TWI626999B - Method of manufacturing pattern forming body - Google Patents

Abstract

The present invention provides a method of producing a pattern forming body capable of suppressing generation of pattern defects and simultaneously producing a pattern forming body in which a film is formed on a surface of a concavo-convex pattern. The method for producing a pattern forming body according to the present invention includes the step of applying a first composition containing a solvent and a film forming component to the surface of the concave-convex pattern, and the surface tension ratio before the surface of the concave-convex pattern is exposed from the applied first composition. The second composition having a low first composition is applied to the region on which the first composition is applied to the concave-convex pattern; and the first composition and the second composition applied to the concave-convex pattern are dried, and the concave-convex pattern is applied. The step of forming a film on the surface.

Description

Method of manufacturing pattern forming body

The present invention relates to a method of producing a pattern forming body. More specifically, it relates to an optical recording medium such as a semiconductor integrated circuit, a planar screen, a microelectromechanical system, a sensor element, a compact disk, a high-density memory disk, or the like, a diffraction grating or a concave-convex photographic film. Parts, nano components, optical components, optical films or polarizing elements for flat panel displays, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillars, liquid crystal alignment Fabrication of ribs, microlens arrays, immunoassay wafers, DNA separation wafers, microreactors, nano-biocomponents, optical waveguides, optical filters, photonic liquid crystals, imprint dies, permanent films, etc. A method of producing a pattern forming body used in the present invention.

The "imprint method" is a technique in which a fine pattern is transferred onto a material by pressing a mold (generally referred to as a "mold" or a "die"). Since a precise fine pattern can be easily produced by using an imprint method, it has been expected to be applied to various fields in recent years. In particular, a nanoimprint technique that forms a fine pattern of nanometer level has attracted attention.

As the imprint method, a method called "hot stamping method" or "photoimprint method" has been proposed in accordance with the transfer method. The hot stamping method is to pressurize the thermoplastic resin to the glass transfer temperature after pressing the mold on the thermoplastic resin heated to the glass transition temperature or higher. After the mold is demolded below, the method of transferring the fine structure on the resin on the substrate is performed.

On the other hand, in the photoimprint method, the curable composition is light-cured by a light-transmitting mold or a light-transmitting substrate, and then the mold is peeled off, whereby the fine pattern is transferred onto the photocured material. method. This method is an imprint of an uncured material, so that it is easy to produce a fine pattern without high-pressure, high-temperature heating. In addition, since it can be imprinted at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as fabrication of a semiconductor integrated circuit.

Moreover, in recent years, a concavo-convex pattern obtained by an imprint method has been studied as a permanent film. When a concave-convex pattern is used as a permanent film, a composition (a film-forming composition) containing a solvent and a film-forming component is applied to the surface of the uneven pattern to form a film, and an attempt is made to impart functionality.

Patent Document 1 describes that a decane material is applied onto an embossed pattern produced by a sol-gel method to form a water-repellent layer.

Further, Patent Document 2 proposes a method of using a multilayer film in the step of imprinting photolithography, and describes that a polymerizable composition containing no antimony is used for the pattern forming layer, and a polymerizable composition containing antimony is used as a laminated structure. Things.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-183554

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-541193

However, when a film is formed on the surface of the concavo-convex pattern, as shown in FIG. 2, when the film-forming composition is dried, the pattern convex portion 1 is bent and collapsed to cause pattern defects. In addition, a composition containing a solvent having a large surface tension is used for the film-forming composition from the viewpoint of the solubility of the film-forming component, the coating property, and the like. However, when a film-forming composition having a large surface tension is used, This problem is particularly prone to occur.

Accordingly, an object of the present invention is to provide a method for producing a pattern forming body which can suppress the generation of pattern defects and simultaneously produce a pattern forming body in which a film is formed on the surface of the uneven pattern.

As a result of intensive studies, the inventors of the present invention have found that the film forming composition applied to the surface of the uneven pattern is dried. When the liquid surface is equal to or less than the pattern convex portion, the capillary force of the film forming composition is applied to the pattern convex portion. This causes pattern defects such as pattern collapse. Further, it is considered that if the capillary force applied to the pattern convex portion can be made smaller, generation of pattern defects can be suppressed, and the present invention can be completed. The present invention provides the following.

<1> A method for producing a pattern forming body, comprising: applying a first composition including a solvent and a film forming component to a surface of the concave-convex pattern; and before the surface of the concave-convex pattern is exposed from the applied first composition, The second composition having a lower surface tension than the first composition is applied to the region of the concave-convex pattern to which the first composition is applied, and the first composition and the second composition applied to the concave-convex pattern are dried. A step of forming a film on the surface of the concavo-convex pattern.

The method of producing a pattern forming body according to the above aspect, wherein a difference between a surface tension of 25 ° C of the first composition and a surface tension of 25 ° C of the second composition is 2 mN/m or more.

<3> The method for producing a pattern forming body according to the above aspect, wherein the surface tension of the first composition at 25 ° C exceeds 23 mN/m.

The method for producing a pattern forming body according to the above aspect, wherein the second composition has a surface tension at 25 ° C of 23 mN/m or less.

The method for producing a pattern forming body according to any one of the aspects of the present invention, wherein, after applying the first composition to the uneven pattern, the second composition is applied within 10 seconds. A region on the concave-convex pattern to which the first composition is applied.

The method for producing a pattern forming body according to any one of the above aspects, wherein the uneven pattern is a concave-convex pattern formed using a photocurable composition.

The method for producing a pattern forming body according to the above aspect, wherein the photocurable composition is a polymerizable compound containing one polymerizable group.

The method of producing a pattern forming body according to the above aspect, wherein the photocurable composition is 0% by mass to 60% by mass based on the total amount of the polymerizable compound contained in the photocurable composition. The proportion of % contains a polymerizable compound having one polymerizable group.

The method for producing a pattern forming body according to any one of the aspects of the present invention, wherein the uneven pattern is a concave-convex pattern formed by an imprint method.

The method for producing a pattern forming body according to any one of the above aspects, wherein the uneven pattern includes a pattern having a width of 300 nm or less.

According to the present invention, it is possible to suppress the generation of pattern defects and simultaneously produce a pattern forming body in which a film is formed on the surface of the concavo-convex pattern.

1‧‧‧ pattern convex

11‧‧‧ concave pattern

12‧‧‧ film

Fig. 1 is a conceptual diagram showing an example of a pattern formation body obtained by the method of the present invention.

Fig. 2 is a conceptual diagram showing a mechanism of generating a pattern defect.

Hereinafter, the contents of the present invention will be described in detail.

In the present specification, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic group" means acrylic group and methacryl group, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile.

In the present specification, "imprint" preferably means a pattern transfer of a size of from 1 nm to 10 mm, and more preferably a pattern transfer of a size (nano embossing) of about 10 nm to 100 μm.

In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes not only a group having no substituent (atomic group) but also a group having a substituent (atomic group). For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl).

In the present specification, "light" includes not only light of a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared, or the like, but also electromagnetic waves, and also includes radiation. The radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser may be used. The light may be monochromatic light (single-wavelength light) passing through the optical filter, or light of a plurality of different wavelengths (composite light).

