegner, ESACURE 1001M (1-[4-benzylidenephenyl-p-aminophenylsulfonyl-54- 200846824 Phenyl-2-phenyl-2-(4-methylphenylsulfonyl)propan-1-one, ADEKA OPT〇MER (registered trademark) N-1414 available from N-1414 Asahi Chemical Co., Ltd. (carbazole benzophenone), ADEKA 〇PT〇MER (registered trademark) N-1717 (acridine), ADEKA 〇PTOMER (registered trademark, standard) Ν·1 606 (three-well system), Sanwa Chemical TFE-three tillage (2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)_1,3,5-tri.), three-chemical ΤΜΕ-tripper (2-[2-(5-methylfuran-2-) ) vinyl]-4,6-bis(trichloromethyl)-1,3,5-triad), tri-chemically ΜΡ-tri-trap (2-(4-methoxyphenyl)) -4,6-bis(trichloromethyl)_1,3,5-triazine), green chemical system Ding-82-1(2-[2-(3,4-dimethoxyphenyl)ethylene) 4-[6,6-bis(trichloromethyl)-1,3,5_three tillage), green chemical system TAZ-108 (2-(3,4-dimethoxyphenyl)-4, 6-bis(trichloromethyl)-1,3,5-triad), diphenyl ketone, 4,4 '-bisdiethylaminodiphenyl ketone, methyl-2-diphenyl Ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 4-phenyldiphenyl ketone, ethyl Michler's ketone, 2-chlorothioxanthone, 2 -methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloroφ-4-propoxyphenoxy Tox ketone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzene Affinity isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, trichloroacetophenone, diethoxyacetophenone and diphenyl Cycloheptanone, benzhydryl benzoic acid methyl, 2-benzylidene naphthalene, 4-benzylidenebiphenyl, 4-benzylidene diphenyl ether '1,4-benzhydrylbenzene , benzyl, 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane), 2-ethylhydrazine, 2,2-bis(2-chloro Phenyl) 4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2-bis(fluorenyl-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-biimidazole, -55- 200846824 ginseng (4-dimethylaminophenyl)methane, ethyl-4-(dimethyl Amino)benzoic acid ester, 2-(dimethylamino)ethyl benzoate, propoxyethyl 4-(dimethylamino) benzoate, and the like. Further, the composition of the present invention may be added with a photo-sensitizer in addition to the photopolymerization initiator to adjust the wavelength in the U V domain. Representative sensitizers which can be used in the present invention are, for example, those of Criven(R) (JVCrivello, Adv. in Polymer Sci, 62, 1 (1984)), in particular, For example, hydrazine, hydrazine, acridine orange, thioxanthone, 2-chloroφylthioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthracene, fragrant Beans, benzohydrofuranone, phenanthrene, anthracene, phenothiazine derivatives, and the like. The content ratio of the photosensitizer in the composition of the present invention is preferably 15% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less. The lower limit of the content ratio of the photosensitizer is not particularly limited, but the lower limit of the photosensitizer content ratio is about 0.1% by mass in order to produce an effect.

In the composition of the present invention, a photoacid generator which starts photopolymerization by receiving an energy ray such as ultraviolet rays may be added for the purpose of promoting photohardening reaction or the like. The commercially available product of the photoacid generator may, for example, be 丨RGACURE261, IRGACURE OXE01, IRGACURE CGI-1 397 (above, manufactured by Steam Barbine Chemicals Co., Ltd.). The above photoacid generators may be used alone or in combination of two or more. Further, the above acid generator can be used in combination as a photopolymerization initiator. In this case, the photoacid generator is used in the range of 0. 5 to 3.0% by mass, and the photopolymerization initiator and the photoacid generator are used in the range of 0.5 to 15.0% by mass. The range to use is as expected. The light system for starting polymerization in the present invention includes not only light of a wavelength range such as ultraviolet light, near-ultraviolet light, far ultraviolet light, visible light, infrared light, but also electric, magnetic waves, and radiation, and the radiation system includes, for example, microwaves and electrons. Beam, EUV, X-ray. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser may be used. These light systems may also use monochromatic light (single wavelength light) passing through an optical filter or multiple Φ different wavelengths of light (composite light). The exposure system may be multiple exposures, and may further perform overall exposure after pattern formation for the purpose of improving film strength, uranium resistance, and the like. The photopolymerization initiator used in the present invention is required to be appropriately selected for the wavelength of the light source to be used, but it is preferred that no gas is generated during pressurization/exposure of the mold. Since the mold is contaminated when the gas is generated, the mold must be washed frequently, and the hardenable composition for photon printing lithography is deformed in the mold, and the transfer pattern accuracy is deteriorated. Etc. If the gas body is not produced, the cleaning frequency of the mold is reduced due to the difficulty of contamination of the mold, and the hardening composition for the photolithographic printing lithography is not easily deformed in the mold. It is preferable from the viewpoint of that the accuracy of the transfer pattern is not easily deteriorated. Surfactant The composition of the present invention contains at least one of a fluorine-based surfactant, a lanthanoid surfactant, and a fluorine-barium-based surfactant in an amount of 1 to 5% by mass based on 〇·〇 。. The ratio of the above surfactant in the composition is preferably 0.02 to 4% by mass, particularly preferably 5% to 5% by mass. -57- 200846824 The fluorine-based surfactant, the lanthanide surfactant, and the fluoro-antimony surfactant are less than 0 · 〇 〇 1 in the composition. /. In addition, the effect of coating uniformity is insufficient, and on the other hand, it exceeds 5 mass. /. At the time, it is not good because the mold transfer is deteriorated. The fluorine-based interface activity 4, the statistic surfactant, and the fluorine-cracking surfactant used in the present invention may be used singly or in combination of two or more. The present invention preferably contains both a fluorine-based surfactant and a tactical surfactant, or a fluorine/sand-based surfactant. In particular, a fluorine-containing rhodium-based surfactant is preferred. Here, the fluorine/lanthanum surfactant is considered to have both a fluorine-based surfactant and a lanthanoid surfactant. By using such a surfactant, the composition of the present invention is intended to solve a silicon wafer for semiconductor element manufacturing, a glass four-corner substrate for manufacturing a liquid crystal element, a chromium film, a molybdenum film, a molybdenum alloy film, and a giant. When a film, a giant alloy film, a tantalum nitride film, an amorphous ruthenium film, an oxygen-tin-tin is used as a coating liquid, an indium oxide (I τ 0 ) film, a tin oxide film, or the like, a substrate formed of various films or the like is coated. The problem of poor coating of the stripe or scaly pattern (dry spots of the photoresist film) caused by the coating, and the fluidity of the composition into the cavity of the mold cavity is good, and the mold and light are formed. The peeling property between the resists is good, the adhesion between the photoresist and the substrate is good, and the viscosity of the composition is lowered. In particular, by adding the above-mentioned surfactant to the composition of the present invention, coating uniformity can be greatly improved, and in the coating using a spin coater or a slit scan coater, it is excellent regardless of the substrate size. Coating suitability. Examples of the nonionic fluorine-based surfactant used in the present invention include

For example, the trade name is Fluorad FC-430, FC-431 (manufactured by Sumitomo Mitsui Co., Ltd.), the trade name Surflon "S-382" (made by Asahi Glass Co., Ltd.), and EFT0P -58-200846824 "EF-122A, 122B, 122C, EF-121. EF-126, EF-127, MF-100" (manufactured by Torkemu Products), trade name PF-636' PF-6320, PF-656, PF-6520 (both OMNOVA), trade name Ftergent FT250, FT 2 51. DFX18 (all manufactured by NE〇S Co., Ltd.), trade name Unidyne DS-401, DS-403, DS-451 (both manufactured by Daikin Industrial Co., Ltd.), and trade name MEGAFAC 171, 172, 173 178K, 178A, (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and examples of the nonionic lanthanum surfactant are, for example, trade name SI-110 series (made by Takemoto Φ Oil Co., Ltd.), MEGAFAC Paintad3 1 ( Kokusai Ink Chemical Industry Co., Ltd.), KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the fluorine-fluorene-based surfactant used in the present invention are, for example, trade names Χ-70-090, Χ-70-09 1 , X - 7 0 0 9 2, X - 7 0 - 0 9 3, ( All are manufactured by Shin-Etsu Chemical Co., Ltd., and the trade names are MEGAFAC R-08 and XRB-4 (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.). In addition to the above, the composition of the present invention may have other φ nonionic surfactants for the purpose of improving the flexibility of the curable composition for photonic printing and the like. A commercially available product of a non-ionic surfactant is exemplified by D-3110, D-3120, D-3412, D-3440, D-3510, D- of the Pioneering series manufactured by Takeshiba Oil & Fats Co., Ltd. D605, D-1315, D-1405, D-1420, D-1504, D-1508, D-1, 1 1 1 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 A polyoxyethylene alkyl ether, a polyoxyethylene mono-fatty acid ester such as D-2112-A, D-2112-C, D-2123-C, etc. of the pioneer series manufactured by Takeshiba Oil Co., Ltd., and a bamboo grease ( The company's Pioneer series of D-2405-A, D-2410-D, D-2110-D and other polyoxyethylene di-fatty acid esters, and bamboo oils-59-200846824 (shares) company's pioneer series Polyoxyethylene alkylphenyl ethers such as D-406, D-410, D-414, and D-418, and 1 4 4 S, 4 of the ^ S urfy η ο 丨 series manufactured by Nissin Chemical Industry Co., Ltd. Polyoxyethylene tetramethyl decynediol diether such as 2 0, 4 4 0, 4 6 5, 4 8 5 or the like. Further, a reactive surfactant having a polymerizable unsaturated group can also be used together with the surfactant used in the present invention. For example, allyloxy polyethylene glycol monomethacrylate (Japanese fat (stock) trade name: Blemmer ΡΚΕ series), nonyl phenoxy polyethylene glycol monomethacrylate (Japanese fats and oils) Product name: BI emmer PNE series@column), mercaptophenoxy polypropylene glycol monomethacrylate (Japanese fat (stock) trade name: BI emmer PNP series), nonylphenoxy poly(ethylene glycol-propylene glycol ) Monomethacrylate (Japanese oil (stock) trade name · B丨emmer PNEP-600), Akuaron RN-10, RN-20, RN-30, RN-50, RN-2025, HS-05, HS -10, HS-20 (manufactured by First Industrial Pharmaceutical Co., Ltd.), etc. The amount of the other nonionic surfactant added is preferably 〇 0 0 1 to 5 mass%, and 0.005 to 3 mass. /. It is better. Inorganic oxide microparticles

