KR20100004055A - Curable composition for nanoimprint and cured material using the same and member for liquid crystal display device - Google Patents

Abstract

PURPOSE: A curable composition for nanoimprint is provided to ensure excellent imprint property, substrate adhesion, heat resistance, resilience rate and voltage characteristic after thermal hardening. CONSTITUTION: A curable composition for nanoimprint comprises (A) a silane coupling agent, (B) a polymer silicide compound, and (C) a photopolymerization initiator. The compound having a photopolymerizable group is occupied in the amount of 50 weight% or more in the total content of the silane coupling agent and polymer silicide compound.

Description

Curable composition for nanoimprint, hardened | cured material using this, and member for liquid crystal display devices {CURABLE COMPOSITION FOR NANOIMPRINT AND CURED MATERIAL USING THE SAME AND MEMBER FOR LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a curable composition for nanoimprint, a cured product using the same, and a member for a liquid crystal display device using the cured product.

The nanoimprint method develops an embossing technique that is well known in optical disc manufacturing, presses a mold original (commonly referred to as a mold, a stamper, and a template) in which a pattern of irregularities is formed into a resist and dynamically deforms the micropattern. It is a technique to make a transfer. Once a mold is produced, since it is economical and it is a nano processing technology with few harmful wastes and discharges, since microstructures, such as a nanostructure, can be simply and repeatedly shape | molded, application to various fields is anticipated in recent years.

The nanoimprint method includes a thermal nanoimprint method using a thermoplastic resin as a work material (see, for example, S. Chou et al .: Appl. Phys. Lett. Vol. 67, 3114 (1995)), and photocurability. Two techniques of photo nanoimprint using compositions (see, eg, M. Colbun et al, Proc. SPIE, Vol. 3676, 379 (1999)) have been proposed. In the case of the thermal nanoimprint method, the microstructure is transferred to the resin on the substrate by pressing the mold onto the polymer resin heated to the glass transition temperature or higher, and releasing the mold after cooling. Since this method is applicable also to various resin materials and glass materials, application to various aspects is expected. For example, US Pat. No. 5,772,905 and US Pat. No. 5,956,216 disclose a thermal nanoimprint method for inexpensively forming nanopatterns using thermoplastic resins.

On the other hand, in the photo-nanoimprint method of irradiating light through a transparent mold or a transparent substrate and photocuring the photocurable composition, it is not necessary to heat the material transferring the pattern when the mold is pressed, so that imprint at room temperature is possible. Become. In recent years, new developments such as a nanocasting method combining these advantages and a reversal imprint method for producing a three-dimensional laminated structure have also been reported.

In such a nanoimprint method, the following application techniques are proposed. As a 1st technique, it is a case where the shape (pattern) itself has a function, and can be applied as an element part or structural member of various nanotechnology. Examples thereof include various micro-nano optical elements, high-density recording media, optical films, structural members in flat panel displays, and the like. As a second technique, a laminated structure is constructed by simultaneous integral molding of a micro structure and a nano structure or by simple interlayer positioning, and is intended to be applied to the production of a micro-total analysis system (TA-TAS) or a biochip. The third technique is to apply high-density semiconductor integrated circuits, liquid crystal displays to transistors, and the like, instead of conventional lithography, by high-precision positioning and high integration. Including the above-described techniques, the response to the practical use of the nanoimprint method for these applications has been actively promoted in recent years.

As an application example of the nanoimprint method, first, an application example for fabricating a high density semiconductor integrated circuit will be described. In recent years, semiconductor integrated circuits have progressed in miniaturization and integration, and high precision of photolithography apparatuses has been advanced as a pattern transfer technique for realizing the microfabrication. However, in accordance with the demand for further miniaturization, the processing method is approaching the wavelength of the light source of light exposure, and conventional lithography techniques are also approaching the limit. For this reason, instead of lithography techniques, an electron beam drawing apparatus, which is a kind of charged particle beam apparatus, has been used in order to further refine the fine pattern and high precision. The pattern formation using the electron beam by an electron beam drawing apparatus etc. uses the method of drawing a mask pattern unlike the package exposure method in pattern formation using light sources, such as an i line | wire and an excimer laser. For this reason, as there are many patterns to draw, it takes exposure (drawing) time, and it becomes a fault that it takes time for pattern formation. For this reason, with 256 mega, 1 giga, and 4 giga, as the integration degree of a semiconductor integrated circuit increases remarkably, the pattern formation time will also increase remarkably long, and there is a concern that the throughput will be significantly inferior. Therefore, in order to speed up pattern formation by an electron beam drawing apparatus, development of the batch figure irradiation method which combines the mask of various shapes, irradiates an electron beam to them collectively, and forms an electron beam of a complicated shape is advanced. However, while the finer the pattern has progressed, the necessity of increasing the size of the electron beam drawing apparatus has arisen, and a disadvantage has arisen in that the apparatus cost is high, such as a mechanism for more precisely controlling the mask position.

On the other hand, as a technique for performing fine pattern formation at low cost, using a nano imprint lithography technique (photo nanoimprint method) is examined. For example, US Pat. Nos. 5,772,905 and 5,259,926 disclose nanoimprint techniques that use a silicon wafer as a stamper to form microstructures of 25 nanometers or less by pattern transfer. In addition, Japanese Patent Application Laid-Open No. 2005-527110 discloses a composite composition using nanoimprint applied to the field of semiconductor microlithography.

With this trend, nanoimprint lithography can be applied to the fabrication of semiconductor integrated circuits such as the production of fine molds, durability of molds, manufacturing costs of molds, peelability of molds and resins, imprint uniformity, alignment accuracy, and inspection techniques. Reviews are beginning to be active.

Next, application examples of the photo nanoimprint method to flat displays such as liquid crystal displays (LCDs) and plasma displays (PDPs) will be described.

In accordance with the trend of larger and higher resolution LCD and PDP substrates, optical nanoimprint lithography has recently attracted attention as an inexpensive lithography instead of the conventional photolithography method used in the manufacture of thin film transistors (TFTs) and electrode plates. The development of photocurable resists in place of the etched photoresists used in conventional photolithography methods has been required.

In addition, applications of photonic nanoimprint lithography are beginning to be examined for transparent protective film materials used as structural members such as LCDs, spacers for defining cell gaps in liquid crystal displays, and the like (for example, Japanese Patent Laid-Open No. 2005). -197699 and Japanese Unexamined Patent Publication No. 2005-301289. Unlike the above-mentioned etching resist, such a resist for structural members is finally left in a display such as a flat display panel, and thus may be referred to as a "permanent resist" or a "permanent film".

As a permanent film to which a conventional photolithography technique is applied, for example, a protective film formed on a TFT substrate of a liquid crystal panel, or a step difference between R, G, and B layers is reduced, so that the ITO film is resistant to high temperature treatment during the production of a sputtered film. In order to provide, the protective film etc. which are formed on a color filter are mentioned. Conventionally, photocurable resins and thermosetting resins, such as a siloxane polymer, a silicone polyimide, an epoxy resin, and an acrylic resin, were used for the transparent permanent film for color filters (Unexamined-Japanese-Patent No. 2000-39713 and Unexamined-Japanese-Patent No. 6). 43643). In forming these protective films (permanent films), various properties such as uniformity of the coating film, adhesion to the substrate, high light transmittance after heat treatment exceeding 200 ° C, planarization properties, solvent resistance, scratch resistance, and the like are required. have.

Moreover, in the field of the spacer used for a liquid crystal display, in the conventional photolithographic method, the photocurable composition which consists of resin, a photopolymerizable monomer, and an initiator is generally used widely (for example, Unexamined-Japanese-Patent No. 2004- See 240241). Generally, after the color filter is formed or after the formation of the protective film for the color filter, the spacer forms a pattern having a size of about 10 μm to 20 μm by photolithography using a photocurable composition on the color filter substrate. It is formed by heat curing by post-baking. Spacers used for such liquid crystal displays require high mechanical properties, hardness, developability, pattern accuracy, adhesion, and the like to external pressure.

For this reason, development of the photocurable composition suitable for formation of the permanent film (permanent resist), such as the said transparent protective film and spacer using the nanoimprint method, is calculated | required.

In addition, regarding the coating film uniformity of a photocurable composition, in accordance with the enlargement of a board | substrate, in various parts, such as coating film thickness uniformity in the center part and periphery part of a board | substrate, dimensional uniformity by high resolution, film thickness, a shape, etc. The demands are getting tighter.

Conventionally, in the field of manufacturing a liquid crystal display element using a small glass substrate, a method of spin after center dropping has been used as a resist coating method (see, for example, Electronic Journal 121-123 No. 8 (2002)). However, in the method of spin after central dropping, it is difficult to meet the requirements other than the coating uniformity. For this reason, as a replacement technique, a new resist coating method by a discharge nozzle type that can be applied to a large substrate after the fourth generation substrate, in particular after the fifth generation substrate, has been proposed. The resist coating method by a discharge nozzle type is a method of apply | coating a photoresist composition to the whole surface of the application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively, For example, the discharge port in which the some nozzle hole was arranged in the column shape. Method of using a discharge nozzle which has a slit-shaped discharge port and can discharge a photoresist composition in strip form, or after apply | coating a photoresist composition to the whole surface of the application | coating surface of a board | substrate, spin the board | substrate and adjust a film thickness A method is proposed. Therefore, application uniformity with respect to a base material is calculated | required also for the curable composition for nanoimprints, in order to apply to these liquid crystal display element manufacture fields.

