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WO2009110536A1 - Composition durcissable pour lithographie par nano-impression, produit durci l'utilisant, procédé de fabrication du produit durci et élément d'un dispositif d'affichage à cristaux liquides - Google Patents

Composition durcissable pour lithographie par nano-impression, produit durci l'utilisant, procédé de fabrication du produit durci et élément d'un dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2009110536A1
WO2009110536A1 PCT/JP2009/054134 JP2009054134W WO2009110536A1 WO 2009110536 A1 WO2009110536 A1 WO 2009110536A1 JP 2009054134 W JP2009054134 W JP 2009054134W WO 2009110536 A1 WO2009110536 A1 WO 2009110536A1
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Prior art keywords
composition
curable composition
present
acrylate
meth
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English (en)
Japanese (ja)
Inventor
裕之 米澤
丘 高柳
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN2009801074029A priority Critical patent/CN101959932A/zh
Publication of WO2009110536A1 publication Critical patent/WO2009110536A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Definitions

  • the present invention relates to a curable composition for nanoimprint, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device using the cured product.
  • the nanoimprint method has been developed by developing an embossing technique that is well-known in optical disc production, and mechanically pressing a mold master (generally called a mold, stamper, or template) with an uneven pattern on a resist.
  • a mold master generally called a mold, stamper, or template
  • This is a technology that precisely deforms and transfers fine patterns.
  • Once a mold is made, it is economical because it can be easily and repeatedly formed with fine structures such as nanostructures.
  • it is a nano-processing technology with few harmful wastes and emissions, so it can be applied to various fields in recent years. Is expected.
  • thermoimprint methods There are two types of nanoimprint methods: a thermal nanoimprint method using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1) and an optical nanoimprint using a photocurable composition (for example, see Non-Patent Document 2).
  • the technology has been proposed.
  • the thermal nanoimprint method the mold is pressed onto a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is released to transfer the fine structure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, it is expected to be applied to various fields.
  • Patent Documents 1 and 2 below disclose thermal nanoimprinting methods that form a nanopattern at low cost using a thermoplastic resin.
  • the first technique is a case where a molded shape (pattern) itself has a function and can be applied as various nanotechnology element parts or structural members. Examples thereof include various micro / nano optical elements, high-density recording media, optical films, and structural members in flat panel displays.
  • the second technology is to build a laminated structure by simultaneous integral molding of microstructure and nanostructure and simple interlayer alignment, and try to apply it to ⁇ -TAS (Micro-Total Analysis System) and biochip fabrication. To do.
  • ⁇ -TAS Micro-Total Analysis System
  • biochip fabrication To do.
  • high-precision alignment and high integration are intended to be applied to the fabrication of high-density semiconductor integrated circuits and the fabrication of liquid crystal display transistors in place of conventional lithography. .
  • Pattern formation using an electron beam by an electron beam drawing apparatus or the like uses a method of drawing a mask pattern unlike a batch exposure method in pattern formation using a light source such as i-line or excimer laser. For this reason, the more patterns to be drawn, the longer the exposure (drawing) time, and the longer time it takes to form the pattern. For this reason, as the degree of integration of the semiconductor integrated circuit is dramatically increased to 256 mega, 1 giga, and 4 giga, the pattern formation time is correspondingly increased, and there is a concern that the throughput is remarkably deteriorated.
  • Patent Document 1 and Patent Document 3 below disclose a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nanometers or less is formed by pattern transfer.
  • Patent Document 4 below discloses a composite composition using nanoimprints that is applied to the field of semiconductor microlithography.
  • nanoimprint lithography has been applied to the fabrication of semiconductor integrated circuits such as fine mold fabrication technology, mold durability, mold fabrication cost, mold-resin detachability, imprint uniformity, alignment accuracy, and inspection technology. Considerations for application are starting to increase.
  • optical nanoimprint lithography has recently attracted attention as an inexpensive alternative to conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method.
  • a protective film provided on the color filter in order to impart resistance for example, photo-curing resins and thermosetting resins such as siloxane polymers, silicone polyimides, epoxy resins, and acrylic resins have been used for transparent permanent films for color filters (see Patent Documents 7 and 8 below).
  • these protective films in the formation of these protective films (permanent films), the uniformity of the coating film, adhesion to the substrate, high light transmittance after heat treatment exceeding 200 ° C., planarization characteristics, solvent resistance, scratch resistance Various characteristics such as these are required.
  • photocurable compositions comprising a resin, a photopolymerizable monomer and an initiator have generally been widely used in conventional photolithography methods (for example, patents).
  • Reference 9) The spacer generally forms a pattern having a size of about 10 ⁇ m to 20 ⁇ m by photolithography using a photocurable composition on a color filter substrate after forming a color filter or after forming the color filter protective film. Further, it is formed by heat curing by post-baking.
  • the spacer used in such a liquid crystal display is required to have high mechanical properties against external pressure, such as hardness, developability, pattern accuracy, and adhesion.
  • the coating uniformity of the photocurable composition As for the coating uniformity of the photocurable composition, the coating film thickness uniformity at the center and periphery of the substrate, dimensional uniformity due to higher resolution, film thickness, shape, etc., as the substrate becomes larger The demands are getting severe in various parts.
  • Non-Patent Document 3 a method of spinning after dropping in the center has been used as a resist coating method.
  • the resist application method by the discharge nozzle method is a method of applying a photoresist composition to the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. For example, a plurality of nozzle holes are arranged in a line.
  • a method of adjusting the film thickness has been proposed. Therefore, in order to apply to these liquid crystal display element manufacturing fields, the coating uniformity on the substrate is required for the curable composition for nanoimprint.
  • Patent Documents 10 to 17 a technique for improving the coating property of a protective film such as a positive photoresist, a pigment-dispersed photoresist for producing a color filter or a magneto-optical disk
  • Patent Documents 10 to 17 a technique of adding various surfactants or the like
  • Patent Document 18 an example of using a photocurable resin containing a fluorosurfactant as an optical nanoimprint etching resist for manufacturing a semiconductor integrated circuit are disclosed.
  • a method for improving the substrate coating property of a curable composition for nanoimprinting that does not contain pigments, dyes, and organic solvents used for the permanent film has not been known so far.
  • the optical nanoimprint method it is necessary to improve the fluidity of the photocurable composition in the cavity of the concave portion of the mold surface where the pattern is formed. Moreover, it is necessary to improve the adhesiveness between a resist and a base material (a board
  • a base material a board
  • a liquid curable composition for optical nanoimprint is dropped onto a substrate such as a silicon wafer, quartz, glass, film, or other material such as a ceramic material, a metal, or a polymer, and approximately several tens nm to several It is applied with a film thickness of ⁇ m, a mold having fine irregularities with a pattern size of about several tens of nm to several tens of ⁇ m is pressed and pressurized, and the composition is cured by irradiating with light in the pressurized state. In general, a mold is released from the film to obtain a transferred pattern.
  • a base material or a mold when performing light irradiation in the state which pressurized the mold to the coating film, at least one of a base material or a mold needs to be transparent.
  • light irradiation is generally performed from the mold side.
  • an inorganic material such as quartz or sapphire that transmits UV light, a light-transmitting resin, or the like is often used as the mold material.
  • the optical nanoimprint method is (1) no heating / cooling process is required and high throughput is expected compared to the thermal nanoimprint method, and (2) imprinting at a low pressure is possible because a liquid composition is used.