The composition of the present invention contains inorganic oxide fine particles. The inorganic oxide fine particles which are useful in the composition of the present invention are mainly for improving heat resistance, tackiness, hardness, and the like of the photocurable resin composition, or for scratch resistance, abrasion resistance, mechanical properties, and the like. The mechanical strength is increased for the purpose of addition, and the type, particle size, and morphology are not particularly limited as long as the obtained composition is transparent. Further, the addition of the inorganic oxide fine particles is effective for improving the deterioration of the adhesion of the substrate with the hardening shrinkage. Examples of the inorganic oxide fine particles include, for example, sulphur oxide sand (especially colloidal silica sand), oxidized sulphur, oxidized -60-200846824 titanium, tin oxide, dissimilar element coating liquid tin oxide (antimony, etc.), indium oxide, dissimilar elements Coating liquid indium oxide (丨TO, etc.), cadmium oxide, cerium oxide, zinc oxide, cerium oxide, zirconium oxide, and the like. These may be used singly or in combination of two or more. The inorganic oxide fine particles such as these may be used in any of a powder form, a solvent, and a dispersion sol. In the case of dispersing the sol as a solvent, the dispersing medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; and ketones such as acetone, methyl ethyl ketone, methyl isobutyl φ ketone, and cyclohexanone. Ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, etc.; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene, toluene, xylene, etc. Aromatic hydrocarbons; guanamines such as dimethylformamide, bismethylammoniumamine, and fluorenyl-methylpyrrolidone. Among them, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are particularly preferred. When the solvent-dispersed sol is blended in the composition of the present invention, it is blended with the solvent at the same time. In this case, the content of the organic solvent blended in all the compositions is preferably 3% by mass or less. As described above, in the case where the organic solvent is not contained, since the baking step for the purpose of volatilizing the solvent is not required, there is a great advantage that the process is simplified and effective. Therefore, in the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained. Therefore, it is particularly preferable to add a powder or a particle dispersed in the reactive monomer (diluent) of the present invention as compared with the addition of the solvent-dispersed sol. Further, various surfactants, dispersants, and amines for improving particle dispersibility may be added. The shape of the inorganic oxide fine particles used in the present invention is not particularly limited, and examples thereof include a spherical shape, a hollow shape, and a porous shape. Qualitative, rod-shaped, plate-shaped, -61- 200846824 fibrous, or indefinite shape, preferably spherical. The particle size of the inorganic oxide fine particles is preferably from 2 0 0 n m or less from the viewpoint of transparency of the resulting photocurable resin and the composition layer. It is preferably 1 〇〇 nm or less, more preferably 50 nm or less. Further, the inorganic oxide. The amount of the fine particles added is in the range of 〇 1 to 50% by mass based on the composition of the present invention. It is preferably in the range of 1 to 40% by mass, more preferably 5 to 30% by mass. When the amount of the inorganic oxide fine particles added is less than 0.1% by mass, it is generally considered that the mechanical strength such as scratch resistance, abrasion resistance, and mechanical properties of Φ is not improved, and the amount added exceeds 50%. In the case of %, the liquid viscosity of the photocurable resin composition becomes high, and the preservation stability or transparency is lowered. A commercially available product of the inorganic oxide fine particles used in the present invention, for example, an aqueous dispersion of alumina, for example, manufactured by Nissan Chemical Industries Co., Ltd., trade name: alumina sol-100, -200, - 520. A water-dispersible product of titanium oxide, for example, manufactured by Ishihara Sangyo Co., Ltd., trade name: TTO-W5; and a water-dispersible product of zinc citrate powder, for example, Nissan Chemical Industry Co., Ltd., product|name: C e II una X ; powders and solvent dispersions of oxidized, titanium oxide, tin oxide, indium oxide, zinc oxide, etc., for example, C.1. Chemicals Co., Ltd., trade name: NA Ν Ο TEC Η; The water-dispersible product of the composite oxide of titanium oxide and tin oxide is, for example, a product of Nissan Chemical Industry Co., Ltd., trade name: Η I Τ-1 5 W 1 ; For example, Ishihara Industry Co., Ltd., trade name: S Ν -1 0 0 D; Ί Τ Ο powder system can be, for example, a product made of Mitsubishi Materials (stock); System, trade name: N eed I a I ", tin oxide water dispersion system can be exemplified Ishihara Industry Co., Ltd., trade name: SN - 3 8 F, SN - 8 8 F; water dispersion of zirconia can be, for example, -62- 200846824 Sumitomo Osaka Cement Co., Ltd., trade name: FFT-150W , Nissan Chemical Industry Co., Ltd., trade name: HZ-307W6; _ In the inorganic oxide fine particles used in the present invention, for example, colloidal oxidation is used from the viewpoint of transparency or mechanical properties of the photocurable resin composition layer which is obtained easily or on the price surface. The lanthanide series may, for example, be Nalcoag 1034A (trade name of Nalco Chemical Company, USA), and the product name of Nissan Chemical Industry Co., Ltd.: methanol cerium oxide sol, IPA-ST, MEK-ST, MIBK-ST, NBAST, XBA-ST , Thailand DMAC-ST, EAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-0, ST-50, ST-OL, Fuso Chemical Industry ( Shares, trade names: PL-1-MA, PL-1-TOL, PL-1 _IPA, PL-1-MEK, PL-1-PGME, PL-2L-MA, PL-2L-IPA, etc. Further, the powdered cerium oxide system may, for example, be manufactured by AEROSIL Co., Ltd., trade name: AEROSIL1 30, AEROSIL300, AEROSIL380, AEROSILTT600, AEROSILOX50, Asahi Glass Co., Ltd., trade name: SILDEX H31, H32, H51, H52, H121 , H122, Japan's cerium oxide industry (shares) φ system, trade name · E220A, E220, Fuji 31! _ 丫 81 eight (shares) system, trade name: SYLYSIA470, 曰本板硝子(股) system, trade name: SG FLAKE and so on. When commercially available water or colloidal cerium oxide dispersed in an organic solvent is used in the composition of the present invention, since it is directly blended with water or an organic solvent, a commercially available colloidal cerium oxide dispersion is directly used. In the case, the amount of the cerium oxide component is preferably 5% by mass or less. CH2 = C(R2)COO(CH2)pSiR3n(OR1)3.n(1) (wherein R1 represents a hydrogen atom or a hydrocarbon residue having a total carbon number of 1 to 10., and R2 represents a hydrogen atom or a methyl group. R3 represents a hydrocarbon residue having a total carbon number of 1 to 10, which may have an ether bond, an ester bond, an epoxy-63 - 200846824 bond, a thiol bond or an amine bond, and an integer of η 0 to 2, Ρ An integer of 1 to 6) where a plurality of R1 and/or R3 are contained, and R1 and/or R3 may be the same or different. The decane compound having an allyl group is represented, for example, by the following structural formula (2). CH2 = CHCH2R2SiR3n(OR1)3-n(2) (wherein R1 represents a hydrogen atom or a hydrocarbon residue having a total carbon number of 1 to 10, and R2 φ and R3 represent an ether bond, an ester bond, or an epoxy, respectively. a hydrocarbon residue having a total carbon number of 1 to 10 in a bond, a hydrogenthio group bond or an amine bond, and an integer of 0 to 2 in the formula), wherein R1 and/or R3 are contained in the formula, and R1 and/or Or the R3 series may be the same or different. CH2 = CHSiR2n(OR1)3-n(3) (wherein R1 represents a hydrogen atom or a hydrocarbon residue having a total carbon number of 1 to 10, and R2 represents an ether bond, an ester bond, an epoxy bond, or a hydrogen sulfur; a hydrocarbon residue having a total carbon number of 1 to 10 of a base bond or an amine bond, and an integer of η of 0 to 2)

Where a plurality of R1 and/or R2 are contained in the formula, such R1 and/or R2 may be the same or different. R2 h2c=c- _^SiR3n(OR1) 3-n (4) (wherein R1 represents a hydrogen atom or a hydrocarbon residue having a total carbon number of 1 to 1 Å, and R2 represents a hydrogen atom or a methyl group, and R3 is a a hydrocarbon residue having a total carbon number of 1 to 1 可 which may have an ether bond, an ester bond, an epoxy bond, a thiol bond or an amine bond, and an integer of η 0 to 2) -64- 200846824 In the case of R1 and/or R3, the R1 and/or R3 systems may be the same or different. • When c is 2 or more, each R1 system may be the same or different. 'Alternatively, it is also possible to use a radically polymerizable decane compound and a non-radical poly- decane compound. The use of the molar ratio in the range of 1:9 9 to 9 9 : 1 is better, at 2: 98~ The range of 9 8: 2 is preferred, and the range of 5: 95 to 95: 5 is more preferable, especially in the range of 1 〇: 9 0 to 8 0 : 2 0 is optimal. Further, in order to allow the hydrolysis/condensation reaction to proceed gently and uniformly, it is preferred to use a 0 solvent. As the solvent, a dispersion medium of ceria can be used as it is, or a necessary amount of a new solvent can be added. Examples of the newly added solvent include water; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (Ml oxime); and dioxane. An ether such as tetrahydrofuran (THF). Antioxidant Further, the composition of the present invention may contain a conventional antioxidant. The antioxidant suppresses discoloration due to heat or light irradiation and fading due to various oxidizing gases such as ozone, active oxygen, Ν x, S Ο X (X is an integer). In particular, the present invention has the advantage of preventing the coloration of the cured film or reducing the film thickness caused by decomposition by adding an antioxidant. Examples of such antioxidants include hydrazines, hindered amine-based antioxidants, nitrogen-containing heterocyclic thiol-based compounds, thioether-based antioxidants, hindered phenol-based antioxidants, ascorbic acid, zinc sulfate, and thiocyanate. Salts, thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among them, the hindered phenol-based antioxidant and the thioether-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction in film thickness. -65 - 200846824 For the commercial products of antioxidants, for example, Irg a η ο χ 1 Ο 1 0, 1 〇 3 5 ' 1 〇 7 6 ' 1 222 (above, Ciba Geigy), Antigene Ρ, 3C, FR, SUMIUZER — S, SUMILIZER — GA-80 (manufactured by Sumitomo Chemical Industries), ADKSTAB AO70, AO80, AO503 (made by Adeka), etc. These may be used singly or in combination. The antioxidant is based on the total amount of the composition of the present invention, and is 〇 1 1 1 1 〇 mass. The blending ratio is preferably carried out, and blending is preferably carried out at a ratio of 0.2 to 5% by mass. Other ingredients

In the composition of the present invention, in addition to the above-mentioned components, a release agent, a decane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an aging preventive agent, a plasticizer, an adhesion promoter, and a thermal polymerization may be added as needed. A starter, a colorant, an elastomer particle, a photoacid multiplier, a photobase generator, a basic compound, a flow regulator, an antifoaming agent, a dispersant, and the like. In the composition of the present invention, an organic metal coupling agent may be blended in order to improve heat resistance, strength, or adhesion to a metal deposition layer having a fine concavo-convex pattern. Further, the organometallic coupling agent is effective because it has an effect of promoting the heat-hardening reaction of φ. As the organometallic coupling agent, various coupling agents such as a decane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used. The organic metal coupling agent is arbitrarily blended in a ratio of 0.001 to 10% by mass in the total solid content of the curable composition for photonic printing. When the ratio of the organic metal coupling agent is 0.001% by mass or more, the heat resistance and strength are more effectively improved, and the adhesion to the vapor-deposited layer tends to be imparted. On the other hand, when the ratio of the organic metal coupling agent is 1% by mass or less, it is preferable that the stability of the composition can be suppressed, and the film forming property is insufficient, from -66 to 200846824. Commercial products of the ultraviolet absorber include, for example, Tinuvin p, 234, 320, 3 26, 327, 328, 213 (above 'Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 2 50, 300, 320, 340, 3 50, 4 00 (above, Sumitomo Chemical Industry Co., Ltd.) and so on. The ultraviolet absorber is preferably blended in an amount of from 0.01 to 10% by mass based on the total amount of the curable composition for photolithographic printing.

Commercially available products of the light stabilizer are, for example, Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanoru LS-770, 765, 292, 2626, 1114, 744 (above, Sankyo Chemical Industry Co., Ltd.) ))). The light stabilizer is preferably blended in a ratio of 〇 1 to 1 〇 by mass based on the total amount of the composition. Commercially available products of the anti-aging agent are, for example, Anti Gene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Co., Ltd.). The aging preventive agent is preferably blended in a ratio of 〇 1 to 1 〇 by mass based on the total amount of the composition. The composition of the present invention can be added with a plasticizer for adjusting the adhesion to the substrate, the flexibility of the film, the hardness, and the like. Specific examples of preferred plasticizers are, for example, dioctylbutyrate, di-dodecylbutyrate, triethylene glycol dicaprylate, dimethylene glycol butyrate, tricresyl phosphate, and Octyl adipate, dibutyl sebacate, triethylene glycerol, dimethyl adipate, diethyl adipate, di(n-butyl) adipate, two Methyl suberate, diethyl suberate, di(n-butyl) suberate, and the like, and the plasticizer may be optionally added in an amount of 30% by mass or less based on the composition. It is preferably 20% by mass or less, more preferably 1% by mass or less. In order to obtain the effect of adding plasticizer, -67-

200846824 It is preferably 0.1% by mass or more. When the composition of the present invention is hardened, a starting agent may be added as needed. A suitable thermal polymerization initiator is, for example, a peroxide compound. Specific examples thereof include benzammonium peroxide, perbutyl benzoate, azobisisobutyronitrile, and the like. The composition of the present invention can adjust the shape and feel of the pattern, and a photoinitiator can be added as needed. For example, a suitable one may be nitrobenzylcyclohexylamine formate, triphenylmethanol, 0-amine formazan, hydrazine-amine formazan, [[(2,6-dinitrobenzyl)] Alkylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diaminobenzimidyl)-1-methyl-1-morpholinoethane, (4-tyrosolinyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxyrrolidine, hexaammine cobalt (丨丨丨) ginseng (triphenylmethyl Borate), 2-methylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3 _4-(2'-nitrophenyl)-1, 4-dihydropyridine, 2,6·dimethyl-3 _4-(2',4'-dinitrophenyl)-1,4-dihydropyridine, etc. In the composition of the present invention, the coating film is improved. The coloring agent can be arbitrarily added, and the coloring agent which does not impair the object of the present invention can be a pigment used in a composition for a UV inkjet composition, a color filter for a test image sensor, or the like. Dye. 4 The pigments used can be used in various conventional inorganic pigments. They can be used as inorganic pigments with metal oxides and metal compounds. For example, metal oxides and oxides such as iron, cobalt, donor, copper, chin, magnesium, chromium, zinc, and chains, etc., which can be used as organic pigments, can be exemplified by thermal polymerization of C. The third degree of nitriding oxidation is exemplified as 2-mercaptohydroxycarbonyl]cyclohexyl, 4-(methylthiobenzhydrylcarbonyl)pyridyl-2-dis5-diethylhydrazine, 5-di乙醯. Purpose, also within the 5th, with the object and CCD 2 invention in the energy + or organic Yan i salt, etc., Ming, _, * metal composite yellow 11, 24, -68- 200846824 31,53,83 , 99, 108, 109, 110, 138, 139, 151, 154, 167, CI Pigment Orange 36, 38, 43, CI Pigment Red 105, 122, 149, - 1 5 0, 1 5 5, 1 71, 1 75, 1 76, 1 7 7,209, C. I · Pigment Violet 19,23, .32,39, Cl Pigment Blue 1,2,15,16,22,60,66,Cl Pigment Green 7,36, 37,C_l· Pigment brown 25, 28, Cl pigment black 1, 7, and carbon black. The colorant is preferably blended in a ratio of 0.001 to 2 by mass based on the total amount of the composition.

Further, the composition of the present invention is intended to improve mechanical strength, flexibility, etc., and elastomer particles may be added as an optional component. The elastomer particles to be added as an optional component in the composition of the present invention have an average particle size of preferably from 10 nm to 700 nm, more preferably from 3 to 300 nm, such as polybutadiene, polyisoprene or butyl. Diene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/isoprene copolymer, ethylene/propylene copolymer, ethylene/α-olefin copolymer, ethylene/α·olefin/polyene Particles of an elastomer such as a copolymer, an acrylic rubber, a butadiene/(meth)acrylate copolymer, a φstyrene/butadiene block copolymer, or a styrene/isoprene block copolymer. Further, as the elastomer particles, core/sheath type particles coated with a methyl methacrylate polymer, a methyl methacrylate/glycidyl methacrylate copolymer or the like can be used. The elastomeric particle system can be a crosslinked structure. These elastomer particles may be used singly or in combination of two or more. The content of the elastomer component in the composition of the present invention is preferably from 1 to 35% by mass, more preferably from 2 to 30% by mass, even more preferably from 3 to 20% by mass. /. . In the composition of the present invention, a basic compound may be optionally added for the purpose of suppressing hardening shrinkage, improving heat stability, and the like -69-200846824. The basic compound may, for example, be a nitrogen-containing heterocyclic compound such as an amine or a quinoline or a quinoline, a basic alkali metal compound or a basic alkaline earth metal compound. Among these, 'an amine is preferred from the viewpoint of compatibility with a photopolymerizable monomer, and examples thereof include octylamine, naphthylamine, xylenediamine, dibenzylamine, and diphenylamine. ,dibutylamine, dioctylamine, dimethylaniline, acridine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine , hexamethylenetetramine and triethanolamine. ·

