TWI408498B - Photo-curing composition and producing method of pattern using the same - Google Patents

Abstract

A photocurable composition is provided to have excellent properties such as photocurability, adhesion, demoldability, pattern profiles, coating uniformity, and etching appropriateness. A photocurable composition includes (a) a polymerizable compound, (b) 0.1-15% by mass of a photopolymerization initiator and/or a photoacid generator, and (c) 0.001-5% by mass of at least one selected from fluorine-based surfactants, silicon-based surfactants, and fluorine-silicon-based surfactants, and has a viscosity of 3-18 mPa.s at 25 °C. The polymerizable compound(a) contains (e) a polymerizable unsaturated monomer having a primary irritation index of 4.0 or less and (f) a polymerizable unsaturated monomer having a viscosity of 30 mPa.s or less at 25 °C, wherein the respective monomers are contained in amounts of 50% by mass or more.

Description

Photocurable composition and pattern forming method using same

The present invention relates to a photocurable composition and a pattern forming method using the same.

The nanoimprint method is a embossing technique developed in the manufacture of optical discs. The prototype of a mold (often called a mold, a stamping die, a template) formed with a concave-convex pattern is pressed against the photoresist to cause mechanical deformation. , the technology to precisely transfer fine patterns. Since the nanostructure can be simply reshaped when it is made into a mold at one time, it is a nano processing technology that is harmful in addition to economical waste and has a small amount of waste, and has been expected to be applied to various types in recent years. field.

There are two proposals for nanoimprinting, including the use of thermoplastic resins as materials to be processed (S. Chou et al., Appl. Phys. Lett. Vol. 67, 114, 3314 (1995)); and when using photocurable resins. (M. Colbun et al., Proc. SPIE, Vol. 676, 78 (1999). Thermal nanoimprinting is the pressing of a mold onto a polymer resin that has been heated above the glass transition temperature, after cooling. The mold is demolded to transfer the fine structure to the resin on the substrate. Since it can be applied to various resin materials or glass materials, it is expected to be applied to various applications. US Patent No. 5,772,905, US Patent No. Japanese Patent Publication No. 5,956,216 discloses a method of forming a nanoprinting method using a thermoplastic resin to form a nano pattern at a low cost.

On the other hand, a light nano-printing method in which light is irradiated through a transparent mold to photoharden the photocurable composition can be imprinted at room temperature. Recently, there have also been reports on new developments such as the nano-casting method or the reverse embossing method of three-dimensional laminated structure, which combines the advantages of the two. It is believed that this nanoimprinting method has roughly three stages of application. In the first stage, the shape formed by itself has a function and can be applied as a main part of various nano technologies, and various micro-nano optical main elements or high-density recording media and optical films can be cited. In the second stage, the laminated structure is constructed by the simultaneous molding of the microstructure and the nanostructure, or a simple interlayer positional cooperation, and is applied to manufacture a μ-TAS or a biochip. The third stage is actively applied to the manufacture of high-density semiconductors in place of the previous lithography method, and is intended to be used in the manufacture of liquid crystal displays, etc., through high-precision position matching and high integration. Chemical.

An application example of manufacturing a high-density semiconductor integrated circuit will be described as an application example of the nanoimprint method. In recent years, the semiconductor integrated circuit has progressed toward miniaturization and integration, and in order to realize the microfabrication, the pattern transfer technique and the photolithography apparatus have progressed with high precision. However, when the processing method is close to the wavelength of the light source for light exposure, the lithography technique is also close to the limit. Therefore, in order to innovate the miniaturization and high precision, an electron beam drawing device of a charged particle beam device has been used instead of the lithography technique. When a pattern is formed using an electron beam, it is different from the total exposure method used when forming a pattern using a light source such as an i-ray or a quasi-molecular laser, because the method of drawing a mask pattern is used, and the more the pattern is drawn, the more exposure is required (depicting Time, the more time it takes to form a pattern. Therefore, as the degree of integration is dramatically increased by 256 Mega, 1 Giga, and 4 Giga, the time for forming the pattern corresponding to the degree is also drastically increased, and the yield is significantly deteriorated. Therefore, in order to speed up the electron beam drawing device, the development of the collective pattern irradiation method in which the photomasks of various shapes are combined and the electron beams are collectively irradiated to form an electron beam having a complicated shape is progressing. As a result, although the miniaturization of the pattern has progressed, there is a disadvantage that the cost of the device becomes high because the electron beam drawing device must be large in size, and it is necessary to have a mechanism for controlling the position of the mask or the like with higher accuracy.

In contrast, there is a proposal to disclose a nanoimprint lithography method as a technique for forming a fine pattern in a low cost manner. For example, U.S. Patent No. 5,772,905 and U.S. Patent No. 5,259,926 disclose a nanoimprint technique using a tantalum wafer as a stamping die to form a fine structure of 25 nm or less by transfer.

Further, Japanese Laid-Open Patent Publication No. 2005-527110 discloses a composite composition using nanoimprinting, which can be applied to the field of semiconductor lithography. On the other hand, in order to apply the nanoimprint lithography method to the manufacture of a semiconductor integrated circuit, the micro-die manufacturing technique, the durability of the mold, the manufacturing cost of the mold, the peelability of the mold from the resin, the uniformity of the imprint, or Discussions on quasi-accuracy, inspection techniques, etc. have also begun to be actively pursued.

However, the photoresist used in the nanoimprint lithography method, although similar to the conventional photoresist for semiconductor micromachining, has to be adapted to the etching suitability of various substrates or the peeling suitability after etching, but it is not yet sufficient. Research.

Next, an application example of a nanoimprint lithography method 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-precision movement of LCD or PDP substrates, the nano-imprint lithography method is used as an inexpensive lithography method instead of the previous photolithography method used to fabricate thin film transistors (TFTs) or electrode plates. Special attention is paid. Therefore, it is necessary to develop a photohardenable composition instead of the etching resist used in the previous photolithography method. The etching photoresist used in the previous photolithography method is required to be high-sensitivity, uniformity of coating film, light-resistance, and adhesion to various substrates, etching resistance, heat resistance, etc., instead of the light thereof. The nanoimprint resist must also have the same characteristics.

Regarding the uniformity of the coating film, the uniformity of the thickness of the coating film at the center portion and the peripheral portion of the substrate, or the dimensional uniformity, film thickness, shape, and the like with high resolution are various in various parts as the size of the substrate is increased. The requirements are gradually stricter. Conventionally, in the field of manufacturing liquid crystal display elements using small glass substrates, the photoresist coating method uses a method of centrally dropping and rotating (Electronic Journal 121-123 No. 8 (2002)). Although a coating method in which the center is dripped and rotated can obtain good coatability, for example, when a large-sized glass substrate of 1 m square is used, the amount of photoresist that is thrown off during rotation is considerable, and there is a high-speed rotation. Causes the substrate to rupture or ensure a tact time. In addition, in the case of the method of rotating and squeezing in the center, the coating performance is dependent on the rotation speed at the time of rotation and the amount of photoresist applied, and when it is applied to the fifth-generation substrate of a larger size, there is a lack of a general-purpose type capable of obtaining the necessary acceleration. Motors, if you order such a motor, there will be an increase in the cost of parts. Further, as the size of the substrate or the size of the device is increased, for example, the coating uniformity is ±3%, the production time is 60 to 70 seconds/piece, and the like, and the performance is required to be substantially unchanged in the coating step, and the method of rotating after the center is added and then Requirements other than coating uniformity also become difficult. In view of the current situation, there is a proposal to disclose a discharge nozzle type photoresist coating method which can be applied to a fourth generation substrate, in particular, a large substrate after the fifth generation substrate, as a novel photoresist coating method. The discharge 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 the discharge nozzle relative to the substrate. For example, it is proposed to disclose a method in which a plurality of nozzles are used. The discharge port or the slit-shaped discharge port which is arranged in the form of a row of holes can discharge the nozzle of the photoresist composition in a strip shape. Further, there has been proposed a method of coating a photoresist composition on a coating surface of a substrate by a discharge nozzle type, and rotating the substrate to adjust the film thickness. Therefore, in order to change the photoresist of the conventional photolithography method to a nanoimprint composition, it is applied to the field of manufacturing such liquid crystal display elements, and the uniformity of coating of the substrate is important.

In the production of a semiconductor integrated circuit, a positive photoresist used in the manufacture of a liquid crystal display, or a pigment dispersion resist for color filters, and the like, a fluorine-based and/or a lanthanum-based surfactant is added to solve the coating property, specifically For example, the problem of coating defects such as streaks or scaly patterns (drying unevenness of the photoresist film) when applied on a substrate is known (Japanese Unexamined Patent Publication No. Hei No. Hei 7-230165, No. 2000-181055, No. Bulletin 2004-94241). Further, in order to improve the abrasion resistance or coating property of a protective film such as a compact compact disc (CD) or a magneto-optical disc, it is disclosed that a fluorine-based surfactant or a lanthanoid interface is added to the solvent-free photocurable composition. The active agent is disclosed in JP-A-2004-94241, JP-A-4-149280, JP-A-7-62043, and JP-A-2001-93192. In the same manner, in order to improve the ink discharge property of the composition for inkjet, it is known to add a nonionic fluorine-based surfactant to JP-A-2005-8759. In the holographic image processing die, when a paint composition coated with a thick film such as a brush, a pen, or a bar coater is subjected to embossing, a polymerization of 1% or more is added. The surfactant of the unsaturated double bond, preferably 3% or more, is an example of improving the water swellability of the cured film. As described above, a technique known as a technique for improving the coating property by adding a surfactant to a protective film such as a positive-type resist, a pigment dispersion resist for color filter production, or a magneto-optical disk is known. Further, from the examples of the above-described inkjet or coating composition, it is known that a technique of adding a surfactant to a solventless photocurable resin to improve the properties of each application is also known. However, a method of improving the substrate coating property of a low-viscosity photocurable nanoimprint resist composition which is not an essential component of a pigment, a dye or an organic solvent has not been known.

Further, in the field of flat panel displays, when the previous photolithography method is changed to the step of the nanoimprint lithography method, the photocurable composition is strongly required during coating, exposure, mold peeling, and heating (post-baking). The constituents are not volatile. When the photopolymerizable monomer component of the photocurable composition generally used in the step of photon lithography is compared with the novolak resin or naphthoquinone diazide sensitizer used in the previous photolithography method, It has a small molecular weight and is more volatile (evaporated). When the components of the photocurable composition are volatilized, step contamination occurs, which not only deteriorates the yield when manufacturing the display, but also affects the operator's skin inflammation and the like when the operator inhales or contacts the volatilized vapor. Security. From this point of view, it is necessary to select a material which is applied to the photocurable composition of the nanoimprint, and it is necessary to select a material which is not easily volatilized and which has a primary skin irritation (PII value) as small as possible.

Further, when a photon imprinting resist containing an organic solvent is used, it is necessary to volatilize the solvent after coating. When a composition containing an organic solvent having such a consideration is used, since the solvent which is volatilized by suction or the like is unfavorable to the safety of the operator or the simplification of the number of steps, it is strongly required to develop a composition which does not contain an organic solvent.

The prior art of the light nanoimprint of the application range of the present invention is explained in more detail. The light nanoimprint lithography method generally has a liquid photocurable composition dripped on a substrate of ruthenium wafer, quartz, glass, film, or other material such as ceramic material, metal or polymer, to approximately A film thickness of several tens of nanometers to several micrometers is applied, and a mold having fine unevenness of a pattern size of about several tens of nanometers to several tens of micrometers is pressed and pressurized, and light is irradiated under pressure to harden the composition. A method of releasing a mold from a coating film to obtain a transferred pattern. Therefore, in the case of the photon imprint lithography method, at least one of the substrate or the mold must be transparent for the purpose of illumination. Usually, in general, light irradiation is performed from the mold side, and most of the mold material is an inorganic material that transmits UV light such as quartz or sapphire, or a light-transmitting resin.

When comparing the nano-imprint method with the hot nano-imprint method, the following main advantages can be mentioned: (1) the heating/cooling step is not required, and the expected yield is high, and (2) because of the use of the liquid composition, Low pressurization is used for nanoimprinting, (3) no dimensional change due to thermal expansion, (4) the mold is transparent, so alignment is easy, and (5) after hardening, a strong three-dimensional crosslinked body can be obtained. In particular, it is suitable for use in, for example, microfabrication applications requiring alignment precision semiconductor microfabrication or in the field of flat panel displays.

Moreover, the other characteristics of the photon imprinting method are compared with the conventional photolithography method because the resolution does not depend on the wavelength of the light source, and the microfabrication of the nanometer level does not require a high price such as a stepper or an electron beam drawing device. The characteristics of the device. On the other hand, the photon imprint lithography method must be equal to the mold, because the mold must be in contact with the resin, and the durability or cost of the mold must be considered. Further, in the photonic embossing lithography step, a residual film is easily generated (the position where the convex portion of the mold is pressed against the photocurable composition). The thinner the residual film layer is, the more precise the structure can be formed by nanoimprinting, and the more the residual film is, the more easily the wire width control property or the etching residue is at the time of etching.

Thus, when applying thermal and/or photon imprinting to imprint a nano-sized pattern over a large area, it is not only required to suppress the uniformity of the pressure or the flatness of the original (mold), but also must be controlled. The action of the light resistance that flows out due to being pressed. Since the prior semiconductor technology can arbitrarily set a region that is not used as an element on a wafer, it is possible to provide a photoresist outflow portion outside the embossed portion using a small original plate. Further, in the semiconductor case, the defective portion is not used as a defective element. However, for example, when it is applied to a hard disk or the like, since it is necessary to use the entire surface as a function of the element, it is necessary to specifically seek to prevent the printing defect from occurring. .

The mold used in the photon lithography method can be manufactured from various materials such as metal, semiconductor, ceramic, SOG (Spin On Glass), or a prescribed plastic. For example, the proposal described in the pamphlet of International Publication WO99/22849 discloses a mold having a soft polydimethyl siloxane having a desired fine structure. In order to form a three-dimensional structure on the surface of the mold, various lithography methods can be used in accordance with the specifications of the size of the structure and its decomposition performance. The lithography of electron ray and X-ray can generally be used for structural sizes of less than 300 nm. Direct laser exposure and UV lithography can be used for larger structures.

Regarding the photon imprint method, the releasability of the mold and the photocurable composition is important, and the surface treatment of the mold or the mold, specifically, attempts to use hydrogenated silsesquioxane (HSQ: Hydrogen Silsequioxane) or fluorination. Ethylene propylene copolymer mold to solve the adhesion problem.

Here, the photocurable resin used in the photo nanolithography method will be described. The photocurable resin which can be applied to nanoimprinting can be roughly classified into a radical polymerization type, an ion polymerization type, or a mixed type depending on the reaction mechanism. Any of the components can be embossed, usually using a radically polymerized type with a wide range of material selection (F.Xu et al., SPIE Microlithography Conference, 5374, 232 (2004)) . The radical polymerization type is usually a composition using a monomer or oligomer having a radically polymerizable vinyl group or a (meth) propylene group and a photopolymerization initiator. At the time of light irradiation, radicals generated from the photopolymerization initiator attack the vinyl group and undergo chain polymerization to form a polymer. When a bifunctional or higher polyfunctional monomer or oligomer is used as a component, a crosslinked structure can be obtained. DJ Resnick et al., J. Vac. Sci. Technol. B, Vol. 21, No. 6, 2624 (2003) discloses a composition that can be used at low pressure by using a low viscosity UV curable monomer. Imprint at room temperature.