  • Major advantages include (3) no dimensional change due to thermal expansion, (4) the mold is transparent and easy to align, and (5) a robust three-dimensional crosslinked body is obtained after curing. It is done. It is particularly suitable for semiconductor micromachining applications where alignment accuracy is required and for micromachining applications in the field of flat panel displays.
  • optical nanoimprint method Another feature of the optical nanoimprint method is that the resolution does not depend on the light source wavelength as compared with ordinary optical lithography. Therefore, expensive devices such as a stepper and an electron beam drawing device are also used for fine processing on the nanometer order. The feature is not required.
  • the optical nanoimprint method requires an equal-magnification mold, and since the mold and the resin are in contact, there are concerns about the durability and cost of the mold.
  • Molds used in optical nanoimprint lithography can be manufactured from various materials such as metals, semiconductors, ceramics, SOG (Spin On Glass), or certain plastics.
  • a flexible polydimethylsiloxane mold having a desired microstructure described in Patent Document 19 has been proposed.
  • various lithography methods can be used depending on the size of the structure and the specifications for its resolution.
  • Electron beam and x-ray lithography are typically used for structure dimensions below 300 nm.
  • Direct laser exposure and UV lithography are used for larger structures.
  • the optical nanoimprint method the releasability of the mold and the curable composition for optical nanoimprinting is important.
  • the mold and the surface treatment of the mold specifically, hydrogenated silsesquioxane or fluorinated ethylene propylene copolymer mold. Attempts have been made so far to solve the adhesion problem using slag.
  • the photo-curable resin applied to nanoimprint is roughly classified into radical polymerization type and ion polymerization type due to the difference in reaction mechanism, and these hybrid types are added.
  • Any type of curable composition can be used for nanoimprint applications, but since a wide range of materials can be selected, a radical polymerization type curable composition is generally used (for example, non-patent literature). 4).
  • a radical polymerization type curable composition a composition containing a monomer (monomer) or oligomer having a vinyl group or (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used. It is done.
  • Non-Patent Document 5 discloses a composition that can be imprinted at low pressure and room temperature by using a low-viscosity and UV-curable monomer.
  • Non-Patent Document 6 the main requirement items shown in Non-Patent Document 6 below are applicability, substrate adhesion, low viscosity ( ⁇ 5 mPa ⁇ s), peelability, low cure shrinkage, fast curability, and the like.
  • a low-viscosity material in applications that require imprinting at a low pressure or a reduction in the remaining film ratio.
  • the refractive index of light, light transmittance, etc. are mentioned, for example.
  • Non-Patent Document 6 discloses a photocurable material having a viscosity of about 60 mPa ⁇ s (25 ° C.) as a material applied to such optical nanoimprint lithography.
  • Non-Patent Document 7 discloses a fluorine-containing photosensitive resin having a viscosity of 14.4 mPa ⁇ s whose main component is monomethacrylate and improved peelability.
  • the composition used in optical nanoimprinting there has been no report on a design guideline for a material to be adapted to each application although there is a description of a demand for viscosity.
  • Patent Documents 20 and 21 below disclose examples in which a photocurable resin containing a polymer having an isocyanate group is used for embossing for producing a relief hologram or a diffraction grating.
  • Patent Document 22 below discloses a curable composition for optical nanoimprinting for imprinting that contains a polymer, a photopolymerization initiator, and a viscosity modifier.
  • Non-Patent Document 8 includes (1) a functional acrylic monomer, (2) a functional acrylic monomer, and (3) a photocurable radical polymerizable composition in which a functional acrylic monomer and a photopolymerization initiator are combined.
  • a photo-cationic polymerizable composition containing a photocurable epoxy compound and a photoacid generator is applied to nanoimprint lithography to examine thermal stability and mold releasability.
  • Non-Patent Document 9 below discloses a technique for improving problems such as peelability between a photocurable resin and a mold, film shrinkage after curing, and reduction in sensitivity due to photopolymerization inhibition in the presence of oxygen (1).
  • a curable composition for optical nanoimprint which comprises a) a functional acrylic monomer, (2) a functional acrylic monomer, a silicone-containing monofunctional acrylic monomer, and a photopolymerization initiator.
  • Non-Patent Document 10 uses a surface-treated mold by applying a curable composition for optical nanoimprinting containing a monofunctional acrylic monomer, a silicone-containing monofunctional monomer, and a photopolymerization initiator on a silicone substrate. Thus, it is disclosed that pattern defects after molding are reduced. Further, in the following Non-Patent Document 11, a curable composition for optical nanoimprinting containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is applied on a silicone substrate, and high resolution is achieved by using a SiO 2 mold. A composition having excellent coating uniformity is disclosed.
  • Non-Patent Document 12 discloses an example in which a 50 nm pattern size is formed by a cationic polymerizable composition in which a specific vinyl ether compound and a photoacid generator are combined. This composition is characterized by low viscosity and high curing speed, but it is stated that template peelability is an issue.
  • Non-Patent Documents 8 to 12 Although various photocurable resins in which an acrylic monomer, an acrylic polymer, and a vinyl ether compound having different functional groups are applied to optical nanoimprint lithography are disclosed, a curable composition is disclosed. Guidelines regarding material design such as preferred types, optimum monomer types, monomer combinations, optimum monomer or resist viscosity, preferred resist solution properties, and improved resist coatability are not fully disclosed. For this reason, a combination of preferable materials for widely applying the curable composition to optical nanoimprint lithography applications is not known, and curable compositions for optical nanoimprint capable of exhibiting satisfactory performance in various applications have been heretofore The actual situation was not proposed.
  • compositions disclosed in Non-Patent Documents 11 and 12 have low viscosity, but when both are photocured to form a pattern and subsequently subjected to heat treatment, the transmittance of the finished cured film is obtained. Is low (colored), and the hardness is insufficient, so that practical performance as a permanent film is not sufficient.
  • Non-Patent Documents 13 and 14 below propose inorganic / organic hybrid materials composed of a mixture of silica sol treated with a photofunctional cross-linking material, (meth) acrylic monomer, and photopolymerization initiator. Application has been reported. Further, Non-Patent Documents 13 and 14 report that a 200 nm line pattern formation example of an imprint material and a patterning up to a line width of 600 nm as a molding material are reported. However, this material also has problems such as insufficient releasability from the mold and insufficient hardness of the cured film, and is not always satisfactory.
  • Non-Patent Documents 13 and 14 low-viscosity materials are also disclosed, but both have low transmittance of the cured film after photocuring to form a pattern and subsequent heat treatment. (In other words, the cured film is colored) and the hardness is insufficient.
  • Patent Document 23 discloses a pattern forming method using a fluorine-containing curable material in order to improve the releasability from the mold, as well as colloidal silica subjected to surface treatment, and a specific ( A composition for a hard coat containing a (meth) acrylic monomer, a leveling agent, and a photopolymerization initiator is disclosed, and its application to an optical disk having both film hardness and low curing shrinkage has been reported.
  • these compositions have insufficient mold releasability and substrate coatability, and are difficult to apply to optical nanoimprint lithography. Further, when heat treatment is performed after photocuring, the pattern is colored, and it is difficult to apply as a permanent film requiring low transmittance and light transmittance.
  • Non-patent literature 15 and patent literature 24 have reported the curable composition containing polysiloxane for nanoimprint applications.
  • Patent Document 25 reports a composition for producing an optical article by a stamper method.