In the composition of the present invention, a chain shifting agent may be added in order to improve photocurability. Specifically, for example, 4-bis(3-hydrothiobutoxy)butane, 1,3,5-gin(3-hydrothiobutoxyethyl) 1,3,5-three哄-2,4,6(1 H,3H,5H)-trione, pentaerythritol oxime (3-hydrogenthiobutyrate). An antistatic agent may also be added to the composition of the present invention as needed. Next, a method of forming a pattern (especially a fine uneven pattern) of the composition of the present invention will be described. The present invention coats and hardens the composition of the present invention to form a pattern. Specifically, a pattern forming layer composed of at least the composition of the present invention may be applied to a substrate or a support, and may be dried as necessary to form a layer (pattern forming layer) composed of the composition of the present invention. The pattern receiving body is pressed against the surface of the pattern forming layer of the pattern receiving body, processed into a transfer mold pattern, and exposed to the fine uneven pattern forming layer to be cured. The photolithography of the pattern forming method according to the present invention can be layered or patterned a plurality of times, and can also be used in combination with usual thermal printing. Further, the composition of the present invention can be applied by coating the composition of the present invention on a substrate or a support, exposing and hardening the layer of -70-200846824 composed of the composition, and drying (baking) as needed. To make a permanent film such as an overcoat or an insulating film. Hereinafter, a pattern forming method and a pattern 转印 transfer method using the composition of the present invention will be described. The composition of the present invention may be in accordance with a generally well-known coating method, and may be, for example, a dip coating method, a knife coating method, a curtain coating method, a metal bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, A slit scanning method or the like is formed by coating. The film thickness of the layer formed by the composition of the present invention varies depending on the use used, 〇 0 5 // m 〜 3 0 // m. Further, the composition of the present invention can be applied a plurality of times. The substrate or supporting system for coating the composition of the present invention may be a metal substrate of quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film, Ni, Cu, Cr, Fe, etc., paper, SOG, poly A polymer substrate such as an ester film, a polycarbonate film or a polyimide film, a TFT array substrate, an electrode plate of a PDP, a glass or a transparent plastic substrate, a conductive substrate such as ITO or a metal, an insulating substrate, or a crucible A semiconductor-made substrate such as tantalum nitride, polycrystalline germanium, cerium oxide, or amorphous germanium is not particularly limited. The shape of the substrate may be a plate shape or a roll shape. The light system for curing the composition of the present invention is not particularly limited, and examples thereof include light or radiation of a wavelength of a high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, infrared, or the like. Can be used as a source of high-energy ionizing radiation, such as by Cockcroft type accelerator, Van de Giraff type accelerator, linear accelerator, betatron, cyclotron ( Accelerators such as 〇¥〇丨〇”〇11), the accelerated electron beam system is most convenient and economical to use in industry, and others can also use -71 - 200846824 γ-rays emitted by radioactive isotope elements or atomic furnaces. Radiations such as X-ray '^ lines, neutron beams, proton beams, etc. Examples of the ultraviolet light source include ultraviolet fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, carbon arc lamps, solar lamps, and the like. For example, microwaves, E UV, LEDs, semiconductor lasers, or 24 nm nm KrF excimer laser light, or 193 nm ArF excimer lasers, etc., can also be suitably used in semiconductor lasers. Invention. These light systems can use monochromatic light or a plurality of different wavelengths of light (mixed light).

Next, a mold mold which can be used in the present invention will be described. The photonic printing lithography using the composition of the present invention requires at least one of the mold and/or the substrate to be a material having a light transmissive property. The optical printing lithography to which the present invention is applied is to apply a curable composition for photonic printing lithography on a substrate, stack a light transmissive mold, and irradiate light from the back surface of the mold to make the light The rice printing lithography is hardened with a hardenable composition. Further, the curable composition for the photonic printing lithography is applied onto the light-transmissive substrate, the mold is pressed, and the light is irradiated from the back surface of the mold, and the hardenability composition of the photo-printing lithography can be made φ. Hardening of matter. The light irradiation may be carried out in a state in which the mold is attached, or may be carried out after the mold is peeled off, and the present invention is preferably carried out in a state in which the mold is adhered. The mold mold which can be used in the present invention employs a mold having a pattern to be transferred. The mold system can be patterned by a desired processing precision by, for example, photolithography or electron beam drawing, but the mold pattern forming method in the present invention is not particularly limited. The translucent mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, for example, a transparent film such as glass, quartz, yttrium MA, or a polycarbonate resin, a transparent metal vaporized film, a soft film such as a polydimethyloxygen, or the like can be used. Hardened film, metal film, etc. In the case of using the transparent substrate of the present invention, the non-transparent over-molded molding material to be used is not particularly limited as long as it has a predetermined strength. Specifically, examples thereof include a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, a substrate such as SiC, tantalum, tantalum nitride, polycrystalline germanium, germanium oxide, or amorphous germanium. Etc., there are no special restrictions. The @shape system may be any of a plate mold and a roll mold. The roll-form mold system is suitable for the case where continuous productivity such as transfer is necessary. The mold mold used in the present invention may be used for the purpose of removing the peeling property of the curable composition for photolithographic printing and the mold. A commercially available release agent such as Daikin Industries, Optzuru DSX, Sumitomo 3M, Novec EGC-1 720, or the like can be suitably used as a treatment by a decane coupling agent such as a fluorene or a fluorine-based compound. In the case of performing photolithography using the present invention, it is usually preferred that the pressure of the mold φ is 1 Torr or less. When the mold pressure is 1 Torr or less, the mold or the substrate is less likely to be deformed and the pattern accuracy tends to be improved. Further, it is preferable to use a device for reducing the pressure to be reduced. The pressure of the mold is preferably in the range in which the residual film of the curable composition for photonic printing lithography of the mold mold is reduced, and it is preferable to select a transfer mold uniformity. In the present invention, the light irradiation system for photolithography is preferably larger than the amount of irradiation necessary for curing. The amount of irradiation necessary for hardening is determined by investigating the consumption of unsaturated bonds in the hardenable composition of photon nanolithography, or the cured film.

200846824 Adhesion is determined. Further, in the photolithography which is applied to the present invention, the temperature of the light-irradiated substrate is usually carried out at room temperature, and light irradiation is performed in order to improve the heating of the reaction. In the pre-formed state in the pre-light irradiation stage, in order to effectively prevent the incorporation of air bubbles, suppress the decrease in reactivity due to oxygen incorporation, and improve the adhesion of the mold to the hard material for photolithographic printing, it is also possible to vacuum Light is irradiated in the state. The preferred degree of vacuum is from 1 (T1Pa to atmospheric pressure). After mixing the above components, the composition of the present invention can be filtered by a filter having a pore diameter of 〇5 // m to 5.0 μm. Filtration is carried out as a solution. The mixing and dissolution of the curable composition for photonographic printing lithography is carried out in the range of 〇 ° C to 1 〇〇 ° C. The filtration system can be repeated in multiple stages. The filtered solution may be further filtered. The material to be used may be a polyethylene resin, a polypropylene resin, a fluorocarbon resin, or the like, and is not particularly limited. The case where the composition of the present invention is applied to an etching photoresist is described. The step can be carried out by appropriately selecting from a conventional etching treatment method by removing the pattern of the base portion to the film which is not covered by the photoresist pattern. The etching liquid can be processed (wet etching) and pressed. Any of the treatments for the activation of the reactive gas by the plasma discharge (dry uranium). The etching liquid used in the wet etching described above is represented by a ferric chloride/hydrochloric acid/nitric acid system or a hydrogen bromide acid system. Developed The following mixture can be used separately, and a mixture of cerium nitrate or cerium nitrate and hydrogen peroxide can be used for the fluid, and the fluoric acid can be diluted with Ti for the purpose of vacuuming. , by, for example, modulating the solution, filtering the resin, uranium engraving, or in the nucleus), the salt etched I solution, hydrofluoric acid-74-200846824 • nitric acid mixture 'T a mixture of molybdenum solution and hydrogen peroxide water' M 0 is a mixture of hydrogen peroxide water, ammonia water and hydrogen peroxide water, a mixture of phosphoric acid and nitric acid, and a mixture of MoW and AI phosphate/nitric acid. , a mixture of hydrofluoric acid and nitric acid, a mixture of phosphoric acid, nitric acid and acetic acid 1 το diluted aqua regia, ferric chloride solution, hydrogen iodide water, SiNx or Si〇2 buffered hydrofluoric acid, hydrofluoric acid·fluorine Ammonium mixed solution, a mixture of S i, poly S i hydrofluoric acid, nitric acid and acetic acid, W is a mixture of ammonia and hydrogen peroxide, PSG is a mixture of nitric acid and hydrofluoric acid, and BSG is hydrofluoric acid. Fluorinated money mixture, etc.

The wet etching system can be sprayed or immersed. However, since the etching speed, in-plane uniformity, and wiring width are highly dependent on the processing temperature, they are used depending on the type of substrate, use, and line width. The need for optimal conditions. Further, in the case of the wet etching described above, in order to prevent undercut due to the penetration of the etching liquid, post-baking is desirable. Usually, such post-baking is carried out at a temperature of from 90 ° C to 140 ° C, but is not limited thereto. The dry etching is basically a parallel plate type dry etching apparatus in which a substrate having one pair of parallel electrodes disposed in a vacuum apparatus is disposed on one electrode. The high-frequency power source for generating plasma is classified into an ion-based reactive ion etching (RIE) mode by connecting electrodes on the side of the substrate or connecting opposite electrodes, and radicals are mainly involved in electricity generation. Plasma etching (PE) mode. The etchant gas system used in the above dry etching can use an etchant gas suitable for various film types. For example, a _ sj / n + or s _ si is a carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine), a-SiNx is tetrafluorinated Carbon + oxygen, a-SiOx with carbon tetrafluoride + oxygen, carbon trifluoride + -75- 200846824 oxygen, Ta with carbon tetrafluoride (sulfur hexafluoride) + oxygen, MoTa / Mow with PTFE Carbon + oxygen, Cr for chlorine + oxygen, AI with boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, etc. In the dry engraving step, the structure of the photoresist is greatly deteriorated due to ion rushing or 'heating, and the peeling property is also affected. - A method of peeling off the photoresist used for pattern transfer of the underlying substrate after etching is described. The stripping system can be removed (dry stripping/de-ashing) or by ozone by removing it in the liquid (wet stripping) or by oxidizing it into a gas by plasma discharge of oxygen gas under reduced pressure. The photoresist is removed by several kinds of peeling methods, such as removing (dry stripping/UV deashing) by oxidizing with UV light to form a gas Φ. The stripping solution is generally known to have an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution such as ozone-dissolved water, and an organic solvent system such as a mixture of an amine and dimethyl hydrazine or N-methyl hydral ketone. The latter case is well known as a monoethanolamine/dimethylaluminum mixture (mass mixing ratio = 7/3). The peeling speed of the photoresist is greatly dependent on the temperature, the amount of liquid, the time, the pressure, and the like, and can be optimized according to the substrate type and use. In the present invention, the substrate is immersed in a temperature range of from room temperature to 100 ° C (minutes to several minutes), and a solvent such as butyl acetate is rinsed and washed with water. From the viewpoint of improving the rinsing property, the particle removability, and the corrosion resistance of the peeling liquid itself, it is also possible to rinse only with water. The water washing system may be, for example, pure water spray or drying. For example, air knife drying is preferred. When the amorphous material is exposed on the substrate, since the oxide film is formed in the presence of water and air, it is easy to cut off the air, and it can also be applied to the ash (ashing) and the medicine. The method of peeling off the liquid. The ash removal system can be, for example, a plasma ash removal, a down flow type (d〇wn_f|〇w), ash removal using ozone, and UV/ozone deashing. For example, in the case of processing the A substrate by dry etching, a chlorine-based gas is generally used, but there is a case where the -76-chloro and the AI product, aluminum chloride, are rot. In order to prevent the use of a stripping solution with a preservative.

200846824 The etching step, the peeling step, the rinsing step, and the water other steps are not particularly limited, and may be appropriately selected, for example, from the conventional drawing steps. For example, a hardening treatment step or the like can be mentioned. One type may be used alone or two or more types may be used. The hardening treatment step is limited in nature, and may be appropriately selected depending on the purpose thereof, and is preferably an example of heat treatment or full exposure treatment. The method of the above comprehensive exposure treatment is, for example, a method in which the exposure is comprehensive. By the full exposure, the hardening in the composition of the formation layer can be promoted, and the surface hardness of the aforementioned pattern can be improved to improve the etching resistance. The apparatus for performing the above-described overall exposure is not limited to being appropriately selected depending on the purpose thereof, and a U V exposure machine such as a silver lamp or the like is preferably used. EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples. The materials, the amounts, the ratios, the contents of the treatments, and the treatments that are not included in the examples are not subject to the scope of the present invention, and may be appropriately changed. The scope of the invention is not limited to the specific examples shown below. Polymerizable unsaturated monomer <1 functional monomer>

R-1 ··Compound (Ι-2)γ-butyrolactone acrylate (manufactured by GBLA Division) R-2: Compound (Ι-3) α-propylene oxime 1, accounting for dimethyl ester (made by Aldrich Co., Ltd.) In the case of the above-mentioned "washing", there is no such thing as the sensitization of the figure which is formed in a comprehensive manner. Therefore, there are special procedures such as ultra-high pressure water, and therefore, the ENF-based Γ-丁内-77- 200846824 R-3 : Compound (Bu 4) mevalonate (meth) acrylate (Synthetic product: synthesized according to JP-A-2004-243) R-4: Compound (I 3) 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane (BISCOAT MEDOL 10: manufactured by Osaka Organic Industries Co., Ltd.), R-5: Compound (11-5) 4-propenyloxymethyl-2cyclohexyl-1,3-dioxolane (BISCOAT HDOL10, manufactured by Osaka Organic Chemical Industry Co., Ltd.) R-6: Compound (11-7) (3-methyl-3-oxo) Cyclobutane) methacrylate (BISCOAT OXE10 Osaka Organic Chemical Industry Co., Ltd.)