The mass average molecular weight and the number average molecular weight in the present invention are those measured by gel permeation chromatography (GPC) unless otherwise specified. GPC is a polymer obtained, which can be separated by removing the solvent, and the obtained solid component is diluted to 0.1% by mass with tetrahydrofuran, and is linked in series by HLC-8020GPC (manufactured by Tosoh Corporation). Three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) were used as the column. As a condition, the sample concentration can be set to 0.35% by mass, the flow rate can be set to 0.35 mL/min, the sample injection amount can be set to 10 μL, and the measurement temperature can be set to 40 ° C, and a refractive index (RI) detector can be used. And proceed.

In the present specification, "all solid components" means the total mass of components from which solvent is removed from all compositions of the composition.

The solid content in the present specification is a solid component at 25 °C.

In this specification, the surface tension is SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd., using platinum. The plate was measured at 25 ± 0.2 ° C, and the lower end of the plate was immersed in the measurement sample and then pulled up. The platinum plate was subjected to surface cleaning by heating with an alcohol lamp before the measurement.

In this specification, the viscosity is a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd. at 0.5 ± 0.2 °C at 25 ± 0.2 °C. Above s, less than 5mPa. When s, the rotation speed at the time of measurement is set to 100 rpm at 5 mPa. Above s, less than 10mPa. When s, the rotation speed at the time of measurement is set to 50 rpm at 10 mPa. Above s, less than 30mPa. When s, the rotation speed at the time of measurement is set to 20 rpm at 30 mPa. Above s, less than 60mPa. In the case of s, the rotational speed at the time of measurement was set to a value measured at 10 rpm.

The method for producing a pattern forming body according to the present invention includes the step of applying a first composition containing a solvent and a film forming component to the surface of the concave-convex pattern, and the surface tension ratio before the surface of the concave-convex pattern is exposed from the applied first composition. The second composition having a low first composition is applied to the region on which the first composition is applied to the concave-convex pattern; and the first composition and the second composition applied to the concave-convex pattern are dried, and the concave-convex pattern is applied. The step of forming a film on the surface.

According to the invention, after the first composition is applied to the surface of the concavo-convex pattern, the surface of the concavo-convex pattern is applied to the concavo-convex pattern before the first composition is exposed, and the second composition having a lower surface tension than the first composition is applied to the concavo-convex pattern. In the region of the first composition, the composition applied to the surface of the uneven pattern is dried to make the liquid surface equal to or lower than the convex portion, and the capillary force applied to the pattern convex portion can be made more than the case where only the first composition is applied. small. Therefore, it is possible to suppress the occurrence of pattern defects such as pattern collapse accompanying drying of the composition, and to form a film on the surface of the uneven pattern. Especially when using surface sheets In the case where the composition having a high force is the first composition, the capillary force applied to the convex portion of the pattern can be made smaller according to the method of the present invention.

First, the concave and convex pattern will be described.

The material of the concave-convex pattern is not particularly limited. The photocurable composition, the thermosetting composition, ruthenium, tantalum carbide, metal, etc. are mentioned, and a photocurable composition is preferable. The uneven pattern formed by the photocurable composition is often low in strength. Therefore, when a film is formed on the surface of the uneven pattern, the pattern tends to collapse due to the conventional method, and according to the method of the present invention, Even in the uneven pattern having low strength, generation of pattern defects such as pattern collapse can be suppressed, and a film can be formed on the surface.

The uneven pattern preferably includes a pattern having a width of 300 nm or less, and more preferably a pattern having a width of 100 nm or less.

The pattern formed by the imprint method may be used as a mask, and the substrate may be processed by etching or the like to form a concavo-convex pattern.

Further, the concavo-convex pattern may be formed by a pattern inversion method. The "pattern inversion method" specifically forms a resist pattern on a substrate such as a carbon film (SOC). Next, after the resist pattern is coated by a Si-containing film (SOG) or the like, the upper portion of the Si-containing film is etched back to expose the resist pattern, and the exposed resist pattern is exposed by oxygen plasma or the like. Removal, whereby an inverted pattern of the Si-containing film can be formed. Further, the reverse pattern of the Si-containing film is used as an etching mask, and the underlying substrate is etched, whereby the reverse pattern is transferred onto the substrate. Finally, a method of etching the substrate by using a substrate on which the reverse pattern is transferred is used as an etching mask. An example of such a method can be referred to Japanese Patent Laid-Open No. Hei 5-267253, No. 2002-110510, Japanese Patent Laid-Open Publication No. 2006-521702, paragraph 0016 to paragraph 0030, the contents of which are incorporated herein by reference.

In the present invention, the method of forming the uneven pattern is more preferably an imprint method, and more preferably a photo imprint method, for the reason that a fine pattern can be formed at low cost and with high precision.

<Method of Forming Concavo-Concave Pattern by Imprint Method>

The method for forming a concavo-convex pattern by an imprint method includes the steps of: applying a photocurable composition to a substrate or a patterned mold to form a pattern forming layer; and performing the pattern forming layer by sandwiching the substrate and the mold a step of crimping; a step of irradiating the pattern forming layer with light; and a step of demolding the mold from the surface of the pattern forming layer. This will be explained below.

The photocurable composition is applied to a substrate or a patterned mold to form a pattern forming layer.

The photocurable composition will be described later.

The substrate is not particularly limited and can be selected according to various uses. Examples thereof include quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, and Fe, paper, spin on carbon (SOC), and spin-on glass. (Spin On Glass, SOG), polyester film, polycarbonate film, polymer substrate such as polyimide film, thin film transistor (TFT) array substrate, plasma display panel (PDP) Electrode plate, conductive substrate such as Indium-Tin Oxide (ITO) or metal, insulating substrate, germanium, tantalum nitride, polycrystalline germanium, germanium oxide, amorphous germanium, etc. Board and so on.

The shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. Further, a light-transmitting or non-translucent substrate can be selected in accordance with a combination with a mold or the like.

In order to improve the adhesion to the photocurable composition, a substrate having a lower film formed by applying a composition for forming an underlayer film on the surface of the substrate may be used. As the resin composition for forming the underlayer film, for example, a composition containing a polymerizable compound and a solvent can be used. For the resin composition for forming an underlayer film, for example, those described in paragraph number 0017 to paragraph number 0068 of JP-A-2014-24322, and paragraph number 0016 to paragraph number 0044 of JP-A-2013-93552, The content thereof can be incorporated into the specification of the present application. The application method of the resin composition for forming an underlayer film is preferably a coating method. The coating method is, for example, the above method.

A pattern to be transferred is formed on the mold. The pattern on the mold can be patterned by, for example, photolithography or electron beam drawing or the like according to a desired processing precision. For example, it is preferable to form a pattern having a width of 300 nm or less in the mold, and it is more preferable to form a pattern having a width of 100 nm or less. Moreover, the aspect ratio of the pattern is preferably from 0.1 to 10, more preferably from 1 to 5.

The material of the mold is not particularly limited, and may have a predetermined strength and durability. Specifically, a light-transparent resin such as glass, quartz, acrylic resin, or polycarbonate resin, a transparent metal vapor-deposited film, a soft film such as polydimethyl siloxane or a photocured film, a metal film, or the like can be exemplified. Further, in the case of using a light-transmitting substrate, a non-light-transmitting mold can also be used. The material of the non-transmissive mold is not particularly limited, and may have a predetermined strength. Specifically, ceramic materials, vapor deposited films, and magnetic materials can be exemplified A metal film such as a film, a reflective film, or Ni, Cu, Cr, or Fe, SiC, tantalum, tantalum nitride, polycrystalline germanium, cerium oxide, or amorphous germanium is not particularly limited. Further, the shape of the mold is not particularly limited, and may be any of a plate mold and a roll mold. In particular, a roll mold is applied in the case of continuous productivity requiring transfer.