  • the main technical problems as a permanent film include pattern accuracy, adhesion, transparency after heat treatment exceeding 200 ° C., high mechanical properties (strength against external pressure), scratch resistance, flattening properties, There are many problems such as solvent resistance and reduction of outgas during heat treatment.
  • the nanoimprint curable composition is applied as a permanent film, the uniformity of the coating film, (2) transparency after heat treatment, and (3) scratch resistance, as in the case of a resist using a conventional acrylic resin, etc. Gender is important.
  • Non-Patent Document 15 and Patent Document 25 for nanoimprint applications.
  • the compositions reported in these documents are both highly viscous. For this reason, when forming a structure by a nanoimprint method using a large-sized substrate, the pattern accuracy decreases due to a decrease in the fluidity of the resist (composition) in the concave portion of the mold, and further within the substrate (that is, Thickness variation (at the center and end of the substrate) becomes a problem. However, this problem is not disclosed in Non-Patent Document 15 and Patent Document 25.
  • Patent Document 26 a composition for producing optical articles by a stamper method is reported in Patent Document 26 regarding a curable composition containing polysiloxane.
  • the stamper method it is generally possible to form a structure using a composition having a high stamper pressure and a high viscosity.
  • the optical nanoimprint application there arises a problem that the pattern accuracy is lowered and a thickness unevenness in the substrate surface.
  • compositions that have been known for use in inkjet compositions and protective films for magneto-optical disks, and curable compositions for optical nanoimprints that are used as etching resists are optical nanoimprints that are used in the production of permanent films.
  • the curable composition for use and the material the required characteristics are greatly different from the viewpoint of high-temperature heat treatment and mechanical strength. For this reason, if a photo-curable resin applied for inkjet, magneto-optical disk protective film or etching resist application is applied as it is as a permanent film resist, it is quite practical in terms of transparency, mechanical strength, solvent resistance, etc. No one can withstand.
  • various materials are disclosed for the curable composition for optical nanoimprint, there is no sufficient design guideline for the curable composition suitable for producing a permanent film. It is.
  • the present invention is to provide a curable composition for nanoimprinting that is excellent in photocurability, and particularly suitable for a transparent protective film such as a flat panel display or a permanent film such as a spacer, Specifically, a curable composition for nanoimprints excellent in pattern accuracy, surface hardness, light transmittance and heat resistance after heat curing, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device The purpose is to provide.
  • a compound containing a compound having an oxetane ring, a functional acid anhydride, a photoradical polymerizable monomer, and a photoradical polymerization initiator, and having a radical polymerizable functional group in the composition A curable composition for nanoimprints, wherein the total content is 50 to 99.5% by mass.
  • a light transmittance of 400 nm is 95% or more when a thin film having a thickness of 3.0 ⁇ m is formed by exposure and heating.
  • a curable composition for nanoimprint is described in any one of [1] to [6].
  • a liquid crystal display device member comprising the cured product according to [8].
  • cured material characterized by including.
  • cured material using this, its manufacturing method, and the member for liquid crystal display devices can be provided.
  • (meth) acrylate represents “acrylate” and “methacrylate”
  • (meth) acryl represents “acryl” and “methacryl”
  • (meth) acryloyl” represents “ Represents “acryloyl” and “methacryloyl”.
  • “monomer” and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less.
  • “functional group” refers to a group involved in polymerization.
  • the nanoimprint referred to in the present invention refers to pattern transfer having a size of about several tens of nanometers to several tens of micrometers, and is not limited to nano-order ones.
  • the curable composition for nanoimprinting of the present invention includes a compound having an oxetane ring, a functional acid anhydride, a photoradical polymerizable monomer, a photo A radical polymerization initiator, and the total content of molecules having radical polymerizable functional groups in the composition is 50 to 99.5% by mass.
  • the composition of the present invention contains a compound having an oxetane ring and a functional acid anhydride that is a curing agent in addition to the photoradical polymerizable monomer and the photoradical polymerization initiator, so that it is photocurable. In addition, it has thermosetting properties. Thereby, after hardening a composition by light irradiation, the composition of this invention can raise surface hardness etc. more by heating by a heating process further.
  • the curable composition for nanoimprints of the present invention can be widely used for optical nanoimprint lithography, and can have the following characteristics. (1) Since the composition of the present invention is excellent in solution fluidity at room temperature, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. In any of the recesses, it is difficult for residues to remain after photocuring. (2) The cured film after curing the composition of the present invention has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peelability between the coating film and the mold. A good pattern can be formed because the pattern is not broken when the film is peeled off, and the surface of the coating film is not threaded to cause surface roughening (good pattern accuracy).
  • the curable composition for nanoimprints of the present invention is, for example, a member for semiconductor integrated circuits and liquid crystal display devices that have been difficult to develop (particularly, thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, etc. And other applications such as partition materials for plasma display panels, flat screens, micro electromechanical systems (MEMS), sensor elements, optical disks, and high-density memories.
  • MEMS micro electromechanical systems
  • Magnetic recording media such as discs, optical parts such as diffraction grating relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, column materials, liquid crystal alignment rib materials, microlenses Array, immunoassay chip, DNA separation chip , Microreactors, nanobio devices, optical waveguides, can also be widely applied to manufacturing, such as an optical filter, photonic crystal.
  • the total content of compounds having radically polymerizable functional groups in the composition is 50 to 99.5% by mass.
  • the “compound having a radically polymerizable functional group” is a compound having a radically polymerizable functional group having an ethylenically unsaturated bond such as a (meth) acryl group, a vinyl group, or an allyl group.
  • the compound having an oxetane ring in the present invention described later is oxetane (meth) acrylate
  • the (meth) acryl group is a radical polymerizable functional group, it corresponds to the compound having the radical polymerizable functional group. To do.
  • the total content of the compound having a radical polymerizable functional group in the composition of the present invention is less than 50% by mass, it cannot be sufficiently cured even by light irradiation, and the mold pattern cannot be accurately transferred. In addition, physical properties such as hardness of the cured film are insufficient. Further, when the total content of the compound having a radical polymerizable functional group in the composition of the present invention exceeds 95.5% by mass, additives such as a photo radical polymerization initiator and a surfactant do not function sufficiently. The pattern accuracy and the physical properties of the cured film are deteriorated. From the viewpoint of pattern accuracy and cured film physical properties, the total content of the compound having a radical polymerizable functional group in the composition of the present invention is preferably 60 to 99% by mass, and more preferably 70 to 98% by mass.
  • the curable composition for nanoimprinting of the present invention contains a compound having an oxetane ring (hereinafter sometimes simply referred to as “oxetane compound”). Since the composition of the present invention contains a compound having an oxetane ring, excellent hardness can be obtained by heating.
  • the number of oxetane ring structures (oxetanyl groups) contained in the compound having an oxetane ring in the present invention is preferably 1 to 4, and more preferably 1 to 3, from the viewpoint of curing speed and cured film properties.
  • the total number of carbon atoms of the compound having an oxetane ring is preferably 5 to 50, and more preferably 5 to 20 from the viewpoint of reducing the viscosity of the composition.
  • the molecular weight of the compound having an oxetane ring in the present invention is preferably from 100 to 1,000, and more preferably from 100 to 400, from the viewpoint of reducing the viscosity of the composition.
  • the compound having an oxetane ring in the present invention preferably has a photoradically polymerizable functional group.