Moreover, as a technique of improving the applicability | paintability of protective films, such as a positive type photoresist, pigment dispersion photoresist for color filter manufacture, and a magneto-optical disk, the technique of adding various surfactant etc. is known (for example, Unexamined Japanese Patent Japanese Patent Laid-Open No. 7-230165, Japanese Laid-Open Patent Publication No. 2000-181055, Japanese Laid-Open Patent Publication No. 2004-94241, Japanese Laid-Open Patent Publication No. 4-149280, Japanese Laid-Open Patent Publication No. 7-62043, Japanese Laid-Open Patent Publication 2001 -93192, Japanese Unexamined Patent Publication No. 2005-8759, Japanese Unexamined Patent Publication No. 2003-165930), and a photoresist containing a fluorine-based surfactant as an etching resist for photo nanoimprint for semiconductor integrated circuit fabrication. An example is disclosed (for example, see Unexamined-Japanese-Patent No. 2007-84625). However, the method for improving the substrate coating property of the curable composition for nanoimprints which does not use as a essential component the pigment, dye, and the organic solvent used for a permanent film is not known until now.

Moreover, in the photo nanoimprint method, it is necessary to improve the fluidity | liquidity of the photocurable composition in the cavity of the mold surface recessed part in which the pattern was formed. In addition, it is necessary to improve the adhesion between the resist and the substrate (substrate, support) while improving the peelability between the mold and the resist. However, it was difficult to simultaneously satisfy all of the fluidity in the cavity of the curable composition for photo nanoimprint, the peelability with the mold, and the adhesion with the substrate.

In photo nanoimprint lithography, a liquid curable composition for photo nanoimprint is added dropwise onto a substrate such as a silicon wafer, quartz, glass, film, or other material, for example, a ceramic material, a metal, or a polymer. After coating with a film thickness of 占 퐉, and pressing and pressing a mold having a fine concavo-convex with a pattern size of approximately tens of nm to several tens of 占 퐉, and curing the composition by light irradiation in a pressurized state, the mold is released from the coating film. In general, a method of obtaining a transferred pattern is common. Thus, when light irradiation is performed in the state which pressed the mold to the coating film, at least one of a base material or a mold needs to be transparent. Usually, light irradiation from the mold side is common. In this case, many inorganic materials, such as quartz and sapphire, which transmit UV light, an optically transparent resin, etc. are used for a mold material.

The photo nanoimprint method has a (1) heating / cooling process unnecessary because of the thermal nanoimprint method, high throughput is expected, and (2) an imprint at low pressure is possible because the liquid composition is used. And (3) there are no dimensional changes due to thermal expansion, (4) the mold is transparent, alignment is easy, and (5) major hardening points such as a rigid three-dimensional crosslinked product are obtained after curing. In particular, it is suitable for the semiconductor microfabrication application which requires alignment precision, or the microfabrication application in the field of flat panel displays.

In addition, another feature of the optical nanoimprint method is that the resolution does not depend on the wavelength of the light source as compared with the conventional optical lithography, and therefore, an expensive device such as a stepper or an electron beam drawing device is required even when the nanometer order is finely processed. It is characterized by not. On the other hand, the photo nanoimprint method requires an equal magnification mold and is concerned about the durability and cost of the mold because the mold and the resin are in contact with each other.

As described above, in order to apply a thermal and / or optical nanoimprint method to large-scale imprint of a micrometer or nanometer size pattern, not only the uniformity of the pressing pressure and the flatness of the disk (mould) are required, but also the above-mentioned. It is also necessary to control the fluidity of the composition with respect to the cavity of one mold recess and the behavior of the composition which is pressed out.

Molds used in photo nanoimprint lithography can be manufactured from various materials, such as metals, semiconductors, ceramics, spin on glass (SOG), or certain plastics. For example, a mold of a flexible polydimethylsiloxane having the desired microstructure described in pamphlet of WO 99/22849 has been proposed. In order to form a three-dimensional structure on one surface of this mold, various lithographic methods can be used depending on the size of the structure and the specification for its resolution. Lithography of electron beams and X-rays is commonly used in structure dimensions of less than 300 nm. Direct laser exposure and UV lithography are used for larger structures.

As for the photo nanoimprinting method, the peelability of the mold and the curable composition for photo nanoimprinting is important, and the adhesion problem is caused by using the surface treatment of the mold or the mold, specifically, hydrogenated silsesquioxane or fluorinated ethylene propylene copolymer mold. Attempts have been made to solve the problem.

Photocurable resins applied to nanoimprints are largely classified into photo-radical polymerization type and ionic polymerization type from differences in reaction mechanisms, and hybrid types thereof are added. Although any type of curable composition can be used for nanoimprint applications, since a wide range of materials is selected, photocurable compositions of photo-radical polymerization type are generally used (for example, F. Xu et al .: See SPIE Microlithography Conference, 5374, 232 (2004). As a photo radical polymerization type curable composition, the composition containing the monomer (monomer) or oligomer which has a vinyl radical or a (meth) acryl group which can be radically polymerized, and a photoinitiator is generally used. In the radical photopolymerizable curable composition, when light is irradiated, optical radicals generated by the photopolymerization initiator attack the vinyl group, and chain polymerization proceeds to form a polymer. Moreover, when a bifunctional or more than polyfunctional monomer and oligomer are used, a crosslinked structure can be obtained. D. J. Resnick et al .: J. Vac. Sci. Technol. In B, Vol. 21, No. 6, 2624 (2003), a composition capable of imprinting at low pressure and room temperature is disclosed by using a monomer having low viscosity and UV curing.

Although the required properties of the materials used in the photo nanoimprint lithography often depend on the application to be applied, the demands on the process characteristics are common regardless of the application. For example, the main requirement items disclosed in the latest resist material handbook, P1, 103-104 (2005, published by the Information Agency) include applicability, substrate adhesion, low viscosity (<5 mPa · s), peelability, low Curing shrinkage, fast curing, and the like. In particular, there is a strong demand for being a low viscosity material in applications requiring imprint at low pressure, reduction of residual film ratio, and the like. On the other hand, for example, the refractive index of the light, the light transmittance, etc. are mentioned about an optical member by request | requirement characteristic by use. Moreover, about etching resist, etching resistance, residual film thickness reduction, etc. are mentioned. How to control these required characteristics and balance various characteristics is key to the material design. For this reason, the material needs to be developed according to a process and a use because at least a required characteristic differs significantly in a process material and a permanent film. As a material applied to such an optical nanoimprint lithography application, the photoresist material which has a viscosity of about 60 mPa * s (25 degreeC) is disclosed by the latest resist material handbook, P1, 103-104 (2005 Information published). have. Similarly, CMC Publications: Development and Application of Nanoimprint P159 to 160 (2006) disclose fluorine-containing photosensitive resins having improved peelability with a viscosity of 14.4 mPa · s containing monomethacrylate as a main component.

However, with respect to the composition used in the photo nanoimprint, although there is a request for viscosity, there has been no report on the design guide of the material to suit each application.

In addition, JP-A-2004-59820 and JP-A-2004-59822 use embossing to this using the photocurable resin containing the polymer which has an isocyanate group for preparation of a relief hologram and a diffraction grating. An example is disclosed. Moreover, Unexamined-Japanese-Patent No. 2000-143924 discloses the curable composition for imprints containing a polymer, a photoinitiator, and a viscosity modifier.

In addition, N. Sakai et al .: J. Photopolymer Sci. Technol. Vol. 18, No. 4, 531 (2005) discloses a photocurable radical polymerizable composition comprising (1) a functional acrylic monomer, (2) a functional acrylic monomer, (3) a functional acrylic monomer and a photopolymerization initiator. The photocationic polymerizable composition containing a photocurable epoxy compound and a photo-acid generator etc. is applied to nanoimprint lithography, and the example which investigated thermal stability and mold peelability is disclosed.

M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005) describe problems such as peelability of photocurable resins and molds, film shrinkage after curing, and reduction of sensitivity by inhibiting photopolymerization in the presence of oxygen. The curable composition for photo nanoimprints containing (1) functional acryl monomer, (2) functional acryl monomer, a silicone containing monofunctional acryl monomer, and a photoinitiator as a study for improving this is disclosed.

T. Beiley et al .: J. Vac. Sci. Technol. B18 (6) and 3572 (2000) provide a curable composition for photo nanoimprint containing a monofunctional acrylic monomer, a silicon-containing monofunctional monomer, and a photopolymerization initiator on a silicon substrate, and using a surface-treated mold, It is disclosed that the defect of a later pattern is reduced. In addition, B. Vratzov et al .: J. Vac. Sci. Technol. In B21 (6) and 2760 (2003), a curable composition for photo nanoimprint containing a silicone monomer, a trifunctional acrylic monomer, and a photopolymerization initiator is provided on a silicon substrate, and a high resolution and uniformity of coating are applied by a SiO ₂ mold. This excellent composition is disclosed. EK Kim et al .: J. Vac. Sci. Technol, B22 (1), 131 (2004) discloses an example in which a 50 nm pattern size is formed by a cation polymerizable composition combining a specific vinyl ether compound and a photoacid generator. This composition is characterized by low viscosity and high curing rate, but is described as a template peelability.

N. Sakai et al .: J. Photopolymer Sci. Technol. 18, No. 4, 531 (2005), M. Stewart et al .: MRS Buletin, Vol. 30, No. 12, 947 (2005), T. Beiley et al .: J. Vac. Sci. Technol. B18 (6), 3572 (2000), B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) and E. K. Kim et al .: J. Vac. Sci. As disclosed in Technol, B22 (1), 131 (2004), various types of photocurable resins in which acrylic monomers, acrylic polymers, and vinyl ether compounds having different functional groups are applied to photo nanoimprint lithography are disclosed. Guidance on the design of materials such as optimum monomer species, combinations of monomers, optimal viscosity of monomers or resists, preferred solution properties of resists, and improved applicability of resists is not fully disclosed. For this reason, the combination of the preferable material for widely applying a curable composition to a photo nanoimprint lithography use is unknown, and the curable composition for photo nano imprints which can exhibit the satisfactory performance in various uses is not proposed until now. It is not true.