R-7: compound (ΠΙ-2) Ν-vinyl succinimide (synthetic) according to

Dokiady Akademii Nauk Respubliki Uzbekistan (l), 39 Volume - 49 (1 993) Synthetic R-8: Compound (m-6) N-1-piperidylethyl acrylate (synthetic) according to Journal fuer Praktische Chemie (Leipzig), 7 , 308-1 0. (1 959) synthesized R-9: compound (丨丨|-7) 2-acrylic acid 2-methyl-oxiranyl methyl ester (synthetic) according to 68 (^8 1乂11663〇(1), 109-14, (1993) Synthesis #R-1 〇: Compound (UI-8) N-glypholine ethyl acrylate (synthetic) According to American Chemical Society, 71, 3164 -5, (1949) Synthetic R-11: Compound (IV-1) N-vinyl-2-pyrrolidone (ARONIX M-150: manufactured by Toagosei Co., Ltd.) R-1 2 : Compound (ιν-2 ) Ν-vinyl caprolactone (tested by Aldrich) R -1 3 : compound (丨V-3) N-vinyl succinimide (synthetic) according to -78- 200846824

Kunststoffe Plastics, 4, 257-64, (1957) Synthesis of R_14··Compound (IV-5) 1-vinylimidazole (Aldrich, 1986). R-15: Compound (|V-8)N -Acetylmercapto-porphyrin (ACMO: Xingrengong - Division) R·16 ··Compound (V-1)4·Vinyl_1_cyclohexene noxide (CELL OXIDE 2000 Daisy Chemical Industry Co., Ltd. R-1 7 : Compound (ν-2) 2-vinyl-2-oxazoline (VOZO: manufactured by Xingrengong Φ Division) R-18: Compound (\/-6) 4 - B; I# 1,3 -dioxolan-2-one (a reagent manufactured by Aldrich Co., Ltd.) R-19: Compound (νμΐ) norbornene acrylate (aronix Μ -1 5 6 : manufactured by Toagosei Co., Ltd.) R-20 : Compound (VI-1 0) 2-methylpropenyloxyethyl isocyanate (CAINZ Μ0Ι: manufactured by Showa Denko Co., Ltd.) R-21: Compound (V丨2) Ν-hydroxyethyl acrylamide (ΗΕΑΑ: Xing φ person company system)

R-22: Compound (VI) 1 Ν-vinylcarbamide (BEAMSET 770: manufactured by Arakawa Chemical Industry Co., Ltd.) R-23: Compound (|χ-2) 3-(trimethoxydecane)propyl acrylate ( Tokyo Chemicals Co., Ltd.) R-24: Compound (|χ-2〇) 2-methylpropenyloxyethyl acid phosphate, salt (light ester Ρ _ 1 Μ ··Kyoeisha Chemical Co., Ltd.) R -25: Ethoxydiethylene glycol acrylate (light acrylate EC-A: manufactured by Kyoeisha Chemical Co., Ltd.) -79- 200846824 R-26: Benzyl acrylate (BISC〇AT #160: Osaka Organic Chemical Co., Ltd. )) R-27 ··Phenoxyethyl acrylate (light acrylate PO-A: total " manufactured by Rongshe Oil Co., Ltd.) • R_28: epoxy acrylate (EBECRIL 3701: made by Daisy UCB) R-29: α-methylstyrene (a reagent obtained by Tokyo Chemical Industry Co., Ltd.) R-30: Compound (ΙΧ-20) 2-methylpropenyloxyethyl acid phosphate salt (light ester) P-1 Μ :Kyoeisha Chemical Co., Ltd.) <2-functional monomer> S-01 : Compound (ΙΧ-23) Ethylene oxide modified phosphoric acid dimethacrylate (KAYAMER ΡΜ-21: Nippon Chemical Company system) S-02: Hydroxytrimethylacetic acid Neopentyl glycol diacrylate (KAYASED MANDA: Nippon Kayaku Co., Ltd.) S-03: polyethylene glycol diacrylate (NEW FRONTIER PE-300: ichi Kogyo Seiyaku Co., Ltd.)

S-04: Tripropylene glycol diacrylate (KAYASED TPGDA: manufactured by Nippon Kayaku Co., Ltd.) S-05: Ethylene oxide modified neopentyl glycol diacrylate (FOTOMER 4160: 3 3 11〇卩〇〇〇) S-06: 1,6-hexanediol diacrylate (FRONTIER HDDA: manufactured by Daiichi Kogyo Co., Ltd.) S - 0 7 : Ethylene oxide modified bisphenol A diacrylate (SR-6 0 2 : S-080: Ethylene oxide modified bisphenol A diacrylate (eight feet 0! ^1乂-80- 200846824 Μ - 2 1 1 B: manufactured by Toagosei Co., Ltd.) 'S-09 : Tricyclodecane dimethanol acrylate (KAYASED R684: manufactured by Kosei Chemical Co., Ltd.) • s_10: ethylene glycol dimethacrylate (light ester EG: Kyoei Seok-lu-School Co., Ltd.) < 3 A monomer or oligomer having a function or more> S-11 : Ethylene oxide modified trimethylolpropane triacrylate (SR-454: manufactured by SARTOMER Co., Ltd.)

S-12: propylene oxide modified trimethylolpropane triacrylate (NEW FRONTIER TMP-3P: manufactured by Dai-Il Pharmaceutical Co., Ltd.) S-1 3 : pentaerythritol ethoxytetraacrylate (Ebercryl 40 · Daisy) Manufactured by UCB) S-1 4: Dipentaerythritol hexaacrylate (KAYASED DPHA: manufactured by Nippon Kayaku Co., Ltd.) S-1 5 : Trimethylolpropane triacrylate (ARONIX M-309: manufactured by Toagosei Co., Ltd.) S -16: Akuaron RN-20: The abbreviations of the photopolymerization initiator and the photoacid generator used in the examples and comparative examples of the present invention manufactured by Daiichi Kogyo Co., Ltd. are as follows. <Photopolymerization initiator> P-1: 2,4,6-trimethylbenzimidyl-ethoxyphenyl-phosphine oxide (L uciri η TP 〇-L: manufactured by BASF Corporation) 卩- 2:2,2-dimethoxy-1,2-diphenylethan-1-one (|"93〇1^6651: manufactured by Ciba Specialty Chemicals Co., Ltd.) P-3: 2-hydroxy-2 -Methyl-1-phenylpropan-1_.(Darocure1173: -81- 200846824 manufactured by Ciba Specialty Chemicals Co., Ltd.) P-4: 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide Mixture with 2_hydroxy• -2 -methyl·1·phenyl-propan-1-one (Darocure 4265: manufactured by Steam Bart Chemical Co., Ltd.) • P-5 : 2·benzyl-2-dimethyl Mixture of Amino-1-(4-morpholinophenyl)-butanone d with 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 1 300: Ciba Specialty Chemistry Manufactured by Pico Co., Ltd.) P-6 : 1-[4-Benzylnonylphenyl-p-aminophenylsulfonyl]phenyl-2-methyl-2-(4-methylphenylsulfonyl)propene- Ketone (ESACUR1001M: manufactured by Siber Hegner Co., Ltd.) P-7: 2-methyl-1-[4-(methylthio)phenyl]-2- morpholinopropane-" (lrgacure-907: Ciba Specialty Chemicals P- 8 : Hydroxycyclohexyl phenyl ketone (Ciba specialization) Manufactured by the company: I rgacu re-1 84) The abbreviations of the surfactant and the additive used in the examples and comparative examples of the present invention are as follows. φ <surfactant> W -1 : fluorine-based surfactant (manufactured by τ 〇rkemu P r 〇ducts: fluorine-based surfactant) W-2 : lanthanide surfactant (Daily Ink Chemical Industry Co., Ltd.) System: MEGAFAC Paintad 31 ) W-3 : Fluoride-based surfactant (Mega FAC R-08) manufactured by Dainippon Ink and Chemicals Co., Ltd. VV-4 : Fluoride-based surfactant (Daily Ink Chemical Industry Co., Ltd. System: MEGAFAC XRB-4) -82- 200846824 W-5: Fluoride-based surfactant (manufactured by Dainippon Ink and Chemicals Co., Ltd.: F-173) W-6: Fluorine-based surfactant (manufactured by Sumitomo 3M Co., Ltd.: FC- 430) CS-1: Colloidal cerium oxide (manufactured by Nissan Chemical Industries, Ltd.: MIBK-ST, 30% methyl isobutyl ketone solution) CS-2: Water dispersion of tin oxide (made by Ishihara Sangyo Co., Ltd.: SN-38F ) a solution substituted with a propyl carbonate solvent, 30% solution)

CS _ 3 : Surface treatment of cerium oxide CS-4 synthesized in Synthesis Example 1: Surface treatment of cerium oxide CS - 5 synthesized in Synthesis Example 2: Surface treatment of cerium oxide CS-6 synthesized in Synthesis Example 3: Synthesis Surface Treatment of Cerium Oxide CS-7 Synthesized in Example 4: Surface Treatment of Cerium Oxide CS - 8 Synthesized in Synthesis Example 5: Surface Treatment of Cerium Oxide CS-9 Synthesized in Synthesis Example 6: Synthesis in Synthesis Example 7 Surface treatment of sulphur dioxide eve CS-10: Surface treatment of synthetic sulphur dioxide synthesized in Synthesis Example 8 <Additive> A-1 : 2-Chlorothioxanthone A-2: 9,10-dipropoxy蒽 (made by Kawasaki Chemical Industry Co., Ltd.) A-3 : decane coupling agent (vinyl triethoxy decane) (Shin-Etsu Company A-4: oyster sauce (made by Japan UNICAR Co., Ltd.: L-7001) A-5 : 2- Methylaminoethyl benzoate A-6 : Diphenyl ketone A-7 : 4-dimethylamino benzoic acid ethyl A-8: modified dimethyl polydecane (BYK Japan) System: BYK-307) -83 - 200846824 A-9: Red 225 (SUDAN III) A-10: Polyether modified dimethyl oxime oil (ΒγΚ曰 Κ曰 Κ曰 Κ 0 3 0 2 ) <Light Evaluation of hardenable compositions for rice printing lithography t; Each of the compositions obtained in Examples 1 to 27 and Comparative Example 1' was measured and evaluated according to the following evaluation method. Tables 1 and 4 show the polymerizable unsaturated sheets used in the composition, respectively. The blend ratio of the bodies (Examples, Comparative Examples).

Tables 2 and 5 show the blending ratios of the respective components in the composition (Examples, Comparative Examples). Tables 3 and 6 show the evaluation results of the compositions (Examples, Comparative Examples). <Viscosity measurement> The viscosity was measured by using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd. at 25 ± 0.2. The rotation speed at the time of measurement may be 0.5 MPa or more and 100 rpm or less, and 5 MPa or more and 50 rpm or less, and 10 mPa.s or more and less than 30 mPa·s. It is 20 rpm; 30 mPa·s or more, less than 60 mPa, 10 rpm when s; 60 mPa·s or more, less than 120 mPa, 5 rpm when s; 1 rpm or 0.5 rpm when 120 mPa·s or more. <Measurement of photohardening speed (photocuring property)> Measurement of photocurability is carried out by using a high-pressure mercury lamp as a light source, and using a Fourier transform infrared spectroscopy device (FT-IR) to change the absorption of the monomer at 810 cm·1. The 'hardening reaction rate·(monomer consumption rate) is performed at the actual time (rea|time) -84-200846824. The A system indicates a case where the curing reaction rate is 〇 · 2 /sec or more, and the b system indicates a case where the curing reaction rate is less than 0.2 / sec. <Adhesiveness> Adhesive tape is a photocurable photoresist which is photocured by visual observation and adhesion when the adhesive tape is attached to the surface of the photohardenable photocurable photoresist pattern. The pattern is attached and evaluated as follows.

A: There is no pattern adhesion on the tape side B: very thin pattern adhesion is observed on the tape side C: very clear pattern adhesion is observed on the tape side &lt;peelability&gt; Peeling is peeling after light hardening In the case of the mold, whether or not the unhardened material remained on the mold was observed with an optical microscope, and evaluation was performed as follows. A: no residue B: part of residue C: total residue φ &lt; observation of residual film property and pattern shape&gt; The shape of the pattern after transfer and the residue of the transfer pattern were observed by a scanning electron microscope. The residual film properties and pattern shape were evaluated as follows. (Residual film property) A: No residue was observed B: A small amount of residue was observed C: Many residues (pattern shape) were observed A: The pattern shape of the mold was the same as that of the original pattern which was originally formed -85-200846824 B : The pattern shape of the mold is different from the original pattern shape formed by the portion of the original pattern (the difference from the original pattern is less than 20%) _ C : the pattern shape of the mold and the original pattern formed. The film thickness of the pattern or the pattern is different from that of the original pattern by more than 20%. <Rot coating adaptability> Coating property (I) The composition of the present invention is formed to have a film thickness of 4000 angstroms (Å). Aluminum (ΑΙ) was spin-coated on a glass substrate having a thickness of 4 mm and a thickness of 0.7 mm on a φ film to a thickness of 5.0 μm, and then the glass substrate was allowed to stand for 1 minute and observed in a plane, as described below. Evaluation. A: no shrinkage spots and coating streaks (striped) were observed. B '·A few applied stripes were observed. C: Strong shrinkage spots or coating streaks were observed. &lt;Slit coating suitability&gt; Coating property (11)

The composition of the present invention is applied to a aluminum (AI) film having a film thickness of 4000 angstroms by using a slit coater photoresist coating device for a large substrate coating (head coating machine system manufactured by Hirata Kogyo Co., Ltd.). A photoresist film having a film thickness of 3.0/m was formed on a glass substrate (550 mm x 650 mm) having a thickness of 0.7 mm and a thickness of 0.7 mm, and the presence or absence of the unevenness of the ribs exposed in the longitudinal and lateral directions was observed, and the evaluation was carried out as follows. A: No unevenness was observed. B: A slight unevenness was observed. C: Unevenness was observed clearly, or it was observed in the photoresist film. -86-200846824 Constriction &lt;Etchability&gt; After the composition of the present invention is patterned and hardened on the aluminum (AI) formed on the glass substrate, the aluminum thin film is uranium-etched by a phosphorus-nitric acid etchant, and visually and microscopically observed at 10 /zm. Line (line) / interval (space) (I ine / sapce), as evaluated below. A : Obtain an aluminum wire with a line width of 1 0 ± 2.0 /z m B : A line with a line width deviation exceeding ± 2.0 μ m