  • radical photopolymerizable functional group examples include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, an allyl group, and a styryl group are preferable.
  • the number of radically polymerizable groups contained in the compound having an oxetane ring in the present invention is preferably 1 to 4, more preferably 1 to 2, from the viewpoint of pattern accuracy during light irradiation and adhesion to the substrate.
  • the compound having an oxetane ring contained in the composition of the present invention may be one type or two or more types.
  • an oxetane compound having a photoradically polymerizable functional group and an oxetane compound not having this may be used in combination.
  • the compound (x) which has a photoradically polymerizable functional group, and the oxetane compound (y) which does not have this as the content ratio (x: y, x reference
  • the content of the compound having an oxetane ring in the entire composition is preferably 5 to 50% by mass from the viewpoint of pattern accuracy after light irradiation, and is 10 to 30% by mass. Further preferred.
  • the compound having an oxetane ring in the present invention has a photo-radical polymerizable functional group, the content thereof, as described above, considers the content of the compound having a radical polymerizable functional group in the composition of the present invention. Can be determined.
  • the content of the oxetane compound having a photoradically polymerizable functional group is related to the content of the compound having another radical polymerizable functional group or the content of the oxetane compound having no photoradically polymerizable functional group. It is determined appropriately from the relationship.
  • Examples of the compound having an oxetanyl group in the present invention include 3-ethyl-3-hydroxymethyloxetane (trade name: OXT-101, manufactured by Toagosei Co., Ltd.), 1,4-bis [[(3-ethyl- 3-Oxetanyl) methoxy] methyl] benzene (trade name: OXT-121, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (phenoxymethyl) oxetane (trade name: OXT-211, manufactured by Toagosei Co., Ltd.) ), Di [1-ethyl (3-oxetanyl)] methyl ether (trade name: OXT-221, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name: OXT-212, manufactured by Toagosei Co., Ltd
  • the curable composition for nanoimprinting of the present invention contains a functional acid anhydride.
  • the acid anhydride compound in the present invention functions as a curing agent for the compound having an oxetane ring. Since the composition of the present invention contains a functional acid anhydride, a high surface hardness can be obtained after heat curing.
  • the “functional acid anhydride” means a compound obtained by dehydration condensation of two molecules of oxo acid and chemically bonded to other functional groups by heating or the like.
  • Examples of the functional acid anhydride in the present invention include phthalic anhydrides, citraconic anhydrides, succinic anhydrides, propionic anhydrides, maleic anhydrides, acetic anhydrides, and the like, from the viewpoint of viscosity reduction and composition stability. Therefore, phthalic anhydrides and maleic anhydrides are preferable.
  • the total number of carbon atoms of the functional acid anhydride in the present invention is preferably 10 to 100, more preferably 10 to 50, from the viewpoint of reducing the viscosity of the composition.
  • the molecular weight of the functional acid anhydride in the present invention is preferably from 100 to 1,000, more preferably from 100 to 500, from the viewpoint of reducing the viscosity of the composition.
  • the functional acid anhydride in the present invention preferably has a radically polymerizable functional group.
  • the photoradical polymerizable functional group include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, an allyl group, and a styryl group are preferable.
  • the number of radical photopolymerizable groups contained in the functional acid anhydride in the present invention is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of pattern accuracy during light irradiation and adhesion to the substrate. 1 type may be sufficient as the functional acid anhydride contained in the composition of this invention, and 2 or more types may be sufficient as it.
  • the composition of this invention may use together the functional acid anhydride which has a photoradically polymerizable functional group, and the functional acid anhydride which does not have this.
  • the compound (q) which has a radical photopolymerizable functional group, and the functional acid anhydride (w) which does not have this as the content ratio (q: w, q reference
  • the content of the functional acid anhydride in the entire composition is preferably 5 to 50% by mass, and preferably 10 to 30% by mass from the viewpoint of pattern accuracy after light irradiation. Further preferred.
  • the functional acid anhydride in the present invention has a photo-radical polymerizable functional group
  • the content thereof considers the content of the compound having a radical polymerizable functional group in the composition of the present invention. Can be determined.
  • the content of the functional acid anhydride having a photoradically polymerizable functional group is related to the content of a compound having another radical polymerizable functional group or a functional acid having no photoradically polymerizable functional group. It is determined appropriately from the relationship with the anhydride content.
  • the content ratio (a: b, a basis) of the compound (a) having a oxetane ring and the functional acid anhydride (b) in the present invention is unreacted. From the viewpoint of minimizing the amount of functional groups, 3/1 to 1/3 is preferable, and 2/1 to 1/2 is more preferable.
  • Examples of the functional acid anhydride in the present invention include methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: Epicron B570, manufactured by Dainippon Ink and Chemicals), methyl-hexahydrophthalic anhydride.
  • the curable composition for nanoimprinting of the present invention contains a photoradical polymerizable monomer. Since the composition of the present invention contains a photo-radically polymerizable monomer, good pattern accuracy can be obtained after light irradiation.
  • the “photo radical polymerizable monomer” means a monomer capable of causing a polymerization reaction by light irradiation to form a high molecular weight product.
  • the main function of the photoradically polymerizable monomer used in the present invention is appropriately selected for the purpose of adjusting the viscosity of the composition and the mechanical properties of the cured film. From the viewpoint of adjusting the viscosity of the composition, it is preferable to use a low-viscosity photo-radically polymerizable monomer.
  • the viscosity of the composition is usually preferably 18 mPa ⁇ s or less, and for that purpose, a polymerizable monomer having a viscosity as low as possible is used. preferable.
  • the reduction in viscosity of photoradical polymerizable monomers can be achieved by taking low molecular weight and low molecular interactions into consideration. Can be achieved.
  • the radical photopolymerizable monomer used in the present invention is preferably a compound having a viscosity of 100 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or less, particularly preferably 10 mPa ⁇ s or less, from the viewpoint of adjusting the viscosity of the composition.
  • the weight average molecular weight of the photoradically polymerizable monomer in the present invention is preferably 500 or less, more preferably 100 to 400, and particularly preferably 100 to 300, from the viewpoint of adjusting the viscosity of the composition.
  • Examples of the photoradically polymerizable functional group possessed by the photoradically polymerizable monomer in the present invention include a functional group having an ethylenically unsaturated bond, such as (meth) acryl group, vinyl group, allyl group, styryl. Groups are preferred. 1 type may be sufficient as the radical photopolymerizable monomer contained in the composition of this invention, and 2 or more types may be sufficient as it. Further, the composition of the present invention comprises a photoradical polymerizable monomer having a photoradically polymerizable functional group and a photoradical polymerizable monomer having no photoradical polymerizable functional group (for example, a polymerizable monomer having a cationic polymerizable group). (Mer) may be used in combination.
  • a photoradical polymerizable monomer having a photoradically polymerizable functional group and a photoradical polymerizable monomer having no photoradical polymerizable functional group (for example, a polymeriz
  • the polymerizable monomer used in the present invention is a combination of a low-viscosity monomer for adjusting viscosity and a polyfunctional monomer for imparting mechanical properties of a cured film, or an oxetane compound or a functional acid anhydride in the present invention. It is selected comprehensively considering the combination of objects.
  • the content of the photoradically polymerizable monomer in the entire composition is preferably 20 to 90% by mass, and preferably 30 to 70% by mass from the viewpoint of pattern accuracy after light irradiation. % Is more preferable.