In addition, B. Vratzov et al .: J. Vac. Sci. Technol. B21 (6), 2760 (2003) and E. K. Kim et al .: J. Vac. Sci. Some of the compositions disclosed in Technol, B22 (1), 131 (2004) have low viscosity, but when all are photocured to form a pattern and subsequently subjected to heat treatment, the transmittance of the finished cured film is low (colored and The hardness is also insufficient, and practical performance as a permanent film is not sufficient.

Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006) and Science and Industry, Vol. 80, No. 7, 322 (2006) include silica sol, (meth) acrylic monomer, and photopolymerization treated with a photofunctional crosslinking material. Inorganic-organic hybrid materials consisting of a mixture of initiators have been proposed, and applications to photo nanoimprint lithography have been reported. In addition, Proc. SPIE Int. Soc. Opt. Eng., Vol.6151, No.Pt2, 61512F (2006) and Science and Industry, Vol. 80, No.7, 322 (2006) are examples of pattern formation of 200 nm lines of imprint material and 600 nm as a mold material. It has been reported that patterning is possible up to line width. However, also in this material, there existed a problem, such as peelability with a mold, or hardness of a cured film, and was not necessarily able to be satisfied. In addition, Proc. SPIE Int. Soc. Opt. Eng., Vol. 6171, No. Pt2, 61512F (2006) and the compositions of Science and Industry, Vol. 80, No. 7, 322 (2006) also disclose low-viscosity materials, but all of them are photocured and patterned. The transmittance of the cured film after the formation and subsequent heat treatment was low (that is, the cured film became colored), and the hardness was also insufficient.

In addition, Japanese Laid-Open Patent Publication No. 2000-143924 discloses a pattern forming method using a fluorine-containing curable material in order to improve the peelability with a mold, and in addition to colloidal silica and surface treatment, The composition for hard-coat containing a (meth) acryl monomer, a leveling agent, and a photoinitiator is disclosed, The application to the optical disc which made film hardness and low hardening shrinkage compatible is reported. However, in these compositions, peelability with a mold and substrate coating property are inadequate, and application to optical nanoimprint lithography is difficult. Moreover, when heat processing is performed after photocuring, coloring is seen in a pattern, low transmittance | permeability, and it is difficult to apply it as a permanent film | membrane which requires light transmittance.

JP 2007-25078 A describes a coating composition for hard coat containing a silane coupling agent, a polymer of a silane coupling agent, and a photopolymerization initiator. However, there is no description or suggestion in this document that this composition can be used for the composition for nanoimprint.

Japanese Laid-Open Patent Publication No. 2007-72374 describes a composition for photo nanoimprint containing a high molecular silicon compound. In the Example of this document, what condensed the alkoxysilane is used as an example of a high molecular silicon compound.

Here, the permanent film requires excellent imprintability, substrate adhesion, heat resistance, elastic recovery rate and voltage characteristics. And these demands are increasing day by day.

As described above, there is a demand for a composition for nanoimprint that can provide excellent imprintability, substrate adhesion, heat resistance, elastic recovery rate and voltage characteristics.

Here, Japanese Unexamined Patent Application Publication No. 2007-72374 discloses the use of a high molecular silicon compound. As a result of the inventor's examination, in the composition described in Examples of Japanese Unexamined Patent Publication No. 2007-72374, imprintability and substrate adhesiveness are disclosed. I found it still insufficient.

An object of the present invention is to provide a composition for nanoimprint that can provide excellent imprintability, substrate adhesion, heat resistance, elastic recovery rate and voltage characteristics.

As a result of earnest examination by the inventors of the present application under the foregoing problem, it has been found that the above problem can be solved by using a polymer silicon compound and a silane coupling agent in combination. That is, as shown in JP 2007-72374 A, the aforesaid problem can be solved by not condensing an alkoxysilane, but employing one containing both a high molecular silicon compound and a silane coupling agent in a coating liquid state. Came out. Specifically, it achieved by the following means.

(1) 50% by weight or more of the total content of A) a silane coupling agent, B) a high molecular silicon compound and C) a photopolymerization initiator, and having a photopolymerizable group in the total content of A) a silane coupling agent and B) a high molecular silicon compound; And C) a photopolymerization initiator is used for polymerization of the photopolymerizable group.

(2) The composition for photo nano imprint as described in (1) in which A) a silane coupling agent contains a photopolymerizable group.

(3) The composition for optical nanoimprints as described in (1) or (2) whose B) polymeric silicon compound is a silsesquioxane.

(4) The composition for optical nanoimprints as described in (1) or (2) whose B) polymeric silicon compound is cage silsesquioxane.

(5) B) The composition for optical nanoimprints in any one of (1)-(4) in which a polymeric silicon compound has a photopolymerizable group.

0.25 (중량비) 인, (1) ∼ (5) 중 어느 1 항에 기재된 광 나노 임프린트용 조성물.(6) A) content of silane coupling agent + B) content of polymeric silicon compound / B) content of polymeric silicon compound

The composition for optical nanoimprints in any one of (1)-(5) which is 0.25 (weight ratio).

(7) The composition for photo nanoimprints in any one of (1)-(6) in which A) a silane coupling agent occupies 25-99 weight% of a composition.

(8) B) The composition for optical nanoimprints in any one of (1)-(7) in which a polymeric silicon compound occupies 1-75 weight% of a composition.

(9) The composition for optical nanoimprint according to any one of (1) to (6), wherein the composition contains A) 25 to 99% by weight of the silane coupling agent and B) 1 to 75% by weight of the polymer silicon compound.

(10) The composition for photo nanoimprints according to any one of (1) to (9), wherein the C) photopolymerization initiator is an optical radical polymerization initiator.

(11) Surfactant is contained, The composition for optical nanoimprints in any one of (1)-(10) characterized by the above-mentioned.

(12) It contains antioxidant, The composition for optical nanoimprints in any one of (1)-(11) characterized by the above-mentioned.

(13) The viscosity of a composition is 3-200 mPa * s, The composition for optical nanoimprints in any one of (1)-(12) characterized by the above-mentioned.

Hardened | cured material formed by hardening | curing the composition for photo nanoimprints in any one of (14) (1)-(13).

The member for liquid crystal display devices containing the hardened | cured material as described in (15) (14).

According to the present invention, it is possible to provide a curable composition for nanoimprint that is excellent in overall imprintability, substrate adhesiveness, heat resistance, elastic recovery rate and voltage characteristics after heat curing.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

In addition, in this specification, "(meth) acrylate" shows "acrylate" and "methacrylate", "(meth) acryl" shows "acryl" and "methacryl", and "(meth) acryl" Loyl "refers to" acryloyl "and" methacryloyl ". In addition, in this specification, a "monomer" and a "monomer" have the same meaning. The monomer in this invention is distinguished from an oligomer and a polymer, and a weight average molecular weight says the compound of 1,000 or less. In this specification, a "functional group" means the group which participates in superposition | polymerization.

In addition, the nanoimprint referred to in this invention means pattern transfer of about several tens nm-several tens of micrometers, and is not limited to the thing of a nano order.

[Curable composition for nano imprint]

The curable composition for nanoimprint of the present invention (hereinafter may be simply referred to as the "composition of the present invention") contains A) a silane coupling agent, B) a polymeric silicon compound, and C) a photopolymerization initiator, and A) a silane coupler. Among the total contents of the ring agent and the B) polymeric silicon compound, those having a photopolymerizable group occupy 50% by weight or more of the total amount of the total composition. Among the total contents of the A) silane coupling agent and B) the polymeric silicon compound, those having a photopolymerizable group preferably occupy 65% by weight or more of the total, and more preferably 80% by weight or more of the total.

Moreover, the curable composition for nanoimprints of this invention can be widely used for optical nanoimprint lithography, and it can be set as having the following characteristics.

(1) Since the composition of the present invention has excellent solution fluidity at room temperature, the composition easily flows into the cavity of the mold recessed portion, and since the atmosphere is difficult to be accepted, no bubble defects occur, and the mold convex portion The residue hardly remains after photocuring in any of the recesses.

(2) Since the cured film after hardening the composition of this invention is excellent in mechanical property, is excellent in adhesiveness of a coating film and a base material, and excellent in peelability of a coating film and a mold, pattern collapse when removing a mold. In addition, since slippage does not occur on the surface of the coating film to cause surface roughness, a good pattern can be formed (good pattern accuracy).

(3) Since it is excellent in coating uniformity, it is suitable for the field of application | coating and fine processing with respect to a large base material.

(4) Since the mechanical properties such as light transmittance, residual film resistance, and scratch resistance and solvent resistance are high, it can be preferably used as various permanent films.

For this reason, the curable composition for nanoimprints of the present invention is, for example, a semiconductor integrated circuit or a liquid crystal display member, which has been difficult to develop until now (particularly, a thin film transistor of a liquid crystal display, a protective film of a liquid crystal color filter, a spacer, and other liquid crystals). It can be preferably applied to fine processing of a member for a display device, etc.), and other uses, for example, a partition wall material for a plasma display panel, a flat screen, a microelectromechanical system (MEMS), a sensor element, an optical disk, and a high density memory. Magnetic recording media such as disks, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, optical films, polarizing elements, organic transistors, color filters, overcoat layers, pillar materials, liquid crystal alignment rib materials, micro lens arrays , Immunoassay chips, DNA separation chips, micro reactors, nano biodevices, luminous intensity As it may be applied broadly to the production of such an optical filter, a photonic crystal.

(A) silane coupling agent

The silane coupling agent used in the present invention is not particularly defined as long as it is a compound having a group causing a coupling reaction and a hydrolyzable group, and a known silane coupling agent can be widely adopted. As molecular weight of a silane coupling agent, 100-600 are preferable and 150-350 are more preferable.

As a group which causes the coupling reaction which a silane coupling agent has, a vinyl group, an epoxy group, a (meth) acryloxy group, an amino, a ureide group, a chloropropyl group, a mercapto group, a sulfide group, an isocyanate group, an allyl group, and an jade Cetanyl group is mentioned as a preferable example, an allyl group, a vinyl group, an epoxy group, a (meth) acryloxy group is more preferable, and a (meth) acryloxy group is still more preferable.