C: The defective part of the line exists partially, or part of the line is entangled together D: the entire defective part exists, or the line is entangled together>Comprehensive evaluation> The comprehensive evaluation is as follows Benchmarking. In essence, the B level is practically tolerable. A : B grade is less than one item. B : B grade is 2 items. C : The case where the B level is 3 or more, or the C level is 1 item. D _· The case where the D level is one item. Synthesis Example 1 · Surface treatment of colloidal cerium oxide; Synthesis of CS-3 120 g of isopropyl alcohol, Nalcoag 1 034A (manufactured by Nalco Chemical Co., 35% colloidal cerium oxide aqueous dispersion) 60.6 g, γ-A A mixture of propylene methoxy propyl trimethoxy decane 5.8 g was heated at 80 ° C for 'reflow for 3 hours, and the solvent was distilled off to a half degree under reduced pressure' and then 1 4 was added to the solution. 0 g of propoxyethanol and the solvent was distilled off to obtain 30 masses of ethoxybutanol of the surface ceria-treated ceria. /〇溶 -87 - 200846824 Liquid (CS-3). Synthesis Example 2: Surface treatment of colloidal cerium oxide; Synthesis of CS-4 • Heating of 5 butyl butanol, heart 1 〇〇 39 1034 八 16_69, 7-methyl propylene methoxy propyl trimethoxy After the mixture of decane 1 · 4 9 was refluxed for 5 minutes*, the solvent was distilled off under reduced pressure to a half degree 'and then 14 4 g of propoxyethanol was added to the solution to distill off under reduced pressure. a solvent to obtain a 30% by mass solution of ethoxybutanol having a surface treated with a decane compound (CS-4) 〇© Synthesis Example 3: surface treatment of colloidal cerium oxide; synthesis of CS-5 is provided In a flask of a stirrer, a condenser, and a thermometer, 63.0 g of hydrazine PA-ST (isopropyl alcohol dispersed colloidal cerium oxide sol, manufactured by Nissan Chemical Industries Co., Ltd., cerium oxide particle size: 15 nm, cerium oxide solid content 30) was added. (% by mass) and 〇. 2 parts as a polymerization inhibitor Μ EHQ, 50 g of a dilute hydrochloric acid aqueous solution as a hydrolysis catalyst, and the temperature of the water bath was raised to 80 ° C while stirring. At the same time as the reflux was started, γ-acryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: φ 503, molecular weight 290), 11.7 g, trimethyl methoxy decane was dropped for 30 minutes. (Shin-Etsu Chemical Industry Co., Ltd., trade name LS - 5 10 0, molecular weight 1 0 4) 1 · 6 g of the mixed solution, after the end of the dropwise addition, it was stirred by heating for about 2 hours to be dispersed in isopropanol. 'To obtain a 30% by mass solution of ceria having a surface treated with a decane compound (C s - 5 &gt; Synthesis Example 4: Surface treatment of colloidal ceria; synthesis of cs_6 in a solid content of 20.0 mass%. Methanol dispersion colloidal silica sand 2 0.0g, trimethyl methoxy decane (Toray DOW CORNING Co., Ltd.) 〇.6g was added, and heated and stirred in 6CTC for 3 hours. Subsequently, methoxy group was added. 88- 200846824 14.0 g of propanol was concentrated at a temperature of 80 ° C to obtain a dispersed colloidal cerium oxide (CS-6) having a solid content of 30% by mass. Synthesis Example 5: Colloidal cerium oxide Surface treatment; synthesis of CS-7 in PL-1-IPA (isopropyl alcohol dispersed colloidal oxygen) 300, Fuso Chemical Industry Co., Ltd., ruthenium dioxide solids (12.5 wt%) 300 g, isopropanol 12 00 g and acetic acid 15 g, r propylene methoxy propyl trimethoxy decane 9.20 g and η-hexyl 8.20 g of trimethoxydecane and heated to reflux.

Thereafter, isopropyl alcohol was distilled off to obtain a surface-treated cerium oxide (CS-7) having a solid content of 12% by mass and dispersed. Synthesis Example 6: Surface treatment of colloidal cerium oxide; synthesis of CS-8 in ME K-ST (methyl ethyl ketone dispersed colloidal cerium oxide, manufactured by Nissan Chemical Industries Co., Ltd., cerium oxide solid content 30% by weight In 3 Og, 200 g of methyl ethyl ketone and 2.0 g of dilute hydrochloric acid aqueous solution and 2.5 g of methacryloxypropyltrimethoxydecane were added, and heated under reflux to obtain surface-treated cerium oxide (CS-8). . Synthesis Example 7: Surface treatment of colloidal cerium oxide; Synthesis of CS-9 In 300 g of methanol, 20% by weight of a solid component of cerium oxide, methanol dispersed colloidal cerium oxide 1 〇〇g, formic acid 5.0 g, r - 2.60 g of acryloxypropyltrimethoxydecane 1·〇〇9 and n-decyltrimethoxydecane were stirred at room temperature for 24 hours. Subsequently, methanol was distilled off while being superheated to 80 °, and 80 g of methyl isobutyl ketone was added thereto to obtain methyl isobutyl ketone dispersed surface-treated cerium oxide (CS-9). Synthesis Example 8: Surface treatment of colloidal cerium oxide; synthesis of CS-1 0 In 91 _3 g of IPA-ST, 1% aqueous acetic acid solution was added 1. 〇g and 7-acryloxypropyltrimethoxy decane 8.3 After 5 g, and heating back to -89-200846824 over 3 hours, hexamethyldioxanylamine 1.47 g' was added and then heated under reflux for 1 hour to obtain a surface-treated cerium oxide (CS-1 oxime). Example 1 'Grain scale as a polymerizable unsaturated monomer γ-butyrolactone acrylate mono-body (R-01) 19.096 g, tripropylene glycol diacrylate monomer (S-04) 66·84 g, ethylene oxide modified trimethylolpropane triacrylate monomer (S-1 1 ) 9.548g, as a photopolymerization initiator 2,4,6-trimethylbenzylidene-B Oxyphenyl-phosphine oxide (Lucirin β Τ Ρ Ο - L manufactured by BASF Corporation) ( P · 1 ) 2 · 50 g, and EFT〇P EF-122A (fluorine-based surfactant, as a surfactant) W-1) 0.02 g, colloidal cerium oxide (manufactured by Nissan Chemical Industries, Ltd.: Ml BK-ST, 30% methyl isobutyl ketone solution) 6.67 g, stirred at room temperature until methyl ethyl ketone was lower than 2 quality. /〇, forming a homogeneous solution. The composition ratio of the polymerizable unsaturated monomer used herein is shown in Table 1, and the solid content blend ratio of the composition is shown in Table 2. The adjusted composition was applied onto a glass substrate having a thickness of 4 inches and 0 -7 m of an aluminum (A I) film having a film thickness of 400 Å to form a thickness of φ 5 · 0 # m. The spin-coated coating base film was placed in a nano-printing device using a high-pressure mercury lamp (optical power 2000 mW/cm 2 ) manufactured by 〇R c Co., Ltd., and a vacuum of 0.8 k N was applied from the mold. Polydimethyl phthalal oxide of 1 # To rr with a row/space pattern of 10 0 m and a groove depth of 5 · 0 // m (made by Toray DOW CORNING, SILPOT184 is hardened by 80 ° C for 60 minutes) The back surface of the mold of the material was exposed to a condition of 100 mJ/cm 2 , and after exposure, the mold was removed to obtain a photoresist pattern. Next, the aluminum (AI) portion which is not coated with the photoresist is removed by a phosphorus-nitric acid etchant to form an electrode pattern made of aluminum (AI). Then, the photoresist stripping -90-200846824 was carried out using a monoethanolamine/dimethyl hydrazine mixed stripping solution, and immersing treatment at 80 ° C for 3 minutes. The results are shown in Table 3. According to the results of Table 3, the composition of the present invention can satisfy the adhesion, peeling property, residual film property, pattern shape, coating property (spin coating property, slit coating property), and etching property. Characteristics. Example 2 As a polymerizable unsaturated monomer, α-propenyloxy-^,/3-dimethyl-γ-butyrolactone monomer (R-2) 38.11 g, hydroxytrimethylacetic acid 47.74 g of neopentyl sulphide diacrylate monomer (S-2), 9.547 g of propylene oxide modified trimethylolpropane triacrylate (S-1 2), and 2 as a photopolymerization initiator. 4,6-trimethylbenzimidyl-ethoxyphenyl-phosphine oxide (Lucirin TP〇-L manufactured by BASF Corporation) (P-1) 2_5g, manufactured by Dainippon Ink Chemical Industry Co., Ltd. as a surfactant MEGAFAC R-08 (fluorine-antimony surfactant) (W-3), and surface treated colloidal ceria 30% by mass solution 6.6 7 g 'stirred at room temperature until methyl ethyl ketone is less than 2 % by mass to form a homogeneous solution. This composition was exposed and patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 3. According to the results of Table 3, it is considered that the composition of the present invention comprehensively satisfies adhesion, peelability, residual film property, pattern shape, coatability (spin coating property, slit coating property), and etching property. Example 3 to Example 2 7 In the same manner as in Example 1, the polymerizable unsaturated single system was mixed at a ratio shown in Table 1, and the composition described in Table 2 was adjusted. The adjusted 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. Example 3 to 2 7 -91 - 200846824 The composition of each of them satisfies all of photocurability, adhesion, peelability, residual film property, pattern shape, and coatability (spin coating property, slit coating property) ), . * The composition described in the fourth embodiment of the ultraviolet curable coating material for a disc protective film disclosed in Japanese Laid-Open Patent Publication No. Hei No. 7-7749, is the same as that of the first embodiment of the present invention. The polymerizable unsaturated single system was mixed at a ratio shown in Table 4, and adjusted to the composition shown in Table 5. The composition adjusted by φ was patterned in the same manner as in Example 1 to adjust the characteristics of the composition. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 1 was not synthesizable in all of its characteristics. In the same manner as in the first embodiment of the present invention, the composition described in the examples of the optical disk overcoat layer composition disclosed in Japanese Laid-Open Patent Publication No. Hei-4-149280, the polymerizable unsaturated single system. The mixture was mixed in the ratio shown in Table 5, and the composition was adjusted. The adjusted composition was patterned in the same manner as in Example 1 and the characteristics of the composition were investigated. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 2 was not synthesizable to satisfy various characteristics. Comparative Example 3 The composition described in Example 1 of the protective coating composition disclosed in Japanese Laid-Open Patent Publication No. Hei 7-62043 was carried out in the same manner as in Example 1 of the present invention, and a polymerizable unsaturated monomer was used. The mixture was mixed at -92-200846824 in the ratio shown in Table 5, and the composition was adjusted. The adjusted composition was patterned in the same manner as in Example 1, and the characteristics of the composition were investigated. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 3 was not synthesizable enough to satisfy each of the * characteristics. Comparative Example 4 The composition described in Comparative Example 2 of the protective coating composition disclosed in JP-A No. 200 1 -93 1 92 was carried out in the same manner as in the example of the present invention, and polymerizability was carried out. The unsaturated single system was mixed 'in the proportions shown in Table 5' and the composition was adjusted. The adjusted composition was patterned in the same manner as in Example 1, and the characteristics of the composition were investigated. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 4 was not synthesizable in all of its characteristics. In the same manner as in the first embodiment of the present invention, the composition described in the second embodiment of the ultraviolet ray and the electron beam φ-curable composition disclosed in Japanese Laid-Open Patent Publication No. Hei. The polymerizable unsaturated single system was mixed 'in the proportions shown in Table 5' and the composition was adjusted. The adjusted 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 6. As shown in Table 6, the composition of Comparative Example 5 is not synthesizable in addition to the residual film property, the pattern shape, the coatability (I), and the etching property. The composition described in Example 1 of the protective coating composition disclosed in Japanese Laid-Open Patent Publication No. Hei 7-53895 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability was not The saturated single system was mixed in the proportions shown in Table 5, and the composition was adjusted. The adjusted composition was patterned in the same manner as in Example 1 and the characteristics of the composition were investigated. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 6 was not synthesizable in all of its characteristics. Comparative Example 7

The composition described in Example 1 of the coating composition disclosed in Japanese Patent Publication No. 2 0 0 3 -1 6 5 9 3 0 was subjected to 'polymerization unsaturated' in the same manner as in Example 1 of the present invention. The single system was mixed in the ratios shown in Table 5, and the composition was adjusted. The adjusted 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 6. As shown in Table 6, the composition of Comparative Example 7 was not synthesizable except for adhesion, residual film properties, pattern shape, and etching property. ΦComparative Example 8 The composition of NVP (N-vinylpyrrolidone) described in the "Investigation of the Beginning of the Beginnings Book 38" by the Industrial Research Society and the 2005 issue, N-N-vinylpyrrolidone, is implemented in accordance with the present invention. Example 1 was similarly patterned, and the composition characteristics were investigated. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 8 was not synthesizable except for the coating property and the etching property. The composition (viscosity 3 5cP) ' described in Example 5 of the composition for hard coating resin-94-200846824 disclosed in JP-A-2006-63244 is the same as that of Example 1 of the present invention. The manner in which the 'polymerizable unsaturated single system was mixed in the ratio shown in Table 5' was carried out and the composition was adjusted. The adjusted composition was patterned in the same manner as in Example 1 and the characteristics of the composition were investigated. The results are shown in Table 6. As shown in Table 6, in addition to the deterioration of coatability, it is not synthesizable to satisfy various characteristics. Comparative Example 1 0

Photonic printing composition disclosed in Proc. SPiE Int. Soc. Opt. Eng., Vol. 61 51 , No. Pt2, 6 1 5 1 2F (2 0 0 6 ) (sample name: KRIP - 0 9 The viscosity of 8.2 9 cP) was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated single system was mixed at a ratio shown in Table 5, and the composition was adjusted. Since the specific chemical name of the (meth)acrylic monomer is not described in this document, a commercially available monomer can be arbitrarily selected to adjust the composition. The monofunctional single system can select an acrylic monomer, a bifunctional single system can select a (meth)acrylic acid monomer, and a trifunctional single system can select an acrylic monomer. The photopolymerization initiator ^ was compounded with the compound disclosed in the literature (DAROCURE 4265) 1 · 25 %. Since the surfactant is not incorporated in this document, it is not blended. As shown in Table 6, the composition of the comparative example 1 was inferior to the peelability and the coating property (H>, and it was not synthesizable to satisfy the respective characteristics. Comparative Example 1 1

Photonic printing composition disclosed in Proc. SPiE Int. Soc. Opt. Eng., Vol. 61 51 , No. Pt2, 61 512F (2 0 0 6) (sample name: κ RI p -1 1, The viscosity 9.7c P) was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated single system was mixed in the proportions shown in Table 5, and the composition -95 - 200846824 was adjusted. Since the specific chemical name of the (meth)acrylic monomer is not described in this document, a commercially available monomer can be arbitrarily selected to adjust the composition. 1 functional. The single system can select acrylic monomer, the bifunctional single system can select methacrylic acid monomer, and the trifunctional single system can select acrylic monomer. The photopolymerization initiator was blended with the compound disclosed in the literature (DAROCURE 4265) 1.25%. Since the surfactant is not incorporated in this document, it is not blended. As shown in Table 6, the composition of Comparative Example 1 1 was not synthesizable except for the difference in peelability and coatability (Π). • Comparative Example 1 2 The monofunctional polymerizable unsaturated monomer of the present invention (a moiety having an ethylenically unsaturated bond in the molecule and a monofunctional polymerizable unsaturated having at least one of an oxygen, a nitrogen, or a sulfur atom) A monomer-specific α-methylstyrene (reagent) was used as a monofunctional polymerizable unsaturated monomer in place of the oxime functional monomer of Example 9, and was carried out in the same manner as in Example 1 of the present invention. The polymerizable unsaturated single system was mixed in the proportions shown in Table 5, and the composition was adjusted. However, in Comparative Example 12, inorganic oxide particles were not added. The adjusted composition of 0 was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 6. As shown in Table 6, the composition of Comparative Example 1 2 was not able to exhibit various characteristics in addition to photocurability, residual film property, and pattern shape. Comparative Example 1 3 Surface-treated silica (CS_3) was blended in the composition used in Comparative Example 12 in the same manner as in Example 1 of the present invention, and the composition was adjusted. The adjusted 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 6. -96- 200846824 As shown in Table 6, the composition of Comparative Example 13 is not synthesizable to satisfy various characteristics.