The characteristics of the materials used in the photon lithography method will be described in detail. The required characteristics of the materials vary depending on the application, but the requirements of the step characteristics have in common with the use. For example, in the latest photoresist materials manual, page 1, page 103~104 (2005, published by the intelligence agency), the main items are coating properties, substrate adhesion, low viscosity (<5mPa.s), mold release. , low hardening shrinkage rate, quick hardenability, etc. In particular, in applications where low pressure imprinting is required and the residual film ratio is lowered, it is known that a low viscosity material is strongly required. On the other hand, when characteristics required for use are mentioned, for example, the optical member has a refractive index, light transmittance, and the like, and the etching resistance of the etching resist or the thickness of the residual film is lowered. How to control these characteristics and how to achieve a balance of various features becomes the key to material design. Because at least the material of the step differs from the desired properties of the permanent film, the material must be developed in accordance with the steps or uses. Materials used in such photon nanoimprint lithography methods, recently disclosed in the Handbook of Photoresist Materials, page 1, pages 103-104 (2005, published by the intelligence agencies) have about 60mPa. Photocurable materials of s (25 ° C) viscosity are well known. Similarly, CMC Publishing, Development and Application of Nanoimprint, 159-160 (2006) discloses a fluorine-containing photosensitive resin (with a monomethyl acrylate as a main component and a viscosity of 14.4 mPa·s, which has been improved). Release property).

Regarding the composition for use in such a photon embossing, there is a description of the viscosity of the composition, but there is no report example of a design policy for materials suitable for each application.

An example of a photocurable resin which has been conventionally applied to a photon lithography method will be described. JP-A-2004-59820 discloses an embossing process using a photocurable resin having an isocyanate group for producing an embossed hologram or diffraction. A polymer of lattices. Further, U.S. Patent Publication No. 2004/110856 discloses a photocurable composition for nanoimprinting containing a polymer, a photopolymerization initiator, and a viscosity modifier.

N. Sakai et al., J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), discloses combining (1) functional acrylic monomers, (2) functional acrylic monomers, (3) functional groups. Photocurable radical polymerizable composition obtained by using an acrylic monomer and a photopolymerization initiator, or a photo-cationic polymer composition containing a photocurable epoxy compound and a photoacid generator, etc., is applied to photon imprinting The lithography method is used to adjust examples of thermal stability or mold peelability.

M. Stewart et al., MRS Bu1etin, No. 30, 947 (2005), discloses a photocurable composition comprising (1) a functional acrylic monomer, (2) a functional acrylic monomer, and a ruthenium containing The monofunctional acrylic monomer and the photopolymerization initiator are used to improve the peelability of the photocurable resin and the mold, the film shrinkage after curing, and the low sensitivity caused by photopolymerization inhibition in the presence of oxygen. And other issues.

T. Beiley et al., J. Vac. Sci. Technol. B18 (6), 3572 (2000) discloses the formation of a monofunctional acrylate monomer, a monofunctional fluorene containing monomer, and a photopolymerization initiator on a ruthenium substrate. The photocurable composition can reduce defects after molding using a surface-treated mold by a photo nano-imprint lithography method.

B. Vratzov et al., J. Vac. Sci. Technol. B21 (6), 2760 (2003), discloses the formation of photohardenability on a ruthenium substrate containing a ruthenium monomer, a trifunctional acrylate monomer, and a photopolymerization initiator. In the composition, a composition excellent in high resolution and uniform coating properties can be obtained by the SiO ₂ mold.

EKKim et al., J. Vac. Sci. Technol. B22(1), 131 (2004) disclose the use of a cationically polymerizable composition comprising a combination of a specific vinyl ether compound and a photoacid generator to form 50 Nai. An example of the size of a rice pattern. Although it has the characteristics of low viscosity and fast curing speed, it also describes the problem of template peelability.

However, as in N. Sakai et al., J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005), M. Stewart et al., MRS Buletin, No. 30, 947 (2005), T. Beiley et al., J. Vac. Sci. Technol. B18 (6), 3572 (2000), B. Vratzov et al., J. Vac. Sci. Technol. B21 (6), 2760 (2003), EKKim Et al., J. Vac. Sci. Technol. B22(1), 131 (2004), although different functional acrylic monomers, acrylic polymers, vinyl ether compounds are applied to the photon imprinting micro There are various revelations of the light-curing composition of the photo method, but the best kind of composition, the best monomer species, the combination of monomers, the optimum viscosity of the monomer or photoresist, and the photoresist The material design guidelines for improving the physical properties of the solution and the improvement of the coating properties of the photoresist are not disclosed at all. Therefore, in the use of photon nanoimprint lithography, it is not known that a good composition can be widely used for the composition, and the photon imprinting resist composition which can be absolutely satisfied can not be actually There are proposals.

In order to improve the compound of the PII value of the photopolymerizable composition, for example, by adding ethylene oxide, propylene oxide, or the like to the acrylic monomer, high molecular weight, ring structure of the monomer, change of branching, etc. The backbone of the ester group is attempted to reduce skin irritation (RadTech Research Society: New UV-EB Hardening Technology and Application Development, CMC (1997), US Patent No. 5,543,557). In general, methacrylate has a lower reactivity than acrylate, but is also known to have low reactivity. Further, in comparison with the acrylate, the vinyl ether compound has an advantage of being able to improve the PII value, but has low reactivity. In this way, although the improvement of skin irritation has been reviewed until now, there are problems such as an increase in viscosity and a decrease in reactivity.

Japanese Laid-Open Patent Publication No. Hei-4-149280, JP-A-2001-93192, JP-A-2003-165930, JP-A No. 2-6562, JP-A-7-70472, and JP-A No. 7-53895 disclose a relatively low disclosure. A photocurable composition having a low viscosity and a low skin irritation is a (meth)acrylic monomer or acrylamide having a low PII value applied to a protective film, a coating material, or an ink for a compact laser or a magneto-optical disk. However, any of these compositions has a high viscosity, and when applied to a nanoimprinting composition, after the transfer of the mold, there are many residual films, and it is difficult to apply a photoresist for substrate processing. Moreover, when it is a protective film of a small compact disc or a magneto-optical disk, these photocurable compositions tend to have poor pattern formation performance and etchability of substrate processing.

The application of the etching resist for substrate processing will be described in detail. Etching photoresist is not a major component left directly, but is a pattern used to replicate semiconductor or transistor circuits. In order to manufacture a circuit pattern, components containing the photoresist patterns must be transferred to various layers. The method of transferring the pattern can be performed by an etching step of selectively removing a portion not covered by the photoresist. For example, the electrode plate for manufacturing the TFT array substrate and the PDP is coated and etched on each layer of the thin film by a sputtered conductive substrate or an insulating substrate on a glass or transparent plastic substrate, and dried. The steps of pattern exposure, development, etching, and photoresist peeling are performed. In the past, most of the etching photoresist was a positive photoresist. In particular, a photoresist having a base-soluble phenol novolak resin and a 1,2-benzoquinonediazide compound as a main component or a chemically amplified photoresist having a (poly)hydroxystyrene as a polymer, because of high etching resistance, Moreover, peeling is also easy, and it has been widely used in the etching resist of a semiconductor or a TFT transistor, and has accumulated a lot of knowledge. Etching is performed by a wet etching method using various liquid etchants, and using ions or radicals generated by decomposing a gas by plasma in a decompression device to vaporize and remove the substrate. Dry etching of the film. The etching process is an important step that has a significant influence on the design accuracy, transistor characteristics, yield, and cost of the device. The etching photoresist must be a material that can be applied to either dry etching or wet etching, and must have step suitability. . When the composition used in the photon lithography method is applied to the field of photoresist using the conventional lithography method, it must have the same etching property as the conventional photoresist because it is not sufficiently reviewed in the etching step. There will be a wide variety of problems.

The main technical problems of etching photoresist are the improvement of the dimensional accuracy of the pattern processing, the improvement of the control of the taper angle processing (the improvement of the undercut shape), the improvement of the etching uniformity on the large substrate, and the selective etching with the lower layer. There are many problems such as improvement in lifting speed, improvement in etching processing speed, overall film etching resistance, waste liquid, exhaust gas, and the like, and improvement of defects (particles, residues) on the film after etching. When the photocurable composition for photon imprinting is applied as an etching resist, (1) the suitability of an etchant or an etching gas selected for the film type, similar to the previous positive resist (2) In order to improve the adhesion between the pattern and the etching substrate in order to prevent the occurrence of the depression, (3) it is important to impart wettability between the etching liquid and the photoresist in order to improve the controllability of the pattern size before etching.

However, in addition to the above (1) to (3), the nanoimprinted photocurable composition is more technically difficult from the viewpoints of (4), (5), and (6) described below. (4) In order to improve the peeling property with the mold and make the photoresist film hydrophobic, the wettability of the etching liquid and the photoresist is further deteriorated, and etching residue is likely to occur. (5) Since the photocurable composition has a three-dimensional network structure, it is difficult to peel off when compared with a positive photoresist, and although the mesh structure becomes strong, etching resistance can be improved, but peeling is changed. It is even harder. (6) When compared with the conventional photolithography method, the photon nanoimprint lithography method is likely to cause residue in the portion to be etched and removed after the mold is peeled off, and the residue is likely to be generated by etching.

Regarding the photocurable composition for nanoimprinting, although various materials have been disclosed, there is currently no nanoimprint which can be applied to any step of the photolithography step, the etching step, and the stripping step of the nanoimprinting. Material disclosure or material design guidelines. In addition, the photocurable composition known in the past for the use of the composition for imprint or the protective film for a magneto-optical disk has a common portion in the photolithography step, but there is no etching step or peeling step. The difference from the etching photoresist is large. Therefore, when the photocurable resin applied for such applications is directly applied as an etching photoresist, a problem often occurs in the etching step or the peeling step.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel composition excellent in photocurability. In particular, the object of the present invention is to provide a composition excellent in any of photocurability, adhesion, mold release property, residual film property, pattern shape, coatability (I), coatability (II), and etching suitability. Object

Based on the above-mentioned problems, the inventors of the present invention have found that the above problems can be solved by the following methods.

(1) A photocurable composition comprising (a) a polymerizable compound, (b) 0.1 to 15% by mass of a photopolymerization initiator and/or a photoacid generator, and (c) 0.001 to 5% by mass of a fluorine-based compound At least one of a surfactant, a lanthanide surfactant, and a fluorine-antimony surfactant, and (d) has a viscosity at 25 ° C of 3 to 18 mPa. In the photocurable composition of the range of s, the (a) polymerizable compound contains (e) a polymerizable unsaturated monomer having a primary skin irritation (PII value) of 4.0 or less and 50% by mass or more, respectively ( f) The viscosity at 25 ° C is 30mPa. a polymerizable unsaturated monomer of s or less (wherein part or all of the (e) polymerizable unsaturated monomer and the polymerizable unsaturated monomer of the above (f) may be the same polymerizable unsaturated monomer) .

(2) The photocurable composition according to (1), which comprises a photoradical polymerizable unsaturated monomer and/or a photocationic polymerizable unsaturated monomer as the above (a) polymerizable compound.

(3) The photocurable composition according to (1), which contains a monomer having an ethylenically unsaturated bond-containing group as the (a) polymerizable compound.

(4) The photocurable composition according to (1), wherein the compound containing ethylene oxide is contained as the (e) polymerizable unsaturated monomer.

(5) The photocurable composition according to (1), wherein the compound having an oxetane is contained as the (e) polymerizable unsaturated monomer.

(6) A photocurable composition according to (1), which contains a vinyl ether as the above (a) polymerizable compound.

(7) The photocurable composition according to (1), which contains a styrene derivative as the above (a) polymerizable compound.

(8) The photocurable composition according to any one of (1) to (7), which is used in a photon lithography method.

(9) A photoresist comprising the photocurable composition according to any one of (1) to (7).

(10) A method of forming a pattern, comprising the step of applying a photocurable composition according to any one of (1) to (7) and curing the pattern.

(11) A method of forming a photoresist pattern, comprising the steps of: coating a photocurable composition according to any one of (1) to (7); and pressing the light transmissive mold onto the substrate a photoresist layer for deforming the photocurable composition; a step of irradiating light from the back surface of the mold or the back surface of the substrate to harden the coating film to form a photoresist pattern of a desired pattern; and coating the light transmissive mold a step of desorbing the film; a step of etching the substrate with the photocurable composition as a mask; and a step of peeling off the photocurable composition after etching.

According to the present invention, a composition excellent in any of photocurability, adhesion, and coating properties can be obtained.

Hereinafter, the contents of the present invention will be described in detail. In addition, the "~" used in the present specification means that the numerical values described before and after are included as the lower limit and the upper limit.

The present invention will be described in detail below. In the present specification, (meth)acrylic acid means acrylate and methacrylate, (meth)acrylic means acrylic acid and methacrylic acid, and (meth)acryloyl group means acrylonitrile group and (meth) Base) propylene fluorenyl. Further, in the present specification, the monomer is the same as the monomer, and the monomer of the present invention is different from the oligomer and the polymer, and means a compound having a mass average molecular weight of 1,000 or less.

Further, the term "nano embossing" as used in the present invention means transferring a pattern having a size of about several micrometers to several tens of nanometers.

The photocurable composition of the present invention can be widely used in a photonic lithography method, and can provide, for example, high light transmittance before curing, formation performance of fine concavo-convex patterns, coating suitability, and other processing suitability. , volatility, and skin irritation and other ecological safety, and sensitivity after hardening (rapid hardening), resolution, line edge roughness, film strength, peelability from the mold, residual film characteristics , etching resistance, low hardening shrinkage, substrate adhesion or other excellent coating properties.

In other words, when the photocurable composition of the present invention is used in a photon lithography method, it has the following characteristics: (1) Since the solution has excellent fluidity at room temperature, the composition can be easily The flow into the groove of the mold recess does not cause air bubble defects because it is not easily contained in the air, and no residue is generated even after the convex portion and the concave portion of the mold are hardened.

(2) Because the volatility is small and the skin irritation is small, the safety of the operator is excellent.

(3) Since the cured film is excellent in mechanical properties, the adhesion between the coating film and the substrate is excellent, and the release property of the coating film and the mold is excellent, and when the mold is peeled off, pattern collapse or brushing of the surface of the coating film is not caused. The surface is roughened, so that a good pattern can be formed.

(4) Since the volume shrinkage after photohardening is small and the mold transfer characteristics are excellent, the fine pattern can obtain correct formability.

(5) Since it is excellent in coating uniformity, it can be applied to the application of a large substrate, the field of microfabrication, and the like.

(6) Since the film has a high photohardening speed, productivity is high.

(7) Since it is excellent in etching precision and etching resistance, it can be suitably used as an etching resist for substrate processing such as a semiconductor element or a transistor.

(8) Since the photoresist peeling property after etching is excellent, no residue is generated, and it is suitable as an etching photoresist.

First, the viscosity of the photocurable composition of the present invention will be described. In the present invention, unless otherwise specified, it means the viscosity at 25 °C.

The photocurable composition of the present invention has a viscosity of 3 to 18 mPa at 25 ° C. The scope of s.

By such a viscosity, it is possible to impart fine unevenness forming properties before curing, coating suitability, and other processing suitability, and resolution after hardening, line edge roughness, residual film characteristics, substrate adhesion, or the like. Excellent coating properties. Here, the latest photoresist material manual page 1, page 103~104 (2005, published by the intelligence agencies), recorded a viscosity of 5mPa. The following is preferable, but the inventors of the present invention have concentrated on the results of the study, and found that the viscosity of the composition is not simply lower, the better, only in the specific viscosity range, that is, has 3 to 18 mPa. The object of the invention can be achieved with a specific viscosity range of s.