Although the silane coupling agent used by this invention may have a photopolymerizable group, it is more preferable to have a photopolymerizable group. By having a photopolymerizable group, favorable cured film characteristics are acquired at the time of photocuring. As a photopolymerizable group here, a (meth) acryloxy group, a vinyl group, an epoxy group, an allyl group, and an oxetanyl group are mentioned.

As a silane coupling agent in this invention, vinyl trichlorsilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy silyl-N- (1,3-dimethyl-butyl Liden) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidepropyltriethoxysilane , 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane Etc. can be mentioned.

Only one type may be used for the silane coupling agent in this invention, and two or more types may be used for it.

(B) high molecular silicon compound

The high molecular silicon compound used by this invention refers to the high molecular compound containing silicon, A siloxane type polymer compound, a silicon carbide type polymer, and a polysilane type high molecular compound are preferable, and a siloxane type high molecular compound is more preferable.

Among the siloxane polymer compounds, those having a network structure skeleton are preferable, and a silsesquioxane compound is more preferable. Silsesquioxane is polysiloxane represented by a composition formula (RSiO _3/2 ) _n , In this invention, polysiloxane which has any structure, such as cage type, ladder type, and random, may be sufficient, and the polysiloxane which has cage structure is more preferable. desirable. In addition, in composition formula (RSiO _3/2 ) _n , R may be a substituted or unsubstituted siloxy group or any other substituent. In addition, n is preferably 8, and n R's may be the same or different, respectively.

In addition, although the polymeric silicon compound in this invention does not need to contain a polymeric group, it is preferable that it contains a polymeric group. In this case, a vinyl group, a (meth) acryloxy group, an oxetanyl group, an allyl group, etc. are mentioned.

In addition, only 1 type may be used for the polymeric silicon compound in this invention, and 2 or more types may be used for it.

Although the polymeric silicon compound used by this invention is illustrated below, this invention is not limited to these.

Here, the preferable blend form of A) a silane coupling agent and B) a polymeric silicon compound in this invention is demonstrated.

In this invention, it is preferable to occupy 25-99 weight% of A) silane coupling agents in the composition for optical nanoimprints, It is more preferable to occupy 30-85 weight%, It is further more preferable to occupy 50-75 weight%. Moreover, it is preferable to occupy 1-75 weight% of B) polymeric silicon compounds, It is more preferable to occupy 10-75 weight%, It is further more preferable to occupy 25-70 weight%.

0.25 (중량비) 인 것이 바람직하고, A) 실란 커플링제의 함량 + B) 고분자 규소 화합물의 함량 / B) 고분자 규소 화합물의 함량

0.5 (중량비) 인 것이 보다 바람직하다. 이와 같은 범위로 함으로써 저점도이고 임프린트 특성이 우수한 것이 얻어진다.In addition, in the composition of the present invention, A) content of the silane coupling agent + B) content of the polymeric silicon compound / B) content of the polymeric silicon compound

It is preferably 0.25 (weight ratio), A) content of silane coupling agent + B) content of polymeric silicon compound / B) content of polymeric silicon compound

It is more preferable that it is 0.5 (weight ratio). By setting it as such a range, the thing with low viscosity and excellent imprint characteristic is obtained.

(C) photopolymerization initiator

The curable composition for nanoimprints of the present invention contains a photopolymerization initiator. The photoinitiator here is a photoinitiator for polymerizing the photopolymerizable group which A) a silane coupling agent and B) a polymeric silicon compound have. That is, in this invention, both a radical photopolymerization initiator and a photocationic polymerization initiator can be employ | adopted suitably according to the kind of photopolymerizable group, etc., and a radical photopolymerization initiator is preferable. The composition of this invention can make the pattern precision after light irradiation more favorable by containing the radical photopolymerization initiator which starts an optical radical polymerization reaction by light irradiation.

As content of the photoinitiator used for this invention, 0.1-15 mass% is preferable in the whole composition, More preferably, it is 0.2-12 mass%, Especially preferably, it is 0.3-10 mass%. When using two or more types of photoinitiators, the total amount becomes said range.

If the ratio of the said photoinitiator is 0.1 mass% or more, since it exists in the tendency for a sensitivity (fast curing property), resolution, line edge roughness, and coating film strength to improve, it is preferable. On the other hand, by making the ratio of the radical photopolymerization initiator 15 mass% or less, there exists a tendency for light transmittance, coloring property, handleability, etc. to improve, and it is preferable.

The radical photopolymerization initiator used by this invention mix | blends what has activity with respect to the wavelength of the light source to be used, and uses what generate | occur | produces suitable active species.

As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. Examples thereof include Irgacure (registered trademark) 2959 available from Ciba, Inc. (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (Registered trademark) 184: (1-hydroxycyclohexylphenyl ketone), Irgacure (registered trademark) 50: (1-hydroxycyclohexylphenyl ketone, benzophenone), Irgacure (registered trademark) 651: (2,2- Dimethoxy-1,2-diphenylethan-1-one), Irgacure (registered trademark) 369: (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure (Registered trademark) 907: (2-methyl-1 [4-methylthiophenyl] -2-morpholinopropan-1-one, Irgacure (registered trademark) 819: (bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide, Irgacure (registered trademark) 1800: (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 1-hydroxycyclohexyl-phenyl-ketone) Irgacure® 1800: (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, 2- Idroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure (registered trademark) OXE01: (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), Darocur (registered trademark) 1173: (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242 (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO available from BASF: ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO-L: (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M available from Nippon Siebel Heg Screw: (1 -[4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, N-1414 Adekaoptoma (registered trademark) N-1414 available from Asahi Telephone Co., Ltd. : (Carbazole phenone system), adeka optoma (registered trademark) N-1717: (acridin system), adeka optoma (registered trademark) N-1606: (triazine system), Sanwa TFE-triazine from Chemicals: (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TME from Acids and Chemicals Triazine: (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), acid and chemical manufactured MP- Triazine: (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Chemical Co., Ltd. TAZ-113: (2- [2- (3 , 4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Chemical Co., Ltd. TAZ-108 (2- (3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4 ' -Methyldiphenyl sulfide, 4-phenylbenzophenone, ethyl mihilerketone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 2-methylthio Santone, thioxanthone ammonium salt, benzoin, 4,4'- dimethoxy benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1, 1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberon, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenylether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ', 5' Tetrakis (3,4,5-trimethoxyphenyl) 1,2'-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1, 2'-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate Etc. can be mentioned.

Moreover, in addition to the radical photopolymerization initiator, the photosensitive agent can be added to the curable composition for nanoimprints of this invention, and the wavelength of a UV region can also be adjusted. Typical sensitizers that can be used in the present invention include Cribelo [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, pyrene, perylene, acridine orange, thioxanthone, 2-chloro thioxanthone, benzoflavin, N- Vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives, and the like.

As a photocationic polymerization initiator used by this invention, the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation and starts cationic polymerization is mentioned, A well-known compound and its mixture can be selected suitably, and can be used. Examples of the photocationic polymerization initiator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazo disulfones, disulfones and o-nitrobenzyl sulfonates. have. More specifically, the thing of Unexamined-Japanese-Patent No. 2008-031303 can be used individually by 1 type or in combination of 2 or more type.

(Antioxidant)

Moreover, it is preferable that the curable composition for nanoimprints of this invention contains antioxidant. Content of antioxidant used for this invention is 0.01-10 mass% in whole composition, Preferably it is 0.2-5 mass%. When using two or more types of antioxidant, the total amount becomes said range.

The oxidizing agent is to inhibit the fading of a variety of oxidizing gases such as fade and ozone, active oxygen, NO _x, SO _x (X is a positive number) by heat or light irradiation. In particular, in the present invention, by adding an antioxidant, there is an advantage that the coloring of the cured film can be prevented and the film thickness reduction due to decomposition can be reduced. Such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives and the like. Among these, especially a hindered phenol type antioxidant and a thioether type antioxidant are preferable from a viewpoint of coloring of a cured film, and a film thickness reduction.

As a commercial item of the said antioxidant, brand name Irganox 1010, 1035, 1076, 1 222 (above, Chiba kaigi Co., Ltd. product), brand name Antigene P, 3C, FR, Sumiraiza S, Sumiraiza GA80 (Sumitomo Chemical Co., Ltd.) (Trade name), brand names adecastabu AO70, AO80, AO503 (manufactured by ADEKA Corporation), and the like. These may be used independently, or may mix and use them.

(Surfactants)

The curable composition for nanoimprints of the present invention may contain a surfactant. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass of the total composition, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass. When using two or more types of surfactant, the total amount becomes said range. When surfactant is in the range of 0.001-5 mass% in a composition, the effect of the uniformity of application | coating is favorable, and it does not bring about deterioration of the mold transfer characteristic by the excess of surfactant.

As said surfactant, it is preferable to contain at least 1 sort (s) of a fluorine-type surfactant, a silicone type surfactant, and a fluorine-type silicone surfactant, and it is more preferable to contain both a fluorine type surfactant and a silicone type surfactant, or a fluorine-type silicone surfactant. Preferably, it is most preferable to contain a fluorine-silicone surfactant. Moreover, as said fluorine-type surfactant and silicone type surfactant, nonionic surfactant is preferable.

Here, "fluorine-silicone surfactant" means having both the requirements of a fluorine-type surfactant and a silicone type surfactant.