-97- 200846824

Polymerizable Unsaturated Monomer 1 Functional 2 Functional 3 Functional More Example 1 R-01(20) S-04(70) S-11(10) Example 2 R-02(40) S-02(50) 8 -12(10) Example 3 R-03(10) R-11(20) S-02(50) 8-12(20) Example 4 R-04(50) S-03(40) S-13 (10) Example 5 R-05(40) S-05(50) S-14(10) Example 6 R-06(35) S-04(60) S-13(5) Example 7 R- 07(15) R-12(15) S-04(65) S-11(05) Example 8 R-08(30) S-04(60) S-12(10) Example 9 R-09( 60) S-02(30) S-11(10) Example 10 R-10(50) S-03(10) S-12(40) Example 11 R-11(65) - S-11(25 S-14(10) Example 12 R-12(50) S-04(30) 8-12(20) Example 13 R-13(20) R-19(20) S-05(30) S -11(30) Example 14 R-14(10) R-12(20) S-02(50) S-12(20) Example 15 R-15(45) S-03(15) S-04 (25) S-11(15) Example 16 R-16(40) S-05(30) S-12(30) Example 17 R-17(40) S-04(40) S-12(20 Example 18 R-18(20) R-12(35) S -03(35) S-11(10) Example 19 R-19(20) R-12(20) S-03(50) S -12(10) Example 20 R-20(10) R-12(30) S-02(45) S-11(15) Example 21 R-21(10) R-11(30) S-02 (40) S-12(20) -98- 200846824

Example 22 R-22(50) 8-04(30) 8-11(10) S-13(10) Example 23 R-12(20) R»23(5) S-04(50) 8- 12(25) Example 24 R-22(40) R-23(10) R-30(5) 8-04(35) S-12(5) S-14(5) Example 25 R-15( 30) R-12(20) S-04(25) S-01(5) S_11(20) Example 26 R-12(20) R-26(20) 8-04(50) S-12(10 Example 27 R-11(15) R-25(10) S-02(60) S-12(15) Example 28 R-09(60) S-02(30) S-11(10) Implementation Example 29 R-13(20) R-19(20) 5-05(30) S-11 (30) Example 30 R-03(10) R-11(20) S-02(50) S-12 (20) Example 31 R-12(50) S-04(30) S-12(20) Example 32 R-05(40) S-05(50) S-14(10) Example 33 R- 16(40) S-05(30) 3-12(30) Example 34 R_18(20) R-12(35) S-03(35) S-11(10) Example 35 R-15(45) S-03(15) S-04(25) S-11(15) The inside of the formula () shows the mass % relative to the total amount of the polymerizable unsaturated monomer. -99- 200846824

Table 2 Polymerizable unsaturated monomer η Inorganic oxide particle photopolymerization initiator Surfactant, additive Example 1 (95.48) CS-0K2.0) P-1 (2.5) W-K0.02) Example 2 (95.47) CS-02(2.0) P-1 (2.5) W-3(0 03) Example 3 (89.95) CS-03(5.0) P-2(5.0) W-2(0.05) Example 4 ( 89.70) CS-04(7.5) P-1 (2.5) W-3(0.20) A-1(0.10) Example 5 (93.65) CS-05(2.0) P-2(4.0) W-4(0.30) A-2 (0.05) Example 6 (85.20) CS-03 (10.0) P-3 (4.5) W-1 (0.15) W-2 (0.15) Example 7 (82.70) CS-04 (12.5) P- 7(4.5) W-K0.30) Example 8 (88.90) CS-05(50) P-2(3.5) W-4(0.50) A-5(0.10) Example 9 (91.20) CS-03( 2.5) P-3(6.0) W-3(0.30) Example 10 (91.50) CS-01(2.0) CS-02(1.5) P-5(4.5) W-1(0.50) Example 11 (79.30) ' CS-04(15.0) P-4(5.5) W-4(0.20) Example 12 (73.40) CS-03(20.0) P-2(6_5) W-4(0.10) Example 13 (88.60) CS -04(5.0) P_4(6.0) W-3(0.20) A-7(0_20) Example 14 (89.45) CS-05(7.5) P-6(3.0) W-3(0_05) Example 15 (86.80 CS-04(10.0) P-1(3.0) W-1(0.10) W-2(0.10) Example 16 (84.94) CS-03(12.5) P-2(2_5) W-3(005) A -4 (0.01) Example 17 (84.49) CS-01(2.5) CS-03(10.0) P-2(2.0) P-3(1.0) W-4(0.01) Example 18 (79.70) CS-04(15.0) P- 1(5.0) W-1(0.30) Example 19 (84.50) CS-03(10.0) P-3(5.0) W-4(0.20) A-K0.30) Example 20 (90.80) CS-02( 2.5) P-1 (3.0) P-8(3.0) W-3(0.10) A-2(0.60) Example 21 (87.90) CS-04(7.5) P - 2(4.0) W-1(0.30) A-6(0.30) -100- 200846824

Example 22 (69.10) CS-03(25.0) P-1 (4.5) Ρ-7Π.0) W-3(0.10) A-2(0.30) Example 23 (87.97) CS-03(7.5) P- 2(4.5) W-4(0.01) A-3(0.02) Example 24 (91.80) CS-06(2.5) P-1 (4.0) P-2(1.5) W-3(0.20) Example 25 ( 91.00) CS-04(5_0) P-3(3.5) W-2(0.50) Example 26 (86.80) CS-04(10.0) P-1(3.0) V\M(0.10) W-2(0.10) Example 27 (93.30) CS-03(2.5) P-3(4.0) W-3(0.20) Example 28 (91.20) CS-07(2.5) P-3(6.0) W-3(0_30) Example 29 (88.60) CS-08(5.0) Ρ·4(6·0) W«3(0.20) A-7(0.20) Example 30 (92.95) CS-09(5.0) P-2(2.0) W- 2 (0.05) Example 31 (73.40) CS-07 (20.0) P-2 (6.5) W-4 (0.10) Example 32 (93.65) CS-10 (2.0) P-2 (4.0) W-4 ( 0.30) A-2 (0.05) Example 33 (84.94) CS-08 (12.5) P-2 (2.5) W-3 (0.05) A-4 (0.01) Example 34 (79.70) CS-09 (15.0) P-1 (5.0) W-1 (0.30) Example 35 (86.80) CS-10 (10.0) P-1 (3.0) W-1 (0.10) W-2 (0.10) Γ) Use the conditions described in Table 1. Polymeric Unsaturated Monomer - 1 0 1 - 200846824 Table 3

Photocurable adhesive peelable residual film pattern shape coatability (I) Coating property (H) Overall evaluation of the etching property Example 1 BAAAAAAAA Example 2 BBAAAAAAB Example 3 AAAAAAAAA Example 4 AAAAAAAAA Example 5 AAAAAAAAA Example 6 ABAAAAAAA Embodiment 7 BAAAAAAAA Embodiment 8 ABAAAAAAA Embodiment 9 AAAAAAAAA Embodiment 10 BAAAAAAAA Embodiment 11 AAAAAAAAA Embodiment 12 AAAAAAAAA Embodiment 13 AAAAAAAAA Embodiment 14 AAAAAAAAA Embodiment 15 AAAAAAAAA Embodiment 16 AAAAAAAAA Embodiment 17 AAAAAAAAA Embodiment 18 AAAAAAAAA Implementation Example 19 AAABAAAAA Embodiment 20 AAABAAAAA Embodiment 21 AABAAAAAA Embodiment 22 AAABAAAAA Embodiment 23 AAAAAAAAA Embodiment 24 AAABAAAAA Embodiment 25 AAABAAAAA Embodiment 26 AABAAAAAA Embodiment 27 AAABAAAAA Embodiment 28 AAAAAAAAA Embodiment 29 AAAAAAAAA Example 30 AAAAAAAAA Example 31 AAAAAAAAA Example 32 AAAAAAAAA Example 33 AAAAAAAAA Example 34 AAAAAAAAA Example 35 AAAAAAAAA -102· 200846824 Table 4 (Meth)acrylic monomer 1-functional 2-functional 3-functional or higher Comparative Example 1 R- 27(25.0) 8-02(35.0) S-01(0.10) S-11(40.0) Comparative Example 2 R-01(10.8) S-04(32.2) S-15(57.0) Comparative Example 3 - S-07 (16.5) S-06(16.5) S-0K0.1) S-15(67.0) Comparative Example 4 R-27(20.0) S-04(20_0) S-11(60.0) Comparative Example 5 R-28(70.0 ) R-21(30.0) I - Comparative Example 6 R-27(20.0) S-05(50.0) S-01(0.1) S-11(30.0) Comparative Example 7 R-15(35.0) S-17( 5.0) S-08(60.0) - Comparative Example 8 R-11(29.0) S-04(57) S-15(10) Comparative Example 9 R-27(15.0) S-09(18.75) S-13(25.0 S-11(41.25) Comparative Example 10 R-26(47.37) S-19(26.32) S-11(26.32) Comparative Example 11 R-26(67.74) S-10(16.12) S-11(16.12) Comparison Example 12 R-29(60.0) S-02(30.0) S-11(10.0) Comparative Example 13 R-29(60.0) S-02(30.0) S-11(10.0)

The inside of the table indicates the mass % relative to the total amount of the polymerizable unsaturated monomer.

-1 0 3 - 200846824

Table 5 (Meth)acrylic monomer (*) Inorganic oxide particle photopolymerization initiator Surfactant, additive Comparative Example 1 93.0% - Ρ-03 (7.0 ° / 〇) A comparative example 2 93.0% - Ρ -08 (7.0%) - Comparative Example 3 89.6% - Ρ-08 (7.9%) W-5 (0.5%) Α-4 (1·0%) Α-5 (1.0%) Comparative Example 4 95.2% - Ρ -03 (4.8%) W-6 (0.01%) Comparative Example 5 99.8% One Ρ-08 (0.2%) One Comparative Example 6 92.6% — Ρ-08 (4.6%) A-6 (0.9%) Α-7 (1·9%) Comparative Example 7 947% One Ρ-07 (4.7%) Α-8 (0·1%) Α-9 (0.5%) Comparative Example 8 96.0% — Ρ-2 (4.0%) — Comparison Example 9 73.9% CS-03 (20.0%) Ρ-03 (6.0°/〇) Α-10 (0.1%) Comparative Example 10 93.83% CS-03 (4.94%) Ρ-04 (1.23%) A comparative example 11 76.55% CS-03 (22.22 ° / 〇) Ρ -04 (1·23%) - Comparative Example 12 93.54% One Ρ-3 (6_15%) W-3 (0.308) Comparative Example 13 88.54% CS-03 (5.0 %) Ρ-3 (6.15%) W-3 (0.308) Γ) Using the polymerizable unsaturated monomer described in Table 4

Table 6 Photocurable adhesive peeling residual film shape pattern coating property (1) Coating property (II) Comprehensive evaluation of etching property Comparative Example 1 BABAABBAC Comparative Example 2 BBAAABBBC Comparative Example 3 AAABBABB c Comparative Example 4 BBBAAAAB c Comparative Example 5 BAACCCBC c Comparative Example 6 ABBAAABB c Comparative Example 7 ACACCBAC c Comparative Example 8 ABAAACCDD Comparative Example 9 AAAABCCBC Comparative Example 1 〇 AACAABCAC Comparative Example 11 AACAABCAC Comparative Example 12 CAACCAABC Comparative Example 13 BAABBAABC -104- 200846824 &lt;Evaluation of Photocurable Composition - η &gt; The composition of the present invention was evaluated as a permanent film (protective film). &lt;Residual Film Rate&gt; 旋转 The film thickness of 4 μ m of the photocurable composition of the present invention is spin-coated on a glass substrate, and a nano-printing device using a high-pressure mercury lamp as a light source is provided, from the back of the mold The exposure was carried out under conditions of 500 mJ/cm 2 , and after exposure, the mold was removed from the mold and heated in an oven at 230 ° C for 150 minutes. The film thickness of the photocurable resin pattern portion before and after heating was measured by Φ PROFILER - P11 manufactured by Tenkor Co., Ltd. to determine the residual film ratio after heating. The results are not shown in Table 7. A: residual film ratio exceeding 90% B: residual film ratio 8 5 to 9 0 % C : residual film ratio lower than 8 5 % &lt;transmittance&gt; Spin coating of the photocurable composition of the present invention on a glass substrate A film thickness of 4 // m was set, and a nano-printing device φ with a high-pressure mercury lamp as a light source was placed, and ultraviolet rays were exposed from the back surface of the mold at 500 mJ/cm 2 to form a cured film. After exposure, the mold was removed and heated in an oven at 230 ° C for 1 50 minutes. The light transmittance of the photocurable resin pattern portion after heating was measured by a spectrophotometer, and the light transmittance (T / %) at a wavelength of 550 nm was measured to obtain the transmittance after heating. The obtained light transmittance was judged based on the following criteria. The results are shown in Table 7. A: The light transmittance is more than 90%. B: The light transmittance is from 8 5 to less than 90%. C: The light transmittance is lower than 8 5 . -105- 200846824 &lt;Scratch resistance test&gt; After the photocurable composition was spin-coated on a ruthenium wafer, ultraviolet light was irradiated with a high-pressure mercury lamp to have an exposure amount of 3 〇〇mJ/crn2 to form a thickness of 5 μ. a hardened film of m. The hardened film was placed on a vibration-type abrasion tester, and a load of 200 g was applied to the steel wool for 1 round trip. The condition of the scratch is determined by the naked eye according to the following criteria. The results are shown in Table 7. A: No scars at all