In order to improve the peelability of the photocurable composition from the surface of the mold, the mold may be used for demolding. Such a mold can also be suitably used for a treatment of a decane coupling agent such as a lanthanide or a fluorine-based oxime coupling agent, such as OPTOOL DSX manufactured by Daikin Industries Co., Ltd., or a product manufactured by Sumitomo 3M Co., Ltd. A commercially available release agent such as Novec EGC-1720.

The application method of the photocurable composition is preferably a coating method. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, and a gravure coating method. , an extrusion coating method, a spin coating method, a slit scanning method, an inkjet method, or the like.

The film thickness of the pattern forming layer varies depending on the use to be used. For example, it is preferred that the film thickness after drying is about 0.03 μm to 30 μm. Further, the photocurable composition may be applied by multiple coating. In the method of providing droplets on a substrate by an inkjet method or the like, the amount of droplets is preferably from about 1 pl to about 20 pl, and it is preferred to arrange droplets on the substrate or on the mold at intervals.

Next, in order to transfer the pattern onto the pattern forming layer, the mold is crimped onto the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred onto the pattern forming layer.

Further, when the mold is pressed against the surface of the pattern forming layer, helium gas may be introduced between the mold and the surface of the pattern forming layer. By using this method, gas can be promoted to pass through the mold, thereby promoting the disappearance of residual bubbles. Further, by reducing the dissolved oxygen in the pattern forming layer, it is possible to suppress the radical polymerization inhibition during exposure. Further, a condensable gas may be introduced between the mold and the pattern forming layer instead of the helium gas. By using such a method, the phenomenon in which the introduced condensable gas is condensed and the volume is reduced can further promote the elimination of residual bubbles. The term "condensed gas" means a gas which is condensed by temperature or pressure. For example, trichlorofluoromethane or 1,1,1,3,3-pentafluoropropane or the like can be used. For the condensable gas, for example, the description of paragraph 0023 of Japanese Patent Laid-Open Publication No. 2004-103817, and paragraph 0003 of Japanese Patent Laid-Open Publication No. 2013-254783, the contents of which are incorporated herein by reference.

Next, light irradiation is performed in a state where the mold is pressed, and the photocurable composition is cured. The irradiation amount of the light irradiation may be sufficiently larger than the irradiation amount required for the curing of the photocurable composition. The amount of irradiation required for hardening can be appropriately determined by investigating the consumption of the unsaturated bond of the photocurable composition or the viscosity of the cured film.

The substrate temperature at the time of light irradiation is usually performed at room temperature, and in order to improve the reactivity, light irradiation may be performed while heating. When it is set to a vacuum state in advance, it is effective in preventing the incorporation of air bubbles, suppressing the decrease in reactivity due to the incorporation of oxygen, and improving the adhesion between the mold and the photocurable composition. Light irradiation can be performed under vacuum. The preferred degree of vacuum at the time of light irradiation is preferably in the range of 10 ^-1 Pa to atmospheric pressure.

The light for hardening the photocurable composition is not particularly limited, and for example, Light or radiation of wavelengths in areas of high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, infrared, etc. are listed. High-energy ionizing radiation sources, such as electron beams accelerated by an accelerator such as a Cockcroft type accelerator, a van de graaff type accelerator, a linear accelerator, a beta accelerator, a cyclotron, etc. It is most convenient and economical to use, and radiation such as gamma rays, X rays, alpha rays, neutron rays, and neutron rays emitted from a radioactive isotope or a nuclear reactor may be used. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a sun lamp. The radiation includes, for example, microwaves and extreme ultraviolet rays (EUV). Further, a laser light used in microfabrication of a semiconductor such as a light emitting diode (LED), a semiconductor laser beam, or a 248 nm KrF excimer laser light or a 193 nm ArF excimer laser light can also be used. It is suitably used in the invention. The light can use monochromatic light, and a plurality of different wavelengths of light (mixed light) can also be used.

At the time of exposure, it is desirable to set the exposure illuminance to a range of 1 mW/cm ² to 50 mW/cm ² . When the exposure time is 1 mW/cm ² or more, the exposure time can be shortened, and the productivity is improved. When the thickness is 50 mW/cm ² or less, it is preferable to suppress deterioration of characteristics of the permanent film due to side reactions. . Over exposure amount is 5mJ / cm range of ² ~ ^1000mJ / cm ² in. When it is this range, the hardenability of the photocurable composition is favorable. Further, at the time of exposure, in order to prevent the inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be introduced to control the oxygen concentration to less than 100 mg/L.

Patterning layer (including photocurable composition) by light irradiation After the layer) is hardened, it may optionally include a step of heating the hardened pattern to further harden it. The heating temperature is, for example, preferably from 150 ° C to 280 ° C, more preferably from 200 ° C to 250 ° C. Further, the heating time is, for example, preferably from 5 minutes to 60 minutes, more preferably from 15 minutes to 45 minutes.

After the photocurable composition is cured as described above, the mold is peeled off from the substrate, whereby a pattern (concavo-convex pattern) along the shape of the mold can be formed on the substrate. The pattern size varies depending on the application. For example, it is preferably a pattern having a width of 300 nm or less, and more preferably a pattern having a width of 100 nm or less. Moreover, the aspect ratio of the pattern is preferably from 0.1 to 10, more preferably from 1 to 5.

For the details of the pattern forming method using the imprint method, the description of Paragraph No. 0103 to Paragraph No. 0115 of Japanese Patent Laid-Open No. 2010-109092 (corresponding US Application No. US 2011/199592) can be incorporated into the present disclosure. In the application note.

<Method of Manufacturing Pattern Forming Body>

Next, a method of producing the pattern forming body of the present invention will be described.

The method for producing a pattern forming body according to the present invention includes the step of applying a first composition containing a solvent and a film forming component to the surface of the uneven pattern (step 1); and before the surface of the concave-convex pattern is exposed from the applied first composition, The second composition having a lower surface tension than the first composition is applied to the region of the concave-convex pattern on the region where the first composition is applied (step 2); the first composition applied to the concave-convex pattern and the second composition The composition is dried to form a film on the surface of the concavo-convex pattern (step 3).

Hereinafter, each step will be described.

<<Step 1>>

In the step 1, a first composition containing a solvent and a film forming component is applied to the surface of the uneven pattern.

The film-forming component is a component remaining as a solid in the dried film, and varies depending on the use and purpose. For example, a hydrophilic coating agent, a hydrophobic coating agent, a hard coating agent, an antistatic agent, a metallic ink, an ultraviolet absorber, a heat ray-cutting agent, a fingerprint-resistant coating agent, a refractive index adjusting agent, etc. are mentioned.

Examples of the hydrophilic coating agent include the LABIC series manufactured by Osaka Organic Chemical Industry.

