Curable composition, film formation method and manufacturing method

Abstract

To provide a novel technique relating to a curable composition.SOLUTION: A curable composition contains a polymerizable compound (a), a photoinitiator (b), and a solvent (c). In the curable composition, the curable composition has viscosity of 1.3 mPa s or more to 60 mPa s or less at 23°C and under 1 atmospheric pressure. A content of the solvent (c) with respect to the whole curable composition is 5 vol% or more to 95 vol% or less and a boiling point of the solvent (c) is 135°C or higher under 1 atmospheric pressure. When surface tension of a nonvolatile component consisting of the polymerizable compound (a) and the photoinitiator (b) under 1 atmospheric pressure is defined as γ1 [mN / m] and surface tension of the solvent (c) at 23°C and under 1 atmospheric pressure is defined as γ2 [mN / m], γ1 is equal to or less than 30, γ2 is equal to or less than 24 and γ1 is larger than γ2.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a curable composition, a film-forming method, and a production method. [Background technology]

[0002] In semiconductor devices, MEMS, and the like, the demand for miniaturization is increasing, and imprinting technology (photoimprinting technology) has attracted attention as a microfabrication technology. In imprinting technology, a mold (type) having a fine concave-convex pattern formed on its surface is brought into contact with a curable composition supplied (applied) onto a substrate, and the curable composition is cured in that state. In this way, the pattern of the mold is transferred to a cured film of the curable composition, and a pattern is formed on the substrate. With imprinting technology, a fine pattern (structure) on the order of several nanometers can be formed on the substrate.

[0003] The master mold used in the imprinting technique is very expensive because a fine pattern is formed on the surface of silicon, quartz glass, metal, etc. by precision machining. Therefore, a replica mold is produced on the surface of a mold base material (e.g., quartz glass) by the imprinting technique, where a cured layer to which the fine pattern of the master mold is transferred is formed. As a curable composition for forming the cured layer of the replica mold, a composition containing fluorine atoms has been proposed (see Patent Document 1).

[0004] A method for manufacturing a replica mold using the imprint technique will be described. First, a liquid curable composition (replica curable composition) is dropped (placed) discretely in a pattern formation region on a mold base material (substrate). The droplets of the curable composition placed in the pattern formation region spread on the mold base material. This phenomenon is called press spreading. Next, a master mold (mold) is brought into contact (pressed) with the curable composition on the mold base material. As a result, the droplets of the curable composition spread over the entire gap between the mold base material and the master mold by capillary action. This phenomenon is called spreading. The curable composition is also filled into the recesses constituting the pattern of the master mold by capillary action. This phenomenon is called filling. The time until spreading and filling are completed is called filling time. When filling of the curable composition is completed, the curable composition is irradiated with light to cure the curable composition. Then, the master mold is separated from the cured curable composition on the mold base material. By carrying out these steps, the pattern of the master mold is transferred to the curable composition on the mold substrate, and a pattern of the curable composition (cured layer) is formed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5794387 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the conventional technology, when the droplets of the curable composition arranged on the substrate are not in contact with each other and the substrate is brought into contact with the mold, air bubbles entrapped between the droplets of the curable composition in the space between the mold and the substrate become large. Therefore, it takes a long time for such air bubbles to diffuse into the mold or substrate and disappear, which is one of the factors that reduces productivity (throughput).

[0007] The present invention has been made in consideration of such problems in the conventional technology, and an exemplary object of the present invention is to provide a new technology relating to a curable composition. [Means for solving the problem]

[0008] In order to achieve the above object, one aspect of the present invention provides a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), wherein the curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atmospheric pressure, the content of the solvent (c) relative to the entire curable composition is 5 vol% to 95 vol%, and the boiling point of the solvent (c) is 135°C or higher at 1 atmospheric pressure, and wherein, when the surface tension of the composition excluding the solvent (c) at 1 atmospheric pressure is γ1 [mN / m], and the surface tension of the solvent (c) at 23°C and 1 atmospheric pressure is γ2 [mN / m], γ1 is 30 or lower, γ2 is 24 or lower, and γ1 is greater than γ2.

[0009] Further objects or other aspects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. Effect of the Invention

[0010] According to the present invention, for example, a new technique relating to a curable composition can be provided. [Brief description of the drawings]

[0011] [Figure 1] 1A to 1C are diagrams illustrating a film forming method according to one aspect of the present invention. [Diagram 2] FIG. 13 is a diagram for explaining the flow behavior of droplets of a curable composition during a waiting step. [Diagram 3] 1A to 1C are diagrams illustrating a film forming method according to one aspect of the present invention. [Figure 4] FIG. 1 is a diagram showing a comparison between the contacting process in the prior art and the contacting process in the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the embodiments will be described in detail with reference to the attached drawings. Note that the following embodiments do not limit the invention according to the claims. Although the embodiments describe a number of features, not all of these features are essential to the invention, and the features may be combined in any manner. Furthermore, in the attached drawings, the same reference numbers are used for the same or similar configurations, and duplicated descriptions are omitted.

[0013] In providing a new technology relating to curable compositions, the inventors have discovered a curable composition and process conditions that enable droplets of the curable composition that are discretely arranged on a substrate to bond with each other and form a substantially continuous liquid film before contact with a mold.

[0014] [Curable composition] The curable composition (A) in the present invention is a curable composition for inkjet. The curable composition (A) in the present invention is a composition containing at least a component (a) which is a polymerizable compound, a component (b) which is a photopolymerization initiator, and a component (c) which is a solvent. The curable composition (A) in the present invention may further contain at least one of a component (as) which is a polymerizable silicon compound, a component (af) which is a polymerizable fluorine compound, and a component (d) which is a non-polymerizable compound.

[0015] In the present specification, the term "cured film" refers to a film obtained by polymerizing and curing a curable composition on a substrate. The shape of the cured film is not particularly limited, and the surface of the cured film may or may not have a pattern.