  • the content of the photoradical polymerizable monomer in the present invention is determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention as described above.
  • silsesquioxane compound only one kind may be contained, or two or more kinds thereof may be contained.
  • the silsesquioxane compound is preferably contained in a proportion of 1 to 40% by mass, more preferably 1 to 20% by mass. By setting it as such a range, the composition viscosity and the mechanical characteristic of a cured film can be made compatible.
  • Examples of the photoradical polymerizable monomer in the present invention include a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer). Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxy
  • a bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups can also be preferably used.
  • the bifunctional polymerizable unsaturated monomer include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol.
  • neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate and the like are preferably used in the present invention. It is done.
  • a polyfunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups can also be preferably used.
  • the polyfunctional polymerizable unsaturated monomer include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, and EO-modified phosphorus.
  • Acid triacrylate trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxy) Ethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol Roxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (me
  • EO-modified glycerol tri (meth) acrylate PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.
  • a vinyl ether compound may be used as the radical photopolymerizable monomer used in the present invention.
  • the vinyl ether compound can be appropriately selected from known ones such as 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether.
  • vinyl ether compounds are, for example, the method described in Stephen C. Lapin, Polymers Paint Paint, Journal 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.
  • a styrene derivative can also be employed as the radical photopolymerizable monomer used in the present invention.
  • the styrene derivative include p-methoxystyrene, p-methoxy- ⁇ -methylstyrene, p-hydroxystyrene, and the like.
  • vinyl naphthalene derivatives can also be used.
  • 1-vinylnaphthalene ⁇ -methyl-1-vinylnaphthalene, ⁇ -methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene 4-methoxy-1-vinylnaphthalene and the like.
  • trifluoroethyl (meth) acrylate pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl
  • Compounds having a fluorine atom such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate are also used in the present invention. It can be used as a photoradical polymerizable monomer or used in combination with the photoradical polymerizable monomer in the present invention.
  • propenyl ether and butenyl ether can be blended as the radical photopolymerizable monomer used in the present invention.
  • a compound having a radical polymerizable group and an oxetane ring, a polymerizable acid anhydride, a photo radical polymerizable monomer hereinafter, these are collectively referred to as “polymerizable unsaturated monomer”.
  • the monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent and is effective in reducing the viscosity of the composition of the present invention. Usually, 10 mass of the total polymerizable unsaturated monomer. % Or more is added.
  • the monofunctional polymerizable unsaturated monomer is better as a reactive diluent, it is preferable to add 10% by mass or more of the total polymerizable unsaturated monomer.
  • the monomer having two unsaturated bond-containing groups is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 80% by mass or less of the total polymerizable unsaturated monomer. Preferably, it is added in a range of 70% by mass or less.
  • the ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. It is added in the range of mass%.
  • the ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably the total polymerizable unsaturated monomer. Is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered
  • the curable composition for nanoimprints of the present invention contains a radical photopolymerization initiator.
  • the composition of this invention can make the pattern precision after light irradiation favorable by including the radical photopolymerization initiator which starts radical polymerization reaction by light irradiation.
  • Photoradical polymerization initiator The content of the photoradical polymerization initiator used in the present invention is, for example, preferably from 0.1 to 15 mass%, more preferably from 0.2 to 12 mass%, based on the entire composition. Particularly preferred is 0.3 to 10% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.
  • the ratio of the radical photopolymerization initiator When the ratio of the radical photopolymerization initiator is 0.1% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved, which is preferable. On the other hand, when the ratio of the radical photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable.
  • various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied for ink jet compositions and dye display / color pigment compositions for liquid crystal display color filters, but for nanoimprinting.
  • a preferred photopolymerization initiator and / or photoacid generator addition amount for the curable composition for photo nanoimprint lithography is not reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment is not an essential component, and the optimum range of the photopolymerization initiator is different from that in the field of an ink jet composition or a liquid crystal display color filter composition. There is.
  • radical photopolymerization initiator used in the present invention a compound having activity with respect to the wavelength of the light source to be used is blended to generate an appropriate active species.
  • radical photopolymerization initiator used in the present invention for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A No. 2008-105414 can be preferably used.
  • a photosensitizer can be added to the curable composition for nanoimprinting of the present invention to adjust the wavelength in the UV region.
  • Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymers Sci, 62, 1 (1984)], specifically pyrene.
  • Perylene acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.
  • the curable composition for nanoimprinting of the present invention may contain a surfactant.
  • the surfactant used in the present invention contains, for example, 0.001 to 5% by mass in the total composition, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass. It is. When using 2 or more types of surfactant, the total amount becomes the said range. The total amount is in the above range.
  • the surfactant is in the range of 0.001 to 5% by mass in the composition, the effect of coating uniformity is good, and mold transfer characteristics are hardly deteriorated due to excessive surfactant.
  • the surfactant preferably includes at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant, and includes both a fluorine-based surfactant and a silicone-based surfactant.
  • it preferably contains a fluorine / silicone surfactant, and most preferably contains a fluorine / silicone surfactant.
  • the fluorine-based surfactant and the silicone-based surfactant are preferably nonionic surfactants.
  • the “fluorine / silicone surfactant” refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
  • a silicon wafer for manufacturing a semiconductor element a glass square substrate for manufacturing a liquid crystal element, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, Striation that occurs when the nanoimprint curable composition of the present invention is applied to a substrate on which various films are formed, such as an amorphous silicone film, an indium oxide (ITO) film doped with tin oxide, and a tin oxide film, It becomes possible to solve the problem of poor coating such as a scale-like pattern (unevenness of drying of the resist film).
  • ITO indium oxide
  • the fluidity of the composition of the present invention into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, the adhesion between the resist and the substrate is improved, the viscosity of the composition is decreased, etc. Is possible.
  • the nanoimprint composition of the present invention can significantly improve the coating uniformity by adding the surfactant, and in a coating using a spin coater or a slit scan coater, good coating suitability regardless of the substrate size. Is obtained.
  • nonionic fluorosurfactants examples include trade names Fluorard FC-430 and FC-431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Surflon S-382 (Asahi Glass ( EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by Tochem Products), trade names PF-636, PF-6320, PF -656, PF-6520 (all OMNOVA Solutions, Inc.), trade names FT250, FT251, DFX18 (all manufactured by Neos), trade names Unidyne DS-401, DS-403, DS-451 (all All are made by Daikin Industries, Ltd.) and trade names Megafuk 171, 172, 173, 178K, 178A (all are Dainichi) Ink and Chemicals Co., Ltd.) and the like.
  • nonionic silicone surfactant examples include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink & Chemicals, Inc.), KP -341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • fluorine / silicone surfactant examples include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd. )), And trade names Megafuk R-08 and XRB-4 (both manufactured by Dainippon Ink & Chemicals, Inc.).
  • the curable composition for nanoimprints of the present invention contains an antioxidant.
  • the content of the antioxidant used in the present invention is, for example, 0.01 to 10% by mass, preferably 0.2 to 5% by mass in the total composition. When using 2 or more types of antioxidant, the total amount becomes the said range.
  • the antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO x , SO x (X is an integer).
  • an antioxidant there is an advantage that coloring of a cured film can be prevented and a reduction in film thickness due to decomposition can be reduced.
  • antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.
  • hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.