Examples of the hydrophobic coating agent include a decane compound, a fluororesin, and the like. Examples of the decane compound include a decane coupling agent, a decane, and the like. Commercial products of the decane coupling agent include the OPTOOL series manufactured by Daikin Industries Co., Ltd., the KBM series manufactured by Shin-Etsu Chemical Co., Ltd., and the KBE series. The oxime may be KPN-3504 (a hydroxyl group containing a hydrolyzable group) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Further, examples of the fluororesin include a CYTOP series manufactured by Asahi Glass Co., Ltd., and the like.

Examples of the hard coating agent include the LCH series manufactured by Toyo Ink Co., Ltd., and the like.

Examples of the antistatic agent include the LAS series, the YYS series, and the TYP series manufactured by Toyo Ink Co., Ltd.

Examples of the metal ink include gold ink, silver ink, and copper ink.

The content of the film-forming component of the first composition is preferably 0.001% by mass to 20%. The amount % is more preferably 0.01% by mass to 10% by mass.

The solvent is not particularly limited as long as it is a soluble film-forming component. For example, ethyl acetate, carbon tetrachloride, acetic acid, propylene glycol-1-monomethyl ether-2-acetate, benzene, cyclohexanone, etc. are mentioned. By using a solvent having a large surface tension, the solubility of the film-forming component is good, and the occurrence of coating unevenness can be suppressed. Moreover, the concentration of the film forming component can also be increased. Further, since the solubility of the film-forming component is good, the degree of freedom in the selection of the film-forming component is high. The surface tension at 25 ° C of the solvent used in the first composition is preferably 24 mN/m or more. Specific examples thereof include ethyl acetate (24 mN/m), carbon tetrachloride (27 mN/m), acetic acid (28 mN/m), propylene glycol-1-monomethyl ether-2-acetate (28 mN/m), and benzene. (29 mN/m), cyclohexanone (35 mN/m), and the like.

The surface tension at 25 ° C of the first composition varies depending on the combination of the film forming component and the solvent, and is preferably more than 23 mN/m. Thereby, the solubility of the film formation component is good, and the occurrence of coating unevenness can be suppressed.

Further, in the conventional method, as the surface tension of the composition applied to the uneven pattern becomes large, there is a tendency that the pattern collapses during drying of the composition, and the surface of the pattern tends to be rough. According to the method of the present invention, Even if a composition having a large surface tension is applied to the uneven pattern, the occurrence of the problem can be suppressed.

The viscosity of the first composition at 25 ° C is preferably 0.1 mPa. s~2000mPa. s, more preferably 1mPa. s~1000mPa. s. When the viscosity is in the above range, the coatability is good.

The application method of the first composition is not particularly limited, and a coating method is preferred. Examples of the coating method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and ink jet. .

In the present invention, the first composition is applied to the surface of the concavo-convex pattern, and the first composition covers a desired region (region where the film is formed) of the surface of the concavo-convex pattern. Preferably, the pattern concave portion is buried by the first composition, and the surface of the concave-convex pattern is covered by the first composition.

In the present invention, after the application of the first composition, drying may be performed before the second step described later. Productivity can also be improved by drying. Examples of the drying method include heat drying, warm air drying, and the like.

<Step 2>

Next, before the surface of the concavo-convex pattern is exposed from the applied first composition, the second composition having a lower surface tension than the first composition is applied to the region of the concavo-convex pattern to which the first composition is applied.

The application of the second composition is performed before the surface of the concavo-convex pattern is exposed from the first composition applied to the surface of the concavo-convex pattern. In other words, the region to which the first composition is applied is applied to the uneven pattern while the surface of the concave-convex pattern is covered with the first composition. By applying the second composition as described above, when the composition applied to the surface of the uneven pattern is dried, it is possible to suppress the capillary force of the pattern convex portion from being subjected to the first composition during drying, and as a result, the pattern convex portion can be made. The applied capillary force becomes small. In the present invention, the surface of the concave-convex pattern is exposed from the first composition to be applied, and the surface of the concave-convex pattern as the region to which the first composition is applied as the concave-convex pattern is not present in the first composition. The state of the part covered by the object.

The timing of application of the second composition can be performed while observing the liquid surface of the first composition applied to the surface of the concave-convex pattern by a sensor or the like. In addition, the first composition is applied to the surface of the uneven pattern in accordance with the type, the coating amount, and the drying conditions (temperature, humidity, and air volume) of the first composition, and then the surface of the uneven pattern is exposed from the first composition. At the time T ⁰ , when the application of the first composition and drying are carried out under the same conditions, the second composition can be applied within T ⁰ . For example, after the first composition is applied to the uneven pattern, the second composition is applied to the region of the concave-convex pattern in which the first composition is applied within 10 seconds.

The application method of the second composition is not particularly limited, and the same method as the application method of the first composition can be used.

In the present invention, the second composition is a composition having a lower surface tension than the first composition.

The difference between the surface tension at 25 ° C of the first composition and the surface tension at 25 ° C of the second composition is preferably 2 mN/m or more, and more preferably 4 mN/m or more. Thereby, the generation of pattern defects can be more effectively suppressed.

The surface tension at 25 ° C of the second composition is preferably 23 mN/m or less. Thereby, the generation of pattern defects can be more effectively suppressed. In addition, the roughness of the surface of the pattern after coating can be more effectively suppressed.

As the second composition, a composition containing a solvent is used.

The solvent can be mentioned as described in the first composition. It is preferred to use a solvent having a surface tension smaller than that used in the first composition. Particularly preferred is a solvent having a surface tension of less than 24 mN/m at 25 °C. Specific examples thereof include decafluoropentane (14 mN/m), hexane (18 mN/m), ethanol (23 mN/m), methanol (23 mN/m), and acetone (23 mN/m).

The second composition may further include a film forming component. The film formation component can be mentioned as described in the first composition.

When the second composition contains a film-forming component, the content of the film-forming component is preferably 0.001% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass.

The viscosity of the second composition at 25 ° C is preferably 0.1 mPa. s~2000mPa. s, more preferably 1mPa. s~1000mPa. s. When the viscosity is in the above range, the coatability is good.

<Step 3>

Next, the first composition and the second composition applied to the uneven pattern are dried. As described above, by drying the solvent, a pattern forming body of the film 12 derived from the film forming component is formed on the surface of the uneven pattern 11 as shown in FIG. 1 .

Examples of the drying method include heat drying, warm air drying, and the like. The drying conditions can be appropriately selected depending on the boiling point, the coating amount, and the like of the first composition and the second composition. For example, in the case of heat drying, it is preferably carried out at 80 ° C to 300 ° C for 3 seconds to 30,000 seconds.

The method for producing a pattern forming body of the present invention can also be applied to a roll type process.

The "roll-type process" is a production system in which a flexible substrate wound in a roll shape is wound up and processed, and the processed flexible substrate is wound again into a roll shape.

For example, a pattern forming layer is formed by applying a photocurable composition to a flexible substrate, and a finely patterned roll mold is pressed onto a pattern forming layer on a substrate, and the pattern is irradiated by energy irradiation. Forming layer hardening, thereby forming a seamless Concave and concave pattern. The flexible substrate on which the uneven pattern is formed may also be wound into a roll shape. Further, the processing described later may be continued without winding.