[0016] <Component (as): Silicon-containing polymerizable compound> The silicon compound as component (as) may be understood as a silicon-containing polymerizable compound. In this specification, the silicon-containing polymerizable compound is a compound that reacts with a polymerization factor (radical, etc.) generated from a photopolymerization initiator (component (b)) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0017] Examples of the silicon-containing polymerizable compound include radical polymerizable compounds. The polymerizable compound of component (as) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0018] Examples of the silicon-containing radically polymerizable compound include (meth)acrylate-based compounds, (meth)acrylamide-based compounds, vinylbenzene-based compounds, allyl ether-based compounds, vinyl ether-based compounds, and maleimide-based compounds.

[0019] The silicon-containing polymerizable compound may be linear or branched. Examples of the silicon-containing polymerizable compound include the following structures. Examples of the polymerizable functional group in the group Q having a polymerizable functional group include radically polymerizable functional groups. Specific examples of the radically polymerizable functional group include (meth)acrylate-based compounds, (meth)acrylamide-based compounds, vinylbenzene-based compounds, allyl ether-based compounds, vinyl ether-based compounds, and maleimide-based compounds. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0020] [ka]

[0021] Other examples of the silicon-containing polymerizable compound include a silsesquioxane skeleton as shown in the following formula (1) and a silicon skeleton as shown in the following formula (2). In formula (1), m+n=8 (8≧m≧1), and R1 is a divalent organic group. In formula (2), A, B, and R 2、 R3 is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an alkoxy group, a phenyl group, or a hydroxyl group; t is an integer of 1 to 3; and at least one of A and B is a polymerizable functional group.

[0022] [ka]

[0023] [ka]

[0024] The polymerizable functional group in the groups Q, A, and B having a polymerizable functional group may be, for example, a radically polymerizable functional group. Specific examples of the radically polymerizable functional group include (meth)acrylate-based compounds, (meth)acrylamide-based compounds, vinylbenzene-based compounds, allyl ether-based compounds, vinyl ether-based compounds, and maleimide-based compounds. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0025] The silicon-containing (meth)acrylate compound includes a compound having one or more acryloyl groups or methacryloyl groups. Examples of the monofunctional (meth)acrylate compound having one silicon-containing acryloyl group or methacryloyl group include, but are not limited to, the following: (2-acryloylethoxy)trimethylsilane, N-(3-acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, acryloxymethyltrimethoxysilane, (acryloxymethyl)phenethyltrimethoxysilane, acryloxymethyltrimethylsilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-acryloxypropyl)methyldichlorosilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)trichlorosilane, (3-acryloxypropyl)trimethoxysilane, (3-acryloxypropyl)tris(trimethylsiloxy)silane, acryloxytriisopropylsilane, acryloxytrimethylsilane, methacryloxymethyltrimethoxysilane, 0-(methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (Methacryloxymethyl)methyldimethoxysilane, (Methacryloxymethyl)methyldiethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltrimethoxysilane, Methacryloylpropyltriisopropoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyldimethylethoxysilane, (Methacryloxymethyl)dimethylethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl silatrane, methacryloxypentamethyldisiloxane, (Methacryloxymethyl)phenyldimethylsilane, methacryloxytrimethylsilane, methacryloxymethyltrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyl pentamethyldisiloxane, 0-(methacryloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propylcarbamate, methacryloxymethyltris(trimethylsiloxy)silane, methacryloxyethoxytrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyltris(vinyldimethylsiloxy)silane, methacryloxypropyltris(trimethylsiloxy)silane, 3-methacryloxypropyltriacetoxysilane, methacryloxypropylmethyldichlorosilane, methacryloxypropyltrichlorosilane, 3-methacrylic acid propyl bis(trimethylsiloxy)methyl silane, 3-Methoxypropyldimethylchlorosilane, 0-Methacryloxy(polyethyleneoxy)trimethylsilane, Poly(methacrylic propyl silsesquioxane), Methacryloxypropylheptaisobutyl-T8-silsesquioxane, Methacryloxypropyltris(trimethylsiloxy)silane Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0 , SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481 .43, SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM648 6.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM6 491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, SIM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, SIM6486.65 (all manufactured by GELEST) TM-0701T, FM-0711, FM-0721, FM-0725 (all manufactured by JNC) Silicon-containing (meth)acrylamide compounds include compounds having one or more acrylamide groups or methacrylamide groups. Examples of monofunctional (meth)acrylamide compounds having one silicon-containing acrylamide group or methacrylamide group include, but are not limited to, the following: 3-Acrylamidepropyltrimethoxysilane, 3-Acrylamidepropyltris(trimethylsiloxy)silane Examples of commercially available silicon-containing monofunctional (meth)acrylamide compounds include, but are not limited to, the following: SIA0146.0, SIA0150.0 (both manufactured by GELEST) Furthermore, examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Linear polydimethylsiloxane modified with acryloxypropyl groups at both ends Linear polydimethylsiloxane modified with methacryloxypropyl groups at both ends Cyclic siloxane modified with multiple acryloxypropyl groups Cyclic siloxane modified with multiple methacryloxypropyl groups Silsesquioxane modified with multiple acryloxypropyl groups Silsesquioxane modified with multiple methacryloxypropyl groups Examples of commercially available products of the above-mentioned silicon-containing polyfunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (all manufactured by GELEST) FM-7711, FM-7721, FM-7725 (all manufactured by JNC) X-22-2445 (Shin-Etsu Chemical) AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20 (all manufactured by Toagosei) In addition, for example, the following can be synthesized and / or obtained from known document 1. Linear modified polydimethylsiloxane (MA-Si-12) with both ends modified with methacryloxypropyl groups, 8-ring siloxane modified with four methacryloxypropyl groups, 10-ring siloxane modified with five methacryloxypropyl groups, Reference 1: “Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography” by Ogawa et al. <Component (a): Silicon-free polymerizable compound> Component (a) includes a silicon-free polymerizable compound. In this specification, the silicon-free polymerizable compound is a compound that reacts with a polymerization factor (radical, etc.) generated from a photopolymerization initiator (component (b)) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0026] Examples of such polymerizable compounds include radically polymerizable compounds. The polymerizable compound of component (a) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0027] Examples of the radically polymerizable compound include silicon-free (meth)acrylic compounds, silicon-free styrene-based compounds, silicon-free vinyl-based compounds, silicon-free allyl-based compounds, silicon-free fumaric compounds, and silicon-free maleyl-based compounds.