By using such a surfactant, the silicon wafer for semiconductor element manufacture, the glass-angle board | substrate for liquid crystal element manufacture, the chromium film, the molybdenum film, the molybdenum alloy film, the tantalum film, the tantalum alloy film, the silicon nitride film, and the amorphous silicon Streaking and scale-like shape that occurs when the nanoimprint curable composition of the present invention is applied onto a substrate on which various films are formed, such as an indium oxide (ITO) film doped with a film, tin oxide, or a tin oxide film. It becomes possible to solve the problem of coating defects, such as a dry nonuniformity. Furthermore, the fluidity | liquidity improvement of the composition of this invention with respect to the cavity of a mold recessed part, the peelability improvement between a mold and a resist, the adhesiveness improvement between a resist and a board | substrate, the viscosity of a composition, etc. become possible. In particular, the nanoimprint composition of the present invention can greatly improve the coating uniformity by adding the surfactant, and in coating using a spin coater or a slit scan coater, good coating suitability can be obtained regardless of the substrate size.

As an example of the nonionic fluorine-type surfactant which can be used by this invention, a brand name Florard FC-430, FC-431 (made by Sumitomo 3M), a brand name Saffron S-382 (made by Asahigara Corporation), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by Tochem Products Co., Ltd.), trade names PF-636, PF-6320, PF-656, PF-6520 ( All OMNOVA Solutions, Inc.), brand name Futagent FT250, FT251, DFX18 (all are manufactured by Neos), brand name Udine DS-401, DS-403, DS-451 (all manufactured by Daikin Industries Co., Ltd.), The brand name Megapak 171, 172, 173, 178K, 178A, and (all are the Dai Nippon Ink Chemical Co., Ltd. product) are mentioned.

Moreover, as an example of the said nonionic silicone type surfactant, brand name SI-10 series (made by Takemoto fats and oils), Megapak Painted 31 (made by Dainippon Ink Chemical Co., Ltd.), KP-341 (Shin-Etsu Chemical Co., Ltd.) Co., Ltd.) is mentioned.

In addition, as an example of the said fluorine-silicone surfactant, brand name X-70-090, X-70-091, X-70-092, X-70-093 (all are the Shin-Etsu Chemical Co., Ltd. product), brand name Megapak And R-08 and XRB-4 (both manufactured by Dainippon Ink and Chemicals, Inc.).

(Other ingredients)

In the composition of the present invention, a polymerizable compound, a polymer component, a mold release agent, an organometallic coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, an adhesion promoter, a thermal polymerization initiator, and a photobase, as necessary, in addition to the above components. You may add a generator, a coloring agent, elastomer particle, a photoacid growth agent, a basic compound, and other flow regulators, an antifoamer, a dispersing agent, etc.

In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer having a higher molecular weight than that of the other polyfunctional polymerizable monomer may be blended within the range of achieving the object of the present invention. Examples of the polyfunctional oligomer having photopolymerizable properties include hydrolyzed condensates of various acrylate oligomers such as ester acrylate, polyurethane acrylate, polyether acrylate and epoxy acrylate, and trimethoxysilylpropyl acrylate. As addition amount of an oligomer component, 0-30 mass% is preferable with respect to the component except the solvent of a composition, More preferably, it is 0-20 mass%, More preferably, it is 0-10 mass%, Most preferably, 0-5 Mass%.

The curable composition for nanoimprints of the present invention may further contain a polymer component from the viewpoint of improvement of imprint suitability, curability, and the like. As said polymer component, the polymer which has a photopolymerizable group in a side chain is preferable. As a weight average molecular weight of the said polymer component, 2000-100000 are preferable from a compatible viewpoint with a polymeric compound, and 5000-500000 are more preferable. As addition amount of a polymer component, 0-30 mass% is preferable with respect to the component except the solvent of a composition, More preferably, it is 0-20 mass%, More preferably, it is 0-10 mass%, Most preferably, it is 2 mass% or less to be. In addition, it is preferable that the resin component is as few as possible from a viewpoint of pattern formation, and it does not contain a resin component except surfactant and a trace amount additive.

In order to further improve the peelability, another release agent may be optionally added to the composition of the present invention. Specifically, the mold pressurized to the layer of the composition of the present invention is added for the purpose of allowing the surface of the resin layer to be peeled off cleanly without causing the surface of the resin layer to become rough or falling off. When adding a mold release agent to the curable composition for nanoimprints of this invention, it is preferable to mix | blend in the ratio of 0.001-10 mass% in composition whole quantity, and it is more preferable to add in 0.01-5 mass%. When content of a mold release agent exists in the range of 0.01-5 mass%, the peelability improvement effect of a mold and the curable composition layer for nanoimprints improves, and the problem of the roughness of the coating film surface by the cratering at the time of coating of a composition arises. In addition, it is possible to suppress the adhesion of the substrate itself or an adjacent layer, for example, a vapor deposition layer, or the occurrence of film breakage (too weak in strength) during transfer in the product.

You may mix | blend organometallic coupling agents other than a silane coupling agent with the composition of this invention in order to improve the heat resistance of a surface structure which has a fine uneven | corrugated pattern, strength, or adhesiveness with a metal vapor deposition layer. The said organometallic coupling agent can be mix | blended arbitrarily in the ratio of 0.001-10 mass% in solid content whole quantity of the curable composition for nanoimprints of this invention. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective for improving the provision of heat resistance, strength, and adhesion to the vapor deposition layer. On the other hand, since the ratio of an organometallic coupling agent is 10 mass% or less, there exists a tendency which can suppress the stability of a composition and the film-forming defect, and is preferable.

In order to improve storage stability etc., you may mix | blend a polymerization inhibitor with the curable composition for nanoimprints of this invention. As said polymerization inhibitor, For example, Phenols, such as hydroquinone, tert- butyl hydroquinone, a catechol, hydroquinone monomethyl ether; Quinones such as benzoquinone and diphenyl benzoquinone; Phenothiazines; Copper etc. can be used. It is preferable to mix | blend a polymerization inhibitor in the ratio of 0.001-10 mass% arbitrarily with respect to the whole amount of the composition of this invention.

An ultraviolet absorber can also be used for the curable composition for nanoimprints of this invention. As a commercial item of the said ultraviolet absorber, Tinuvin P, 234, 320, 326, 327, 328, 213 (above, Chiba-Geigi Co., Ltd. make), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (above, Sumitomo Chemical Co., Ltd. product) etc. are mentioned. It is preferable to mix | blend a ultraviolet absorber in the ratio of 0.01-10 mass% arbitrarily with respect to the whole amount of the curable composition for photo nano imprints.

An optical stabilizer can also be used for the curable composition for nanoimprints of this invention. As a commercial item of the said light stabilizer, Tinuvin 292, 144, 622LD (above, Chiba-Igi Co., Ltd. product), Sanor LS-770, 765, 292, 2626, 1114, 744 (above, Sankyo Chemical Co., Ltd. make) ), And the like. It is preferable to mix | blend an optical stabilizer in the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

An anti-aging agent can also be used for the curable composition for nanoimprints of this invention. As a commercial item of the said anti-aging agent, Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Co., Ltd. product) etc. are mentioned. It is preferable to mix | blend anti-aging agent in the ratio of 0.01-10 mass% with respect to the whole amount of a composition.

It is possible to add a plasticizer to the curable composition for nanoimprint of the present invention in order to adjust the adhesiveness to the substrate, the flexibility of the film, the hardness and the like. Specific examples of preferred plasticizers include, for example, dioctylphthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and dimethyl adipate. , Diethyl adipate, di (n-butyl) adipate, dimethyl suverate, diethyl suverate, di (n-butyl) suverate, 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 acquire the effect of adding a plasticizer, 0.1 mass% or more is preferable.

In order to adjust adhesiveness with a board | substrate, you may add an adhesion promoter to the curable composition for nanoimprints of this invention. Examples of the adhesion promoter include benzimidazoles, polybenzimidazoles, lower hydroxyalkyl substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thioureas, organophosphorus compounds, 8-oxyquinoline, and 4-hydroxycyteridine. , 1,10-phenanthroline, 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldi Ethanolamine, N-ethyl diethanolamine, N-ethylethanolamine and derivatives, benzothiazole derivatives and the like can be used. Adhesion promoter is 20 mass% or less in a composition, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain an effect.

The curable composition for nanoimprints of the present invention may add a photobase generator as necessary for the purpose of adjusting pattern shape, sensitivity, and the like. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, [[(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, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine And 2,6-dimethyl-3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine and the like can be given as preferred ones.

You may arbitrarily add a coloring agent to the curable composition for nanoimprints of this invention for the purpose of improving the visibility of a coating film. A coloring agent can use the pigment and dye used by UV inkjet composition, the composition for color filters, the composition for CCD image sensors, etc. in the range which does not impair the objective of this invention. As the pigment which can be used in the present invention, various conventionally known inorganic pigments or organic pigments can be used. Examples of the inorganic pigments are metal compounds represented by metal oxides, metal complex salts, and the like, and specific metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal complex oxides are mentioned. Can be. As an organic pigment, CI Pigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139, 151, 154, 167, CI Pigment Orange 36, 38, 43, CI Pigment Red 105, 122 , 149, 150, 155, 171, 175, 176, 177, 209, CI Pigment Violet 19, 23, 32, 39, CI Pigment Blue 1, 2, 15, 16, 22, 60, 66, CI Pigment Green 7, 36, 37, CI Pigment Brown 25, 28, CI Pigment Black 1, 7 and carbon black can be illustrated. It is preferable to mix | blend a coloring agent in the ratio of 0.001-2 mass% with respect to the whole amount of a composition.

Moreover, in the curable composition for nanoimprints of this invention, you may add an elastomer particle as an arbitrary component for the purpose of improving mechanical strength, flexibility, etc.