  • antioxidants Commercially available products of the antioxidants include trade names “Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), trade names“ Antigene P, 3C, FR, Sumilizer S, and Sumilizer GA80 (Sumitomo Chemical Industries, Ltd.).
  • the composition of the present invention includes a polymer component, a release agent, an organometallic coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesive.
  • Accelerators, thermal polymerization initiators, photobase generators, colorants, elastomer particles, photoacid multipliers, basic compounds, and other flow regulators, antifoaming agents, dispersants, and the like may be added.
  • a polyfunctional oligomer having a molecular weight higher than that of the other polyfunctional polymerizable monomer may be blended within a range that achieves the object of the present invention.
  • the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as ester acrylate, polyurethane acrylate, polyether acrylate, and epoxy acrylate, and hydrolysis condensation products of trimethoxysilylpropyl acrylate.
  • the addition amount of the oligomer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0 to 5% by mass with respect to the component excluding the solvent of the composition. % By mass.
  • the curable composition for nanoimprinting of the present invention may further contain a polymer component from the viewpoint of improving imprintability and curability.
  • the polymer component is preferably a polymer having a polymerizable functional group in the side chain.
  • the weight average molecular weight of the polymer component is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoint of compatibility with the polymerizable compound.
  • the addition amount of the polymer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 2% by mass or less, relative to the component excluding the solvent of the composition. It is. Further, from the viewpoint of pattern formability, it is preferable that the resin component is as few as possible, and it is preferable that the resin component is not included except for surfactants and trace amounts of additives.
  • a release agent can be arbitrarily blended in the composition of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate.
  • the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used.
  • these mold release agents can be adhered to the mold.
  • the silicone-based mold release agent has particularly good releasability from the mold when combined with the photo-curable resin used in the present invention, and the phenomenon of taking a plate hardly occurs.
  • the silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, and silicone acrylic resin. Further, it is possible to apply a silicone leveling agent generally used in a hard coat composition.
  • the modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil.
  • the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification.
  • the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification. Two or more modification methods as described above may be performed on one polysiloxane molecule.
  • the modified silicone oil preferably has an appropriate compatibility with the composition components.
  • a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step.
  • silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it is excellent in characteristics after curing because it is crosslinked with the composition of the present invention.
  • Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeded out to the surface, and excellent adhesion to metal deposition and overcoat layer. This is preferable.
  • the release agent can be added alone or in combination of two or more.
  • a release agent When a release agent is added to the curable composition for nanoimprints of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass in the total amount of the composition, and added in a range of 0.01 to 5% by mass. More preferably.
  • the content of the release agent is in the range of 0.01 to 5% by mass, the effect of improving the peelability between the mold and the curable composition layer for nanoimprinting is improved, and further due to the repellency when the composition is applied.
  • the problem of surface roughness of the coating film occurs, the adhesion of the substrate itself or the adjacent layer, for example, the deposited layer in the product, or the destruction of the film during transfer (film strength becomes too weak) occurs. Can be suppressed.
  • an organic metal coupling agent may be blended in order to improve the heat resistance, strength, or adhesion to the metal vapor deposition layer of the surface structure having a fine concavo-convex pattern.
  • the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction.
  • various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, a tin coupling agent, can be used, for example.
  • silane coupling agent examples include vinyl silanes such as vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; ⁇ -methacryloxypropyl Trimethoxysilane; epoxy silane such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane; N- ⁇ - (amino Aminosilanes such as ethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇
  • titanium coupling agent examples include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite).
  • zirconium coupling agent examples include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, and zirconium butoxyacetylacetonate.
  • zirconium coupling agent examples include bis (ethyl acetoacetate).
  • Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl Examples thereof include acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetoacetate) and the like.
  • the organometallic coupling agent can be arbitrarily blended at a ratio of 0.001 to 10% by mass in the total solid content of the curable composition for nanoimprinting of the present invention.
  • the ratio of the organometallic coupling agent is 0.001% by mass or more because the stability of the composition and the deficiency in film formability can be suppressed.
  • a polymerization inhibitor may be blended in order to improve storage stability and the like.
  • the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; copper and the like.
  • the polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the composition of the present invention.
  • An ultraviolet absorber can also be used for the curable composition for nanoimprinting of the present invention.
  • Commercially available products of the ultraviolet absorber include Tinuvin P, 234, 320, 326, 327, 328, 213 (manufactured by Ciba Geigy Co., Ltd.), Sumsorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.
  • the ultraviolet absorber is preferably blended arbitrarily in a proportion of 0.01 to 10% by mass with respect to the total amount of the curable composition for optical nanoimprint.
  • a light stabilizer can also be used in the curable composition for nanoimprinting of the present invention.
  • Commercially available light stabilizers include Tinuvin® 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) ) And the like.
  • the light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.
  • An anti-aging agent can also be used in the curable composition for nanoimprinting of the present invention.
  • examples of commercially available anti-aging agents include Antigene® W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.).
  • the antiaging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.
  • a plasticizer can be added to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like.
  • preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate , Di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or
  • An adhesion promoter may be added to the curable composition for nanoimprints of the present invention in order to adjust adhesion to the substrate.
  • the adhesion promoter include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10- Phenanthroline, 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethyl Ethanolamine and derivatives, benzothiazole derivatives and the like can be used.
  • the adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further
  • a thermal polymerization initiator can be added as necessary.
  • Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.
  • the thermal polymerization initiator in the composition is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 4.0% by mass or less. In order to obtain the effect, the addition of the thermal polymerization initiator is preferably 3.0% by mass or more.
  • a photobase generator may be added as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like.
  • the photobase generator include 2-nitrobenzylcyclohexyl carbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamin
  • a colorant may be optionally added for the purpose of improving the visibility of the coating film.
  • the colorant pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired.
  • the pigment that can be used in the present invention conventionally known various inorganic pigments or organic pigments can be used.
  • the pigment that can be used in the present invention for example, those described in paragraph No. 0121 of JP-A No. 2008-105414 can be preferably used.
  • the colorant is preferably blended in a proportion of 0.001 to 2% by mass with respect to the total amount of the composition.
  • elastomer particles may be added as an optional component for the purpose of improving mechanical strength, flexibility and the like.
  • the elastomer particles that can be added as an optional component to the composition of the present invention have an average particle size of preferably 10 nm to 700 nm, more preferably 30 to 300 nm.
  • core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used.
  • the elastomer particles may have a crosslinked structure.
  • Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resin Chemical Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.
  • elastomer particles can be used alone or in combination of two or more.
  • the content of the elastomer component in the 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.
  • a basic compound may be optionally added to the composition of the present invention for the purpose of suppressing cure shrinkage and improving thermal stability.
  • the basic compound include amines, nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like.
  • amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.
  • a chain transfer agent may be added to the composition of the present invention to improve photocurability.
  • Specific examples of the chain transfer agent include 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2, Examples include 4,6 (1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutyrate).
  • the curable composition for nanoimprints of the present invention preferably has a water content of 2.0% by mass or less, more preferably 1.5% by mass, and even more preferably 1.0% by mass or less at the time of preparation.
  • a water content of 2.0% by mass or less, more preferably 1.5% by mass, and even more preferably 1.0% by mass or less at the time of preparation.
  • a solvent can be used in the curable composition for nanoimprinting of the present invention.
  • the content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the composition of the present invention preferably contains other monofunctional and / or bifunctional monomers as described above as reactive diluents, the organic solvent for dissolving the components of the composition of the present invention is It is not always necessary to contain.