[0028] <(Component af): Fluorine-containing polymerizable compound> The fluorine compound as component (af) may be understood as a fluorine-containing polymerizable compound. In this specification, the fluorine-containing polymerizable compound is a compound that reacts with a polymerization factor (radical, etc.) generated from a photopolymerization initiator (component (b)) to form a film made of a polymer compound by a chain reaction (polymerization reaction).

[0029] The fluorine-containing polymerizable compound may be, for example, a radical polymerizable compound. The polymerizable compound, which is the component (af), may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0030] Examples of the fluorine-containing radically polymerizable compound include (meth)acrylate-based compounds, (meth)acrylamide-based compounds, vinylbenzene-based compounds, allyl ether-based compounds, vinyl ether-based compounds, and maleimide-based compounds.

[0031] Examples of commercially available products of the above-mentioned fluorine-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following. 2,2,2-trifluoroethyl acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1H,1H,2H,2H-nonafluorohexyl methacrylate, 1H,1H,2H,2H-nonafluorohexyl acrylate, 1H,1H,2H,2H-nonafluorohexyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, pentafluorophenyl acrylate, 2,2,3,3,3-pentafluorobutyl methacrylate 1H,1H,2H,2H-Tridecafluoro-n-octyl acrylate, 1H,1H,2H,2H-Tridecafluoro-n-octyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 1H,1H,5H-octafluoropentyl acrylate, and pentafluorophenyl methacrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.) C6 (meth)acrylate, C4 (meth)acrylate, C2 (meth)acrylate (all manufactured by Unichem) Viscoat 3F, Viscoat 4F, Viscoat 8F, Viscoat 8FM, Viscoat 13F (all manufactured by Osaka Organic Chemical Industry) 1H,1H,2H,2H-heptadecafluorodecyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, pentafluorophenyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate (all manufactured by Polysciences) Methyl-2-fluoroacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-(perfluorobutyl)ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,7H-dodecafluoroheptyl acrylate, 1H-1-(trifluoromethyl)trifluoroethyl acrylate, 1H,1H,3H-hexyl Subfluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 1H,1H,3H-tetrafluoropropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, 1H,1H,7H-dodecafluoroheptyl methacrylate, 1H-1-(trifluoromethyl)trifluoroethyl methacrylate, 1H,1H,3H-hexafluorobutyl methacrylate (all manufactured by Daikin Industries, Ltd.) When the method disclosed in Japanese Patent No. 3963028 is used, examples of the above-mentioned fluorine-containing polyfunctional (meth)acrylate compound include, but are not limited to, the following. A linking group is introduced to the polyhydric alcohol moiety of trimethylolethane (3), pentaerythritol (4), or dipentaerythritol (6) using a standard organic synthesis reaction, and then a core with a high fluorine content is formed by a perfluorination reaction, with an acrylic group introduced at the end. The silicon-free (meth)acrylic compound includes a compound having one or more acryloyl groups or methacryloyl groups. Examples of silicon-free monofunctional (meth)acrylic compounds having one acryloyl group or methacryloyl group include, but are not limited to, the following: Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, EO modified phenoxy (meth)acrylate, PO modified phenoxy (meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate t) acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pliers (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, chinoabenzyl(meth)acrylate, Examples of commercially available products of the above-mentioned non-silicon-containing monofunctional (meth)acrylic compounds include, but are not limited to, the following. Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (all manufactured by Toagosei) MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) Light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A, OPP-EA (all manufactured by Kyoeisha Chemical) KAYARAD (registered trademark) TC110S, R-564, R-128H (all manufactured by Nippon Kayaku) NK Ester AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin-Nakamura Chemical Co., Ltd.) FA-511A, 512A, 513A (all manufactured by Hitachi Chemical) PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Seiyaku) VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kohjin) Furthermore, examples of non-silicon-containing polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO,PO modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m- or p-benzenedi(meth)acrylate, o-, m- or p-xylylenedi(meth)acrylate Examples of commercially available products of the above-mentioned non-silicon-containing polyfunctional (meth)acrylic compounds include, but are not limited to, the following. Upimer (registered trademark) UV SA1002, SA2007 (manufactured by Mitsubishi Chemical) Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical) KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku) Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei) Lipoxy (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Polymer) OGSOL EA-0200, OGSOL EA-0300 (both manufactured by Osaka Gas Chemicals) In the above-mentioned compound group, (meth)acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. (Meth)acryloyl group means acryloyl group or methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are bonded via a block structure of an ethylene oxide group. PO represents propylene oxide, and PO-modified compound B represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are bonded via a block structure of a propylene oxide group.

[0032] Specific examples of non-silicon-containing styrene-based compounds include, but are not limited to, the following: Alkylstyrenes such as styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene and iodine. halogenated styrenes such as styrene; compounds having a styryl group as a polymerizable functional group, such as nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl; Specific examples of the non-silicon-containing vinyl-based compound include, but are not limited to, the following: Vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate and acrylonitrile; conjugated diene monomers such as butadiene, isoprene and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, (meth)acrylonitrile, etc.), compounds having a vinyl group as a polymerizable functional group. In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0033] Examples of non-silicon-containing allyl compounds include, but are not limited to, the following: Allyl acetate, Allyl benzoate, Diallyl adipate, Diallyl terephthalate, Diallyl isophthalate, Diallyl phthalate Examples of non-silicon-containing fumaric compounds include, but are not limited to, the following: Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate Examples of non-silicon-containing maleyl compounds include, but are not limited to, the following: Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate Examples of other non-silicon-containing radical polymerizable compounds include, but are not limited to, the following: Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, dibenzyl itaconate, etc.), N-vinylamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimide and its derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.) When component (a) is composed of multiple compounds having one or more polymerizable functional groups, it preferably contains a monofunctional compound and a polyfunctional compound, because the combination of a monofunctional compound and a polyfunctional compound can provide a cured film with excellent balance of properties such as high mechanical strength, high dry etching resistance, and high heat resistance.