B: Scars with 1 to 3 strips C: Scars with 4 to 10 strips D: Scars with 10 or more strips &lt;Solvent resistance&gt; The photocurable composition of the present invention is spin-coated to glass A nano-printing device with a high-pressure mercury lamp as a light source formed on the substrate with a film thickness of 4 μm is exposed from the back surface of the mold to a condition of 500 m J / c m 2 , and after exposure, the mold is removed from the mold. , heated in an oven at 230 ° C for 150 minutes. After heating, it was immersed in each solution of N-methylpyrrolidone (Ν Μ P ), 5% sodium hydroxide, and 5% HCl hydrochloric acid for 30 minutes to obtain a change in film thickness before and after immersion. The results are shown in Table 7. A: No change in film thickness was observed (less than 1%). Change in film thickness was observed slightly (1 to less than 5%). C: Change in film thickness (5 % or more) was observed slightly. <Comprehensive evaluation> Comprehensive evaluation It is based on the following criteria. Substantial B level or above is practically competent. The results are shown in Table 7. A : B grade is less than 2 items. -106- 200846824 B : B grade is 3 items. C : B grade is 4 or more, or C grade is 1 item. • D: The C level is 2 or more, or the D level is 1. [Example 36] The type, the blending ratio of the monomer, the photopolymerization initiator, the surfactant, and the inorganic oxide particles used in Example 3 were not changed, and 2 masses were added to the composition. /. The antioxidant (ADKA STAB AO503, manufactured by ADEKA) was adjusted in the same manner as in Example 1. The adjusted φ composition was spin-coated on a glass substrate to form a film thickness of 4 # m, and the coated base film which was spin-coated was placed on a high-pressure mercury lamp (optical power: 2000 mW/cm 2 ) manufactured by Ο RC Co., Ltd. The nano-printing device of the light source is a polydimethyl methoxy oxane (manufactured by Toray DOW CORNING Co., Ltd.) having a mold pressure of 1 〇 kN/cm 2 and a vacuum degree of 〇 2 Torr during exposure and having a square pattern of 5 mm. The back surface of the mold of the material of SILPOT1 84 at 80 ° C and cured for 60 minutes was exposed to a condition of 500 m J / cm 2 , and after exposure, the mold was removed from the mold and the light before and after heating was measured. The residual film ratio, the transmission φ ratio, and the scratch resistance of the curable resin pattern portion. Subsequently, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 7. The composition of Example 36 was excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and was excellent in properties as a permanent film. Example 3 7 The monomer, photopolymerization initiator, surfactant, inorganic oxide particle type, blend ratio used in Example 7 were not changed, and 2% by mass of anti-intrusion was strongly applied to the composition. The oxidizing agent (made by ADECA, ADKSTAB AO503) was adjusted in the same manner as in Example 1. The adjusted composition was spin-coated on a glass substrate to form a film of -4 m thickness -107-200846824 thick, and the coated base film was spin-coated by a high-pressure mercury lamp manufactured by ORC Co., Ltd. (optical power 2000 mW/ Cm2) is a nano-printing device for light source, from a mold pressure of 10 kN/cm2, a vacuum of 〇.2 Torr during exposure, and a polydimethyl methoxyoxane having a 5 mm square pattern (Dongli) DOW - CORNING company's SILPOT184 is cured at 80 °C and cured for 60 minutes. The surface of the mold is exposed to 500 m J/cm2. After exposure, it is separated from the mold and measured before and after heating. The residual film ratio, transmittance, and scratch resistance of the photocurable resin pattern portion. Subsequently, the φ solvent resistance of the photohardenable film was investigated. The results are shown in Table 7. The composition of Example 3 is excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and is also excellent in properties as a permanent film. Example 3 8 The monomer, photopolymerization initiator, surfactant, inorganic oxide particle type, blend ratio used in Example 15 were not changed, and 2.0% by mass of an antioxidant was added to the composition. (Sumitomo Chemical Co., Ltd., SUM丨LIZER - GA80), in the same manner as in the first embodiment, the group φ product was adjusted. The adjusted composition was spin-coated on a glass substrate to form a film thickness of 4 // m, and the spin-coated coated base film was placed on a high-pressure mercury lamp manufactured by ORC Co., Ltd. (optical power 20 00 m W/cm 2 ). A nano-printing device that is a light source, from a mold with a mold pressure of 1 〇 kN/cm 2 , a vacuum of 0.2 Torr during exposure, and a polydimethyl methoxyoxane having a 5 mm square pattern (Dongli DOW CORNING Co., Ltd.) The back surface of a mold made of SILPOT 184 at 80 ° C for 60 minutes was exposed to 500 mJ/cm 2 , and after exposure, the mold was removed from the mold, and the photocurable resin pattern portion before and after heating was measured. Residual film rate, transmittance, and scratch resistance. Subsequently, the solvent resistance of the film of the hard film -108-200846824 was investigated. The results are shown in Table 7. The composition of Example 3 8 was excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and was excellent in film properties. Example 3 9 &quot; The type, the blending ratio of the monomer, photopolymerization initiator, surfactant, inorganic oxide particles used in Example 1 7 were not changed, and 2.0 mass was added to the composition. /. The antioxidant (S U Μ I LI Z E R - G A 8 0 manufactured by Sumitomo Chemical Co., Ltd.) was adjusted in the same manner as in Example 1. φ The adjusted composition was spin-coated on a glass substrate to form a film thickness of 4 M m, and the coated base film which was spin-coated was placed on a high-pressure mercury lamp (optical power 2000 mW/cm 2 ) manufactured by Ο RC Co., Ltd. The nano-printing device of the light source is a polydimethyl methoxy oxane (manufactured by Toray DOW CORNING Co., Ltd., SILPOT1) having a mold pressure of 10 kN/cm 2 and a vacuum degree of 〇 2 Torr during exposure. 84. The back surface of the mold of the material which was cured at 80 ° C for 60 minutes was exposed to 500 mJ/cm 2 , and after exposure, the mold was removed, and the photocurable resin pattern φ portion before and after heating was measured. Residual film rate, transmittance, and scratch resistance. Subsequently, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 7. The composition of Example 39 was excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and was also excellent in properties as a permanent film. Example 4 0

The kind of the monomer, the photopolymerization initiator, the surfactant, the inorganic oxide particles, the sensitizer, and the blending ratio used in Example 19 were not changed, and 0.5 mass was added to the composition. /. The antioxidants (manufactured by Sumitomo Chemical Co., Ltd., SUMILIZER - GA80: 2.0% by mass, manufactured by ADEKA, ADKSTAB-109-200846824 A 503) were adjusted in the same manner as in Example 1. The adjusted composition was spin-coated on a glass substrate to form a film of 4 #m. The film was coated with a high-pressure 'mercury lamp (optical power 2000 mW/cm2) manufactured by 〇RC Co., Ltd. by spin coating. The nano-printing device for the light source is a polydimethyl methoxyoxane (Toray DOW CORNING Co., Ltd.) with a mold pressure of 1 OkN/cm2, a vacuum of 〇2 Torr during exposure, and a 4 mm square pattern. The back surface of a mold made of SILPOT1 84 at 80 ° C and cured for 60 minutes was exposed to 50 0 m J/cm 2 , and after φ exposure, the mold was removed from the mold and the photohardening before and after heating was measured. The residual film ratio, transmittance, and scratch resistance of the resin pattern portion. Subsequently, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 7. The composition of Example 40 was excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and was also excellent in properties as a permanent film. Example 4 1 The monomer, photopolymerization initiator, surfactant, inorganic oxide particles, sensitizer type, blend ratio used in Example 22 were not changed, and φ was added to the composition at a mass of 2.0. % of the antioxidant (Sumitomo Chemical Co., Ltd., SUMILIZER - GA8 0) was adjusted in the same manner as in Example 1. The adjusted composition was spin-coated on a glass substrate to form a film thickness of 4 // m, and the coated base film was subjected to spin coating to a high-pressure mercury lamp (optical power 2000 mW/cm 2 ) manufactured by RC RC Co., Ltd. A nano-printing device for a light source, which is a polydimethyl siloxane having a mold pressure of 10 kN/cm 2 and a vacuum degree of 0.2 Torr during exposure and having a square pattern of 5 mm (Dongly Dow CORNING Co., Ltd. The back surface of the mold of SILPOT 184 which was cured at 80 ° C for 60 minutes was exposed to -110-200846824 under conditions of 500 mJ/cm 2 , and after exposure, the mold was removed from the mold and the photocurable resin before and after heating was measured. The residual film ratio, transmittance, and scratch resistance of the pattern portion. Subsequently, the solvent resistance of the hard film was investigated. The results are shown in Table 7. The composition of Example 4 1 was excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and was excellent in film properties. Example 42 As a polymerizable unsaturated monomer, benzyl acrylate monomer (R-26) 28 g, neopentyl glycol diacrylate monomer (KAYARAD NPGDA; Φ Nippon Kasei Co., Ltd.) 22_0 g, trihydroxyl Methylpropane triacrylate monomer (S-15) 1.9 g, 2,4,6-trimethylbenzylidene-ethoxyphenyl-phosphine oxide as a photopolymerization initiator (manufactured by BASF Corporation) Lucirin TPO-L) (P-1) 3.0 g, EFTOP EF-122A (fluorine-based surfactant, W -1 ) as a surfactant 0.0 5 g, 2.0 g of antioxidant (Sumitomo Chemical Co., Ltd., SUMILIZER) —GA80), 83.3 g of a surface-treated colloidal ceria 30% by mass solution, and stirred at room temperature until methyl ethyl ketone is less than 2% by mass to form a uniform solution. The adjusted composition was spin-coated on a glass substrate to form a film thickness of 4 /zm, and the coated base film which was spin-coated was placed on a high-pressure mercury lamp (optical power: 2000 mW/cm 2 ) manufactured by 〇RC Co., Ltd. The nano-printing device of the light source is a polydimethyl siloxane having a mold pressure of 1 OkN/cm 2 and a vacuum degree of 0.2 Torr during exposure, and having a pattern of 5 mm square (SILPOT1 84 manufactured by Toray CORNING Co., Ltd.) The back surface of the mold having a material of 8 CTC and cured for 60 minutes was exposed to 500 mJ/cm 2 , and after exposure, the mold was removed from the mold, and the residual film ratio of the photocurable resin pattern portion before and after heating was measured. Transmittance, scratch resistance. Subsequently, the solvent resistance of the photohardenable film was investigated. The results are shown in Table 7 -111- 200846824. The composition of Example 42 was excellent in residual film ratio, permeability, and solvent resistance, and was also characterized as a permanent film. Example 4 3 ^ The monomer used in Example 29 was not changed, photopolymerization - The type of the surfactant, the type of the inorganic oxide particles, and the blending ratio were adjusted to 2% by mass of an antioxidant (ADKA, AO503), and the adjusted composition was rotated in the same manner as in Example 1. Coating onto a glass substrate to form a thickness of Φ, and applying the spin-coated coating base film to a nano-printing mold with an ORC male mercury lamp (optical power 2000 mW/cm 2 ) as a light source has a pressure of 1 〇 kN/cm 2 . The degree of vacuum during exposure is (the back surface of a mold with a 5 mm square pattern of polydimethyl siloxane (SIL Ρ Ο T 1 8 4 8 0 ° C ' Μ 6 0 5 made of CORNING), at 500 mJ After exposure to the conditions of /cm2, the mold was removed from the mold, and the residual film ratio, transmittance, and scratch resistance of the photocured portion before and after heating were measured. Then, the resistance to the grain was investigated. The results are shown in Table 7. 4 3 group rate, transmittance, scratch resistance, solvent resistance, and sex is also The present invention was carried out without changing the type, the type, and the blending ratio of the monomer, the photopolymerizable surfactant, and the inorganic oxide particles used in Example 31, and adding 2% by weight of an antioxidant (ad ΕΚΑ Α) Ο 5 0 3 ), in the same manner as in Example 1, and adjusting the composition of the adjusted composition to be spin-coated on the glass substrate to form a transmittance and rubbing resistance. The initiator, the boundary, and the composition ADKSTAB The high-pressure U device made of 4 μm film is exposed from .2 To rr, and the Toray DOW is cured, and the resin film is cured by the permanent film of the film. A special initiator, a composition, and an ADKSTAB product. The 4/zm film-112-200846824 was thick and spin-coated, and the coated base film was placed on a nano-printing device using a high-pressure mercury lamp (optical power 2000 mW/cm2) manufactured by 0 RC Co., Ltd. as a light source. The mold mold pressure is 10 kN/cm2, and the vacuum degree during exposure is 〇.2 Torr, and