  • the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained. As described above, the composition of the present invention does not necessarily contain an organic solvent.
  • the organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in curable compositions for optical nanoimprints and photoresists, which dissolves and uniformly disperses the compound used in the present invention. There is no particular limitation as long as it does not react with these components.
  • organic solvent examples include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene
  • a high boiling point solvent can also be added. These may be used alone or in combination of two or more. Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.
  • the surface tension of the curable composition for nanoimprinting of the present invention is preferably in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.
  • the moisture content at the time of preparation of the curable composition for nanoimprinting of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, and further preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the composition of the present invention can be made more stable.
  • the viscosity of the curable composition for nanoimprints of the present invention will be described.
  • the viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified.
  • the curable composition for nanoimprints of the present invention preferably has a viscosity at 25 ° C. of 3 to 18 mPa ⁇ s, more preferably 5 to 15 mPa ⁇ s, and particularly preferably 7 to 12 mPa ⁇ s.
  • the viscosity of the composition of the present invention By setting the viscosity of the composition of the present invention to 3 mPa ⁇ s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa ⁇ s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. A composition having a viscosity of 3 mPa ⁇ s or more is also easier to prepare than a composition having a viscosity of less than 3 mPa ⁇ s.
  • the viscosity of the composition of the present invention is 18 mPa ⁇ s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion. Further, when the viscosity of the composition of the present invention is 18 mPa ⁇ s or less, the viscosity hardly affects the formation of a fine pattern.
  • the viscosity of the composition can be adjusted by blending various monomers, oligomers and polymers having different viscosities.
  • the nanoimprint curable composition of the present invention preferably has a 400 nm light transmittance of 95% or more when a thin film (cured product) having a thickness of 3.0 ⁇ m is formed by exposure and heating.
  • the light transmittance at 400 nm means the light transmittance at a wavelength of 400 nm.
  • the 400 nm light transmittance is more preferably 97% or more.
  • the 400 nm light transmittance can be measured by, for example, “UV-2400PC” manufactured by Shimadzu Corporation.
  • the curable composition for nanoimprinting of the present invention contains nitrogen atoms in the composition.
  • the content of the monomer to be contained is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.
  • the light transmittance (400 nm light transmittance) can also be improved by adding the above-mentioned antioxidant to the composition of the present invention.
  • corrugated pattern can be formed by hardening the composition of this invention through the process of irradiating light.
  • the curable composition for nanoimprints of the present invention is preferably cured by light and heat.
  • the cured product obtained by the method for producing a cured product of the present invention is excellent in pattern precision, curability, and light transmittance, and is particularly suitable as a protective film for liquid crystal color filters, spacers, and other liquid crystal display device members. Can be used.
  • a layer (pattern forming layer) consisting of the composition of the present invention is applied on a base material (substrate or support) by applying at least a pattern forming layer consisting of the composition of the present invention and drying as necessary.
  • a pattern receptor with a pattern-forming layer provided on the substrate
  • press the mold against the surface of the pattern-receiving layer of the pattern receptor and transfer the mold pattern.
  • the concavo-convex pattern forming layer is cured by light irradiation and heating. Light irradiation and heating may be performed a plurality of times.
  • the optical imprint lithography according to the pattern forming method (a method for producing a cured product) of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.
  • the composition of the present invention is applied on a substrate or a support, and a layer comprising the composition is exposed, cured, and dried (baked) as necessary.
  • a permanent film such as an overcoat layer or an insulating film can be produced.
  • the concentration is 1000 ppm or less, preferably 100 ppm or less.
  • cured material using the curable composition for nanoimprints of this invention is described concretely.
  • the composition of this invention is apply
  • a coating method when the curable composition for nanoimprinting of the present invention is coated on a substrate generally known coating methods such as a dip coating method, an air knife coating method, a curtain coating method, and a wire bar coating method are used. It can be formed by coating by a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method or the like.
  • the film thickness of the pattern forming layer comprising the composition of the present invention is about 0.05 to 30 ⁇ m, although it varies depending on the intended use.
  • the composition of the present invention may be applied by multiple coating.
  • the substrate (substrate or support) on which the curable composition for nanoimprinting of the present invention is applied can be selected depending on various applications, such as quartz, glass, optical film, ceramic material, vapor deposition film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (spin on glass glass), polymer film such as polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass or transparent There are no particular restrictions on plastic substrates, conductive substrates such as ITO and metals, insulating substrates, semiconductor fabrication substrates such as silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. Further, the shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. Furthermore, as described later, as the substrate, a light transmissive or non-light transmissive material can be selected according to the combination with the mold or the like.
  • a mold in order to transfer the pattern to the pattern forming layer, a mold is pressed against the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.
  • a light-transmitting material is selected for at least one of a molding material and / or a substrate.
  • a curable composition for nanoimprinting of the present invention is applied on a substrate to form a pattern forming layer, and a light-transmitting mold is pressed on this surface, The pattern forming layer is cured by irradiating light from the back surface.
  • the curable composition for optical nanoimprint can be apply
  • the light irradiation may be performed with the mold attached or after the mold is peeled off. In the present invention, the light irradiation is preferably performed with the mold in close contact.
  • a mold having a pattern to be transferred is used as the mold that can be used in the present invention.
  • the pattern on the mold can be formed according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
  • the light-transmitting mold material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film are exemplified.
  • the non-light transmissive mold material used in the case of using the transparent substrate of the present invention is not particularly limited as long as it has a predetermined strength.
  • Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone.
  • the shape of the mold is not particularly limited, and may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.
  • the mold used in the method for producing a cured product of the present invention may be a mold that has been subjected to a release treatment in order to improve the releasability between the curable composition for optical nanoimprint and the mold surface.
  • examples of such molds include those that have been treated with a silane coupling agent such as silicone or fluorine, such as OPTOOL DSX manufactured by Daikin Industries, Ltd. or Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. Commercially available release agents can also be suitably used.
  • the mold pressure it is usually preferable to perform the mold pressure at 10 atm or less in the method for producing a cured product of the present invention.
  • the mold pressure it is preferable to select a region in which the uniformity of mold transfer can be ensured within a range in which the remaining film of the curable composition for optical nanoimprinting on the mold convex portion is reduced.
  • the irradiation amount of the light irradiation in the process of irradiating light to the said pattern formation layer should just be sufficiently larger than the irradiation amount required for hardening.
  • the irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint and the tackiness of the cured film.
  • the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
  • a pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprinting. It may be irradiated with light.
  • a preferable degree of vacuum at the time of light irradiation is in the range of 10 ⁇ 1 Pa to normal pressure.
  • the light used for curing the curable composition for nanoimprints of the present invention is not particularly limited.
  • light or radiation having a wavelength in a region such as high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, infrared, etc.
  • the high-energy ionizing radiation source for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used.
  • an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron
  • radiation such as ⁇ rays, X rays, ⁇ rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used.
  • the ultraviolet ray source examples include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp.
  • the radiation includes, for example, microwaves and EUV.
  • laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic lights, or may be lights having different wavelengths (mixed lights).
  • the exposure illuminance is in the range of 1 mW / cm 2 to 50 mW / cm 2 .
  • the exposure dose is desirably in the range of 5 mJ / cm 2 to 1000 mJ / cm 2 .
  • the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted materials to the mold can be prevented. Also.