Next, the flexible substrate on which the uneven pattern is formed is sequentially applied to the treatment region 1 to which the first composition is applied, the treatment region 2 to which the second composition is treated, and the first composition and the second composition to be applied. After drying the dried processing zone 3, the film is wound into a roll shape, whereby the pattern forming body can be produced by a roll-to-roll process.

In the application of the respective compositions of the treatment region 1 and the treatment region 2, for example, a flexible substrate can be immersed in a chemical solution layer filled with each composition, and each composition can be applied to the surface of the concave-convex pattern by dip coating. Further, various coating devices (inkjet nozzles, etc.) may be provided to apply the respective compositions to the surface of the concave-convex pattern.

In the case where the pattern forming body is continuously produced by a method such as a roll-to-roll process, the second composition is applied after a part of the uneven pattern is exposed from the first composition even in the continuous processing. The application of the second composition before the remaining uneven pattern is exposed from the first composition is also included in the method for producing the pattern formed body of the present invention.

<Photocurable composition>

Next, the photocurable composition used for forming the uneven pattern of the pattern forming body of the present invention will be described.

In the present invention, as the photocurable composition, a photocurable composition used in the imprint method can be used. That is, the photocurable composition is preferably a photocurable composition for imprinting.

The photocurable composition preferably contains a polymerizable compound and a photopolymerization initiator. As an example of the photocurable composition, for example, a content of the polymerizable compound is 70% by mass or more, and a content of a component having a weight average molecular weight of more than 2,000 is preferably 3% by mass or less, and more preferably an ethylenic unsaturated layer. The content of the polymerizable compound of the double bond is 70% by mass or more, and the content of the polymerizable compound having a weight molecular weight of more than 2,000 is 3% by mass or less. Hereinafter, each component will be described.

<<Polymerized compound>>

The polymerizable compound is not particularly limited as long as it does not deviate from the gist of the present invention. The polymerizable group which the polymerizable compound has may be a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group or the like. Examples of the group containing an ethylenically unsaturated bond include a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an allyl group, and a vinyl ether group. Preferred is a (meth) acrylate group.

The polymerizable group number is preferably from 1 to 6, more preferably from 1 to 3, still more preferably from 1 or 2.

Examples of the polymerizable compound include a compound having one to six groups containing an ethylenically unsaturated bond; an epoxy compound, an oxetane compound, a vinyl ether compound, a styrene derivative, a propenyl ether, and a butenyl group. Ether, etc. Specific examples of the polymerizable compound are as described in Paragraph No. 0020 to Paragraph No. 0098 of JP-A-2011-231308, the contents of which are incorporated herein by reference. The polymerizable compound is preferably a (meth) acrylate compound.

The content of the polymerizable compound is preferably 70% by mass to 99.9% by mass, more preferably 80% by mass to 99.9% by mass, still more preferably 85% by mass to 99.9% by mass, based on all the components other than the solvent. When two or more types of polymerizable compounds are used, it is preferred that the total amount thereof is in the above range.

A compound (1-functional to 6-functional polymerizable compound) having one to six groups containing an ethylenically unsaturated bond will be described.

As the compound having one group containing an ethylenically unsaturated bond, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and N-vinylpyrrolidone can be exemplified. (N-vinyl pyrrolidinone), 2-propenyloxyethyl phthalate, 2-propenyloxy-2-hydroxyethyl phthalate, 2-propenyloxyethyl hexa Hydrogen phthalate, 2-propenyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth)acrylate, 2 -ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, dimer of acrylic acid, benzyl (meth)acrylate, 1-naphthyl (meth)acrylate or 2-naphthyl (meth)acrylate, (methyl) ) Butoxyethyl acrylate, cetyl (meth) acrylate, ethylene oxide (hereinafter referred to as "EO") modified cresol (meth) acrylate, dipropylene glycol (meth) acrylate, B Oxylated phenyl (meth) acrylate, (meth) acrylate Ester, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid Myristyl ester, lauryl (meth)acrylate, methoxydipropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, Methoxy triethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy Polypropylene glycol (meth) acrylate, octyl (meth) acrylate, p-cumyl phenoxy ethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy propylene Acid ester, phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol ( Methyl) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO Modified succinic acid (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, tris (dodecyl) (meth) acrylate, dimorphism Propylene phenol, N-vinyl pyrrolidone, N-vinyl caprolactam.

From the viewpoint of photocurability, a compound having a group containing an ethylenically unsaturated bond is preferably a monofunctional (meth) acrylate compound. Among the monofunctional (meth) acrylate compounds, a monofunctional (meth) acrylate having an aromatic structure and/or an alicyclic hydrocarbon structure is preferred in order to improve dry etching resistance, and more preferably A monofunctional (meth) acrylate having an aromatic structure.

The monofunctional (meth) acrylate having an aromatic structure and/or an alicyclic hydrocarbon structure is preferably benzyl (meth) acrylate, 2-phenoxyethyl acrylate, and has a substituent on the aromatic ring. Benzyl (meth)acrylate (preferably the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group), 1-naphthyl (meth)acrylate or 2-naphthyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate or 2-naphthylmethyl (meth)acrylate, 1-naphthylethyl (meth)acrylate or 2-naphthylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (methyl) Adamantyl acrylate, more preferably 2-phenoxyethyl acrylate, benzyl (meth) acrylate, benzyl (meth) acrylate having a substituent on the aromatic ring, a monofunctional group having a naphthalene structure (A) Base) acrylate compound.

In the present invention, the polymerizable compound is also preferably a compound having two or more groups containing an ethylenically unsaturated bond.

Examples of the compound having two or more groups containing an ethylenically unsaturated bond include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di(meth) acrylate, and (Meth)acrylated isocyanurate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO modified 1,6- Hexanediol di(meth)acrylate, ECH modified 1,6-hexanediol di(meth)acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di(a) Acrylate, EO modified bisphenol A di(meth) acrylate, PO modified bisphenol A di(meth) acrylate, modified bisphenol A di(meth) acrylate, EO modified double Phenol F di(meth)acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate neopentyl glycol, stearic acid Acid-modified pentaerythritol di(meth)acrylate, ECH modification Di(meth)acrylate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(meth)acrylate, polyester (b) Acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ECH modified propylene glycol di(meth)acrylate, anthrone di(meth)acrylate, triethylene glycol Alcohol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, neopentyl glycol modified trimethylolpropane di Methyl) acrylate, tripropylene glycol di(meth) acrylate, EO modified tripropylene glycol di(meth) acrylate, triglycerin di(meth) acrylate, dipropylene glycol Di(meth)acrylate, divinylexylethylurea,divinylpropylpropylurea, ortho-xylene di(meth)acrylate, m-xylene di(meth)acrylate, p-xylene di(a) Acrylate, 1,3-adamantane diacrylate, norbornane dimethanol diacrylate.

Among these, especially neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(a) Acrylate, hydroxypivalic acid neopentyl glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, phthalic acid (meth) acrylate, isophthalic (meth) 2-functional (such as acrylate, p-phenylene (meth) acrylate, o-xylene di(meth) acrylate, m-xylene di(meth) acrylate, p-xylene di(meth) acrylate (A) The acrylate) can be suitably used in the present invention.