[0034] In the film forming method of the present invention, it takes several milliseconds to several hundred seconds for the droplets of the curable composition (A) arranged discretely on the substrate to combine with each other to form a substantially continuous liquid film, so a waiting step described below is necessary. In the waiting step, the solvent (c) is volatilized while the polymerizable compound (a) must not volatilize. Therefore, the boiling points of the polymerizable compounds (a), which may be contained in a plurality of kinds, under normal pressure are preferably all 250°C or higher, more preferably all 300°C or higher, and even more preferably all 350°C or higher. In addition, in order to obtain high dry etching resistance and high heat resistance in the cured film of the curable composition (A), it is preferable that the cured film contains at least a compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that normal pressure is defined as 1 atmosphere (atmospheric pressure).

[0035] The boiling point of the polymerizable compound (a) generally correlates with the molecular weight. Therefore, the molecular weights of the polymerizable compounds (a) are preferably all 200 or more, more preferably all 240 or more, and even more preferably all 250 or more. However, even if the molecular weight is 200 or less, if the boiling point is 250° C. or more, it can be preferably used as the polymerizable compound (a) in the present invention.

[0036] The vapor pressure of the polymerizable compound (component (a)) at 80° C. is preferably 0.001 mmHg or less. This is because, although it is preferable to heat the curable composition in order to accelerate the volatilization of the solvent (component (c)) described below, the volatilization of the polymerizable compound (component (a)) is suppressed during such heating.

[0037] The boiling points and vapor pressures of various organic compounds under normal pressure can be calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th Edition.5.3.04 or the like.

[0038] Specific examples of the polymerizable compound (component (a)) having a boiling point of 250° C. or higher include, but are not limited to, the following: Dicyclopentanyl acrylate (boiling point 262°C, molecular weight 206), Dicyclopentenyl acrylate (boiling point 270°C, molecular weight 204), 1,3-cyclohexanedimethanol diacrylate (boiling point 310°C, molecular weight 252), m-Xylylene diacrylate (boiling point 336°C, molecular weight 246), 1,4-cyclohexanedimethanol diacrylate (boiling point 339°C, molecular weight 252), 4-Hexylresorcinol diacrylate (boiling point 379°C, molecular weight 302), 6-phenylhexane-1,2-diol diacrylate (boiling point 381°C, molecular weight 302), 7-phenylheptane-1,2-diol diacrylate (boiling point 393°C, molecular weight 316), 1,3-bis((2-hydroxyethoxy)methyl)cyclohexane diacrylate (boiling point 403°C, molecular weight 340), 8-phenyloctane-1,2-diol diacrylate (boiling point 404°C, molecular weight 330), 1,3-bis((2-hydroxyethoxy)methyl)benzene diacrylate (boiling point 408°C, molecular weight 334), 1,4-bis((2-hydroxyethoxy)methyl)cyclohexane diacrylate (boiling point 445°C, molecular weight 340), 3-Phenoxybenzyl acrylate (mPhOBzA, OP 2.54, boiling point 367.4°C, vapor pressure at 80°C 0.0004mmHg, molecular weight 254.3),

[0039] [ka]

[0040] 1-Naphthyl acrylate (NaA, OP 2.27, boiling point 317°C, vapor pressure at 80°C 0.0422mmHg, molecular weight 198),

[0041] [ka]

[0042] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2℃, vapor pressure at 80℃ 0.0006mmHg, molecular weight 268.3),

[0043] [ka]

[0044] 1-Naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1℃, vapor pressure at 80℃ 0.042mmHg, molecular weight 212.2),

[0045] [ka]

[0046] 2-Naphthyl methyl acrylate (Na2MA, OP2.33, boiling point 342.1℃, vapor pressure at 80℃ 0.042mmHg, molecular weight 212.2)

[0047] [ka]

[0048] 4-Cyanobenzyl acrylate (CNBzA, OP 2.44, boiling point 316°C, molecular weight 187),

[0049] [ka]

[0050] DVBzA (OP 2.50, boiling point 304.6℃, vapor pressure 0.0848mmHg at 80℃, molecular weight 214.3) shown in the following formula,

[0051] [ka]

[0052] DPhPA (OP2.38, boiling point 354.5℃, vapor pressure 0.0022mmHg at 80℃, molecular weight 266.3) shown in the following formula,

[0053] [ka]

[0054] PhBzA (OP2.29, boiling point 350.4℃, vapor pressure 0.0022mmHg at 80℃, molecular weight 238.3) shown in the following formula,

[0055] [ka]

[0056] FLMA (OP2.20, boiling point 349.3℃, vapor pressure 0.0018mmHg at 80℃, molecular weight 250.3) shown in the following formula,

[0057] [ka]

[0058] ATMA (OP2.13, boiling point 414.9℃, vapor pressure 0.0001mmHg at 80℃, molecular weight 262.3) shown in the following formula,

[0059] [ka]

[0060] DNaMA (OP 2.00, boiling point 489.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4) shown in the following formula,

[0061] [ka]

[0062] Tricyclodecane dimethanol diacrylate (DCPDA, OP 3.29, boiling point 342°C, vapor pressure at 80°C 0.0024mmHg, molecular weight 304),

[0063] [ka]

[0064] m-Xylylene diacrylate (mXDA, OP3.20, boiling point 336℃, vapor pressure at 80℃ 0.0043mmHg, molecular weight 246),

[0065] [ka]

[0066] 1-phenylethane-1,2-diyl diacrylate (PhEDA, OP3.20, 80℃ vapor pressure 0.0057mmHg, boiling point 354℃, molecular weight 246),

[0067] [ka]

[0068] 2-phenyl-1,3-propanediol diacrylate (PhPDA, OP3.18, boiling point 340°C, vapor pressure at 80°C 0.0017mmHg, molecular weight 260),

[0069] [ka]

[0070] VmXDA (OP 3.00, boiling point 372.4℃, vapor pressure 0.0005mmHg at 80℃, molecular weight 272.3) shown in the following formula,

[0071] [ka]

[0072] BPh44DA (OP2.63, boiling point 444℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.3) shown in the following formula,

[0073] [ka]

[0074] BPh43DA (OP2.63, boiling point 439.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.3) shown in the following formula,

[0075] [ka]

[0076] DPhEDA (OP2.63, boiling point 410℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.3) shown in the following formula,

[0077] [ka]

[0078] BPMDA (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) shown in the following formula,

[0079] [ka]

[0080] Na13MDA (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3) shown in the following formula,

[0081] [ka]

[0082] In the component (a), the amount of the component (as) or the component (af) is preferably 1% by weight or more and 99% by weight or less, more preferably 50% by weight or more and 95% by weight or less, and even more preferably 60% by weight or more and 90% by weight or less.