-올레핀계 공중합체, 에틸렌/

-올레핀/폴리엔 공중합체, 아크릴 고무, 부타디엔/(메트)아크릴산에스테르 공중합체, 스티렌/부타디엔 블록 공중합 체, 스티렌/이소프렌 블록 공중합체 등의 엘라스토머의 입자이다. 또한 이들 엘라스토머 입자를 메틸메타크릴레이트 폴리머, 메틸메타크릴레이트/글리시딜메타크릴레이트 공중합체 등으로 피복한 코어/쉘형의 입자를 사용할 수 있다. 엘라스토머 입자는 가교 구조를 취하고 있어도 된다.As for the elastomer particle which can be added as an arbitrary component to the composition of this invention, average particle size becomes like this. Preferably it is 10 nm-700 nm, More preferably, it is 30-300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene /

-Olefin copolymer, ethylene /

It is particle | grains of elastomer, such as an olefin / polyene copolymer, an acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, a styrene / butadiene block copolymer, and a styrene / isoprene block copolymer. In addition, 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 Regina Bond RKB (manufactured by Regina Chemicals Co., Ltd.), Techno MBS-61, MBS-69 (above, Techno Polymer Co., Ltd.), and the like.

These elastomer particles can be used alone or in combination of two or more thereof. The content rate of the elastomer component in the composition of this invention becomes like this. Preferably it is 1-35 mass%, More preferably, it is 2-30 mass%, Especially preferably, it is 3-20 mass%.

You may arbitrarily add a basic compound to the composition of this invention for the purpose of suppressing hardening shrinkage and improving thermal stability. Examples of the basic compound include an amine, a nitrogen-containing heterocyclic compound such as quinoline and quinolyzine, a basic alkali metal compound and a basic alkaline earth metal compound. Among these, an amine is preferable at the point of compatibility with a photopolymerizable monomer, For example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, Quinuclidin, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, triethanolamine, and the like.

A chain transfer agent may be added to the composition of the present invention for improving the photocurability. Specific examples of the chain transfer agent include 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4 And 6 (1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutylate).

In addition, the amount of water at the time of preparation of the curable composition for nanoimprints of this invention becomes like this. Preferably it is 2.0 mass% or less, More preferably, it is 1.5 mass%, More preferably, it is 1.0 mass% or less. By making the water content at the time of preparation into 2.0 mass% or less, the shelf life of the composition of this invention can be made more stable.

Moreover, a solvent can also be used for the curable composition for nanoimprints of this invention. It is preferable that content of the said organic solvent is 3 mass% or less in all the compositions. That is, since the composition of the present invention preferably contains other monofunctional or bifunctional monomers as the reactive diluent, the organic solvent for dissolving the components of the composition of the present invention does not necessarily need to be contained. In the composition of this invention, content of the organic solvent becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, It is especially preferable not to contain. Thus, although the composition of this invention does not necessarily contain an organic solvent, you may add arbitrarily, such as when dissolving the compound etc. which are not melt | dissolved in a reactive diluent as the composition of this invention, and fine-adjusting a viscosity. As a kind of organic solvent which can be used suitably for the composition of this invention, it is a solvent generally used in the curable composition for photo nanoimprints and a photoresist, What is necessary is just to melt | dissolve and uniformly disperse the compound used by this invention, and these It will not specifically limit, if it does not react with the component of.

As said organic solvent, For example, alcohol, 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: ethylene glycol alkyl ether acetates such as methyl cellosolve 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 alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate: aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and 2-heptanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-methylbutanoate Esters such as lactic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate Can be mentioned.

In addition, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyro High boiling point solvents, such as lactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, can also be added. These may be used individually by 1 type and may use two or more types together.

Among these, methoxy propylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone are especially preferable. Do.

It is preferable that the surface tension of the curable composition for nanoimprints of this invention exists in the range of 18-30 mN / m, and it is more preferable to exist in the range which is 20-28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.

In addition, the amount of water at the time of preparation of the curable composition for nanoimprints of this invention becomes like this. Preferably it is 2.0 mass% or less, More preferably, it is 1.5 mass%, More preferably, it is 1.0 mass% or less. By making water content at the time of preparation into 2.0 mass% or less, the shelf life of the composition of this invention can be made more stable.

(Viscosity of Curable Composition for Nanoimprints of the Present Invention)

The viscosity of the curable composition for nanoimprints of the present invention will be described. The viscosity in this invention says the viscosity in 25 degreeC, unless it mentions specially. It is preferable that the viscosity in 25 degreeC of the curable composition for nanoimprints of this invention is 3-18 mPa * s, More preferably, it is 5-15 mPa * s, Especially preferably, it is 7-12 mPa * s. By making the viscosity of the composition of this invention into 3 mPa * s or more, there exists a tendency which the problem of a board | substrate application | coating suitability and the fall of the mechanical strength of a film | membrane hardly arise. Specifically, the viscosity is 3 mPa · s or more, which is preferable because it causes a surface irregularity at the time of application of the composition or the composition can be suppressed from flowing out of the substrate during application. Moreover, the composition whose viscosity is 3 mPa * s or more is also easy to adjust compared with the composition whose viscosity is less than 3 mPa * s. On the other hand, when 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 brought into close contact with the composition, the composition also flows into the cavity of the recess of the mold, so that the atmosphere becomes difficult to receive. It is preferable because the bubble defects are less likely to occur and the residues hardly remain after the photocuring in the mold convex portion. Moreover, when the viscosity of the composition of this invention is 18 mPa * s or less, a viscosity hardly affects formation of a fine pattern.

In general, the viscosity of the composition can be adjusted by blending various monomers, oligomers, and polymers having different viscosities. In order to design the viscosity of the curable composition for nanoimprints of this invention in the said range, it is preferable to add the composition whose viscosity of a single substance is 5.0 mPa * s or less, and to adjust a viscosity.

(Light permeability of hardened material)

It is preferable that the 400 nm light transmittance of the curable composition for nanoimprints of this invention when forming the thin film (cured product) of 3.0 micrometers in thickness by exposure and heating is 95% or more. Here, 400 nm light transmittance means the light transmittance in the wavelength of 400 nm. As said 400 nm light transmittance, it is more preferable that it is 97% or more.

The said 400 nm light transmittance can be measured, for example by "UV-2400 PC" made from Shimadzu Corporation.

The curable composition for nanoimprints of the present invention has a content of a monomer containing a nitrogen atom in the composition from the viewpoint of improving the light transmittance (400 nm light transmittance) of the cured product (reducing the decrease in light transmittance due to yellowing). It is preferable to use 5 mass% or less, It is more preferable to use 3 mass% or less, It is especially preferable to use 1 mass% or less.

In addition, the said light transmittance (400 nm light transmittance) can be improved also by adding the antioxidant mentioned above to the composition of this invention.

[Method for producing hardened material]

Next, the formation method of hardened | cured material (especially fine uneven | corrugated pattern) using the curable composition for nanoimprints of this invention is demonstrated. The process of forming the pattern forming layer by apply | coating the curable composition for nanoimprints of this invention on a board | substrate or a support body (substrate), pressurizing a mold to the said pattern forming layer surface, and a process of irradiating light to the said pattern forming layer By hardening the composition of the present invention, a fine concavo-convex pattern can be formed. In especially this invention, in order to improve the hardening degree of hardened | cured material, it is preferable to further include the process of heating a pattern formation layer after light irradiation. That is, it is preferable to harden the curable composition for nanoimprints of this invention by light and heat.

The hardened | cured material obtained by the manufacturing method of the hardened | cured material of this invention is excellent in pattern precision, sclerosis | hardenability, and light transmittance, and can be used especially suitably as a protective film of a liquid crystal color filter, a spacer, and another member for liquid crystal display devices.

Specifically, a pattern forming layer made of at least the composition of the present invention is applied onto a substrate (substrate or support), dried as necessary, and a layer (pattern forming layer) made of the composition of the present invention is formed to form a pattern receptor (substrate). The pattern forming layer was formed), the mold was pressed on the surface of the pattern forming layer of the pattern receptor, and the mold pattern was transferred to transfer, and the fine concavo-convex pattern forming layer was cured by light irradiation and heating. Light irradiation and heating may be performed in multiple times. Optical imprint lithography according to the pattern formation method (the method for producing a cured product) of the present invention can be laminated or multi-patterned, and can also be used in combination with a conventional thermal imprint.

Moreover, as an application of the curable composition for nanoimprints of this invention, the composition of this invention is apply | coated on a board | substrate or a support body, and the layer which consists of this composition is exposed, hardened, and dried (baked) as needed, and an overcoat layer or an insulating film is carried out. Permanent films, such as these, can also be manufactured.

In a permanent film (resist for structural member) used in a liquid crystal display (LCD) or the like, in order to avoid impairing the operation of the display, it is preferable to avoid the incorporation of ionic impurities of metals or organic substances in the resist as much as possible. The furnace is 1000 ppm or less, preferably 100 ppm or less.

Hereinafter, the manufacturing method (pattern formation method (pattern transfer method)) of the hardened | cured material using the curable composition for nanoimprints of this invention is demonstrated concretely.

In the manufacturing method of the hardened | cured material of this invention, the composition of this invention is first apply | coated on a base material, and a pattern formation layer is formed.

As a coating method when apply | coating the curable composition for nanoimprints of this invention on a base material, generally the well-known coating method, for example, the dip coat method, the air knife coat method, the curtain coat method, the wire bar coat method, the gravure coat It can form by apply | coating by the method, the extrusion coating method, the spin coat method, the slit scanning method, etc. In addition, although the film thickness of the pattern formation layer which consists of a composition of this invention changes with uses, it is about 0.05 micrometer-about 30 micrometers. Moreover, you may apply the composition of this invention by multiple application. In addition, you may form another organic layer, such as a planarization layer, between a base material and the pattern formation layer which consists of a composition of this invention. Thereby, since a pattern formation layer and a board | substrate do not directly contact, adhesion of the dirt to a board | substrate, damage to a board | substrate, etc. can be prevented.