  • an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.
  • the method for producing a cured product of the present invention it is preferable to include a step (post-baking step) in which the pattern forming layer is cured by light irradiation and then further cured by applying heat to the cured pattern.
  • the heating may be performed either before or after the mold is peeled from the pattern forming layer after light irradiation, but it is preferable to heat the pattern forming layer after the mold is peeled off.
  • the heat for heat-curing the composition of the present invention after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
  • the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
  • the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing.
  • the amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint lithography and the tackiness of the cured film.
  • the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity.
  • the pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing reactivity decrease due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprint lithography. It may be irradiated with light.
  • a preferable degree of vacuum is in the range of 10 ⁇ 1 Pa to normal pressure.
  • the curable composition for nanoimprinting of the present invention can be prepared as a solution by mixing the above components and then filtering with a filter having a pore size of 0.05 ⁇ m to 5.0 ⁇ m, for example.
  • Mixing / dissolution of the curable composition for nanoimprinting is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times.
  • the filtered liquid can be refiltered.
  • Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.
  • the cured product formed by the method for producing a cured product of the present invention can be used as a permanent film (resist for a structural member) or an etching resist used in a liquid crystal display (LCD) or the like.
  • the permanent film is bottled in a container such as a gallon bottle or a coated bottle after manufacture, and is transported and stored.
  • the container is filled with inert nitrogen or argon. It may be replaced.
  • the temperature may be normal temperature, but the temperature may be controlled in the range of ⁇ 20 ° C. to 0 ° C. in order to prevent the permanent film from being altered. Of course, it is preferable to shield from light at a level where the reaction does not proceed.
  • the curable composition for nanoimprinting of the present invention can also be applied as an etching resist for semiconductor integrated circuits, recording materials, flat panel displays, and the like.
  • a desired pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
  • O-1 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .: OXT-101)
  • O-2 Oxetane acrylate (Osaka Organic Chemical Co., Ltd .: OXE-10)
  • H-1 Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd .: MHAC-P)
  • H-2 Anhydride acrylate (manufactured by Sigma-Aldrich Japan Co., Ltd .: Aldrich reagent 330736)
  • M-1 benzyl acrylate (Osaka Organic Chemical Co., Ltd .: Biscote # 160)
  • M-2 Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd .: KARAYAD NPGDA)
  • M-3 trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd .: Aronix M309)
  • N-1 N-vinylformamide (Arakawa Chemical Industries, Ltd .: Beam Set 770)
  • W-1 Non-fluorinated surfactant (manufactured by Takemoto Yushi Co., Ltd .: Pionein D6315)
  • W-2 Fluorosurfactant (Dainippon Ink & Chemicals, Inc .: MegaFuck F780F)
  • A-1 Sumilyzer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
  • H-2, M-1, M-2, M-3, and N-1 correspond to compounds having a radical polymerizable functional group.
  • “Amount” indicates the content of the compound having a radical polymerizable functional group in the entire composition.
  • ⁇ Viscosity measurement> The viscosity was measured at 25 ⁇ 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
  • the rotation speed at the time of measurement is 100 rpm for 0.5 mPa ⁇ s or more and less than 5 mPa ⁇ s, 50 rpm for 5 mPa ⁇ s or more and less than 10 mPa ⁇ s, 20 rpm for 10 mPa ⁇ s or more and less than 30 mPa ⁇ s, and 30 mPa ⁇ s.
  • the product was pressed using a material made of a material cured in 60 minutes, and further exposed from the surface of the mold under the condition of 240 mJ / cm 2. After the exposure, the mold was released to obtain a resist pattern. The obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes.
  • the pattern shape after the transfer was observed with a scanning electron microscope and an optical microscope, and the pattern shape was evaluated according to the following criteria.
  • A Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold.
  • ⁇ There is a part (a range of less than 10% from the original pattern) that is partly different from the original pattern shape of the mold pattern shape.
  • ⁇ There is a part (a range of 10% or more and less than 20% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape.
  • X The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.
  • Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 ⁇ m, and the mold was not subjected to pressure bonding, and was exposed at an exposure amount of 240 mJ / cm 2 in a nitrogen atmosphere. Thereafter, the film cured by heating at 230 ° C. for 30 minutes in an oven was measured for transmittance at 400 nm using “UV-2400PC” manufactured by Shimadzu Corporation.
  • ⁇ The transmittance was 95% or more and less than 97%.
  • ⁇ The transmittance was 90 or more and less than 95%.
  • X The transmittance was less than 90.
  • Comparative Examples 1 and 2 which did not contain a functional acid anhydride or a compound having an oxetane ring, had a particularly high rate of film reduction after heating.
  • the comparative example 3 which does not contain photoradically polymerizable monomers other than the compound which has an oxetane ring, and an acid anhydride had various performance deteriorated.
  • Comparative Example 4 and Comparative Example 5 it can be seen that various performances are deteriorated because the content of the compound containing a radical polymerizable functional group is too small.
  • imprintability is deteriorated because the viscosity of the composition is too high.
  • Comparative Example 6 since no radical photopolymerization initiator is contained, curing is insufficient and various performances are deteriorated.

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Abstract

L'invention concerne une composition durcissable pour lithographie par nano-impression, qui est caractérisée en ce qu'elle contient un composé qui comporte un cycle oxéthane, un anhydride acide fonctionnel, un monomère photopolymérisable radicalairement et un initiateur de photopolymérisation radicalaire. La composition durcissable pour lithographie par nano-impression est également caractérisée en ce que la teneur totale en composés contenant un groupe fonctionnel polymérisable radicalairement dans la composition est de 50 à 99,5 % en masse. La composition présente une excellente précision du motif, une excellente dureté de surface, une excellente transmittance de la lumière et une excellente résistance à la chaleur après durcissement thermique.
PCT/JP2009/054134 2008-03-06 2009-03-05 Composition durcissable pour lithographie par nano-impression, produit durci l'utilisant, procédé de fabrication du produit durci et élément d'un dispositif d'affichage à cristaux liquides Ceased WO2009110536A1 (fr)

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WO2011125335A1 (fr) * 2010-04-09 2011-10-13 富士フイルム株式会社 Procédé de formation de motif, et procédé de fabrication de substrat à motif
US20170204222A1 (en) * 2013-07-26 2017-07-20 Kabushiki Kaisha Toshiba Resist material and pattern forming method using same

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JP6460672B2 (ja) 2013-09-18 2019-01-30 キヤノン株式会社 膜の製造方法、光学部品の製造方法、回路基板の製造方法及び電子部品の製造方法
CN106384745B (zh) * 2016-11-16 2019-01-08 京东方科技集团股份有限公司 显示基板的制备方法
KR102404724B1 (ko) * 2017-06-07 2022-06-02 삼성디스플레이 주식회사 표시 장치
US11249393B2 (en) * 2018-05-09 2022-02-15 Facebook Technologies, Llc Nanoimprint lithography processes for switching mechanical properties of imprint materials
US10892167B2 (en) * 2019-03-05 2021-01-12 Canon Kabushiki Kaisha Gas permeable superstrate and methods of using the same
US11549020B2 (en) * 2019-09-23 2023-01-10 Canon Kabushiki Kaisha Curable composition for nano-fabrication
CN119930995B (zh) * 2025-01-31 2025-09-23 中国科学技术大学 一种偶氮苯聚合物材料及其在纳米压印光刻中的应用

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