That is, the photocurable composition of the present invention has a viscosity of less than 3 mPa. In the case of s, there is a problem that the substrate coating suitability or the mechanical strength of the film is lowered. Specifically, when the viscosity is too low, it is not preferable because the composition causes surface unevenness at the time of coating and the composition flows out from the substrate at the time of coating. However, the effect of such viscosity on coating properties has not been disclosed at all.

In another aspect, the photocurable composition of the present invention has a viscosity greater than 18 mPa. In the case of s, when the mold having the fine concavo-convex pattern is adhered to the photocurable composition, it is difficult for the composition to flow into the groove of the concave portion of the mold, and it is easy to contain air bubbles due to easy inclusion of the atmosphere, and it is easy to leave residue in the convex portion of the mold after photohardening. . In addition, the light-sensitive nano-imprinting composition disclosed in the latest photo resist material manual page 1, page 103-104 (2005, information agency publication), because the viscosity is about 50mPa. s, there are problems such as bubble defects or photohardening, which tend to leave residue in the convex portion of the mold, and the application is limited. For example, it is difficult to develop microfabrication applications such as a semiconductor integrated circuit or a thin film transistor of a liquid crystal display. The photocurable composition of the present invention can be suitably used for such applications, and can be widely applied to other applications such as a flat screen, a micro electro mechanical system (MEMS), a sensor element, a compact disc, a high-density storage disc, and the like. Optical parts such as recording medium, diffraction lattice or embossed hologram, nano element, optical element, optical film or polarizing element, organic transistor, color filter, protective layer, microlens array, immunoassay wafer , DNA separation wafers, microreactors, nano-biocomponents, optical waveguides, filters, photonic liquid crystals, and the like.

Further, in the composition of the (a) total polymerizable compound, the polymerizable compound contained in the photocurable composition of the present invention must contain 50% by mass or more of (e) primary skin irritation (PII value). The polymerizable unsaturated monomer below 4.0, and (f) the viscosity at 25 ° C is 30 mPa. Polymeric unsaturated monomers below s. Here, a part or all of the polymerizable unsaturated monomer of the above (e) and the polymerizable unsaturated monomer of the above (f) may be the same polymerizable unsaturated monomer. The ratio of the above polymerizable compound is preferably 60% or more, more preferably 75% or more. The upper limit is not particularly limited, and is a value of 100% by mass in total of other essential components.

Generally, in order to adjust the viscosity of the composition, various monomers, oligomers, and polymers of different viscosities can be mixed, and in order to achieve the object of the present invention, it is necessary to have a viscosity of 50% or more of 30 mPa. A polymerizable unsaturated monomer below s. That is, in the total composition, if 30mPa. When the mass ratio is less than 50%, the ratio of the polymerizable unsaturated monomer below s is likely to be contained in the concave portion of the mold to cause bubble defects, and the residue remains in the convex portion of the mold after photocuring. When a large amount of residue is left, it is preferable that the etching process of the substrate is hindered, and no residue is left. In the past, the effects of mixing monomers, oligomerization, and polymers of various different viscosities have not been known in the composition of photon imprinting.

Here, the skin irritation once (PII value: Primary Irritation Index) refers to an index of irritation to the skin and inflammation of the skin. Evaluation can be based on, for example, ISO-10933 or Draize's improved method (JHDraize et al., "Methods for the application of substances to local skin and mucous membrane irritation and toxicity; Method for the Study of Irritation and Toxicity of Subastance Applied Topically To the Skin and Mucous Membrance, Journal of the Pharmacology and Experimental Therapcutics, 82, 377, 1984, for evaluation, US Consumer of the Consumer Product Safety Commision of the USA The Code of Federal Regulations, Section 16, paragraph 1500.41. Usually classified as 6 stages, no skin irritation when PII value is 0~0.03, slight skin irritation from 0.04 to 0.99, mild skin irritation from 1.0 to 1.99, and weak skin irritation from 2.0 to 2.99 Sexuality, skin irritation from 3.0 to 5.99, strong skin irritation from 6.0 to 8.0.

When the photocurable composition of the present invention contains a compound having high skin irritation, there is a risk of threatening the ecological safety of the operator. In the photocurable composition of the present invention, a polymerizable unsaturated monomer having a PII value of 3 or less is preferably used, and a PII value of 2 or less is particularly preferable.

That is, in the specific component of the photocurable composition of the present invention, a low-viscosity polymerizable unsaturated monomer and a polymerizable unsaturated monomer having a low skin irritation are selected and used as a reactive dilution. The agent can dissolve the components of the composition so as not to increase the viscosity, and can suitably use an etching resist which is processed as a substrate.

The polymerizable compound of the present invention preferably contains a photoradical polymerizable unsaturated monomer or a photocationic polymerizable unsaturated monomer.

In the specific example of the radically polymerizable unsaturated monomer which can be used in the present invention, it is preferred to use a monomer having an ethylenically polymerizable unsaturated bond-containing group.

Examples of the monomer having one ethylenic polymerizable unsaturated bond-containing group include 2-propenyloxyethyl citrate, 2-propenyloxy 2-hydroxyethyl phthalate, and hexahydrofurfuric acid 2. - propylene methoxyethyl ester, 2-propenyl methoxy propyl phthalate, 2-ethyl-2-butyl propylene glycol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl card Alcohol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methyl (meth) acrylate Oxyethyl ester, 3-methoxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimer of acrylic acid, aliphatic epoxy (meth) acrylate, (meth)acrylic acid Benzyl ester, butanediol (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate Ethylene oxide modified (hereinafter referred to as "EO") cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, bicyclo (meth) acrylate Pentene ester, (meth) propylene Dicyclopentenyloxyethyl ester, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, ( Isodecyl methacrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, isotetradecyl (meth)acrylate, lauryl (meth)acrylate, methoxybispropane Glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, ( Methyl)methyl acrylate, neopentyl glycol benzoic acid (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polypropylene glycol (meth) acrylate, (Meth) acrylate octyl ester, p-cumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, phenoxy ( Ethyl methyl acrylate, phenoxy diglycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethyl b Glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, (meth) acrylate stearate, EO modified succinic acid (meth) acrylate, (meth) acrylate third Ester, tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone (meth)acrylate modified tetrahydrofurfuryl ester, tribromophenyl (meth)acrylate, (meth)acrylic acid EO modified tribromophenyl ester, tridecyl (meth)acrylate, trifluoroethyl (meth)acrylate, mono(meth)acrylate, (meth)acrylic acid Adamantyl ester, 3-hydroxyadamantyl (meth)acrylate, p-isopropenylphenol, 4-vinylpyridine, N-methylpropenylamine, N,N-dimethylpropenamide, N,N - diethyl acrylamide, N-hydroxyethyl acrylamide, N,N-dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, styrene, α- Methylstyrene, acrylonitrile, vinyl caprolactam, vinyl carbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, imidoacrylate, vinyl Oxazoline and the like.

Among these, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isodecyl (meth)acrylate, phenoxy (methyl) Ethyl acrylate, phenoxytetraethylene glycol (meth) acrylate, N-vinyl-2-pyrrolidone, N-propylene fluorenyl Porphyrins and the like are particularly suitable for use in the present invention because of low skin irritation and excellent volatility.

Further, in order to improve the mold release property to the mold or the adhesion to the substrate or the coating property, a ruthenium compound such as a (meth) acrylonitrile-modified oxime, a vinyl-modified oxime or an anthrone hexaacrylate can also be used. Commercially available anthrone acrylate (trade name: DESOLAIT Z7500 (JSR), SHC200, SHC900, UVHC85XX series, UVHC11XX series (any one is manufactured by GE-Toshiba SILICONE Co., Ltd.), dimethyloxane mono Acrylate (FM0711, FM0721, FM0725 (any one is manufactured by CHISSO), dimethyloxane dimethacrylate (DMS-V2 (manufactured by CHISSO)), Ebercryl- 1360 (manufactured by DAICEL Chemical Industry Co., Ltd.). Similarly, trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, (perfluorobutyl)ethyl (meth)acrylate, ( Perfluorobutyl hydroxypropyl methacrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl (meth) acrylate, (methyl) A compound containing a fluorine atom such as tetrafluoropropyl acrylate.

Further, in order to improve the adhesion to the substrate, for example, acid ethyl (meth) acrylate, 3-chloro-2-acid phosphopropyl (meth) acrylate, or acid polyethylene PEG can be used in the present invention. A (meth)acrylic acid monomer containing phosphoric acid such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, or 2-(meth) propylene methoxyethyl hexanoate.

The photocurable composition of the present invention may contain an isocyanate-based (meth) acrylate compound in order to improve the substrate adhesion of the photocurable composition of the present invention or the mechanical properties of the film.

Specific examples of the isocyanate-based (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl isocyanate (meth) acrylate. Ester, isopropyl isocyanate (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, dibutyl methacrylate (meth) acrylate And alkyl isocyanate (meth)acrylate such as isocyanate (meth)acrylate; and (meth) propylene decyl isocyanate, (meth) propylene decyl isocyanate Ethyl ester, n-propyl (meth) propylene decyl isocyanate, isopropyl (meth) propylene sulfonate, n-butyl (meth) propylene phthalate, (meth) propylene (Meth)acrylonitrile isocyanate such as isobutyl phthalocyanate, second butyl (meth) propylene phthalocyanate, and tert-butyl (meth) propylene phthalocyanine Alkyl ester.

Further, a (meth)acrylic acid having a dioxalane skeleton can also be used in the photocurable composition of the present invention.

Specific examples of the (meth)acrylic acid of the dioxalane skeleton include 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4-propene.醯oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-cyclohexyl-1,3- Dioxapentane, 4-methylpropenyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl -2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- Methyl propylene methoxymethyl-2-cyclohexyl-1,3-dioxolane and the like.

Among them, preferred are 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4-propenyloxymethyl-2-methyl. 2-isobutyl-1,3-dioxolane and the like.

Examples of the monomer having two ethylenic polymerizable unsaturated bond-containing groups which can be used in the present invention include diethylene glycol monoethyl ether (meth) acrylate and dimethylol dicyclopentane di ( Methyl)acrylate, di(meth)acrylated trimer isocyanate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO modification 1,6-hexanediol di(meth)acrylate, ECH modified 1,6-hexanediol di(meth)acrylate, propyleneoxypolyethylene glycol acrylate, 1.9-nonanediol II Methyl) acrylate, EO modified bisphenol A di(meth) acrylate, PO modified bisphenol A di(meth) acrylate, modified bisphenol A di(meth) acrylate, EO modification Bisphenol F di(meth)acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, neopentyl glycol caprolactone modified hydroxy trimethyl acetate, Stearic acid modified neopentyl alcohol di(methyl) propyl Ether ester, ECH modified di(meth)acrylate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(methyl) Acrylate, polyester (di) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, ECH modified propylene glycol di(meth) acrylate, fluorenone bis ( Methyl) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified tricarboxymethyl Propane di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerin di(meth)acrylate, dipropylene glycol di(methyl) ) acrylate, divinyl acetal, divinyl acetal.

Further, in order to improve the adhesion to the substrate, a bis(meth)acrylic acid monomer containing phosphoric acid such as EO-modified di(meth)acrylate may be used in the present invention.

Among these, 1.9-nonanediol di(meth)acrylate, tri-propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol (Meth) acrylate, polyethylene glycol di(meth) acrylate, etc. are low viscosity and low skin irritation among bifunctional monomers, and are particularly suitable for use in the present invention.

Examples of the polyfunctional monomer having three or more ethylenic polymerizable unsaturated bond-containing groups which can be used in the present invention include ECH-modified glycerol tris(meth)acrylate and EO-modified glycerol tris(methyl). Acrylate, PO modified glycerol tri(meth) acrylate, neopentyl alcohol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified three Hydroxymethylpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, ginseng (propylene oxy group) Ethyl)trimeric isocyanate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylic acid Esters, alkyl-modified dipentaerythritol hydroxypenta(meth) acrylate, dipentaerythritol poly(meth) acrylate, alkyl-modified dipentaerythritol ginseng (meth) acrylate, Bis-trimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, neopentyltetrakis(meth)acrylate, and the like.

Among these, EO-modified glycerol (meth) acrylate, PO-modified glycerol tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, EO-modified trimethylolpropane Tris(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylic acid A trifunctional or higher monomer such as an ester or neopentyltetrakis(meth)acrylate is low in viscosity and low in skin irritation, and is particularly suitable for use in the present invention.

When a material having two or more photopolymerizable functional groups in one molecule is used, since a large amount of photopolymerizable functional groups can be introduced into the composition as described above, the crosslinking density of the composition becomes extremely large, and after the hardening is cured The effect of various physical properties is high. Among various physical properties after hardening, in particular, by increasing the crosslinking density, heat resistance and durability (abrasion resistance, chemical resistance, and water resistance) can be improved, and even when exposed to high heat, friction, or solvent, It is not easy to cause deformation, disappearance, and damage of the fine concavo-convex pattern.

In order to further increase the crosslinking density, the photocurable composition of the present invention can be formulated with a polyfunctional oligomer or polymer having a molecular weight larger than that of the above polyfunctional body within the scope of achieving the object of the present invention. Examples of the polyfunctional oligomer having a photo-radical polymer include various acrylate oligomers such as polyester acrylate, polyacrylic acid urethane, polyether acrylate, and polyepoxy acrylate, and phosphorus muscle. Acid skeleton, adamantane skeleton, Cardo skeleton, descending An oligomer or a polymer having a high volume structure such as an olefin skeleton.

The polymerizable unsaturated monomer used in the present invention may also be a compound having an oxirane ring. The compound having an oxirane ring may, for example, be an alicyclic polyepoxide, a polyepoxypropyl ester of a polybasic acid, a polycyclopropyl ether of a polyhydric alcohol, or a polycycloethylene polyoxyethylene diol. Hydroxypropyl ethers, polyepoxypropyl ethers of aromatic polyols, hydrogenated compounds of polyepoxypropyl ethers of aromatic polyols, urethane polyepoxides and epoxidized poly Butadiene and the like. These compounds may be used alone or in combination of two or more.

Commercially available products of the epoxy group-containing compound include UVR-6216 (manufactured by Uniion Carbide Co., Ltd.), GLYCIDOL, AOEX24, CYCROMER-A200 (above, manufactured by Daicel Chemical Industry Co., Ltd.), EPICOAT 828, and EPICOAT. 812, EPICOAT 1031, EPICOAT 872, EPICOAT CT 508 (above, oiled SHELL (share) system), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Electrochemical industry (shares) system, etc. These may be used alone or in combination of two or more.

Moreover, such compounds having an oxirane ring are not limited to the preparation method thereof, for example, refer to Maruzen KK Publishing, Fourth Edition Experimental Chemistry Lecture 20 Organic Synthesis II, 213~, Heisei 4, edited by Alfred Hasfner, Heterocyclic Compounds The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Pulication, New York, 1985, Yoshimura, Next, 29 No. 12, 32, 1985, Yoshimura, vol., No. 30, No. 5, No. 42, 1986, Yoshimura, et al., Vol. 30, No. 7, No. 42, 1986, Japanese Patent Laid-Open No. 11-100378, and No. 2906245. It is synthesized by a document such as Japanese Patent No. 2926262.

The polymerizable unsaturated compound used in the present invention may, for example, be an oxetane compound. The oxetane compound can be suitably used, for example, in the oxetane compound described in JP-A-2001-310937, JP-A-2001-210526, and JP-A-2001-310937. Further, in order to improve heat resistance, film hardness, and mold release property, a phthalate compound having an oxetanyl group or a fluorine compound having an oxetanyl group may also be used.