^ Polydimethyl siloxane with 5 mm square pattern (Dongli DOW • C Ο RNING company SILP 〇 T 1 8 4 at 80. (:, hardened by 60 minutes) is the material of the mold The back surface was exposed to a condition of 500 mJ/cm2, and after exposure, the mold was removed from the mold, and the residual film ratio, transmittance, and scratch resistance of the photocurable resin pattern portion before and after heating were measured. The φ solvent resistance of the cured film. The results are shown in Table 7. The composition of Example 44 was excellent in residual film ratio, transmittance, scratch resistance, and solvent resistance, and was excellent in properties as a permanent film. 4 5 The antimony used in Example 36, the photopolymerization initiator, the surfactant, the type of the inorganic oxide particles, the blend ratio, and the resistance of 2% by mass in the composition were not changed. An oxidizing agent (made by ADECA, ADKSTAB AO503) was adjusted in the same manner as in Example 1. The φ-adjusted composition was spin-coated on a glass substrate to form a film thickness of 4 // m, which was rotated. The transfer coated coating base film is set in high pressure mercury manufactured by Ο RC (optical power: 2000 mW/cm2) is a nano-printing device of a light source, which is a polydimethyl methoxyoxane having a mold pressure of 10 kN/cm 2 and a vacuum degree of 0.2 Torr during exposure and having a square pattern of 5 mm. The back surface of the mold of the material of the SILPOT 184 manufactured by Dow Corning Co., Ltd. at 8 (TC, cured for 60 minutes) was exposed at 500 mJ/cm2. After exposure, the mold was removed from the mold and the photohardening before and after heating was measured. Residual film ratio, transmittance, and scratch resistance of the resin pattern portion. Next, the solvent resistance of -113-200846824 of the photocured film was examined. The results are shown in Table 7. The composition of Example 45 was the residual film rate and transmission. The rate, the scratch resistance, and the solvent resistance were excellent, and the properties as a permanent film were also excellent. Comparative Example 1 4 • The adjusted composition used in Comparative Example 1 was patterned in the same manner as in Example 36. The characteristics of the composition were examined. The results are shown in Table 7. Further, the antioxidant added in Example 36 was not added. The composition of Comparative Example 1 is the residual film ratio, permeability, and solvent resistance (n Μ P ) How many have changed | poor tendency, comprehensively Comparative Example 1 5 The adjusted composition used in Comparative Example 2 was patterned in the same manner as in Example 36, and the properties of the composition were examined. The results are shown in Table 7. Comparative Example 1 2 The residual film rate and solvent resistance (Ν μ Ρ) of the composition tend to be somewhat deteriorated, and the permeability is poor, and further, it is also poor in combination. Comparative Example 1 6 Used in Comparative Example 3, adjusted The composition was patterned in the same manner as in Example 3 6 φ, and the characteristics of the composition were investigated. The results are shown in Table 7. In the composition of Comparative Example 12, the residual film ratio and the transmittance were poor, and the solvent resistance (NMP, HCI) also tends to be somewhat deteriorated, and the composition was also inferior. Comparative Example 1 7 The adjusted composition used in Comparative Example 4 was patterned in the same manner as in Example 36, and the characteristics of the composition were investigated. The results are shown in Table 7. In the composition of Comparative Example 1, 3, the residual film ratio, the transmittance, and the solvent resistance (Ν Μ ρ, HCI) tend to be somewhat deteriorated, and the permeability is poor, and further, it is also poor in combination. -114- 200846824 Comparative Example 1 The composition of the composition used in Comparative Example 9 was patterned in the same manner as in Example 36, and the characteristics of the composition were investigated. The results are shown in Table 7. In the composition of Comparative Example 1, the residual film ratio, the transmittance, and the solvent resistance (N a 〇 η ) tend to be somewhat deteriorated, and the permeability is poor, and further, it is also poor in combination. Examples 1 to 4 5

When the viscosity of the photohardenable composition of the present invention in Examples 1 to 4 was measured, it was in the range of 3 to 18 mPa·s. When the viscosity of the photohardness composition in Comparative Examples 1 to 7, 9, 1 2, and 13 was measured, it was 20 mPa or more. Comparative Example 8, 10, and 1 1 When the viscosity of the photohardness composition in Comparative Examples 8, 10, and 1 was measured, it was in the range of 5 to 15 mPa. Table 7

Residual Film Rate Transmittance Scratch Resistance Solvent Resistance Comprehensive Evaluation NMP NaOH HCI Example 36 AAAAAAA Example 37 AAAAAAA Example 38 AAAAAAA Example 39 AAAAAAA Example 40 AAAAAAA Example 41 AAAAAAA Example 42 AAAAAAA Example 42 AAAAAAA Example 43 AAAAIAAA Example 44 AAAAAAA Comparative Example 14 B 1 BABAAB Comparative Example 15 BCABAAC Comparative Example 16 CCABABD Comparative Example 17 BBABABC Comparative Example 18 BBAABAB -115- 200846824 Industrial Applicability The composition of the present invention can be used as a semiconductor Integral circuits, *planar screens, micro-electro-mechanical systems (MEMS), inductive components, optical discs, magnetic recording media such as high-density storage disks, diffraction gratings or embossed holograms, etc.: optical components, nanodevices, Optical device, optical film or polarizing element of flat panel display, thin film transistor of liquid crystal display, organic transistor, color filter, overcoat layer, pillar, rib for liquid crystal alignment, micro-lens array, free Analysis of the production wafer, D N A separate wafer microreactor, Chennai meters biological means, optical waveguide, optical filter, optical crystal or the like is formed on the occasion of printing light nm photoresist composition for fine pattern used. [Simple description of the diagram] None. [Component Symbol Description] None.

-1 1 6 -

Claims (1)

  1. 200846824 X. Patent application scope: 1 _ A hardening composition for photonic printing lithography, which contains 3 5 to 9 9 % by mass of a polymerizable unsaturated monomer, and 5 mass D /. The photopolymerization initiator, at least one of a 0.001 to 5% by mass of a fluorine-based surfactant, a lanthanoid surfactant, and a fluorine-and rhodium-based surfactant, and a 〇·彳~5 〇 mass. /. Inorganic oxide microparticles. 2 . A hardening composition for photon printing lithography, which comprises 4 8 to 9 9
    % by mass of polymerizable unsaturated monomer, 〇. 1 ~ 15 mass. /. The photopolymerization initiator, at least one of a fluorine-based surfactant, a ruthenium-based surfactant, and a fluorinated-ruthenium-based surfactant of from 0. 00 to 5% by mass, and a mass of from 0 to 1 to 50. /. The inorganic oxide fine particles containing at least 15% by mass or more of a monofunctional polymerizable unsaturated monomer as the aforementioned polymerizable unsaturated monomer, wherein the monofunctional polymerizable unsaturated single system contains A site having an ethylenically unsaturated bond in the molecule and a site having at least one of an oxygen atom, a nitrogen atom, and a sulfur atom. 3. A photohardenable composition for photolithographic printing, comprising 48 to 99% by mass of a polymerizable unsaturated monomer, 0.1 to 15% by mass of a photopolymerization initiator, and 0.01 to 5%. At least one of a fluorine-based surfactant, a ruthenium-based surfactant, and a fluorine-ruthenium-based surfactant, and at least 1 to 50% by mass of the inorganic oxide fine particles, and at least 1 in the composition 5% by mass or more of at least one selected from the group consisting of the following compounds (a), (b), and (c): the polymerizable unsaturated monomer as the polymerizable unsaturated monomer, (a) having 1 a polymerizable unsaturated monomer containing a ethylenically unsaturated bond in the molecule and an aliphatic cyclic moiety containing a hetero atom; -117- 200846824 (b) having a site containing an ethylenic unsaturated bond in one molecule, and a polymerizable unsaturated monomer having a c ( = o)- bond and an NR bond (R is a hydrogen atom or a methyl group); (c) a site having an ethylenically unsaturated bond in one molecule, and a carbon number of 6~ A polymerizable unsaturated monomer of the alicyclic moiety of 12. 4. A curable composition for photonic printing lithography, which comprises 4 8 to 9 9
    % by mass of polymerizable unsaturated monomer, 0.1 to 15% by mass of a photopolymerization initiator, 0.001 to 5% by mass of a fluorine-based surfactant, a sand-based surfactant, and a fluorine-based surfactant At least one type and 0.1 to 50% by mass of the inorganic oxide fine particles, and at least 15% by mass or more of the monofunctional polymerizable unsaturated monomer in the composition is used as the polymerizable unsaturated monomer. The monofunctional polymerizable unsaturated single system contains at least one (a) a monofunctional polymerizable unsaturated monomer having a site containing an ethylenically unsaturated bond in one molecule and an aliphatic cyclic moiety containing a hetero atom. 5. The composition of claim 2, wherein the monofunctional polymerizable unsaturated single system is selected from any one of the following general formulae (I) to (v丨丨丨);
    Upper, general formula (1)
    (In the formula (丨), R11 represents a hydrogen atom or a methyl group, and r12, r13, r14, and R15 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, or an ethoxy group. N1 represents 彳 or 2, and m1 represents 〇, ], 2, 'Z represents a methylene group, an oxygen atom, or a —NH— group, and two Z11-118-200846824 systems may be different from each other. W11 represents -c ( = Ο )- or -S Ο 2 -, R 1 2 and R 1 3 and R 1 4 and R 1 5 may be bonded to each other to form a ring) Formula (11) R24 R25
    (In the formula (II), R21 represents a hydrogen atom or a methyl group, and R22, R23, R24 and R25 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group, or a The oxy group, R22 and R23 and R24 and R25 may be bonded to each other to form a ring, η 2 is represented by any one of 1, 2, and 3, and m 2 is represented by any of 〇, 1, and 2. , γ21 represents a methylene group or an oxygen atom) Formula (III)
    (In the formula (III), R32, R33, R34 and R35 each represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, a methoxy group or an ethoxy group. In any of 2 and 3, m3 is represented by any one of 0, 1, and 2, and X31 represents -C (= 0)_, methylene, and ethyl, and the two χ31 series may be different from each other. '丫32 is a methylene or oxygen atom. -119- 200846824 Formula (IV)
    R represents a hydrogen atom (in the formula (IV), a parent, R, and κ..., respectively, a hydrogen atom, a methyl group, an ethyl group, a r ^ 蔘, a halogen atom, a methoxy group, a % 'W41 It means a single bond, no bond, or a part, and the tether is not any of 2, 3, and 4, and the χ42 shows 4...〇)_, _c = c_, -C, 30 methyl Each of the χ42 series may be the same or different, and &lt; represents a hydrocarbon linking group having a carbon number of 1 to 4, an oxygen atom or a nitrogen atom, and each MM system may be the same or different) Formula (V)
    (In the formula (V), 'R51 represents a hydrogen atom or a methyl group, Z52 represents an oxygen atom, -CH=N- or a methylene group, W52 represents a methylene group or an oxygen atom, and γ52 represents a single bond or - C(C = 〇)-, Y53 represents a single bond or &lt;(〇= 〇)·, and r54 and R55 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a halogen atom, or a methoxy group, respectively. Ethoxy, R54 and R55 can be bonded to each other to form a ring of -120-200846824, X51 can be a single bond or no bond, and the old 5 series are 〇, 彳, 2
    Atom) General formula (VI) At least one of R61 R62 contains an oxygen atom or nitrogen ^XN, r63 (in the formula (VI), R61 is a hydrogen atom or a methyl group, and R62 and R63 are each a hydrogen atom or a methyl group. , ethyl, hydroxyethyl, propyl, ((^3) 21^((;^2:^6-(m 6 is 1, 2 or 3), C Η 3 C Ο · (CR 6 4 R 6 5) p 6 _ ( R 6 4 and r 6 5 are respectively a hydrogen atom or a methyl group, p6 is a one of 1, 2 or 3), (CH3)2-N-(CH2)p6-(p6 Is any one of 1, 2 or 3), but in the general formula (VI), the moiety of -NR62 (R63) may be -N = c = 0, and R62 and R63 are not hydrogen at the same time. The atom, and the X6 series -CO-, -C〇CH2-, -COCH2CH2-, -C0CH2CH2CH2-, -C〇OCH2CH2-, and the formula (VII) R71 0 R72 (in the formula (VII), R71 and R72 are each a hydrogen atom or a methyl group. 'R73 is a hydrogen atom, a methyl group or an ethyl group.) General formula (VHI)
    -121 - 200846824 (In the general formula (VI II), 'R81 represents a hydrogen atom, a methyl group or a transmethyl group, and R82, R8, R4 and R85 are each represented by a hydrogen atom, a trans group, a methyl group, an ethyl group, and Hydroxymethyl, hydroxyethyl, propyl and butyl, R82, R83, R84 and r8s
    At least two of them may be bonded to each other to form a ring, W81 is a methylene group, -NH-, -N(CH3)-, -N(C2H5)-, and W82 means a single bond or -C(= 〇) - When W82 is a single bond, R82, r83, r84, and r84 are not hydrogen atoms, and η 7 is an integer of 〇~8). 6. The composition of claim 1, wherein the polymerizable unsaturated monomer further comprises 0.1% by mass or more of a portion having at least one B-storage unsaturated bond, and a ruthenium atom and/or Or a second polymerizable unsaturated monomer of a phosphorus atom. 7. The composition of claim 2, wherein the polymerizable unsaturated monomer further comprises 0.1 mass. /. The above-mentioned site having at least one B-unsaturated unsaturated bond and a second polymerizable unsaturated monomer containing a deuterium atom and/or a phosphorus atom. 8. The composition of claim 1, wherein the inorganic oxide fine particles are colloidal cerium oxide. 9. The composition of claim 2, wherein the inorganic oxide fine particles are colloidal cerium oxide. A composition according to the first aspect of the invention, wherein the inorganic oxide fine particles are colloidal cerium oxide surface-treated with a compound having a reactive (meth) acrylate group. The composition of claim 2, wherein the inorganic oxide fine particles are colloidal silica sand surface-treated with a compound having a reactive (meth) acrylate group -1 2 2 - 200846824. 1 2 · The composition of claim 1 of the patent application contains an antioxidant. _ 1 3 . The composition of claim 2, which contains an antioxidant. • 1 4 • The composition of the first paragraph of the patent application, wherein the viscosity at 25 〇c is 25 mPa*s or less. 1 5 · The composition of the second item of the patent application, which is at 25. (: The viscosity is below 25mPa.s.
    1 6 - a pattern forming method comprising: coating a coating step as in the composition of claim 1; pressing the photoresist layer on the substrate with a light-transmissive mold to make the coated a step of deforming the composition; a step of irradiating light from the back surface of the mold or the back surface of the substrate and hardening the coating film to form a photoresist pattern of a desired pattern; and a step of separating the light-transmitting mold from the coating film. 1 7 - a pattern forming method comprising: coating a coating step as in the composition of claim 2; pressing the photoresist layer on the substrate with a light-transmissive mold to make the coated a step of deforming the composition; a step of irradiating light from the back surface of the mold or the back surface of the substrate and hardening the coating film to form a photoresist pattern of a desired pattern; and a step of separating the light-transmitting mold from the coating film. -123- 200846824 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 4tti* 〇 y\\\
    8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: General formula (1)
TW97102134A 2007-01-23 2008-01-21 Curing composition for photonano-imprinting lithography and pattern forming method by using the same TW200846824A (en)

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