[0083] At least a part of the component (a), of which a plurality of types may be added, may be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, it preferably contains at least one of the constitutional units represented by any one of the following formulas (3) to (8).

[0084] [ka]

[0085] In formulas (3) to (8), the substituents R are each independently a substituent containing a partial structure containing an aromatic ring, and R 1is a hydrogen atom or a methyl group. In the present specification, in the constitutional units represented by formulae (3) to (8), the portion other than R is the main chain of a specific polymer. The formula weight of the substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and further preferably 150 or more. It is practical that the upper limit of the formula weight of the substituent R is 500 or less.

[0086] The polymer having a polymerizable functional group is usually a compound having a weight average molecular weight of 500 or more, preferably 1,000 or more, more preferably 2,000 or more. The upper limit of the weight average molecular weight is not particularly specified, but is preferably 50,000 or less. By making the weight average molecular weight equal to or greater than the above-mentioned lower limit, the boiling point can be made 250°C or more, and the mechanical properties after curing can be further improved. In addition, by making the weight average molecular weight equal to or less than the above-mentioned upper limit, the solubility in the solvent is high, the viscosity is not too high, and the fluidity of the droplets that are discretely arranged can be maintained, and the flatness of the liquid film plane can be further improved. In addition, the weight average molecular weight (Mw) in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified.

[0087] Specific examples of the polymerizable functional group of the polymer include a (meth)acryloyl group, an epoxy group, an oxetane group, a methylol group, a methylol ether group, a vinyl ether group, etc. From the viewpoint of ease of polymerization, a (meth)acryloyl group is particularly preferred.

[0088] When a polymer having a polymerizable functional group is added as at least a part of component (a), the blending ratio can be freely set as long as it falls within the range of the viscosity regulation described later. For example, it is preferably 0.1% by weight or more and 60% by weight or less, more preferably 1% by weight or more and 50% by weight or less, and even more preferably 10% by weight or more and 40% by weight or less, based on the total mass of all components except for the solvent (c). By setting the blending ratio of the polymer having a polymerizable functional group to 0.1% by weight or more, it is possible to improve heat resistance, dry etching resistance, mechanical strength, and low volatility. In addition, by setting the blending ratio of the polymer having a polymerizable functional group to 60% by weight or less, it is possible to fall within the upper limit of the viscosity regulation described later.

[0089] <Component (b): Photopolymerization initiator> Component (b) is a photopolymerization initiator. In this specification, a photopolymerization initiator is a compound that senses light of a specific wavelength and generates the above-mentioned polymerization factor (radical). Specifically, a photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals by light (infrared rays, visible light, ultraviolet rays, far ultraviolet rays, charged particle rays such as X-rays and electron beams, radiation). Component (b) may be composed of only one type of photopolymerization initiator, or may be composed of multiple types of photopolymerization initiators.

[0090] Examples of the radical generator include, but are not limited to, the following: 2,4,5-Triarylimidazole dimers which may have a substituent, such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzo Quinones such as anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;Acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Examples of commercially available radical generators include, but are not limited to, the following: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin® TPO, LR8893, LR8970 (both manufactured by BASF), Ubecryl P36 (manufactured by UCB) Of the above-mentioned radical generators, the component (b) is preferably an acylphosphine oxide-based polymerization initiator. Among the above-mentioned radical generators, the acylphosphine oxide-based polymerization initiator is as follows. Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide The blending ratio of component (b) in the curable composition (A) is preferably 0.1% by weight or more and 50% by weight or less based on the total mass of components (a), (b), and (d) described later, i.e., the total mass of all components excluding the solvent (c). The blending ratio of component (b) in the curable composition (A) is more preferably 0.1% by weight or more and 20% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less based on the total mass of all components excluding the solvent (c). By making the blending ratio of component (b) 0.1% by weight or more, the curing speed of the composition can be increased and the reaction efficiency can be improved. In addition, by making the blending ratio of component (b) 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0091] <Component (c): Solvent> The curable composition (A) contains, as component (c), a solvent having a boiling point of 135°C or more and less than 250°C under normal pressure and a surface tension of 24 [mN / m] or less at normal temperature. Component (c) contains, for example, 10 at% or less of silicon atoms or fluorine atoms. Examples of component (c) include solvents in which components (a), (b) and (d) are soluble, such as ether-based hydrocarbon solvents, perfluorocarbon solvents, alcohol-based fluorine-based solvents, ester-based fluorine-based solvents and halogen-introduced fluorine-based solvents. Further, the component (c) may be a polyhydric alcohol ether in which all the hydroxyl groups of the polyhydric alcohol are alkyl etherified. Further, the component (c) may be ethylene glycol di-tert-butyl ether or diethylene glycol methyl tert-butyl ether. The component (c) may be used alone or in combination of two or more. The boiling point of the component (c) under normal pressure is 130°C or higher, preferably 145°C or higher, and particularly preferably 150°C or higher. The boiling point of the component (c) under normal pressure is less than 250°C, and preferably 200°C or lower. Thus, the boiling point of the component (c) under normal pressure is 130°C or higher and less than 250°C. If the boiling point of the component (c) under normal pressure is less than 130°C, drying proceeds near the inkjet nozzle, causing ejection defects such as adhesion and twisting. In addition, the volatilization rate in the waiting step described later is too fast, so that the component (c) volatilizes before the droplets of the curable composition (A) bond together, and the droplets of the curable composition (A) may not bond together. On the other hand, if the boiling point of the component (c) under normal pressure is 250° C. or higher, ejection defects such as adhesion and twisting are improved, but the volatilization of the solvent (c) is insufficient in the waiting step described later, so that the component (c) may remain in the cured product of the curable composition (A).