The compound having one oxetane ring in the molecule may, for example, be 3-ethyl-3-hydroxymethyloxetane or 3-(methyl)allyloxymethyl-2- Ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetane) Methoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl) 3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl)ether, isodecyloxy B (3-ethyl-3-oxetanylmethyl)ether, isodecyl (3-ethyl-3-oxetanylmethyl)ether, 2-ethylhexyl (3- Ethyl-3-oxetanylmethyl)ether, ethyldiglycol (3-ethyl-3-oxetanylmethyl)ether, dicyclopentadiene (3-ethyl-) 3-oxetanylmethyl)ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl)ether, dicyclopentene (3-ethyl-3) -oxetanylmethyl)ether, tetrahydroindenyl (3-ethyl-3) -oxetanylmethyl)ether, tetrabromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tetrabromophenoxyethyl (3-ethyl- 3-oxetanylmethyl)ether, tribromophenyl(3-ethyl-3-oxetanylmethyl)ether, 2-tribromophenoxyethyl (3-ethyl- 3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl (3-ethyl-3- Oxetanemethyl)ether, butoxyethyl (3-ethyl-3-oxetanyl)ether, pentachlorophenyl (3-ethyl-3-oxetane) Alkylmethyl)ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl)ether, (3-ethyl-3-oxetanylmethyl)ether, 3-(4-bromobutoxymethyl)-3-methyloxetane, (3-methyloxa) Cyclobutane-3-yl)methylbenzoate or the like.

The compound having two or more oxetane rings in the molecule may, for example, be 3,7-bis(3-oxetanyl)-5- Decane, 3,3'-(1,3-(2-methylene)propanediylbis(hydroxymethylene))bis(3-ethyloxetane), 1,4-double [ (3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl] Biphenyl, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxocyclo) Butyryl methoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentene bis(3-ethyl-3-oxa Cyclobutanemethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl) Methyl)ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl)ether, trimethylolpropane ginseng (3-ethyl-3-oxo) Cyclobutanemethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxa Cyclobutane methoxy)hexane, neopentyl alcohol ginseng (3-ethyl-3-oxetanylmethyl)ether, neopentyl sterol oxime (3-ethyl 3-oxetanylmethyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl- 3-oxetanylmethyl)ether, caprolactone modified dineopentalol hexa(3-ethyl-3-oxetanylmethyl)ether, caprolactone modified two new Pentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, bistrimethylolpropane oxime (3-ethyl-3-oxetanylmethyl)ether, EO Modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether , EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetane Alkylmethyl)ether, EO-modified bisphenol F bis(3-ethyl-3-oxetanylmethyl)ether, poly(3-(4-bromobutoxymethyl)-3- Methyloxetane), N-oxetan-2-ylmethoxymethylpropane Indoleamine, 3,5-bis(3-ethyl-oxetanylmethoxy)benzoic acid, 3,5-bis(3-ethyl-oxetanylmethoxy)benzoic acid Methyl ester, 5-(3-ethyl-3-oxetanyl)isodecanoic acid, 1,1,1-gin[4(3-ethyl-3-oxetanylmethoxy) Phenyl]ethane and the like. These may be used alone or in combination of two or more.

The method for producing each of the above compounds having an oxetane ring is not particularly limited and can be carried out according to a previously known method, for example, by Pattison (DB Patticon, J. Am. Chem. Soc., 3455, 79 (1957). A method of synthesizing an oxetane ring from a diol, and the like.

Further, a compound having a high molecular weight of about 1 to 4 oxetane rings having a molecular weight of about 1,000 to 5,000 is also mentioned.

As a commercial product of the oxetane compound, for example, OXT101 (3-ethyl-3-hydroxyoxetane, manufactured by Toagosei Co., Ltd., OXT221 (two [1-ethyl (3-oxa)) can be used. Cyclobutane) methyl ether], 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene manufactured by Toagosei Co., Ltd., OXT211 (3) manufactured by Toagosei Co., Ltd. -ethyl-3-(phenoxymethyl)oxetane), MPO (3,3-dimethyl-2-(p-methoxyphenyl)oxetane) manufactured by Toagosei Co., Ltd. Ube Industries Co., Ltd. ETERNACOLL OXBP.

Among these, an oxetane compound which is a constituent component of the photocurable composition of the present invention can be suitably used, and the number of oxetane rings in the molecule is preferably from 1 to 10, and is from 1 to 4 Better. Specifically, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 1,4-bis[(3-ethyl-2-oxetanylmethoxy) )methyl]benzene, 1,2-bis(3-ethyl-3-oxetanylmethoxy)ethane trimethylolpropane (3-ethyl-3-oxetane) Methyl)ether, 3-ethyl-3-oxetanylmethoxybenzene, and the like.

The polymerizable compound to be used in the invention may be appropriately selected from the group consisting of a vinyl ether compound and a vinyl ether compound, and examples thereof include 2-ethylhexyl vinyl ether and butanediol-1,4-divinyl ether. Cyclohexane dimethanol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,3-propanediol ethylene Ether, 1,3-butanediol vinyl ether, 1,4-butanediol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane three Vinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol divinyl Ethyl ether, neopentyl alcohol trivinyl ether, neopentyl alcohol tetravinyl ether, sorbitol tetravinyl ether, sorbitol penta vinyl ether, ethylene glycol diethyl vinyl ether, triglyceride Alcohol diethyl ether, ethylene glycol dipropyl vinyl ether, triethylene glycol diethyl vinyl ether, trimethylolpropane triethyl ether, three Hydroxymethylpropane di-ethyl vinyl ether, neopentyl alcohol di-ethyl vinyl ether, neopentyl alcohol tri-ethyl vinyl ether, neopentyl alcohol tetraethyl vinyl ether, isoindole Vinyl ether, Vinyl ether, cyclopentyl vinyl ether, 1,1,1-gin[4-(2-hydroxyethoxy)phenyl]ethane, bisphenol A dihydroxyethyl ether, and the like.

These vinyl ether-based compounds are characterized by low viscosity, low odor, and low skin irritation, and are useful in radical polymerization or in cationic polymerization.

Such vinyl ethers can be, for example, by the method described in Stephen. C. Lapin, Polymers Paint Colour Journal. 179 (4237), 321 (1988), that is, by reacting a polyhydric alcohol or a polyhydric phenol with acetylene. Alternatively, the polyol or the polyhydric phenol may be used in combination with a halogenated alkyl vinyl ether. These may be used alone or in combination of two or more.

The polymerizable compound used in the present invention may, for example, be a styrene derivative. The styrene derivative may, for example, be styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, or the like. Methoxy-β-methylstyrene, p-hydroxystyrene, etc., vinylnaphthalene derivatives such as 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinyl Naphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, etc., and examples of the N-vinyl compound include N-vinylcarbazole and N-vinylpyrrolidone. , N-vinyl anthracene, N-vinylpyrrole, N-vinylmorphophene , N-vinylacetanilide, N-vinylethylacetamide, N-vinyl succinimide, N-vinyl quinone imine, N-vinyl caprolactam, N-vinyl Imidazole and the like.

A propenyl ether and a butenyl ether can be formulated as the polymerizable compound used in the present invention. For example, 1-dodecyl-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-nor Alkene, 1-4-bis(1-butoxy)butane, 1,10-bis(1-butoxy)decane, 1,4-bis(1-butoxymethyl) ring Hexane, diethylene glycol bis(1-butenyl)ether, 1,2,3-tris(1-butoxy)propane, propylene ether propylene carbonate, and the like are suitable.

In the photocurable composition of the present invention, various polyol compounds may be formulated as necessary. It is applicable to polyols such as ethylene glycol, glycerin, neopentyl alcohol, dipentaerythritol, trihydroxypropane, ditrihydroxypropane, neopentyl glycol, spiroethylene glycol, various polyether polyols, various kinds of poly Ester polyols and various caprolactone polyols can be used. By adding such various polyols, the hardening speed can be increased. Among these polyols, since the hydroxyl group equivalent is small, the compatibility with the epoxy compound and/or the oxetane compound which is a main component of the photocationic curable composition is excellent, and the viscosity increase due to the addition is small, The use of ethylene glycol or trihydroxypropane is preferred in the present invention.

These polyols may be used alone or in combination of two or more. The molecular weight of the polyol used is preferably from 100 to 50,000, more preferably from 160 to 20,000. By using a polyol having a molecular weight in this range, a photocurable composition having good shape stability and physical stability can be obtained, and the viscosity of the obtained photocurable composition can be suppressed from being excessively large and the modulus of elasticity tends to be lowered.

In the present invention, a photocationic polymerizable reaction component as a polymerizable unsaturated compound is used, and not only a compound having a cationically reactive single functional group such as an epoxy group, an oxetane group or a vinyl group in one molecule, Further, a compound having a plurality of types of functional groups in the same molecule can also be applied.

For example, a compound containing a vinyl ether group and an epoxy group in the same molecule or a reactive compound containing a propenyl ether group and an epoxy group can be used.

Further, as the reactive component of the photocationic polymerizability and the photoradical polymerizability, methyl 3-methyl-3-oxetanyl acrylate (OXE-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3-A can be used. Methyl 3-oxetanyl acrylate (OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd.), vinylcyclohexene oxide 1,2-ethoxy-4-vinylcyclohexane (DAICEL) Chemical industry, CELOXIDE 2000), a compound having a oxetane ring (meth) acrylate compound (ETERNACOLL OXMA, etc.).

The photocurable composition of the present invention may contain a mixture of a reactive component having a radical scavenging mechanism as necessary. In the case of the cation-curable component containing an epoxy compound, an oxetane compound, a vinyl compound or the like as a reactive compound, a radical-curable component such as a compound containing an acryl-based group, and The free radical hardening initiator is obtained. The compound containing a propylene fluorenyl group is preferably a compound having a cationically polymerizable vinyl ether and a radically polymerizable acryl oxime group in the same molecule, such as (meth)acrylic acid-(vinyloxy)ethyl ester. Wait.

The commercially available product of the mixed compound is, for example, methyl 3-methyl-3-oxetanyl acrylate (OXE-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3-methyl-3-oxacyclohexane. Methyl butane acrylate (OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd.), (meth) acrylate compound having oxetane ring (ETERNACOLL OXMA, etc.), Acrylic acid-2-(2- Ethoxyethoxyethyl)ethyl ester or 2-(2-vinyloxyethoxy)ethyl methacrylate (VEEA, VEEA), 3,4-ethoxycyclohexyl (methyl) Acrylate (made by Daicel Chemical Industry Co., Ltd., CYCROMER-A400, A100).

Next, a preferred mixed form of the photoradical polymerizable monomer of the photocurable composition of the present invention will be described. The photocurable composition of the present invention contains 50% by mass or more and a viscosity of 30 mPa. a polymerizable unsaturated monomer of s or less (preferably a monomer having one ethylenically unsaturated bond-containing group, a monomer having two ethylenically unsaturated bond-containing groups, and having three ethylenic unsaturations) The bond is mixed and used in such a manner that one or more of the monomers are contained.

In the present invention, a photoradical polymerizable monomer having one unsaturated bond-containing group can be generally used as a reactive diluent, and is effective for lowering the viscosity of the photocurable composition of the present invention to account for total polymerizability. 80% by mass or less of the compound is preferable, 70% by mass or less is more preferable, and addition in a range of 60% by mass or less is particularly preferable. The cured film obtained by curing the photocurable composition of the present invention has better mechanical strength, etching resistance, and heat resistance by setting the ratio of the monomer having one unsaturated bond-containing group to 80% by mass or less. In the case of using a mold material which is a photon imprint, it is preferable to suppress the tendency of the mold to deteriorate due to swelling of the mold. On the other hand, since it is more preferable to use a monomer having one and/or two unsaturated bond-containing groups as a reactive diluent, a monomer having one and/or two unsaturated bond-containing groups is added. It is better.

The monomer having two unsaturated bond-containing groups is preferably 90% by mass or less based on the total polymerizable compound, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The ratio of the monomer having one and/or two unsaturated bond-containing groups is preferably from 1 to 95% by mass based on the total polymerizable compound, more preferably from 3 to 95% by mass, and from 5 to 90% by mass. The range is added as a special one. The ratio of the monomer having three unsaturated bond-containing groups is preferably 80% by mass or less based on the total polymerizable compound, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting the ratio of the monomer having three or more unsaturated bond-containing groups to 80% by mass or less, it is possible to more easily adjust the viscosity of the composition to the viscosity range of the present invention.

Further, a preferred form of mixing of the photocurable polymerizable monomer in the photocurable composition of the present invention will be described. The mixing range of the photocationic monomer is not particularly limited as long as it does not deviate from the viscosity condition and the PII value of the present invention.

In the present invention, a cationically polymerizable monomer having one cationically polymerizable group can be generally used as a reactive diluent, and is effective for lowering the viscosity of the photocurable composition of the present invention, and accounts for 95% by mass of the total monomer. The following is preferable, and it is more preferably 90% by mass or less, and particularly preferably 85% by mass or less. When the ratio of the monomer having one cationically polymerizable group is 95% by mass or less, the mechanical strength, etching resistance, and heat resistance of the cured film tend to be more excellent, and it is preferable to use an organic polymer. When it is a mold material for photon imprinting, it is possible to suppress swelling due to the mold. Reduce the tendency of the mold to deteriorate. On the other hand, since a single system having one and/or two cationically polymerizable groups is used as a reactive diluent, it is necessary to add a monomer having one and/or two cationically polymerizable groups to account for the total amount. The content is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more.

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

Moreover, the organic solvent content of the photocurable composition of the present invention is preferably 3.0% by mass or less based on the total composition. That is, since the photocurable composition of the present invention preferably contains a specific monofunctional and/or bifunctional monomer as a reactive diluent, it is not necessarily required to dissolve the photocurable composition of the present invention. The organic solvent of the ingredients. In addition, when the organic solvent is not contained, a baking step for the purpose of volatilizing the solvent is not required, and there is an advantage that the steps can be simplified in an efficient manner. Therefore, the organic solvent content of the photocurable composition of the present invention is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and particularly preferably not contained. Although the photocurable composition of the present invention does not necessarily require an organic solvent, when a compound in which the reactive diluent is insoluble is dissolved to form the photocurable composition of the present invention, or when the viscosity is finely adjusted, it can be arbitrarily added. In the preferred solvent which can be used for the photocurable composition of the present invention, a solvent which is a photocurable composition or a photoresist is usually used, and if the compound used in the present invention can be dissolved and uniformly dispersed, it does not The substance to be reacted with these components is not particularly limited.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ether, and ethylene glycol monoethyl ether. Glycol ethers; ethylene glycol alkyl ether acetates such as methyl sarbuta acetate and ethyl sarbuta acetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, two Diethylene glycol such as glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as acid esters; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-glycol Ketones such as ketones; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate , methyl 2-hydroxy-2-methyl decanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl acetate, ethyl acetate, butyl acetate, Methyl lactate, ethyl lactate esters, esters, etc. and the like.

Furthermore, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol High-boiling solvent such as ethyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl racelus acetate . These may be used alone or in combination of two or more.

Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, Methyl isobutyl ketone, 2-heptanone and the like are particularly preferred.

A photopolymerization initiator and/or a photoacid generator can be used as the photocurable composition of the present invention. The photopolymerization initiator and/or photoacid generator used in the present invention has a mass ratio of 0.1 to 15% by mass in the total composition, preferably 0.2 to 12% by mass, and 0.3 to 10% by mass. Better. In the case where other photopolymerization initiators and photoacid generators are used in combination, the total amount of these is in the above range.