Further, a bifunctional-6 functional (meth) acrylate compound having an aromatic structure and/or an alicyclic hydrocarbon structure can also be used. For example, a polyfunctional (meth) acrylate compound having an aromatic group (preferably a phenyl group or a naphthyl group) and having two to four (meth) acrylate groups may be mentioned. Specific examples thereof include the compounds shown below.

Moreover, the photocurable composition may also contain a ruthenium atom and/or a fluorine atom. Polymeric compound. The polymerizable compound having a halogen atom and/or a fluorine atom preferably contains a fluorine atom, and more preferably has a fluorine-containing alkyl group having 1 to 9 carbon atoms.

The substitution ratio of the fluorine atom of the fluorine-containing alkyl group having 1 to 9 carbon atoms is preferably from 40% to 100%, more preferably from 50% to 90%, still more preferably from 65% to 85%. The "replacement ratio of a fluorine atom" means, for example, a ratio (%) in which a hydrogen atom is substituted with a fluorine atom in an alkyl group having 1 to 9 carbon atoms. The fluorine-containing alkyl group having 1 to 9 carbon atoms preferably contains -C _n F _2n+1 or -C _n F _2n H , more preferably contains -C _n F _2n+1 . Here, n represents an integer of 1 to 9, and more preferably represents an integer of 4 to 8.

The polymerizable group of the polymerizable compound having a ruthenium atom and/or a fluorine atom is preferably a (meth) acrylate group. The polymerizable group number is preferably 1 or 2, more preferably 1.

The molecular weight of the polymerizable compound having a halogen atom and/or a fluorine atom is preferably from 100 to 600, more preferably from 300 to 500. The polymerizable compound having a fluorine atom can be referred to, for example, the description of paragraphs 0022 to 0023 of the International Patent Publication No. 2010/137724, the contents of which are incorporated herein by reference. Examples of the polymerizable compound having a fluorine atom include, for example, 2-(perfluorohexyl)ethyl acrylate.

Further, in the present invention, an embodiment in which a polymerizable compound having a ruthenium atom and/or a fluorine atom is substantially not contained may be used.

Among the polymerizable compounds contained in the photocurable composition, a total of a polymerizable compound having one polymerizable group (preferably a polymerizable compound having one (meth) acrylate group) is preferred to the polymerizable property. The total amount of the compound is from 0% by mass to 60% by mass. The upper limit is more preferably 50% by mass or less. The lower limit can be 5% by mass or more, and may be 10% by mass or more. With light curable composition The content of the polymerizable compound of one polymerizable group increases, and the elastic modulus of the obtained uneven pattern tends to increase, and the strength tends to decrease. According to the method of the present invention, even for a pattern having low strength, generation of pattern defects can be suppressed, and a film is formed on the surface.

Further, it may be a composition which does not substantially contain a polymerizable compound having one polymerizable group. The "polymerizable compound having one polymerizable group is not substantially contained in the total amount of the polymerizable compound, for example, is preferably 1% by mass or less, more preferably 0.5% by mass or less, and may not be contained.

Further, the total of the polymerizable compound having two polymerizable groups (preferably a polymerizable compound having two (meth) acrylate groups) is preferably 40% by mass based on the total amount of the polymerizable compound. ~100% by mass. The upper limit is more preferably 95% by mass or less, still more preferably 90% by mass or less. The lower limit is more preferably 50% by mass or more, and still more preferably 55% by mass or more.

In the polymerizable compound component contained in the photocurable composition, the total of the polymerizable compound having an alicyclic hydrocarbon group and/or an aromatic group is preferably 30% by mass to 100% by mass based on the total amount of the polymerizable compound. More preferably, it is 50 mass% - 100 mass%, and further more preferably 70 mass% - 100 mass%.

<<Photopolymerization initiator>>

Any photopolymerization initiator may be any compound which generates an active species which polymerizes the polymerizable compound by light irradiation. The photopolymerization initiator is preferably a radical polymerization initiator and a cationic polymerization initiator, more preferably a radical polymerization initiator. Further, in the present invention, a plurality of photopolymerization initiators may be used in combination.

As the radical photopolymerization initiator, for example, a commercially available initiator can be used. As such an example, those described in Paragraph No. 0091 of JP-A-2008-105414 can be preferably used. Among them, an acetophenone-based compound, a fluorenylphosphine oxide-based compound, and an oxime ester-based compound are preferred from the viewpoint of self-hardening sensitivity and absorption characteristics. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure 127, Irgacure 819, Irgacure 379, Irgacure 369, Irgacure 754, Irgacure 1800, Irgacure 651, Irgacure 907, Lucirin TPO. , Darocur 1173, etc. (above by BASF).

The content of the photopolymerization initiator is preferably from 0.01% by mass to 15% by mass, more preferably from 0.1% by mass to 12% by mass, even more preferably from 0.2% by mass to 7% by mass, based on all the components except the solvent. . The photocurable composition may contain only one photopolymerization initiator, and may contain two or more kinds. When two or more types are contained, it is preferable that the total amount is the said range.

<<Interfacial active agent>>

The photocurable composition may contain a surfactant. The surfactant is preferably a nonionic surfactant.

The "nonionic surfactant" is a compound having at least one hydrophobic portion and at least one nonionic hydrophilic portion. The hydrophobic portion and the hydrophilic portion may be located at the ends of the molecules, respectively, or may be located inside. The hydrophobic portion comprises a hydrophobic group selected from a hydrocarbon group, a fluorine-containing group and a Si-containing group, and the carbon number of the hydrophobic portion is preferably from 1 to 25, more preferably from 2 to 15, further preferably from 4 to 10, most preferably from 5 to 5. 8. The nonionic hydrophilic portion preferably has an alcohol selected from the group consisting of Hydroxyl group, phenolic hydroxyl group, ether group (preferably polyalkylene oxide group, cyclic ether group), decylamino group, quinone imido group, ureido group, urethane group, cyano group, sulfonamide At least one group of the group consisting of a base, a lactone group, an indolyl group, and a cyclic carbonate group. The nonionic surfactant can be hydrocarbon, fluorine, Si, or fluorine. Any of the Si-based nonionic surfactants is more preferably fluorine-based or Si-based, and more preferably fluorine-based. Here, the "fluorine-Si-based surfactant" means a requirement of both a fluorine-based surfactant and a Si-based surfactant.

Commercial products of the fluorine-based nonionic surfactant include, for example, Fluorad FC-4430 manufactured by Sumitomo 3M Co., Ltd., Fluorad FC-4431, and Surflon S- manufactured by Asahi Glass Co., Ltd. 241, Surflon S-242, Surflon S-243, Eftop EF-PN31M-03, Eftop EF-PN31M-04, Eftop EF-PN31M-05, Eftop EF manufactured by Mitsubishi Materials Corporation -PN31M-06, Eftop MF-100, Polyfox PF-636, Polyfox PF-6320, Polyfox PF-656, Polyfox PF-6520, Neos by OMNOVA ) Ftergent 250, Ftergent 251, Ftergent 222F, Ftergent 212M DFX-18, UNIDYNE DS-401, UNIDYNE DS-403 manufactured by Daikin Industries, Ltd. UNIDYNE DS-406, UNIDYNE DS-451, UNIDYNE DSN-403N, Megafac F-430, Megafac F-444, Megafac F-477, Megafac F-553, Megafac F-556, Megafac F-557, Megafac F-559, Megafac F-562, Megafac F-565, Megafac F-567, Megafac F-569, Megafac R-40, Capstone FS-3100, Zonyl FSO-100 manufactured by DuPont.