[0092] Examples of the ether-based hydrocarbon solvent include the following: Ethylene glycol di-tert-butyl ether, diethylene glycol methyl-tert-butyl ether, MFDG-tBu (manufactured by Nippon Nyukazai) Examples of perfluorocarbon solvents include the following: FC-40, FC-43 (and above, made by 3M) Examples of the alcohol-based fluorine-based solvent include the following: 3-(perfluorobutyl)propanol, 3-(perfluorohexyl)propanol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol Examples of the ester-based fluorine-based solvent include the following: Ethyl 5H-octafluoropentanoate Examples of halogen-introduced fluorine-based solvents include the following: 2-(perfluorobutyl)ethyl iodide, 2-(perfluorohexyl)ethyl iodide, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane, 1-bromoheptafluorooctane Of the above-mentioned solvents, ether-based hydrocarbon solvents, perfluorocarbon solvents, ester-based fluorine-based solvents, and halogen-introduced fluorine-based solvents are preferred.

[0093] Further, more preferred solvents include the following: Ethylene glycol di-tert-butyl ether, diethylene glycol methyl-tert-butyl ether Here, in the present invention, when the surface tension of the curable composition at 23°C from which the solvent (c) has been removed is γ1 [mN / m], and the surface tension of the solvent (c) at 23°C is γ2 [mN / m], the curable composition is configured so that γ1 is greater than γ2. In other words, when Δγ=γ1-γ2, the curable composition is configured so that Δγ is greater than zero. Specifically, the solvent (c) is selected so that Δγ is greater than zero. When Δγ is greater than zero, the Marangoni effect accelerates the spread of the droplets of the curable composition in the waiting step described below, and the droplets quickly bond to each other to form a continuous liquid film. In addition, the rapid spread of the droplets accelerates the evaporation of the solvent, so that the waiting step described below can be completed in a short time, and the conditions of the baking step can be relaxed or omitted. Δγ is preferably 0.1 or more (γ1-γ2>0.1 [mN / m]), particularly preferably 1.0 or more (γ1-γ2>1 [mN / m]), and further preferably 2.0 or more. Note that γ1 and γ2 are each the surface tension under normal pressure (1 atm).

[0094] In the present invention, a polymerizable compound having a boiling point of 80° C. or more and less than 250° C. under normal pressure can also be used as component (c). Examples of polymerizable compounds having a boiling point of 80° C. or more and less than 250° C. under normal pressure include the following. Cyclohexyl acrylate (198°C), benzyl acrylate (229°C), isobornyl acrylate (245°C), tetrahydrofurfuryl acrylate (202°C), trimethylcyclohexyl acrylate (232°C), isooctyl acrylate (217°C), n-octyl acrylate (228°C), ethoxyethoxyethyl acrylate (230°C), divinylbenzene (193°C), 1,3-diisopropenylbenzene (218°C), styrene (145°C), α-methylstyrene (165°C) In the present invention, when the entire curable composition (A) is taken as 100% by volume, the content of the solvent (c) is 5% by volume or more and 95% by volume or less, preferably 70% by volume or more and 85% by volume or less, and more preferably 70% by volume or more and 80% by volume or less. If the content of the solvent (c) is less than 5% by volume, a thin film cannot be obtained after the solvent (c) evaporates under conditions in which a substantially continuous liquid film is obtained. Also, if the content of the solvent (c) is more than 95% by volume, it is difficult to obtain a thick film after the solvent (c) evaporates, even if droplets are dropped in close contact by the inkjet method.

[0095] <Component (d): Non-polymerizable compound> In addition to the above-mentioned components (a) and (b), the curable composition (A) may further contain a non-polymerizable compound as component (d) according to various purposes. Such component (d) may be a compound that does not have a polymerizable functional group such as a (meth)acryloyl group and does not have the ability to sense light of a specific wavelength and generate the above-mentioned polymerization factor (radical). Examples of the non-polymerizable compound include a sensitizer, a hydrogen donor, an internal mold release agent, an antioxidant, a polymer component, and other additives. Component (d) may contain multiple types of the above-mentioned compounds.

[0096] The sensitizer is a compound that is appropriately added for the purpose of promoting the polymerization reaction and improving the reaction conversion rate. The sensitizer may be used alone or in combination of two or more kinds.

[0097] Examples of the sensitizer include sensitizing dyes. The sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and interacts with the photopolymerization initiator, which is component (b). Here, the interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator, which is component (b). Specific examples of the sensitizing dye include, but are not limited to, the following: Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes The hydrogen donor is a compound that reacts with the initiation radicals generated from the photopolymerization initiator, component (b), or with radicals at the polymer growth terminal, to generate radicals with higher reactivity. When the photopolymerization initiator, component (b), is a photoradical generator, it is preferable to add a hydrogen donor.

[0098] Specific examples of such hydrogen donors include, but are not limited to, the following: Amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanolamine, and N-phenylglycine; mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionic acid ester. The hydrogen donor may be used alone or in combination of two or more kinds. The hydrogen donor may also function as a sensitizer.

[0099] In order to reduce the interfacial bonding force between the mold and the curable composition, that is, to reduce the demolding force in the demolding step described below, an internal mold release agent can be added to the curable composition. In this specification, the internal mold release agent means that it is added to the curable composition in advance before the placement step of the curable composition. As the internal mold release agent, a surfactant such as a silicon-based surfactant, a fluorine-based surfactant, and a hydrocarbon-based surfactant can be used. However, in the present invention, the amount of the fluorine-based surfactant to be added is limited, as described below. The internal mold release agent in the present invention is not polymerizable. The internal mold release agent may be used alone or in a mixture of two or more types.

[0100] Fluorosurfactants include the following: Polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having perfluoroalkyl groups, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers The fluorosurfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in a part of the molecular structure (for example, a terminal group). For example, pentadecaethylene glycol mono 1H,1H,2H,2H-perfluorooctyl ether, etc. can be mentioned.