Therefore, the photocurable composition of the present invention contains both a material which can be photocured by radical polymerization and/or cationic polymerization, and a product which is photocured.

When the ratio of the photopolymerization initiator and/or the photoacid generator is less than 0.1% by mass, the sensitivity (rapid hardenability), the resolution, the line edge roughness, and the coating film strength are deteriorated, which is not preferable. On the other hand, when the ratio of the photopolymerization initiator and/or the photoacid generator is more than 15% by mass, light transmittance, coloring property, handleability, and the like are deteriorated, which is not preferable. Conventionally, in the inkjet composition containing a dye and/or a pigment, or the liquid crystal display color filter composition, although the amount of the photopolymerization initiator and/or the photoacid generator to be added is variously studied, various studies have been made. The amount of the photopolymerization initiator and/or photoacid generator added to the photocurable composition for nanoimprinting or the like has not been reported. That is, in the case of a system containing a dye and/or a pigment, these have a function as a radical coupling agent, which affects photopolymerization and sensitivity. In consideration of this point, these uses are most suitably determined by the addition amount of the photopolymerization initiator. On the other hand, in the photocurable composition of the present invention, the dye and/or the pigment are not essential components, and the optimum range of the photopolymerization initiator may be a composition for an inkjet or a composition for a color filter of a liquid crystal display. There are different situations in the field.

The photopolymerization initiator used in the present invention is a substance which is active at a wavelength of a light source to be used, and is a substance which can produce an appropriate active species depending on the reaction form (for example, radical polymerization or cationic polymerization). . 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. These may, for example, be Irgacure (registered trademark) 2959 (1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methyl-1-propene-) commercially available from Ciba Corporation. 1-ketone, Irgacure (registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, diphenyl ketone), Irgacure (registered trademark) 651 ( 2,2-dimethoxy-1,2-diphenylethan-1-one), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-) Phenanylphenyl)butanone-1), Irgacure (registered trademark) 907 (2-methyl-1[4-methylthiophenyl]-2- Phenylpropan-1-one, Irgacure (registered trademark) 819 (bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, Irgacure (registered trademark) 1800 (double (2,6-two) Methoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-one), Irgacure (registered trademark) 1800 (double (2,6-) Dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure ( Registered trademark) OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzamide), Darocur (registered trademark) 1173 (1-hydroxy- 2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1-[9-ethyl-6-(2- Methyl benzhydryl)-9H-indazol-3-yl]1-(O-acetamidine), Lucirin TPO (2,4,6-trimethylbenzylidene) available from BASF Diphenylphosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzhydrylphenylethoxyphosphine oxide), ESACURE 1001M (1) available from ESACURE Japan SiberHegner (NSH) -[4-Benzyl fluorenyl Alkylsulfonyl]phenyl)-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, ADEKAOPTOMER (registered trademark) N which can be purchased from N-1414 Asahi Chemical Co., Ltd. -1414 (carbazole-phenol system), ADEKAOPTOMER (registered trademark) N-1717 (acridine system), ADEKAOPTOMER (registered trademark) N-1606 (three Department), three and CHEMICAL TFE-three (2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), three and CHEMICAL TME-three (2-[2-(5-methylfuryl-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), three and CHEMICAL made MP-three (2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI chemical system TAZ-113 (2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI chemical system TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, methyl-2-diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulphide Ether, 4-phenyldiphenyl ketone, ethyl melamine, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone 2,4-Diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethyl Oxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzyl dimethyl ketal, 1,1,1-three Chlorophene benzene, diethoxy acetophenone and dibenzocycloheptanone, methyl phthalic acid benzoate, 2-benzylidene naphthalene, 4-benzylidene biphenyl, 4-benzyl hydrazine Phenyl ether, 1,4-benzylidene benzene, benzoin, 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane), 2-B Base, 2,2-bis(2-chlorophenyl)4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'-diimidazole, 2,2 - bis(o-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-diimidazole, ginseng (4-dimethylamino group) Methane, ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, butoxyethyl-4-(dimethylamino)benzene Formate and so on.

The photocationic polymerization initiator which can be used in the photocurable composition of the present invention is a compound which can form a substance capable of initiating photocationic polymerization by receiving an energy ray such as ultraviolet rays. A phosphonium salt or an aryl iodide salt is preferred.

Further, in the photocurable composition of the present invention, in addition to the photopolymerization initiator and/or the photoacid generator, a photosensitizer may be added to adjust the wavelength of the UV region. Typical sensitizers which can be used in the present invention include those disclosed by Crivello [JVCrivello, Adv. in Polymer Sci, 62, 1 (1984)], and specifically, ruthenium, osmium, acridine orange, Thioxanthone, 2-chlorothioxanthone, benzoxanthin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, oxocoumarin, phenanthrene, camphor Thiophene Derivatives, etc.

In order to induce the light of the polymerization of the present invention, not only ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light or the like, but also light or electromagnetic waves, the radiation system includes, for example, microwave, electron beam, EUV, X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can be used. Such light may be monochromatic light (single wavelength light) transmitted through the filter, or multiple light of different wavelengths (composite light). The exposure may be multiple exposures, and for the purpose of improving film strength and etching resistance, it is also possible to perform full-surface exposure after patterning.

The photopolymerization initiator used in the present invention must be appropriately selected in accordance with the wavelength of the light source to be used, and it is preferred that the gas is not generated during pressurization or exposure of the mold. It is preferable that the gas is not generated, the mold is not contaminated, the frequency of the washing mold can be lowered, and the photocurable composition is not easily deformed in the mold without deteriorating the accuracy of the transfer pattern. .

The photocurable composition of the present invention contains at least one of 0.001 to 5% by mass of a fluorine-based surfactant, a lanthanoid surfactant, and a fluorine-antimony surfactant. The ratio of the above surfactant in the composition is preferably 0.002 to 4% by mass, particularly preferably 0.005 to 3% by mass.

Here, the fluorine-rhodium-based surfactant refers to a material having both a fluorine-based surfactant and a lanthanoid surfactant.

By using such a surfactant, the viscosity of the composition can be reduced, and the purpose of the present invention is to solve the problem of applying the photocurable composition of the present invention to a silicon wafer for manufacturing a semiconductor device or a glass square substrate for manufacturing a liquid crystal device. A chromium film, a molybdenum mold, a molybdenum alloy film, a ruthenium film, a ruthenium alloy film, a nitrogen ruthenium film, an amorphous ruthenium film, an indium oxide (ITO) film in which tin oxide is doped, or a film such as a tin oxide film are formed. Problems such as coating defects such as streaks or scaly patterns (drying unevenness of the photoresist film) generated on the substrate, improvement of the flow of the composition into the grooves of the mold recess, improvement of the release property between the mold and the photoresist, Improve the adhesion between the photoresist and the substrate. In particular, in the photocurable composition of the present invention, coating uniformity can be greatly improved by adding the above-mentioned surfactant, and coating by spin coating or slit coating can be applied regardless of the substrate size. Suitability.

Examples of the nonionic fluorine-based surfactant to be used in the present invention include FRORAD FC-430 and FC431 (manufactured by Sumitomo 3M Co., Ltd.), SARFRON "S-382" (made by Asahi Glass Co., Ltd.), and EFTOP "EF". -122A, 122B, l22C, EF-121, EF-126, EF-127, MF-100" (manufactured by TOHKEM PRODUCT Co., Ltd.), trade name PF-636, PF-6320, PF-656, PF-6520 (any All are manufactured by OMNOVA), trade names FTAGENT FT250, FT251, DFX18 (any one is NEOS (share) system), trade names YUNIDAIN DS-401, DS-403, DS-451 (any one is DAIKIN) Industrial Co., Ltd., and trade names MEGAFAC 171, 172, 173, 178K, and 178A (all of which are manufactured by Dainippon Ink Chemical Industry Co., Ltd.), and examples of the nonionic lanthanum surfactant are exemplified by Product name: SI-10 series (made by Takemoto Oil Co., Ltd.), MEGAFACPENTAD31 (made by Dainippon Ink Chemical Industry Co., Ltd.), KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The fluorine-antimony surfactant used in the present invention may, for example, be trade names X-70-090, X-70-091, X-70-092, X-70-093 (any one is Shin-Etsu Chemical Industry) (product) MEGAFAC R-08, XRB-4 (any one is manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

The blending amount of the fluorine-based surfactant, the rhodium-based surfactant, and the fluorine-fluorene-based surfactant is a total amount of these surfactants, and is adjusted in the range of 0.001 to 5% by mass in the composition to be 0.01. A range of ~3 mass% is preferably added. When the fluorine-based surfactant, the lanthanoid surfactant, and the fluorine-ruthenium-based surfactant are blended in the composition to be less than 0.001% by mass, the effect of uniformity of coating is insufficient. On the other hand, when it is more than 5% by mass, It will make the transfer characteristics of the mold worse, which is not good. The fluorine-based surfactant, the lanthanoid surfactant, and the fluorine-antimony surfactant used in the present invention may be used singly or in combination of two or more. In the present invention, it is preferable to contain both a fluorine-based surfactant and a lanthanoid surfactant, or a fluorine-ruthenium-based surfactant, and it is preferable to contain a fluorine-ruthenium-based surfactant.

For the purpose of improving the flexibility of the photocurable composition, etc., other nonionic surfactants may be used in combination with the photocurable composition of the present invention. A commercially available product of a non-ionic surfactant is exemplified by polyoxane such as D-3110, D-3120, D-3412, D-3440, D-3510, and D-3605 of PIONINE series manufactured by Takemoto Oil Co., Ltd. Polyoxyethylene alkyl ethers of D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, D-1518, etc. of PIONINE series manufactured by ethylene alkylamine and Zhuben Oil Co., Ltd. PIONINE series of D-2112-A, D-2112-C, D-2123-C and other polyoxyethylene mono-fatty acid esters of the PIONINE series, and the PIONINE series of D-made by the bamboo oils and fats. Polyoxyethylene difatty acid esters such as 2405-A, D-2410-D, and D-2110-D, D-406, D-410, D-414, and D-418 of PIONINE series manufactured by Takeshi Oil Co., Ltd. Polyoxyethylene alkyl phenyl ether, etc., polyoxyethylene tetramethyl decyne diol diether such as 104S, 420, 440, 465, and 485 of the SAFINOL series manufactured by Nissin Chemical Industry Co., Ltd., and the like. Further, a reactive surfactant having a polymerizable unsaturated group can also be used in combination with the surfactant used in the present invention. For example, allyloxy polyethylene glycol monomethacrylate (Japanese fat (stock) trade name: BLENMER PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Japanese fats and oils) ): BLENMER PNE series), mercaptophenoxy polypropylene glycol monomethacrylate (Japanese fat (stock) trade name: BLENMER PNP series), nonylphenoxy poly(ethylene glycol-propylene glycol) monomethyl Acrylate (Japanese oil (stock) trade name: BLENMER PNEP-600), AKUARON RN-10, RN-20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (First Industrial Pharmaceutical Co., Ltd.) and the like.

In addition to the above components, the photocurable composition of the present invention may further contain a release agent, a decane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a photostabilizer, an antioxidant, a plasticizer, and an adhesion promoter, as necessary. , a thermal polymerization initiator, a colorant, inorganic particles, elastomer particles, an antioxidant, a photoacid proliferation agent, a photobase generator, a basic compound, a flow regulator, an antifoaming agent, a dispersant, and the like.

In order to improve the heat resistance, the strength, or the adhesion to the metal deposition layer of the surface structure having the fine concavo-convex pattern, the photocurable composition of the present invention may be formulated with an organic metal coupling agent. Further, the organic metal coupling agent has an effect of promoting a heat hardening reaction. As the organic metal coupling agent, for example, 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 organometallic coupling agent may be optionally blended at a ratio of 0.001 to 10% by mass based on the total amount of the solid components of the photocurable composition. When the ratio of the organic metal coupling agent is 0.001% by mass or more, the effect is improved in terms of improving heat resistance, strength, or adhesion to the metal deposition layer. On the other hand, when the ratio of the organic metal coupling agent is 10% by mass or less, it tends to suppress the stability of the composition and the defect of film formability.

The commercially available products of the antioxidants include Irganox 1010, 1035, 1076, and 1222 (above, CIBA-GEIGY Co., Ltd., Antigene P, 3C, FR, SUMILIZER (manufactured by Sumitomo Chemical Industries, Ltd.), etc. The amount of the antioxidant is preferably 0.01 to 10% by mass.

Commercial products of the ultraviolet absorber include, for example, Tinuvin P, 234, 320, 326, 327, 328, and 213 (above, CIBA-GEIGY Co., Ltd., Sumisorb 110, 130, 140, 220, 250, 300, 320). 340, 350, 400 (above, Sumitomo Chemical Co., Ltd.), etc. The ultraviolet absorber is preferably arbitrarily blended in an amount of 0.01 to 10% by mass based on the total amount of the photocurable composition.

Commercial products of the light stabilizers include, for example, Tinuvin 292, 144, and 622 LD (above, CIBA-GEIGY Co., Ltd., SANOL LS-770, 765, 292, 2626, 1114, 744 (above, Sankyo Chemical Industry Co., Ltd.) The system is preferably a ratio of 0.01 to 10% by mass based on the total amount of the composition.

Commercial products of the anti-aging agent include Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Industries Co., Ltd.). The ratio of the antioxidant to the total amount of the composition is preferably 0.01 to 10% by mass.

A plasticizer may be added to the photocurable composition of the present invention in order to adjust the adhesion between the photocurable composition of the present invention and the substrate, or the flexibility, hardness, and the like of the film. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, dilauryl citrate, triethylene glycol dicaprylate, dimethylethanol phthalate, tricresyl phosphate, dioctyl adipate, Dibutyl sebacate, triethyl decyl glycerol, dimethyl adipate, diethyl adipate, di-n-butyl adipate, dimethyl suberate, diethyl suberate, octyl In the composition, the plasticizer can be arbitrarily added in an amount of 30% by mass or less. It is preferably 20% by mass or less, more preferably 10% by mass or less. In order to obtain the effect of adding a plasticizer, it is preferably 0.1% by mass or more.

When the photocurable composition of the present invention is cured, a thermal polymerization initiator can be added as necessary. Preferred examples of the thermal polymerization initiator include a peroxide and an azo compound. Specific examples thereof include benzamidine peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, and the like.

For the purpose of adjusting the shape, sensitivity, and the like, a photobase generator may be added to the photocurable composition of the present invention as necessary. Preferred examples include, for example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-aminoformamidine hydroxyguanamine, O-aminoformamidine, [[(2) ,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzene) Methotyl)-1-methyl-1- Chlorinated ethane, (4- Phenylbenzylidene)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, ginseng(triphenylmethylborate)hexa-cobalt(III) 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butane, 2,6-dimethyl-3,5-diethylindole-4-(2'-nitrophenyl)-1,4-dipyrrolidine, 2,6-dimethyl 3-3,5-Diethylinden-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine or the like.

In order to improve the visibility of the coating film, the photocurable composition of the present invention may optionally be added with a coloring agent. In the range which does not impair the object of the present invention, a pigment or a dye such as a composition for a UV inkjet composition, a composition for a color filter, and a composition for a CCD image sensor can be used as the colorant. As the pigment which can be used in the present invention, various inorganic pigments or organic pigments which are well known in the past can be used. Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal composites. Oxide. The organic pigments can be exemplified by CI Pigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139, 151, 154, 167, CI Pigment Orange, 36, 38, 43, CI Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, CI Pigment Violet 19, 23, 32, 39, CI Pigment Blue 1, 2, 15, 16, 22, 60, 66, CI Pigment Green 7, 36, 37, CI Pigment Brown 25, 28, CI Pigment Black 1, 7 and carbon black.