When the photocurable composition of the present invention contains a surfactant, the content of the surfactant is preferably from 0.1% by mass to 10% by mass, more preferably 0.2% by mass, based on all the components other than the solvent. 5质量%, further more preferably 0.5% by mass to 5% by mass. The photocurable composition may contain only one type of surfactant, and may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range.

Further, in the present invention, an embodiment in which the surfactant is not substantially contained may be used. The content of the surfactant is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and even more preferably not contained.

<<Non-polymeric compound>>

The photocurable composition may also contain a non-polymerizable compound having a polyalkylene glycol structure having at least one hydroxyl group at the terminal or a hydroxyl group etherified, and substantially free of a fluorine atom and a halogen atom. Here, the "non-polymerizable compound" means a compound which does not have a polymerizable group. In addition, the term "substantially free of fluorine atoms and germanium atoms" means that the total content of fluorine atoms and germanium atoms is 1% or less, and it is preferable that fluorine atoms and germanium atoms are not present at all. By containing no fluorine atom or ruthenium atom, compatibility with a polymerizable compound can be improved, and in particular, coating uniformity, pattern formation property at the time of imprinting, and line after dry etching can be applied to a composition containing no solvent. The edge roughness becomes good.

As the polyalkylene structure of the non-polymerizable compound, it is preferably a package The polyalkylene glycol structure having an alkyl group having 1 to 6 carbon atoms, more preferably a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or a mixed structure of the above, further preferably a polyethylene The diol structure, the polypropylene glycol structure, or a mixed structure of these is particularly preferably a polypropylene glycol structure.

Further, it may contain substantially only a polyalkylene glycol structure in addition to the terminal substituent. The term "substantially" as used herein means that the constituent elements other than the polyalkylene glycol structure are 5% by mass or less, and preferably 1% by mass or less. In particular, as the non-polymerizable compound, it is particularly preferred to contain a compound having substantially only a polypropylene glycol structure.

The polyalkylene glycol structure preferably has 3 to 100 alkanediol structural units, more preferably 4 to 50, still more preferably 5 to 30, and particularly preferably 6 to 20.

The non-polymerizable compound preferably has at least one hydroxyl group at the terminal or a hydroxyl group is etherified. It is also possible to use a compound having at least one hydroxyl group at the terminal or, if the hydroxyl group is etherified, the hydrogen atom of the terminal hydroxyl group may be substituted even if the remaining terminal is a hydroxyl group. The group which may also substitute the hydrogen atom of the terminal hydroxyl group is preferably an alkyl group (i.e., a polyalkylene glycol alkyl ether) or a mercapto group (i.e., a polyalkylene glycol ester). More preferably, all of the polyalkylene glycols having a hydroxyl group at the end are used. It is also preferred to use a compound having a plurality of (preferably 2 or 3) polyalkylene glycol chains via a linking group, and preferably a linear structure in which the polyalkylene glycol chain is not branched. Particularly preferred is a glycol type polyalkylene glycol.

Preferred specific examples of the non-polymerizable compound are polyethylene glycol, polypropylene glycol, monomethyl ether or dimethyl ether, monobutyl ether or dibutyl ether, monooctyl ether or dioctyl ether, and monocetyl ether. Or cetyl ether, monostearate, monooleate, polyoxyethylene glyceryl ether, poly Oxypropylene glyceryl ether, these trimethyl ethers.

The weight average molecular weight of the non-polymerizable compound is preferably from 150 to 6,000, more preferably from 200 to 3,000, still more preferably from 250 to 2,000, and particularly preferably from 300 to 1200.

In the present invention, when the photocurable composition contains a non-polymerizable compound, the content of the non-polymerizable compound is preferably from 0.1% by mass to 20% by mass based on all the components excluding the solvent, and more preferably 0.2% by mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass. Further, in the present invention, an embodiment in which substantially no non-polymerizable compound is contained may be used. The content of the non-polymerizable compound is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and even more preferably no content.

<<Solvent>>

The photocurable composition may contain a solvent as needed. A preferred solvent is a solvent having a boiling point of from 80 ° C to 200 ° C under normal pressure. When the type of the solvent is such that the respective components can be dissolved, any solvent can be used, and the same solvent as the solvent described in the resin composition for forming the underlayer film can be used. Among them, from the viewpoint of coating uniformity, a solvent containing propylene glycol monomethyl ether acetate is preferred.

The content of the solvent in the photocurable composition can be adjusted to be optimal depending on the viscosity, coating property, and target film thickness of the photocurable composition, and can be used in the photocurable composition from the viewpoint of improving the coating property. It is contained in the range of 99 mass% or less. When the photocurable composition is applied onto a substrate by an inkjet method, it is preferred that the solvent is substantially not contained (for example, 3% by mass or less). On the other hand, when a pattern having a film thickness of 500 nm or less is formed by a method such as spin coating, it may be 20% by mass to 99% by mass. It is contained in the range of %, preferably 40% by mass to 99% by mass, particularly preferably 70% by mass to 98% by mass.

<<Other ingredients>>

The photocurable composition may contain, in addition to the components, a polymerization inhibitor, a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, a adhesion promoter, and a thermal polymerization initiation. Agent, photobase generator, colorant, inorganic particles, elastomer particles, basic compound, photoacid generator, photoacid proliferator, chain transfer agent, antistatic agent, flow regulator, defoamer, dispersant, Release agent, etc. Specific examples of such a component include those described in paragraph number 0092 to paragraph 0093 of the Japanese Patent Laid-Open Publication No. 2008-105414, and paragraph number 0099 to paragraph number 0137, which can be incorporated into the specification of the present application. in. Further, reference may be made to the corresponding descriptions of the specification of WO2011/126101, the specification of WO2013/051735, the specification of Japanese Patent Laid-Open No. 2012-041521, and the Japanese Patent Laid-Open No. 2013-093552, the contents of which are hereby incorporated herein by reference. in.

The photocurable composition can be prepared by mixing the above components. The mixing of the components is usually carried out in the range of 0 °C to 100 °C. Further, after mixing the components, it is preferably filtered by a filter, for example. Filtration can be carried out in multiple stages or several times. Moreover, the filtered liquid can be refiltered.

The filter is not particularly limited as long as it is used by a user for filtration or the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (PP) may be used (including high density and high density). A filter such as a molecular weight resin). The original Preferred among the materials are polypropylene (including high density polypropylene) and nylon.

The pore diameter of the filter is, for example, suitably from about 0.003 μm to about 5.0 μm. By setting it as this range, it is possible to suppress clogging of the filter, and it is possible to surely remove fine foreign matter such as impurities or aggregates contained in the composition.

When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. In the case where two or more filtrations are performed by combining different filters, it is preferred that the pore diameter after the second time is the same as the pore diameter of the first filtration or smaller than the pore diameter of the first filtration. Further, the first filter having a different pore diameter within the range may be combined. The aperture here can be referred to the nominal value of the filter manufacturer. Commercially available filters are available, for example, from Pall Corporation of Japan, Iddobond Co., Ltd., Japan Inteco Co., Ltd. (formerly Japan Mykrolis Co., Ltd.) or Kitazawa Microfilter Co., Ltd. Among the various filters offered by Ltd., etc.