[0101] As the fluorosurfactant, commercially available products may be used. Examples of commercially available fluorosurfactants include the following: Megafac (registered trademark) F-444, TF-2066, TF-2067, TF-2068, abbreviated name DEO-15 (all manufactured by DIC) Fluorard FC-430, FC-431 (both manufactured by Sumitomo 3M) Surflon (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by Tochem Products) PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA Solutions) Unidyne (registered trademark) DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.) Futergent (registered trademark) 250, 251, 222F, 208G (all manufactured by Neos) The internal mold release agent may be a hydrocarbon surfactant. Examples of the hydrocarbon surfactant include an alkyl alcohol polyalkylene oxide adduct in which an alkylene oxide having 2 to 4 carbon atoms is added to an alkyl alcohol having 1 to 50 carbon atoms, and a polyalkylene oxide.

[0102] Examples of the alkyl alcohol polyalkylene oxide adducts include the following. Methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / propylene oxide adduct The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced by simply adding a polyalkylene oxide to an alkyl alcohol. Such a hydroxyl group may be substituted with other substituents, for example, polar functional groups such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or hydrophobic functional groups such as an alkyl group or an alkoxy group.

[0103] Examples of the polyalkylene oxide include the following. Polyethylene glycol, polypropylene glycol, their mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monoadipate esters, monooleate esters, monostearate esters, monosuccinate esters The alkyl alcohol polyalkylene oxide adduct may be a commercially available product. Examples of commercially available alkyl alcohol polyalkylene oxide adducts include the following: Polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), random polymerization type polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R) manufactured by Aoki Oil Industries, polyoxyethylene methyl ether (Pluriol(R) A760E) manufactured by BASF, polyoxyethylene alkyl ether (Emulgen series) manufactured by Kao Moreover, the polyalkylene oxide may be a commercially available product, for example, ethylene oxide-propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0104] Fluorine-based surfactants have an excellent effect of reducing the releasing force, and are therefore effective as internal mold release agents. The blending ratio of component (d) excluding fluorine-based surfactant in the curable composition (A) is preferably 0% by weight or more and 50% by weight or less based on the total mass of components (a), (b), and (d), i.e., the total mass of all components excluding solvent (c). The blending ratio of component (d) excluding fluorine-based surfactant in the curable composition (A) is more preferably 0.1% by weight or more and 50% by weight or less, and even more preferably 0.1% by weight or more and 20% by weight or less based on the total mass of all components excluding solvent (c). By making the blending ratio of component (d) excluding fluorine-based surfactant 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0105] <Temperature when compounding the curable composition> When preparing the curable composition (A), at least the components (a), (b) and (c) are mixed and dissolved under a predetermined temperature condition. Specifically, the predetermined temperature condition is in the range of 0° C. or higher and 100° C. or lower. The same applies when the curable composition (A) contains the component (d).

[0106] <Viscosity of Curable Composition> The curable composition (A) is liquid. This is because droplets of the curable composition (A) are dropped discretely onto a substrate by an inkjet method in the disposing step described later. The viscosity of the curable composition (A) is 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm, preferably 3 mPa·s to 30 mPa·s, and more preferably 3 mPa·s to 15 mPa·s. If the viscosity of the curable composition (A) is less than 1.3 mPa·s, the ejection of droplets by the inkjet method becomes unstable. If the viscosity of the curable composition (A) is greater than 60 mPa·s, it is difficult to form droplets having a volume of about 1.0 to 3.0 pL, which is preferred in the present invention.

[0107] The viscosity of the composition after the solvent (c) has evaporated from the curable composition (A), i.e., the composition from which the solvent (c) has been removed, at 23°C and 1 atm is 30 mPa·s or more and 10,000 mPa·s or less. The viscosity of the composition from which the solvent (c) has been removed, at 23°C and 1 atm, is preferably 90 mPa·s or more and 2,000 mPa·s or less, for example, 120 mPa·s or more and 1000 mPa·s or less. The viscosity of the composition from which the solvent (c) has been removed, at 23°C and 1 atm, is more preferably 200 mPa·s or more and 500 mPa·s or less. The composition from which the solvent (c) has been removed is also referred to as the curable composition (A'). By making the viscosity of the curable composition (A') at 23°C 1000 mPa·s or less, the spreading and filling are quickly completed when the curable composition (A') is brought into contact with the mold. Therefore, by using the curable composition (A), the imprint process can be performed with high throughput, and pattern defects due to insufficient filling can be suppressed. In addition, by making the viscosity of the curable composition (A') at 23°C 30 mPa·s or more, unnecessary flow of droplets of the curable composition (A') can be prevented. Furthermore, when the curable composition (A') is brought into contact with a mold, the curable composition (A') can be prevented from flowing out from the edge of the mold.

[0108] <Surface tension of curable composition> The curable composition (A) from which the solvent (component (c)) has been removed has a surface tension of 5 mN / m to 30 mN / m at 23°C and 1 atm. The curable composition (A) from which the solvent (component (c)) has been removed has a surface tension of more preferably 7 mN / m to 28 mN / m, and even more preferably 10 mN / m to 26 mN / m at 23°C and 1 atm. In other words, the curable composition (A') has a surface tension of 5 mN / m to 30 mN / m, more preferably 7 mN / m to 28 mN / m, and even more preferably 10 mN / m to 28 mN / m. The higher the surface tension, for example, 5 mN / m or more, the stronger the capillary force, so that when the curable composition (A) is brought into contact with the mold, the filling (spreading and filling) is completed in a short time. Furthermore, by setting the surface tension to 30 mN / m or less, the cured film obtained by curing the curable composition has a smooth surface.

[0109] <Contact angle of curable composition> The contact angle of the curable composition (A) from which the solvent (component (c)) has been removed is preferably 0° to 90°, particularly preferably 0° to 10°, with respect to both the surface of the substrate and the surface of the mold. In other words, the contact angle of the curable composition (A') is preferably 0° to 90°, particularly preferably 0° to 10°. If the contact angle is greater than 90°, the capillary force acts in the negative direction (the direction that shrinks the contact interface between the mold and the curable composition) inside the mold pattern or in the gap between the substrate and the mold, and the curable composition (A) may not fill the mold. The smaller the contact angle, the stronger the capillary force acts, and the faster the filling speed becomes.