The inorganic fine particles are preferably a ratio of 1 to 70% by mass in the total solid content of the photocurable composition, and a ratio of 1 to 50% by mass is particularly preferable. When the ratio of the inorganic fine particles is 1% by mass or more, the formability, the shape retainability, and the mold release property of the photocurable composition of the present invention can be sufficiently increased, and when the ratio of the inorganic fine particles is 70% by mass or less, It is preferable from the viewpoint of the strength after the exposure and the surface hardness.

Moreover, in order to improve mechanical strength, flexibility, and the like, the elastomer particles may be arbitrarily added to the photocurable composition of the present invention.

The average particle size of the elastomer particles which can be added as an optional component to the photocurable composition of the present invention is preferably from 10 nm to 700 nm, more preferably from 30 nm to 300 nm. For example, polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/isoprene copolymer, ethylene/propylene copolymer, ethylene/α -Olefin-based copolymer, ethylene/α-olefin/polyene copolymer, acrylic rubber, butadiene/(meth)acrylate copolymer, styrene/butadiene block copolymer, styrene/isopropylene A particle of an elastomer such as a segment copolymer. Further, core/shell type particles in which the elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate/glycidyl methacrylate copolymer or the like can be used. The elastomer particles may also be crosslinked structures.

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

The photocurable composition of the present invention can contain a well-known antioxidant. Based antioxidant to inhibit discoloration caused by light irradiation and by ozone, active oxygen, NO _x, SO _{x (X} is an integer), and other oxidizing gases of fading was caused. Examples of such antioxidants include anthraquinones, hindered amine-based antioxidants, nitrogen-containing heterocyclic hydrogen sulfide-based compounds, thioether-based antioxidants, hindered phenol-based antioxidants, ascorbic acid, zinc sulfate, thiocyanate, and sulfur. Urea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.

The basic compound may be arbitrarily added to the photocurable composition of the present invention for the purpose of suppressing the curing shrinkage and improving the thermal stability. The basic compound may, for example, be an amine and a quinoline and a quinolin. A nitrogen-containing heterocyclic compound, a basic alkali metal compound, a basic alkaline earth metal compound, or the like. Among them, an amine is preferred from the viewpoint of compatibility with a photopolymerizable monomer, and examples thereof include octylamine, naphthylamine, xylylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, and Methylaniline, quinuclidine, tributylamine, dioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine and triethanolamine.

In the present invention, in the cationic polymerization initiator which generates an acid by an energy ray, a substance which generates a new self-catalytic acid (hereinafter referred to as an acid proliferator) by the action of the generated acid may be combined. Improve the hardening speed. Specific examples of the compound shown in JP-A-H08-248561, JP-A No. 10-1508, and No. 3102640 include 1,4-bis(p-toluenesulfonyloxy). Cyclohexane, cis-3-(p-toluenesulfonyloxy)-2-nonanol, cis-3-(p-octanesulfonyloxy)-2-nonanol, and the like. Commercially available compounds include AKPREX 11M (manufactured by CHEMIX Co., Ltd.) and the like.

Next, a method of forming a pattern (particularly, a fine concavo-convex pattern) using the photocurable composition of the present invention will be described. In the present invention, a curable composition is applied and hardened to form a pattern. Specifically, at least a pattern forming layer composed of the photocurable composition of the present invention is applied onto a substrate or a support, and dried as necessary to form a layer (pattern forming layer) composed of a photocurable composition. The pattern is received and received by the mold, and the surface of the pattern forming layer of the pattern acceptor is pressure-welded to transfer the mold pattern, and then the fine uneven pattern forming layer is exposed and cured. The photoimprint lithography method according to the pattern forming method of the present invention can also be laminated or multi-patterned, and can also be used in combination with a usual hot stamping method.

Further, by applying the photocurable composition of the present invention, the photocurable composition of the present invention is applied onto a substrate or a support, and the layer composed of the composition is exposed, cured, and dried as necessary (baking) ), it is also possible to manufacture a permanent film such as a protective film layer or an insulating film.

Hereinafter, a method of forming a pattern of the photocurable composition of the present invention and a pattern transfer method will be described.

The photocurable composition of the present invention can be applied by a generally known coating method such as a dipping method, a pneumatic blade coating method, a curtain coating method, a bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, or a narrow coating method. The slit coating method is applied by coating. The film thickness of the layer composed of the photocurable composition of the present invention varies from 0.05 μm to 30 μm depending on the intended use. Further, the photocurable composition of the present invention can also be subjected to multiple coating.

A substrate, a supporting system of the photocurable composition of the present invention, a quartz, a glass, an optical film, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate of 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 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 for curing the photocurable composition of the present invention is not particularly limited, and examples thereof include light or radiation having a wavelength of a region such as high energy ionizing radiation, near ultraviolet light, far ultraviolet light, visible light, or infrared light. The high-energy ionizing radiation source is an electron beam accelerated by an accelerator such as a Cockcroft type accelerator, a Vandergrave type accelerator, a linear accelerator, an electron cyclotron, a cyclotron, etc., which is industrially convenient and economical. Further, it is also possible to use radiation such as gamma rays, X rays, alpha rays, neutron rays, or proton rays emitted from a radioactive isotope element or an atomic furnace. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a mercury lamp. Radiation includes, for example, microwaves, EUV. Further, in the present invention, laser light used for semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser is also suitable. These lights may be monochromatic light or multiple light of different wavelengths (mixed light).

A mold material that can be used in the present invention will be described. The light-transmitting lithography method of the photocurable composition of the present invention requires selection of a light-transmitting material in at least one of the mold material and/or the substrate. The photon nanoimprint lithography method applied to the present invention is characterized in that a photocurable composition is coated on a substrate, and then the light transmissive mold is pressed, and light is irradiated from the back surface of the mold to harden the photocurable composition. . Further, the photocurable composition may be applied to the light-transmitting substrate, and then the mold may be pressed to irradiate light from the back surface of the mold to cure the photocurable composition.

The light irradiation may be carried out in a state in which the mold is adhered, or may be performed after the mold is peeled off, and in the present invention, it is preferably carried out in a state in which the mold is adhered.

For the mold that can be used in the present invention, a mold having a pattern to be transferred can be used. The mold can be patterned in accordance with a desired processing precision by, for example, photolithography or electron beam drawing. In the present invention, the mold pattern forming method is not particularly limited.

The light-transmitting mold material which can be used in the present invention is not particularly limited, and may have a predetermined strength and durability. Specifically, a light-transparent resin such as glass, quartz, PMMA or polycarbonate resin, a transparent metal vapor-deposited film, a soft film such as polydimethyl siloxane or a photocured film or a metal film can be exemplified.

When the transparent substrate of the present invention is used, the non-light-transmitting mold material that can be used is not particularly limited, and may have a predetermined strength. Specifically, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, or a substrate such as SiC, tantalum, tantalum nitride, polycrystalline germanium, germanium oxide, or amorphous germanium may be exemplified. Etc., there are no special restrictions. The shape may be any one of a plate-shaped mold and a roll-shaped mold, and the roll-shaped mold can be applied particularly in a case where it is necessary to continuously transfer the production.

The mold used in the above invention may also be subjected to a release treatment to improve the peelability of the photocurable composition from the mold. A commercially available release agent such as DAIKIN Industrial Co., Ltd., trade name: OPTOOL DSX or Sumitomo 3M: trade name Novec EGC-1720 is also suitable for use as a treatment with a decane coupling agent such as a fluorene or a fluorine-based compound.

When photoimprint lithography is carried out using the present invention, it is usually preferred to carry out the pressure at the mold to be 10 or less. When the pressure of the mold is 10 or less, the mold or the substrate is not easily deformed, and the pattern accuracy tends to be improved. Further, since the pressurization is low, there is a tendency that the apparatus can be reduced, which is preferable. The mold pressure is preferably selected in a region where the residual film of the photocurable composition of the mold convex portion is small and the uniformity of the transfer of the mold can be ensured.

In the present invention, it is sufficient that the light irradiation at the time of photoimprint lithography is considerably larger than the amount of irradiation necessary for hardening. The amount of irradiation necessary for hardening is determined by investigating the consumption of the unsaturated bond of the photocurable composition or the adhesiveness of the cured film.

Further, the photoimprint lithography method of the present invention can be applied, and the substrate temperature at the time of light irradiation is usually performed at room temperature, but in order to improve the reactivity, light irradiation may be performed while heating. When the light is in the vacuum stage, it is possible to prevent the bubbles from entering, suppress the decrease in reactivity due to oxygen incorporation, and improve the adhesion between the mold and the photocurable composition. Light irradiation is performed. In the present invention, it is preferred that the degree of vacuum is in the range of from 10 ^-1 Pa to atmospheric pressure.

The photocurable composition of the present invention is prepared as a solution by mixing the above components, for example, by a filter having a pore diameter of 0.05 μm to 5.0 μm. The mixing and dissolution of the photocurable composition are usually carried out in the range of 0 ° C to 100 ° C. Filtration can also be carried out in multiple stages or repeated several times. Alternatively, the filtered liquid can be filtered again. The material used for the filtration may be, for example, a polyethylene resin, a polypropylene resin, a fluororesin, or a nylon resin, and is not particularly limited.

The case where the photocurable composition of the present invention is applied to an etching photoresist will be described. The etching step can be performed by suitably selecting a well-known etching treatment method for removing the underlying portion not covered by the photoresist pattern to obtain a pattern of the thin film. The reactive gas activation treatment (dry etching) is performed by etching liquid treatment (wet etching) or by using plasma discharge under reduced pressure.

A plurality of etching liquids which have been developed, such as ferric chloride/hydrochloric acid, hydrochloric acid/nitric acid, and hydrogen bromide, can be used as the etching liquid in the wet etching. For the Cr, a mixed solution of ammonium cerium nitrate solution or cerium nitrate-hydrogen peroxide water, a mixed solution of hydrofluoric acid, a hydrofluoric acid-nitric acid mixed solution for Ti, a mixed solution of ammonium ammonium hydroxide solution and hydrogen peroxide, and Mo a mixture of hydrogen peroxide water, ammonia water-hydrogen peroxide water, a mixture of phosphoric acid and nitric acid, a mixture of MoW, a phosphoric acid-nitric acid mixture for Al, a mixture of hydrofluoric acid and nitric acid, and a mixture of phosphoric acid and nitric acid-acetic acid. ITO is used to dilute aqua regia, ferric chloride solution, hydrogen iodide water, SiNx or SiO ₂ buffered hydrofluoric acid, hydrofluoric acid-ammonium fluoride mixed solution, Si, polycrystalline fluorene-fluoric acid-nitric acid-acetic acid mixture The mixture of a mixture of ammonia-hydrogen peroxide water, a mixture of nitric acid and hydrofluoric acid for PSG, and a mixture of hydrofluoric acid and ammonium fluoride for BSG are used as described above.

Wet etching can also be a shower method or an immersion method. Since the etching speed, in-plane uniformity, and wiring width accuracy depend very much on the processing temperature, the conditions must be optimized according to the substrate type, application, and line width. Chemical. Further, in the case of the above-described wet etching, it is preferable to perform post-baking in order to prevent the depression of the etching liquid. Usually, such post-baking is carried out at about 90 ° C to 140 ° C, but is not necessarily limited thereto.

The dry etching may use a parallel plate type dry etching apparatus which basically has a pair of electrodes arranged in parallel in the vacuum apparatus and a substrate on the other electrode. By connecting a high-frequency power source to the electrode on the substrate side or to the opposite electrode to generate plasma, it can be classified into a reactive ion etching (RIE) mode in which ions are mainly involved, and free radicals are mainly involved. Plasma etching (PE) mode.

In the etching gas used for the dry etching described above, an etching gas of each film type can be used. Examples of a-Si/n ⁺ or s-Si are carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine), and a-SiNx for carbon tetrafluoride. + oxygen, a-SiOx with carbon tetrafluoride + oxygen, carbon trifluoride + oxygen, Ta with carbon tetrafluoride (sulfur hexafluoride) + oxygen, MoTa / MoW with carbon tetrafluoride + oxygen, For Cr, it is chlorine + oxygen, and A l is boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide, and the like. In the dry etching step, the structure of the photoresist is greatly deteriorated by ion impact or heat, and the peeling property is also affected.

After the etching, the method of transferring the pattern to the photoresist of the underlying substrate is peeled off. The peeling is removed by using a liquid (wet peeling) or by plasma discharge of oxygen under reduced pressure to be oxidized to a gas state (dry peeling/ashing), or by ozone and UV light. The oxidation is removed into a gas form (dry peeling/UV ashing) or the like, and the photoresist can be removed by a number of methods. As the stripping liquid, an aqueous solution such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of ozone, and an organic solvent such as an amine and dimethyl hydrazine or N-methylpyrrolidone are generally known. An example of the latter is known to have an ethanolamine/dimethyl hydrazine mixture (mass mixing ratio = 7/3).

The photoresist peeling speed is equivalent to temperature, liquid amount, time, pressure, etc., and can be optimized according to the type and use of the substrate. For example, it is preferable to immerse the substrate (minutes to several tens of minutes) at a temperature ranging from room temperature to about 100 ° C to perform solvent washing such as butyl acetate or water washing. 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. A preferred example which can be mentioned is that the water is washed with pure water and dried for gas scraping and drying. On the substrate, when the amorphous material is exposed, since an oxide film is formed in the presence of water and air, it is preferable to isolate the air. Moreover, it is also preferable to use a method of ashing and chemical separation. Ashing may include plasma ashing, downward blowing ashing, ozone ashing, and UV/ozone ashing. For example, in the case of processing an Al substrate by dry etching, a chlorine-based gas is usually used, but aluminum chloride or the like which is a product of chlorine and Al may corrode Al. In order to prevent such a situation, a peeling liquid to which a preservative is added may also be used.

The steps other than the etching step, the peeling step, the rinsing step, and the water washing are not particularly limited, and may be appropriately selected from a well-known pattern forming step. For example, a hardening treatment step or the like can be given. These may be used alone or in combination of two or more. The hardening treatment step is not particularly limited, and can be appropriately selected according to the purpose, and for example, a comprehensive heat treatment or a full exposure treatment, which is suitably mentioned, is exemplified.

The method of the above comprehensive exposure treatment may, for example, be a method of forming a full exposure by forming a pattern. Since the curing in the composition of the photosensitive layer can be promoted by the full exposure, the surface of the pattern can be hardened, and the etching resistance can be improved. The apparatus for performing the above-described overall exposure is not particularly limited, and can be appropriately selected according to the purpose, and for example, a UV exposure machine such as an ultrahigh pressure mercury lamp which is suitably used.

Example

The invention will be specifically described below by way of examples. The materials, the amounts used, the ratios, the contents of the treatment, and the treatment procedures in the following examples can be appropriately changed as long as they do not deviate from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

The abbreviations of the respective monomers used in the examples and comparative examples of the present invention are as follows.