The base material (substrate or support body) for apply | coating the curable composition for nanoimprints of this invention can be selected according to various uses, For example, quartz, glass, an optical film, a ceramic material, a vapor deposition film, a magnetic film, a reflective film, Ni Metal substrates such as, Cu, Cr, Fe, paper, SOG (spin-on glass), polyester films, polycarbonate films, polymer substrates such as polyimide films, TFT array substrates, PDP electrode plates, glass or transparent plastic The substrate, conductive substrates such as ITO and metal, insulating substrates, silicon, silicon nitride, polysilicon, silicon production substrates such as silicon oxide, amorphous silicon, and the like are not particularly limited. Moreover, the shape of a base material is not specifically limited, either plate shape or roll shape may be sufficient. In addition, as mentioned later, as said base material, a light transmissive or non-light transmissive thing can be selected according to combination with a mold, etc.

Next, in the manufacturing method of the hardened | cured material of this invention, in order to transfer a pattern to a pattern forming layer, a mold (pressurization) is press-bonded to the surface of a pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.

Optical nanoimprint lithography using the curable composition for nanoimprint of the present invention selects a light transmissive material on at least one of the mold material and / or the substrate. In the optical imprint lithography applied to the present invention, the curable composition for nanoimprint of the present invention is applied onto a substrate to form a pattern forming layer, the light-transmissive mold is pressed on this surface, and light is irradiated from the back of the mold, The pattern forming layer is cured. Moreover, the curable composition for optical nanoimprints may be apply | coated on a light transmissive base material, a mold is pressed, light is irradiated from the back surface of a base material, and the curable composition for optical nanoimprints can also be hardened.

Although the said light irradiation may be performed in the state which stuck a mold, and may be performed after mold peeling, in this invention, it is preferable to carry out in the state which stuck a mold.

As the mold usable in the present invention, a mold having a pattern to be transferred is used. Although the pattern on the said mold can form a pattern according to desired processing precision by the photolithography, the electron beam drawing method, etc., in this invention, the mold pattern formation method is not specifically limited, either.

Although the light transmissive mold material used in this invention is not specifically limited, What is necessary is just to have predetermined intensity | strength and durability. Specifically, light transparent resins, such as glass, quartz, PMMA, and a polycarbonate resin, flexible films, such as a transparent metal vapor deposition film and polydimethylsiloxane, a photocuring film, a metal film, etc. are illustrated.

Although it does not specifically limit as a non-transmissive mold material used when the transparent substrate of this invention is used, What is necessary is just to have predetermined intensity | strength. Specifically, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, and the like are exemplified, It is not particularly limited. Moreover, the shape of a mold is not specifically limited, either, A plate mold and a roll mold may be sufficient. Roll-shaped molds are particularly applied where continuous productivity of transfer is required.

The mold used in the manufacturing method of the hardened | cured material of this invention may use what performed the mold release process in order to improve the peelability of the curable composition for photo nanoimprints, and the mold surface. As such a mold, what was processed by the silane coupling agents, such as a silicone type and a fluorine system, for example, Optool DSX by Daikin Industries, Ltd., Novec EGC-1720 by Sumitomo 3M, etc. are commercially available. A mold release agent can also be used preferably.

When performing optical imprint lithography using the composition of this invention, in the manufacturing method of the hardened | cured material of this invention, it is preferable to perform mold pressure normally at 10 atmospheres or less. By setting the mold pressure to 10 atm or less, the mold and the substrate are hardly deformed and the pattern accuracy tends to be improved. Moreover, since pressurization is low, it is also preferable at the point which there exists a tendency which can reduce a device. It is preferable that mold pressure selects the area | region which can ensure the uniformity of mold transcription | transfer in the range from which the residual film of the curable composition for photo nanoimprints of a mold convex part becomes small.

In the manufacturing method of the hardened | cured material of this invention, the irradiation amount of the light irradiation in the process of irradiating light to the said pattern formation layer should just be large enough than the irradiation amount required for hardening. The irradiation amount required for curing is appropriately determined by irradiating the consumption amount of the unsaturated bonds in the curable composition for photo nanoimprint and the tuckiness of the cured film.

Moreover, in the optical imprint lithography applied to this invention, although the board | substrate temperature at the time of light irradiation is normally performed at room temperature, you may irradiate light while heating in order to improve reactivity. As a preliminary step of light irradiation, since it is effective in preventing bubble mixing, suppressing the reactivity decrease by oxygen mixing, and improving the adhesiveness of the mold and the curable composition for photo nanoimprint, you may perform light irradiation in a vacuum state. Moreover, in the manufacturing method of the hardened | cured material of this invention, the preferable vacuum degree at the time of light irradiation is the range of 10 <^-1> Pa-normal pressure.

선, 중성자선, 양성자선 등의 방사선도 사용할 수 있다. 자외선원으로서는, 예를 들어 자외선 형광등, 저압 수은등, 고압 수은등, 초고압 수은등, 크세논등, 탄소 아크등, 태양등 등을 들 수 있다. 방사선에는, 예를 들어 마이크로파, EUV 가 포함된다. 또한, LED, 반도체 레이저광, 혹은 248㎚ 의 KrF 엑시머 레이저광이나 193㎚ ArF 엑시머 레이저 등의 반도체의 미세 가공에서 이용되고 있는 레이저광도 본 발명에 바람직하게 사용할 수 있다. 이들 광은 모노크로광을 이용해도 되고, 복수의 파장이 상이한 광 (믹스광) 이어도 된다.The light used for curing the curable composition for nanoimprints of the present invention is not particularly limited, and examples include light or radiation of a wavelength in a region such as high energy ionizing radiation, near ultraviolet, far ultraviolet, visible or infrared. Can be. As the high energy ionizing radiation source, for example, electron beams accelerated by accelerators such as cockcroft accelerators, vandegraph accelerators, linear accelerators, betatrons, cyclotrons, etc. are industrially used most conveniently and economically. Γ-rays, X-rays, etc. emitted from sonar reactors, etc.

Radiation such as ray, neutron beam or proton beam can also be used. As an ultraviolet source, 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, a solar lamp etc. are mentioned, for example. Radiation contains microwave and EUV, for example. Moreover, the laser beam used by the microfabrication of semiconductors, such as LED, a semiconductor laser beam, or 248 nm KrF excimer laser beam, a 193 nm ArF excimer laser, can also be used suitably for this invention. Monochrome light may be used for these lights, and light (mixed light) in which a some wavelength differs may be sufficient.

At the time of exposure, it is preferable to make exposure roughness into the range of 1 mW / cm <2> -50 mW / cm <2>. Since the exposure time can be shortened by setting it to 1 mW / cm 2 or more, productivity improves, and by using 50 mW / cm 2 or less, there is a tendency that the deterioration of the characteristics of the permanent film due to side reactions can be suppressed, which is preferable. It is preferable to make exposure amount into the range of 5mJ / cm <2> -1000mJ / cm <2>. If it is 5 mJ / cm <2> or more, exposure margin will become narrow and photocuring may become inadequate, and it may prevent that a problem, such as adhesion of an unreacted substance to a mold, arises. Moreover, when exposure amount is 1000 mJ / cm <2> or less, deterioration of a permanent film by decomposition | disassembly of a composition can be suppressed.

At the time of exposure, in order to prevent inhibition of optical radical polymerization by oxygen, you may flow inert gas, such as nitrogen and argon, and may control oxygen concentration to less than 100 mg / L.

In the manufacturing method of the hardened | cured material of this invention, after hardening a pattern formation layer by light irradiation, it is preferable to include the process (post-baking process) which further hardens by adding heat to the hardened pattern. In addition, although heating may be performed at any time before and after peeling a mold from the pattern forming layer after light irradiation, it is more preferable to heat a pattern forming layer after peeling of a mold. As heat which heat-cures the composition of this invention after light irradiation, 150-280 degreeC is preferable and 200-250 degreeC is more preferable. Moreover, as time to apply heat, 5 to 60 minutes are preferable, and 15 to 45 minutes are more preferable.

In the present invention, the light irradiation in optical imprint lithography may be sufficiently larger than the irradiation amount required for curing. The irradiation amount required for curing is determined by irradiating the consumption amount of the unsaturated bond of the curable composition for photo nanoimprint lithography or the takkines of the cured film.

Moreover, in the optical imprint lithography applied to this invention, although the board | substrate temperature at the time of light irradiation is normally performed at room temperature, you may irradiate light while heating in order to improve reactivity. As a preliminary step of light irradiation, since it is effective in preventing bubble mixing, suppressing the reactivity decrease by oxygen mixing, and improving the adhesiveness of the mold and the curable composition for photo nanoimprint lithography, the light irradiation may be performed in a vacuum state. All. In the present invention, the preferred degree of vacuum is performed in the range of 10 ⁻¹ Pa to atmospheric pressure.

After mixing said each component, the curable composition for nanoimprints of this invention can be prepared as a solution, for example by filtering with a filter of 0.05 micrometer-5.0 micrometers of pore diameters. Mixing and dissolution of the curable composition for nanoimprint is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple steps, and may be repeated several times. The filtrate can also be filtered again. Although the material used for filtration can use polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, etc., It does not specifically limit.

As mentioned above, the hardened | cured material formed by the manufacturing method of the hardened | cured material of this invention can be used as a permanent film (resist for structural members) and an etching resist used for a liquid crystal display (LCD) etc. The permanent membrane is bottled and transported and stored in a container such as a gallon bottle or a coating bottle after production, but in this case, the inside of the container may be replaced with inert nitrogen or argon for the purpose of preventing deterioration. In addition, although it may be normal temperature at the time of transport and storage, in order to prevent the deterioration of a permanent film | membrane, you may control temperature in the range of -20 degreeC-0 degreeC. Of course, it is preferable to shield the light at a level at which the reaction does not proceed.

The curable composition for nanoimprint of the present invention can also be applied as an etching resist such as a semiconductor integrated circuit, a recording material, or a flat panel display.

When using the composition for nanoimprints of the present invention as an etching resist, first, a nano-order is produced by a method for producing a cured product of the present invention on a substrate, using a silicon wafer or the like having a thin film such as SiO ₂ formed thereon as a substrate. To form a fine pattern. Thereafter, a desired pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in wet etching or CF _{4 in} dry etching.