The photocurable composition preferably has a viscosity of 100 mPa at 23 ° C. Below s, more preferably 70mPa. s below, further preferably 50mPa. Below s, especially good for 30mPa. s below. The lower limit is, for example, preferably 1 mPa. Above s, more preferably 2mPa. Above s, especially good for 3mPa. s above.

Further, in the case where a photocurable composition is applied by an inkjet method, the viscosity of the photocurable composition is preferably 15 mPa at 23 °C. Below s, more preferably 12mPa. s below, further preferably 11mPa. Below s, especially good for 10mPa. s below. By setting it as such a range, the inkjet discharge precision or pattern formation property can be improved.

Moreover, a permanent film (structure) used in a liquid crystal display (LCD) or the like In the resist used for the substrate processing of the resist or the electronic material, it is preferable to avoid the incorporation of the ionic impurities of the metal or the organic substance in the resist in order not to hinder the operation of the product. Therefore, when the pattern forming body is used for the above-mentioned use, the concentration of the ionic impurity of the metal or organic substance in the photocurable composition is preferably 1 ppm or less, preferably 100 ppb or less, and further preferably. It is set to 10 ppb or less.

The pattern forming body obtained by the method for producing a pattern forming body of the present invention can be used, for example, as a permanent film such as a protective layer or an insulating film used in a liquid crystal display (LCD) or the like, or a semiconductor integrated circuit, a recording material, or a flat display. It is applied by etching the resist. Further, it can also be used in a resin mold, a water-repellent film, a hydrophilic film or the like.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures, and the like used in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

<Preparation of the first composition, the second composition, and the photocurable composition>

The materials shown in the following tables were mixed, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) filter to prepare each composition.

Further, the surface tension of the first composition and the second composition was SURFACE TENS-IOMETER manufactured by Kyowa Interface Science Co., Ltd. CBVP-A3 was measured at 25 ± 0.2 ° C using a platinum plate. The unit is expressed in mN/m.

The symbols in Table 3 are as follows.

(polymerizable compound)

C-1: Neopentyl glycol diacrylate (Light acrylate NP-A Kyoritsu Chemical Co., Ltd.)

C-2: Dimethylol-tricyclodecane diacrylate (Light acrylate DCP-A Kyoritsu Chemical Co., Ltd.)

C-3: isobornyl acrylate (Light acrylate IB-XA Kyoritsu Chemical Co., Ltd.)

C-4: benzyl acrylate (Viscoat #160 Osaka Organic Chemical Co., Ltd.)

(photopolymerization initiator)

D-1: Irgacure 819 (manufactured by BASF Corporation)

D-2: Irgacure 127 (manufactured by BASF Corporation)

(other ingredients)

E-1: Capstone FS-3100 (manufactured by DuPont)

E-2: polypropylene glycol (Mw=400, manufactured by Wako Pure Chemical Industries, Ltd.)

<Production of concave and convex pattern>

The mold used a quartz mold of a line/space pattern having a line width of 30 nm and a depth of 60 nm.

The photocurable composition (composition 1 to composition 4) was applied onto a tantalum wafer using an inkjet apparatus (DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd.). The droplet size was a square lattice shape with a spacing of 280 μm coated at 6 pL.

In the coating region, the quartz mold was crimped under a helium atmosphere, and after being placed under atmospheric pressure for 30 seconds, the glass mold was subjected to photohardening by a high pressure mercury lamp. The irradiation amount was set to 100 mJ/cm ² . After the exposure, the quartz mold was loosened to obtain a concave-convex pattern. The residual film of the pattern (the film derived from the photocurable composition in the pattern concave portion) was 30 nm.

<Manufacture of Pattern Forming Body>

The first composition was spin-coated on the surface of the concavo-convex pattern obtained by the above method. The rotation speed was 1000 rpm and the rotation time was set to 30 s.

Next, after applying the first composition, the second composition was spin-coated on the region to which the first composition was applied after 5 seconds. The rotation speed was 1000 rpm and the rotation time was set to 30 s. The application of the second composition is performed while the concavo-convex pattern is covered by the first composition.

Further, in Comparative Example 1-2, after the application of the first composition, the second composition was spin-coated on the region to which the first composition was applied after 5 minutes. In Comparative Example 1-2, when the second composition was applied, the uneven pattern was exposed from the first composition.

Next, after coating, it was naturally dried at room temperature (25 ° C) for 30 minutes to obtain a pattern formed body.

<Evaluation of uneven coating>

Coating unevenness of the pattern formation body obtained by the above method was evaluated by an optical microscope (×10×).

A: no shrinkage or agglomeration on the coated surface, no uneven coating was observed

B: shrinkage or agglomeration on the coated surface, uneven coating was observed

<Evaluation of pattern collapse>

The range of 5 μm × 5 μm of the pattern formed body obtained by the above method was observed by an atomic force microscope (AFM, Dimension Icon manufactured by Bruker AXS), and evaluated by the following criteria.

A: Confirm the good pattern transfer throughout the entire surface of the inspection range

B: Pattern collapse is confirmed in an area of less than 10% of the inspection area

C: Pattern collapse occurred in the area of 10% to 70% of the inspection range

D: Pattern collapse occurs throughout the entire surface of the observation range

<Evaluation of pattern roughness>

The surface roughness (Ra, unit of nm) was measured by observing the range of 5 μm × 5 μm of the flat portion of the pattern formed body obtained by the above method using an atomic force microscope (AFM, Dimension Icon manufactured by Bruker AXS). ), evaluated by the following criteria.

A:Ra≦1

B: 1≦Ra≦2

C: 2≦Ra

As shown in the above table, the pattern forming body of the example obtained by the method of the present invention has no pattern defects. In addition, there is no pattern roughness and uneven coating.

On the other hand, the pattern formed body obtained by the method of the comparative example had a pattern defect.

Claims (9)

A method for producing a pattern forming body, comprising: applying a first composition including a solvent and a film forming component to a surface of the concave-convex pattern; and exposing the surface of the concave-convex pattern from the first composition of the application Previously, a second composition having a lower surface tension than the first composition is applied to a region of the concave-convex pattern to which the first composition is applied; and a portion to be applied to the concave-convex pattern The first composition and the second composition are dried to form a film on the surface of the uneven pattern, and the uneven pattern is a pattern obtained by curing the photocurable composition. The method for producing a pattern forming body according to claim 1, wherein a difference between a surface tension of 25 ° C of the first composition and a surface tension of 25 ° C of the second composition is 2 mN/m. the above. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the surface tension of the first composition at 25 ° C exceeds 23 mN/m. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the second composition has a surface tension of 25 m/m or less of 23 mN/m or less. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the second composition is applied to the concave-convex pattern after the first composition is applied to the concave-convex pattern A region to which the first composition is applied, applied to the uneven pattern. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the photocurable composition is a polymerizable compound having one polymerizable group. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the photocurable composition is based on the total amount of the polymerizable compound contained in the photocurable composition. The ratio of 0% by mass to 60% by mass of the polymerizable compound having one polymerizable group is contained. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the uneven pattern is a concave-convex pattern formed by an imprint method. The method for producing a pattern forming body according to the first or second aspect of the invention, wherein the uneven pattern includes a pattern having a width of 300 nm or less.