<Monomer> R-01: benzyl acrylate (BISCOAT #160 Osaka Organic Chemical Co., Ltd.) R-02: Epoxy acrylate (LIGHTACRYLATE PO-A: manufactured by Kyoeisha Oil Co., Ltd.) R-03: Acrylic isophthalic acid Ester (ARONIX M-156: manufactured by Toagosei Co., Ltd.) R-04: N-vinyl-2-pyrrolidone (ARONIX M-150: manufactured by Toagosei Co., Ltd.) R-05: N-acrylonitrile Porphyrin (ACMO: manufactured by Xingren Co., Ltd.) R-06: phenoxyhexanediol acetate (AMP-60G: manufactured by Shin-Nakamura Chemical Co., Ltd.) R-07: phenoxy diglycol acrylate (ARONIX M-101) :East Asia Synthetic Co., Ltd.) R-08: Ethoxydiethylene glycol acrylate (LIGHTACRYLATE EC-A: manufactured by Kyoeisha Chemical Co., Ltd.) R-09: Hydroxytrimethylacetic acid neopentyl glycol diacrylate (KARAYAD MANDA) :Nippon Chemical Co., Ltd.) R-10: Polyethylene glycol diacrylate (NEWFRONTIA PE-300: manufactured by Daiichi Kogyo Co., Ltd.) R-11: Tri-propylene glycol diacrylate (KARAYAD TPGDA: manufactured by Nippon Kayaku Co., Ltd.) R-12: Ethylene oxide modified trimethylolpropane triacrylate (SR-454: manufactured by SATOMER KAYAKU) R-13: propylene oxide modified trimethylolpropane triacrylate (NEWFRONTIA TMP-3P :First Industrial Pharmaceuticals, Ltd.) R-14: Pentaerythritol ethoxytetraacrylate (Ebercryl 40: manufactured by DAICEL-UCB) R-15: dipentaerythritol hexaacrylate (KARAYAD DPHA: Nippon Chemical Company-made) R-16: Ethylene oxide modified phosphodimethacrylate (KAYAMA-PM-21: manufactured by Nippon Kayaku Co., Ltd.) R-17: Ethylene oxide Modified neopentyl glycol diacrylate (PHTOMER 4160: manufactured by SANNOPCO Co., Ltd.) R-18: tetrahydrofurfuryl acrylate (BISCOAT #150 Osaka Organic Chemical Co., Ltd.) R-19: trihydroxypropane triacrylate (ARONIX M- 309: manufactured by Toagosei Co., Ltd.) R-20: 1,6-hexanediol diacrylate (FRONTIA HDDA: manufactured by Daiichi Kogyo Co., Ltd.) R-21: Ethylene oxide modified bisphenol A diacrylate (SR- 602: manufactured by SATOMER KAYAKU Co., Ltd.) R-22: neopentyl glycol diacrylate (SR-351: manufactured by SATOMER KAYAKU Co., Ltd.) R-23: bisphenol epoxy acrylate (RIPOXY SP1509: manufactured by Showa Polymer Co., Ltd.) R -24: Acrylic urethane (BEAMSET 551B: manufactured by Arakawa Chemical Industries, Ltd.) R-25: Epoxy acrylate (Ebercryl 3701: manufactured by DAICEL-UCB) R-26: N-hydroxyethyl acrylamide ( HEAA: manufactured by Xingren Co., Ltd.) R-27: Ethylene oxide modified bisphenol A diacrylate (ARONIX M-211B manufactured by Toagosei Co., Ltd.) R-28: ACARON RN-20: First Industrial Pharmaceutical Co., Ltd.) R- 29: phenylepoxypropyl ether epoxy acrylate R-30: 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane ( MEDOL 10: manufactured by Osaka Organic Industries Co., Ltd.) C-1: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (Cyracure-6105: manufactured by UNION CARBIDE Co., Ltd.) C-2 : 1.2:8,9 Diepylene Terpene (CEROKISAID 3000: manufactured by DAICAL Chemical Industry Co., Ltd.) C-3: 3-ethyl-3-(phenoxymethyl)oxetane (OXT211: manufactured by Toagosei Co., Ltd.) C-4: 3-ethyl-3-hydroxyethyloxetane (OXT101: manufactured by Toagosei Co., Ltd.) C-5: bis[1-ethyl(3-oxetanyl)methyl Ether (OXT221: manufactured by Toagosei Co., Ltd.) C-6: main component 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (OXT121: manufactured by Toagosei Co., Ltd.) C-7: 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT212: manufactured by Toagosei Co., Ltd.) C-8: hydroxybutyl vinyl ether (HBVE: Maruzen Petrochemical Co., Ltd.) C-9: Vinylcyclohexene oxide 1,2-epoxy-4-vinylcyclohexene (CEROKISAID 2000: manufactured by DAICEL Chemical Industry Co., Ltd.) C-10: Triethylene glycol divinyl Ether (RAPI-CURE DVE-3: manufactured by ISP JAPAN) C-11: epoxidized linseed oil (Vikoflex 9040) ATOFINA Inc.)

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

<Photopolymerization initiator> P-1: 2,4,6-trimethylbenzylidene-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF Corporation) P-2: 2,2- Dimethoxy-1,2-diphenylethan-1-one (Irgacure 651: manufactured by CIBA SPECIALTY CHEMICALS) P-3: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173: manufactured by CIBA SPECIALTY CHEMICALS) P-4: 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propyl- 1-ketone mixture (Darocure 4265: manufactured by CIBA SPECIALTY CHEMICALS) P-5: 2-benzyl-2-dimethylamino-1-(4- Mixture of phenyl phenyl)-butanone-1 and 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 1300: manufactured by CIBA SPECIALTY CHEMICALS) P-6: 1-[ 4-benzylidene phenylsulfonyl]phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (ESACUR1001M: manufactured by Siber Hegner, Japan) 2, 4, 6-trimethylbenzimidyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF Corporation) P-7: 2-methyl-1[4-methylthiophenyl]=2= Phenylpropan-1-one (Irgacure-907: manufactured by CIBA SPECIALTY CHEMICALS) P-8: hydroxycyclohexyl phenyl ketone (manufactured by CIBA SPECIALTY CHEMICALS: Irgacure-184)

<Photoacid generator> U-1: manufactured by DOW CHEMICAL Co., Ltd.: SAIRACURE-UVI 6990 U-2: manufactured by MIDORI Chemical Co., Ltd.: DTS-102

The abbreviations of the surfactants and additives used in the examples and comparative examples of the present invention are as follows.

<Interacting Agent> W-1: Fluorine-based surfactant (manufactured by TOHKEM-PRODUCTS: Fluoride surfactant) W-2: Lanthanide surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFACPENTAD31) W-3: Fluorine-ruthenium-based surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFAC R-08) W-4: Fluorine-antimony surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFAC XRB-4) W-5: Alkynediol-based nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.: SAFINOL 465) W-6: Polyoxyethylene polyoxypropylene condensate (manufactured by Takemoto Oil Co., Ltd.: PIONINE P-1525) W-7: Fluoride-based interfacial activity Agent (made by Dainippon Ink Chemical Industry Co., Ltd.: F-173) W-8: Fluorine-based surfactant (produced by Sumitomo 3M Co., Ltd.: FC-430) W-9: Fluorine-based surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) :MEGAFAC 470)W-10: Fluorine-based surfactant (manufactured by Dainippon Ink and Chemicals, Inc.: MEGAFAC EXP.TF907)

<Additive> A-01: 2-chlorothioxanthone A-02: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) A-03: decane coupling agent (vinyl triethoxy decane) ( Shin-Etsu SILICONE system) A-04: Oyster sauce (NIPPON UNICAR company: L-7001) A-05: 2-dimethylaminoethyl benzoate A-06: Diphenyl ketone A-07: 4-dimethylamine Benzoic acid ester A-08: Modified dimethyl polyoxyalkylene (Big Chemie Japan company: BYK-307) A-09: Red No. 225 (Sudan III) A-10: N-ethyldiethanolamine A-11: propylene carbonate (manufactured by Kanto Chemical Co., Ltd.) A-12: dispersant (manufactured by AJINOMOTO FINETECHNO Co., Ltd.: PB822) A-13: CI Pigment Black 7 (manufactured by CLARIANT JAPAN)

<Evaluation of Photocurable Composition> The respective compositions obtained in Examples 1 to 25 and Comparative Examples 1 to 20 were evaluated in accordance with the following evaluation methods.

Tables 1 and 2 each show a polymerizable unsaturated monomer used in the composition (Examples, Comparative Examples).

Table 3, Table 4, and Table 7 each show the mixing ratio of the polymerizable unsaturated monomer used for a composition (Example).

Tables 5 and 8 show the blending ratios of the monomers, photopolymerization initiators, surfactants, and additives used in the composition (Examples, Comparative Examples).

Tables 6 and 9 show the results (Examples and Comparative Examples) of the present invention.

<Viscosity measurement> The viscosity was measured at 25 ± 0.2 ° C using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd.

The rotation speeds at the time of measurement were each as follows, at 0.5 mPa. Above s is less than 5mPa. s series 100rpm, 5mPa. Above s is less than 10mPa. s system 50rpm, 10mPa. Above s is less than 30mPa. s series 20rpm, 30mPa. Above s is less than 60mPa. s series 10rpm, 60mPa. Above s is less than 120mPa. s is 5 rpm, 120 mPa. The above is 1 rpm or 0.5 rpm.

<Measurement of Light Curing Rate> The photohardening speed was measured by using a high-pressure mercury lamp as a light source, and the absorption change of the monomer at 810 cm ^-1 was measured using a Fourier transform infrared spectrometer (FT-IR), and the hardening reaction rate was calculated in real time (single) Body consumption rate). When the A system indicates that the curing reaction rate is 0.2/sec or more, the B system indicates that the curing reaction rate is less than 0.2/sec.

<Adhesiveness> Adhesive tape is attached to the surface of the photocurable photoresist pattern which has been photohardened, and after peeling, it is visually observed whether or not the photohardenable photocurable photoresist pattern is adhered to the tape. Evaluation was performed as follows.

A: The tape side is not attached to the pattern B: It is confirmed that the pattern C is extremely thinly attached to the tape side: it is confirmed that the pattern is remarkably attached to the tape side.

<Removability> After peeling-off photohardening, when the mold was peeled off, whether or not the unhardened material remained on the mold was observed using an optical microscope, and the evaluation was performed as follows. A: no residue B: there is residue

<Observation of Residual Film Property and Pattern Shape> The pattern shape of the transfer and the residue of the transfer pattern were observed by a scanning electron microscope, and the residual film property and the pattern shape were evaluated as follows.

(residual film property) A: No residue was observed B: A small amount of residue was observed C: A large amount of residue was observed

(pattern shape) A: The pattern shape is substantially the same as the original pattern shape of the source mold B: the pattern shape and the original pattern shape of the source mold are different in part

(with the original pattern in the range of less than 20%) C: The pattern shape is significantly different from the original pattern shape of the source mold, or the difference between the pattern thickness of the pattern and the original pattern is 20% or more.

<Rotary coating suitability> Coating property (I) is formed with a film thickness of 4000 On the glass substrate of 4 mm and 0.7 mm thick of the aluminum (Al) film, the photocurable composition of the present invention was spin-coated so as to have a thickness of 6.0 μm, and then the glass substrate was allowed to stand for 1 minute, and then the surface was surfaced. Observe and evaluate as follows.

A: No shrinkage spots and coating lines (streaks) were observed B: A few coated lines were observed C: Significant shrinkage spots and coated lines were observed

<Slit coating suitability> Coating property (II) Using a slit photoresist coating apparatus for a large-substrate coating (Pingda Machining Co., Ltd.), a film thickness of 4000 is formed. The photocurable composition of the present invention was coated on a 4 inch-thick, 0.7 mm-thick glass substrate (550 mm × 650 mm) of an aluminum (Al) film to form a photoresist film having a film thickness of 2.0 μm, and observed in the cross direction. Whether there is a line-like unevenness or not is evaluated as follows.

A: No line-like unevenness was observed. B: Weak line-like unevenness was observed. C: Significant line-like unevenness was observed.

<Etching property> The photocurable composition of the invention is patterned on the aluminum (Al) formed on the glass substrate, and after curing, the aluminum thin film is etched by a phosphorus nitric acid etching solution, visually and microscopically observed. 10 micron lines/pitch and evaluated as follows.

A: It is possible to obtain an aluminum wire B having a line width of 10 ± 2.0 μm: a line having a line width deviation greater than ± 2.0 μm of the line C: a defective portion exists in the line, or the line is not connected

Example 1

9.799 g of benzyl acrylate monomer (R-01) as polymerizable unsaturated monomer, 78.392 g of tripropylene glycol diacrylate monomer (R-11), 9.799 g of ethylene oxide modified trishydroxyl Propane triacrylate (R-12), 2.00 g of 2,4,6-trimethylbenzylidene-ethoxyphenyl-phosphine oxide as a photopolymerization initiator (manufactured by BASF Corporation, Lucirin TPO-L) (P-1) and 0.01 g of EFTOP and EF-122A (fluorine-based, W-1) as surfactants were mixed at room temperature for 24 hours to obtain a homogeneous solution. The number of functional groups, viscosity, and primary skin irritation (PII value) of the polymerizable unsaturated monomer used herein are shown in Table 1, and the composition ratio of the polymerizable unsaturated monomer is shown in Table 3. The matching system is shown in Table 5. The composition (coating property) obtained in Example 1 had a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 90% by mass, and the viscosity of the composition is 18 mPa. s.

Formed with a film thickness of 4000 The thus-adjusted composition was spin-coated on a glass substrate of 4 mm and 0.7 mm thick on an aluminum (Al) film so as to have a thickness of 6.0 μm. The spin-coated base film was mounted on a nano-imprinting apparatus using a high-pressure mercury lamp (light output of 2000 mW/cm 2 ) manufactured by ORC Co., Ltd. as a light source, with a mold pressing pressure of 0.8 kN and an exposure vacuum of 10 A mold made of polydimethyl methoxyoxane (manufactured by TORAY-DOWCORNING Co., Ltd., which has a SILPOT 184 hardened at 80 ° C for 60 minutes) having a line/pitch pattern of 10 μm and a groove depth of 5.0 μm. The back surface was exposed to 100 mJ/cm 2 , and after exposure, the mold was removed to obtain a photoresist pattern. Subsequently, an aluminum (Al) portion which is not coated with a photoresist is removed using a phosphorus nitric acid etching solution to form an electrode pattern made of aluminum (Al). Further, the peeling resist was performed by immersion treatment at 80 ° C for 3 minutes using a monoethanolamine / dimethyl hydrazine mixed stripping solution. The results are shown in Table 6. According to the results of Table 6, the composition of the present invention can be any of photocurability, adhesion, mold release property, mold resilience, pattern shape, coatability (spin coating property, slit coating property), and etching property. Satisfied with things.

Example 2

29.39 g of epoxy ethyl acrylate monomer (R-02) as a polymerizable unsaturated monomer, 48.98 g of hydroxytrimethylacetic acid neopentyl glycol diacrylate monomer (R-09), 9.795 g of three Propylene glycol diacrylate (R-11), 9.795 g of propylene oxide modified trimethylolpropane triacrylate (R-13), 2.0 g of 2,4,6-trimethylbenzene as a photopolymerization initiator Methylmercapto-ethoxyphenyl-phosphine oxide (manufactured by BASF Corporation, Lucirin TPO-L) (P-1), and 0.05 g of MEGAFACPENTAD 31 (lanthanide, W-2) as a surfactant, at room temperature Mix for 24 hours to become a homogeneous solution. The number of functional groups, viscosity, and primary skin irritation (PII value) of the polymerizable unsaturated monomer used herein are shown in Table 1, and the composition ratio of the polymerizable unsaturated monomer is shown in Table 3. The matching system is shown in Table 5. The composition of Example 2 has a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 90% by mass, and the viscosity of the composition is 18 mPa. s. 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 6. According to the results of Table 6, the composition of the present invention can be any of photocurability, adhesion, mold release property, mold resilience, pattern shape, coatability (spin coating property, slit coating property), and etching property. Satisfied with things.