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. The materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below.

As shown in the following table, A) a silane coupling agent, B) a polymeric silicon compound, C) a photoinitiator, surfactant, and antioxidant were mix | blended and the curable composition for nanoimprint was prepared. In addition, the numerical value (excluding viscosity) in a table | surface is the mass%.

Abbreviation Characteristic of the compound product name Silane coupling agent SC1 With reactive group KBM5103 SC2 No reactive group KBM573 High molecular silicon compound SP1 Acryloyl Modified Silsesquioxane AC-SQ Photopolymerization initiator PI1 Photo radical initiator TPO-L Surfactants W1 Fluorine Megapak F780F W2 Nonion Pionine D6315 W3 Silicone X22-3710 Antioxidant AO1 Hindered phenol type Sumiraiza GA-80 AO2 Thioether system Adecastab AO-503 W2 (nonion system) Pionine D6315 Takemoto Yuji Antioxidant AO1 (hindered phenol type) Sumiraiza GA-80 Sumitomo Chemical AO2 (thioether type) Adecastab AO503 Adeka Japan

Moreover, as the comparative example 23, the composition of the Example of Unexamined-Japanese-Patent No. 2007-72374 was prepared.

[Evaluation of Composition for Nanoimprint]

About the composition of each Example and the comparative example, the viscosity, imprintability, board | substrate adhesiveness, heat resistance, elastic recovery rate, and voltage characteristic were measured and evaluated in accordance with the following evaluation method. The results are shown in the table below.

<Viscosity measurement>

The viscosity was measured at 25 ± 0.2 ° C. using a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd. The rotational 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, and 20 rpm for 10 mPa * s or more and less than 30 mPa * s, 30 mPa. S or more and less than 60 mPa * s were implemented at 10 rpm, 60 mPa * s or more and less than 120 mPa * s were implemented at 5 rpm, and 120 mPa * s or more were implemented at 1 rpm or 0.5 rpm.

5: viscosity is 3-20 mPa * s

4: viscosity is 20-50 mPa * s

3: viscosity is 50-120 mPa * s

2: viscosity is 120-300 mPa * s

1: Viscosity is 300 mPa * s or more

<Imprintability>

The extent to which the pattern transferred to the resist can reproduce the shape of the mold was evaluated. Specifically, it spin-coated on the glass substrate so that it might become set to film thickness 3.0 micrometer with respect to each composition. The coated base film spin-coated was set in a nanoimprint apparatus using a high pressure mercury lamp (lamp power 2000 kW / cm 2) manufactured by ORC as a light source, and a mold pressing force of 0.8 kN and a vacuum degree of exposure were 10 Torr ((about 1.33 × 10 ⁴ kPa)). Under the condition of, a polydimethylsiloxane (having cured "SILPOT184" manufactured by Torre Dow Corning Co., Ltd. manufactured at 80 ° C. for 60 minutes) having a line / space pattern of 10 μm and a groove depth of 4.0 μm was used. It was pressurized using a pressure sensitive adhesive and exposed to light at a condition of 240 mJ / cm 2 from the surface of the mold, after exposure, the mold was removed to obtain a resist pattern, and the obtained resist pattern was heated in an oven at 230 ° C. for 30 minutes. The pattern shape after transfer was observed with the scanning electron microscope and the optical microscope, and the pattern shape was evaluated according to the following criteria.

5: 95% or more of transfer rate of mold shape

4: 90-95% transfer rate of mold shape

3: 80-90% transfer rate of mold shape

2: transfer rate 70-80% of mold shape

1: less than 70% transfer rate of mold shape

<Substrate adhesiveness>

It was evaluated how much the pattern transferred to the resist reproduced the shape of the mold. Specifically, it spin-coated on the glass substrate so that it might become set to film thickness 3.0 micrometer with respect to each composition. The coated base film spin-coated was set in a nanoimprint apparatus using a high pressure mercury lamp (lamp power 2000 kW / cm 2) manufactured by ORC as a light source, and a mold pressing force of 0.8 kN and a vacuum degree of exposure were 10 Torr ((about 1.33 × 10 ⁴ kPa)). Under the condition of, a polydimethylsiloxane (having cured "SILPOT184" manufactured by Torre Dow Corning Co., Ltd. manufactured at 80 ° C. for 60 minutes) having a line / space pattern of 10 μm and a groove depth of 4.0 μm was used. It pressed and used, and it exposed on the conditions of 10mW and 300mJ / cm <2> from the surface of the mold.After exposure, the mold was removed and the resist pattern was obtained.How much peeling of a resist pattern occurs when peeling a mold. Was evaluated.

5: no pattern peeling

4: peeling is not more than 5% of total area

3: peeling is 5-10% of the total area

2: peeling is 10-20% of total area

1: peeling is not less than 20% of the total area

<Heat resistance>

Each composition was spin-coated on a glass substrate so that it might become a film thickness of 3.0 micrometers, and it exposed on the conditions of 10 mW and 300 mJ / cm <2> under nitrogen atmosphere, without crimping | molding a mold. Then, it hardened | cured by heating in 230 degreeC for 15 minutes. The film thickness before and after baking in oven was measured, and the reduction rate was calculated | required, and the reduction rate (film reduction) of the film | membrane by heating was evaluated in accordance with the following reference | standard.

5: film reduction of less than 5% before and after baking at 230 ° C-150 min

4: 5-10% film reduction before and after baking at 230 ° C.-150 min

3: 10-15% film reduction before and after baking at 230 ° C-150 min

2: 15-20% film reduction before and after baking at 230 ° C.-150 min

1: 20% or more of film reduction before and after baking at 230 ° C-150 min

<Evaluation of elastic recovery rate>

Each composition was spin-coated on a glass substrate so that it might become a film thickness of 3.0 micrometers, and it exposed at 10mW-200mJ under nitrogen atmosphere, without crimping | molding a mold. Then, the membrane | film | coat which heated and hardened in 230 degreeC and 30 minute (s) for 30 minutes was made into the columnar shape of 20x30x4 micrometer, and elastic recovery rate was measured using Shimadzu Corporation DUH-W201.

5: The elastic recovery rate was 80% or more.

4: The elastic recovery rate was 75% or more and less than 80%.

3: The elastic recovery rate was 70% or more and less than 75%.

2: The elastic recovery rate was 60% or more and less than 75%.

1: The elastic recovery rate was less than 60%.

<Evaluation of Voltage Characteristics>

Each composition was spin-coated on a glass substrate so that it might become a film thickness of 3.0 micrometers, and it exposed at 10mW-200mJ under nitrogen atmosphere, without crimping | molding a mold. Then, the volume resistance of the film | membrane heated in 230 degreeC for 30 minutes and hardened | cured was measured by the four terminal method. The voltage characteristic was measured by the above method. The obtained voltage characteristic was evaluated according to the following evaluation.

5: The volume resistance was 1 × 10 E 15 Ω · m or more.

4: The volume resistance was 5 × 10 E 14 Ω · m to 1 × 10 E 15 Ω · m.

3: The volume resistance was 1 × 10 E 14 Ω · m to 5 × 10 E 14 Ω · m.

2: The volume resistance was 1 × 10 E 13 Ω · m to 1 × 10 E 14 Ω · m.

1: The volume resistance was less than 1 × 10 E 13 Ω · m.

<Comprehensive Evaluation>

The said viscosity, imprintability, board | substrate adhesiveness, heat resistance, and surface hardness were comprehensively evaluated. Specifically, it evaluated as follows.

A: The average of individual ratings is 4.7 or more

B: Average of individual ratings is greater than 4.3 and less than 4.7

C: Average of individual ratings is 4.3 or less

D: At least two evaluations are included in the individual evaluations

As apparent from the table, when the nanoimprint composition of the present invention was used, it was found that a cured film having excellent overall imprintability, substrate density, heat resistance, elastic recovery rate and voltage characteristics was obtained.

Claims (15)

A) silane coupling agent, B) polymeric silicon compounds and C) photopolymerization initiator Wherein, in the total content of A) the silane coupling agent and B) the polymeric silicon compound, having a photopolymerizable group accounts for 50% by weight or more of the total, and C) the photopolymerization initiator is used for polymerization of the photopolymerizable group. The composition for an optical nanoimprint. The method of claim 1, A) The composition for optical nanoimprints in which a silane coupling agent contains a photopolymerizable group. The method of claim 1, B) The composition for optical nanoimprints whose high molecular silicon compound is a silsesquioxane. The method of claim 1, B) The composition for optical nanoimprints whose polymeric silicon compound is cage silsesquioxane. The method of claim 1, B) The composition for photo nano imprint in which a polymeric silicon compound has a photopolymerizable group. The method according to any one of claims 1 to 5, A) content of silane coupling agent + B) content of polymeric silicon compound / B) content of polymeric silicon compound

The composition for optical nanoimprint which is 0.25 (weight ratio). The method of claim 6, A) The composition for optical nanoimprints in which a silane coupling agent comprises 25 to 99 weight% of a composition. The method of claim 6, B) A composition for photo nanoimprint, wherein the high molecular silicon compound accounts for 1 to 75% by weight of the composition. The method of claim 6, The composition is an optical nanoimprint composition comprising A) 25 to 99% by weight of the silane coupling agent and B) 1 to 75% by weight of the polymeric silicon compound. The method of claim 6, Said C) photoinitiator is composition for optical nanoimprints which is radical photopolymerization initiator. The method of claim 6, A composition for photo nanoimprint, comprising a surfactant. The method of claim 6, A composition for photo nanoimprint, comprising an antioxidant. The method of claim 6, The viscosity of a composition is 3-200 mPa * s, The composition for optical nanoimprintes characterized by the above-mentioned. Hardened | cured material formed by hardening | curing the composition for optical nanoimprints in any one of Claims 1-13. The member for liquid crystal display devices containing the hardened | cured material of Claim 14.