Embodiment 3 to Embodiment 18

In the same manner as in Example 1, the polymerizable unsaturated monomers shown in Table 1 were mixed at the ratios shown in Table 3 to prepare the compositions described in Table 5. The composition after the preparation 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. According to the results of Table 6, the composition of any of Examples 3 to 18 was photocurability, adhesion, mold release property, mold resilience, pattern shape, applicability (spin coating property, slit coating property), and etching. Any one of the sexes can satisfy.

Example 19

18.86 g of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate monomer (C-1) as a polymerizable unsaturated monomer, 56.58 g of two [1] -Ethyl (3-oxetanyl)methyl ether (C-5), 18.86 g of triethylene glycol divinyl ether (C-10), 3.0 g of UVI as a photopolymerization initiator 6990 (manufactured by DOW-CHEMICAL Co., Ltd.), 0.2 g of MEGAFAC XRB-4 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) as a lanthanide surfactant, and 0.50 g of 2-chlorothioxanthone as a sensitizer, mixed at room temperature After 24 hours, it became a homogeneous solution. When the viscosity of the composition was measured in the same manner as in Example 1, it was 18 mPa. s. The adjusted composition was spin-coated on a 4 inch glass substrate so as to have a thickness of 6.0 μm. The spin-coated base film was mounted on a nano-imprinting apparatus using a high-pressure mercury lamp (light output of 2000 mW/cm 2 ) manufactured by ORC Co., Ltd. as a light source, and the pressure was 50 Kn/cm 2 and the degree of vacuum in the exposure. As a material of 0.2 Torr, a polydimethyl methoxy oxane having a line/pitch pattern of 10 μm and a groove depth of 5.0 μm (manufactured by TORAY-DOWCORNING Co., Ltd., which is obtained by hardening SILPOT 184 at 80 ° C for 60 minutes) The back surface of the mold was exposed to 170 mJ/cm 2 , and after the exposure, the mold was removed, and the characteristics of the composition were investigated in the same manner as in Example 1. As a result, any of photocurability, adhesion, mold release property, mold resilience, pattern shape, applicability (spin coating property, slit coating property), and etching property can be satisfied.

Example 20~25

In the same manner as in Example 19, the polymerizable unsaturated monomers shown in Table 4 were mixed at the ratios shown in Table 2 to prepare the compositions described in Table 5. The composition after the preparation was patterned in the same manner as in Example 19, and the characteristics of the composition were examined. The results are shown in Table 6. The composition of any of Examples 20 to 25 is any of photocurability, adhesion, mold release property, mold resilience, pattern shape, coatability (spin coating property, slit coating property), and etching property. All can satisfy things.

Comparative Example 1 and Comparative Example 2

The composition described in the fourth embodiment and the fifth embodiment of the ultraviolet curable coating material for a disc protective film disclosed in Japanese Laid-Open Patent Publication No. Hei 7-70472 is the same as that of the first embodiment of the present invention, and is shown in Table 1. The polymerizable unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9.

The composition of Comparative Example 1 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 60% by mass, and the viscosity of the composition is 22 mPa. s.

The composition of Comparative Example 2 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 70% by mass, and the viscosity of the composition is 23 mPa. s.

Further, as shown in Table 9, the composition of Comparative Example 1 was unsatisfactory in mold release property and coatability (spin coating property, slit coatability). The composition of the comparative example 2, the adhesiveness, the coating property (spin coating property, slit coating property), and the etching property were not satisfied.

Comparative Example 3, Comparative Example 4

The composition described in Comparative Example 4 and Comparative Example 5 of the ultraviolet curable coating material for a disc protective film disclosed in Japanese Laid-Open Patent Publication No. Hei 7-70472 is carried out in the same manner as in the first embodiment of the present invention, and is shown in Table 1. The polymerizable unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 3 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 50% by mass, and the viscosity of the composition is 21 mPa. s. The composition of Comparative Example 4 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 90% by mass, and the viscosity of the composition is 20 mPa. s. According to the results of Table 9, the compositions of Comparative Example 3 and Comparative Example 4 were unsatisfactory in mold release property and coatability (spin coating property, slit coatability).

Comparative Example 5, Comparative Example 6

The composition of the optical disk protective film composition disclosed in Japanese Laid-Open Patent Publication No. Hei-4-149280, and the composition described in Comparative Example 1 were carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was not observed. The saturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 5 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 43% by mass, and the viscosity of the composition is 29 mPa. s. The composition of Comparative Example 6 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 0% by mass, and the viscosity of the composition is 24 mPa. s. According to the results of Table 9, the composition of Comparative Example 5 was incapable of satisfying adhesion, residual film property, applicability (spin coating property, slit coating property), and etching property. The composition of Comparative Example 6 was unsatisfactory in mold release property, coating property (spin coating property, slit coating property), and etching property.

Comparative Example 7

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 the polymerizable unsaturated monomer shown in Table 1 was used. The compositions described in Table 8 were prepared by mixing at the ratios shown in Table 7. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 7 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 16.5% by mass, and the viscosity of the composition is 65 mPa. s. According to the results of Table 9, the composition of Comparative Example 7 was not satisfactory in terms of residual film properties, pattern shape, applicability (spin coating property, slit coating property), and etching property.

Comparative Example 8 and Comparative Example 9

The composition described in Example 1 and Comparative Example 2 of the protective coating composition disclosed in JP-A-2001-93192 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was carried out. The unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 8 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 30% by mass, and the viscosity of the composition is 33 mPa. s. The composition of Comparative Example 9 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 40% by mass, and the viscosity of the composition is 31 mPa. s. According to the results as shown in Table 9, the composition of Comparative Example 8 was unsatisfactory in mold release property and etching property. The composition of Comparative Example 9 was incapable of satisfying adhesion and etching properties.

Comparative Example 10

The composition described in Example 1 of the optical disk protective film composition disclosed in JP-A No. 2-6562 was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomer shown in Table 1 was used. The compositions described in Table 8 were prepared by mixing at the ratios shown in Table 7. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 10 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 31.7% by mass, and the viscosity of the composition is 56 mPa. s. According to the results of Table 9, the composition of Comparative Example 10 was not satisfactory in terms of residual film properties, pattern shape, applicability (spin coating property, slit coating property), and etching property.

Comparative Example 11 and Comparative Example 12

The composition described in Example 1 and Example 2 of the ultraviolet-ray and electron beam-curable composition disclosed in JP-A-2001-270973 is carried out in the same manner as in the first embodiment of the present invention, and is shown in Table 1. The polymerizable unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 11 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 0% by mass, and the viscosity of the composition is 1600 mPa. s. The composition of Comparative Example 12 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 0% by mass, and the viscosity of the composition is 920 mPa. s. According to the results of Table 9, the compositions of Comparative Examples 11 and 12 were incapable of satisfying photocurability, residual film properties, pattern shape, applicability (spin coating property, slit coating property), and etching property.

Comparative Example 13, Comparative Example 14

The composition described in Example 1 and Comparative Example 1 of the protective coating composition disclosed in JP-A-H07-53895 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was carried out. The unsaturated monomers were mixed at a ratio shown in Table 7 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 13 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 70% by mass, and the viscosity of the composition is 25 mPa. s. The composition of Comparative Example 14 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 60% by mass, and the viscosity of the composition is 28 mPa. s. According to the results of Table 9, the compositions of Comparative Examples 13 and 14 were unsatisfactory in mold release property, coatability (slit coatability), and etching property.

Comparative Example 15

The composition described in Example 1 of the coating composition disclosed in JP-A-2003-165930 was carried out in the same manner as in Example 1 of the present invention, and the polymerizable unsaturated monomer shown in Table 1 was used. The ratios shown in Table 7 were mixed to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 15 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 35% by mass, and the viscosity of the composition is 130 mPa. s. According to the results of Table 9, the composition of Comparative Example 15 was incapable of satisfying the adhesiveness, residual film property, pattern shape, applicability (spin coating property), and etching property.

Comparative Example 16

The composition described in the example (ink composition 3) of the inkjet composition disclosed in JP-A-2005-8759 was carried out in the same manner as in Example 1 of the present invention, and the polymerizability shown in Table 1 was carried out. The unsaturated monomers were mixed at a ratio shown in Table 4 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 16 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 57.9 mass%, and the viscosity of the composition is 30 mPa. s. According to the results of Table 9, the composition of Comparative Example 16 was incapable of satisfying photocurability, mold release property, pattern shape, and etching property.

Comparative Example 17

In the composition of Comparative Example 16, the coloring agent (A-13) and the dispersing agent (A-12) were removed from the composition, and the other components were the same as those of Comparative Example 16, and the same components as in Example 1 of the present invention were used. The polymerizable unsaturated monomers shown in Table 1 were mixed at a ratio shown in Table 4 to prepare the compositions described in Table 8. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 16 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 57.9 mass%, and the viscosity of the composition is 6 mPa. s. According to the results of Table 9, the composition of Comparative Example 17 was incapable of satisfying photocurability, mold release property, pattern shape, and etching property.

Comparative Example 18

The composition of the first embodiment of the present invention is the same as the first embodiment of the present invention except that the fluorine-based surfactant (W-1) is changed to the acetylene glycol-based nonionic surfactant (W-5). Conduct and evaluate. The results are shown in Table 9. According to the results of Table 9, the composition of Comparative Example 18 was inferior in adhesion, coating property (spin coating property, slit coating property), and etching property.

Comparative Example 19

The composition of the second embodiment of the present invention was carried out in the same manner as in the second embodiment of the present invention except that the lanthanoid surfactant (W-2) was changed to the polyoxyethylene polyoxypropylene condensate (W-6). And evaluation. The results are shown in Table 9. According to the results of Table 9, the composition of Comparative Example 19 was incapable of satisfying adhesion, coating properties (slit coating properties), and etching properties.

Comparative Example 20

The mixing ratio of the polymerizable unsaturated monomer used in Example 12 of the present invention was changed, and propylene carbonate was added for the purpose of lowering the viscosity. Further, a fluorine-based surfactant (W-9) and a photopolymerization initiator (P-1) were added, and the compositions shown in Table 8 were prepared by mixing at the ratios shown in Table 7. The composition to be prepared was patterned in the same manner as in Example 1, and the characteristics of the composition were examined. The results are shown in Table 9. The composition of Comparative Example 20 had a PII value of 4.0 or less and a viscosity of 30 mPa. The ratio of the polymerizable unsaturated monomer below s is 100%, and the viscosity of the composition is 2 mPa. s. According to the results of Table 9, the composition of Comparative Example 20 was incapable of satisfying photocurability, mold release property, coatability (slit coatability), and etching property.

Industrial use possibility

The photocurable composition of the present invention can be used as a photo-nanoimprinting photoresist composition for manufacturing a semiconductor integrated circuit, a flat screen, a micro electro mechanical system (MEMS), a sensor element, a compact disc, and a high-density storage. Optical recording medium such as a disk, an optical component such as a diffraction grating or an embossed hologram, a nano component, an optical component, an optical film or a polarizing element for manufacturing a flat panel display, a thin film transistor for a liquid crystal display, an organic transistor, Color filter, protective layer, column, liquid crystal alignment rib, microlens array, immunoassay wafer, DNA separation wafer, microreactor, nano biocomponent, optical waveguide, filter, photonic liquid crystal, etc. A fine pattern is formed.

In particular, the present invention is suitable for use in forming a fine pattern by a light transmission nano-stamping method, and the light-transmitting nanoimprint method (also referred to as a photon lithography method) comprises the following steps: on a substrate a step of applying a liquid uncured photocurable composition; a step of applying a light transmissive mold to a coating layer on the substrate to deform the coating film; and irradiating light from the back surface of the mold or the back surface of the substrate to form a photohardenable layer a step of hardening to form a photoresist pattern in which a desired pattern is fitted; and a step of desorbing the light-transmitting mold from the coating film.

In particular, the photocurable composition of the present invention can produce a fine structure of an electronic component which is substantially more economical than the conventional photolithography method. Further, the photocurable composition of the present invention has the following characteristics: (1) Since the solution has excellent fluidity at room temperature, the composition can easily flow into the groove of the mold recess, since it is not easy to contain the atmosphere, so Bubble defects are generated, and no residue is generated even after the convex portion and the concave portion of the mold are hardened. Moreover, since the photocurable composition of the present invention has low volatility and small skin irritation, the safety of the operator is excellent.

(2) Since the cured film obtained from the photocurable composition of the present invention is excellent in mechanical properties, the adhesion between the coating film and the substrate is excellent, and when the mold is peeled off, the pattern is not broken or the surface of the coating film is drawn to cause surface damage. Rough, so it can form a good pattern.

(3) Since the photocurable composition of the present invention has a small volume shrinkage after photocuring and excellent mold transfer characteristics, the fine pattern can obtain correct formability.

(4) Since the photocurable composition of the present invention is excellent in coating uniformity, it can be suitably used in the field of coating, microfabrication, and the like of a large substrate.

(5) Since the film of the photocurable composition of the present invention has a high photocuring rate, productivity is high.

(6) Since it is excellent in etching processing precision, etching resistance, and the like, it can be suitably used as an etching resistor for substrate processing such as a semiconductor element or a transistor.

(7) Since the photoresist peeling property after etching is excellent, no residue is generated, and it is suitable as an etching photoresist.

Claims (12)

A photocurable composition comprising (a) a polymerizable compound, (b) 0.1 to 15% by mass of a photopolymerization initiator and/or a photoacid generator, and (c) 0.001 to 5% by mass of a fluorine-based interface activity At least one of a agent, a lanthanide surfactant, and a fluorine-antimony surfactant, and (d) a photocurable composition having a viscosity at 25 ° C of 3 to 18 mPa ‧ , (a) polymerizability The compound contains 50% by mass or more of (e) a polymerizable unsaturated monomer having a primary skin irritation (PII value) of 4.0 or less, and (f) a polymerizable property at a viscosity of 25 mPa·s or less at 25 ° C. A saturated monomer (wherein part or all of the polymerizable unsaturated monomer of (e) and one or more of the polymerizable unsaturated monomer of (f) may be the same polymerizable unsaturated monomer). The photocurable composition according to claim 1, which comprises a photoradical polymerizable unsaturated monomer and/or a photocationic polymerizable unsaturated monomer as the (a) polymerizable compound. The photocurable composition according to claim 1, wherein a monomer having an ethylenically unsaturated bond-containing group is contained as the (a) polymerizable compound. A photocurable composition according to claim 1 which contains a compound having ethylene oxide as the (e) polymerizable unsaturated monomer. A photocurable composition according to claim 1 which contains a compound having an oxetane as the (e) polymerizable unsaturated monomer. A photocurable composition according to claim 1 which contains a vinyl ether as the (a) polymerizable compound. A photocurable composition according to claim 1 which contains a styrene derivative as the (a) polymerizable compound. The photocurable composition of the first aspect of the invention is characterized in that the content of the organic solvent in the photocurable composition is 2% by mass or less. The photocurable composition according to any one of claims 1 to 8, which is used in a photon lithography method. A photoresist comprising the photocurable composition according to any one of claims 1 to 8. A method of forming a pattern comprising the step of applying a photocurable composition according to any one of claims 1 to 8 to harden it. A method for forming a photoresist pattern, comprising the steps of: coating a photocurable composition according to any one of claims 1 to 8; and pressing a light transmissive mold on a substrate a step of deforming the photocurable composition; a step of irradiating light from the back surface of the mold or the back surface of the substrate to harden the coating film to form a photoresist pattern of a desired pattern; and removing the light transmissive mold from the coating film a step of attaching; a step of etching the substrate with the photocurable composition as a mask; and a step of peeling off the photocurable composition after etching.