[0110] <Impurities contained in the curable composition> It is preferable that the curable composition (A) contains as few impurities as possible. The impurities mean those other than the above-mentioned components (as), (a), (b), (c) and (d). Therefore, it is preferable that the curable composition (A) is obtained through a purification process. As such a purification process, filtration using a filter is preferable.

[0111] As for the filtration using a filter, it is preferable to mix the above-mentioned components (a), (b) and (c) and then filter them with a filter having a pore size of 0.001 μm or more and 5.0 μm or less. When performing filtration using a filter, it is more preferable to perform the filtration in multiple stages or to repeat the filtration many times (circulation filtration). In addition, the liquid filtered through the filter may be filtered again, or may be filtered using multiple filters having different pore sizes. Examples of filters used for filtration include filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc., but are not particularly limited. By going through such a purification process, impurities such as particles mixed in the curable composition can be removed. This can prevent impurities mixed in the curable composition from accidentally causing unevenness in the cured film obtained after curing the curable composition, which can cause defects in the pattern.

[0112] When the curable composition (A) is used to manufacture a semiconductor integrated circuit, it is preferable to avoid impurities containing metal atoms (metal impurities) from being mixed into the curable composition as much as possible so as not to impair the operation of the product. The concentration of metal impurities contained in the curable composition is preferably 10 ppm or less, more preferably 100 ppb or less.

[0113] [Drip material] In this specification, the member onto which droplets of the curable composition (A) are discretely dropped (dropping member) is described as a substrate (mold base material) or a mold (master mold).

[0114] The mold substrate is made of, for example, quartz. The mold substrate may have an adhesive layer on the surface. However, the mold substrate is not limited to quartz. For example, the mold substrate can be arbitrarily selected from those known as substrates for semiconductor devices, such as silicon, aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride. The surface of the mold substrate may be improved in adhesion to the curable composition (A) by surface treatment such as silane coupling treatment, silazane treatment, and formation of an organic thin film. As a specific example of the organic thin film formed as a surface treatment, for example, the adhesive layer described in JP-T-2009-503139 can be used.

[0115] [First pattern formation method] With reference to FIG. 1(a) to FIG. 1(g), the first pattern forming method of the present invention will be described. In the first pattern forming method, the member onto which droplets of the curable composition (A) are dropped discretely is a mold substrate. The cured film formed by the present invention is preferably a film having a pattern of 1 nm to 10 mm, more preferably a film having a pattern of 10 nm to 100 μm. In general, a film forming method for forming a film having a nano-sized pattern (uneven structure) (1 nm to 100 nm) using light is called a photoimprint method. The film forming method of the present invention uses the photoimprint method to form a film of the curable composition in the space between the mold substrate and the master mold. However, the curable composition may be cured by other energy (e.g., heat, electromagnetic waves). The film forming method of the present invention may be implemented as a method for forming a film having a pattern, i.e., a pattern forming method, or a method for forming a film without a pattern (e.g., a planarized film), i.e., a planarized film forming method.

[0116] Hereinafter, an example in which the film formation method of the present invention is applied to the first pattern formation method will be described. The first pattern formation method includes, for example, a preparation step, a disposing step, a waiting step, a contact step, a curing step, and a demolding step. The preparation step is a step of preparing an underlayer. The disposing step is a step of disposing droplets of the curable composition (A) discretely on the underlayer. The waiting step is a step of waiting until the droplets of the curable composition (A) are bonded to each other and the solvent (c) is evaporated. The contact step is a step of contacting the curable composition (A or A'), preferably the curable composition (A'), with the master mold. The curing step is a step of curing the curable composition (A or A'), preferably the curable composition (A'). The demolding step is a step of detaching the master mold from the cured film of the curable composition (A or A'). The positioning step is performed after the preparation step, the waiting step is performed after the positioning step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0117] <Placement process> In the disposing step, droplets 102 of a curable composition (A) are discretely disposed on a mold substrate 101, as shown diagrammatically in FIG. 1(a).

[0118] The inkjet method is particularly preferred as a method for disposing the droplets 102 of the curable composition (A) on the mold substrate. The droplets 102 of the curable composition (A) are densely disposed on the region of the mold substrate 101 facing the region where the recesses constituting the pattern of the master mold 106 are densely present. The droplets 102 of the curable composition (A) are sparsely disposed on the region of the mold substrate 101 facing the region where the recesses constituting the pattern of the master mold 106 are sparsely present. As a result, the film (residual film) of the curable composition (A) described later formed on the mold substrate 101 is controlled to a uniform thickness regardless of the density of the pattern of the master mold 106.

[0119] In order to define the volume of the curable composition (A) to be placed on the mold substrate, an index called the average liquid film thickness is defined. The average liquid film thickness is the value obtained by dividing the volume of the curable composition (A) (excluding the solvent (c)) placed in the placing step by the area of ​​the film-forming region of the master mold. The volume of the cured product or cured film of the curable composition (A) (excluding the solvent (c)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (c) has evaporated. According to this definition, even if the surface of the mold substrate is uneven, the average liquid film thickness can be defined regardless of the uneven state.

[0120] <Standby process> In the present invention, a waiting step is provided after the disposing step and before the contacting step (between the disposing step and the contacting step). Here, the average film thickness is defined as the total volume of the droplets of the curable composition (A) dropped in one pattern formation divided by the total area of ​​the region (film formation region) where a pattern is formed in one pattern formation. In the waiting step, the droplets 102 of the curable composition (A) spread on the mold substrate 101 as shown in FIG. 1(b). As a result, the pattern formation region of the mold substrate 101 is covered with the curable composition (A) over the entire region. When the average film thickness is 130 nm or more, the droplets of the curable composition (A) bond to each other on the mold substrate to form a substantially continuous liquid film 103 as shown in FIG. 1(c). When the average film thickness is 150 nm or more, the surface of the liquid film 103 becomes flat. The liquid film 103 having an average thickness of 130 nm or more is formed by dispersing the droplets 102 of the curable composition (A) having a volume of 1.0 pL or more at a rate of 130 droplets / mm 2 Similarly, a liquid film 103 having an average thickness of 150 nm or more can be obtained by disposing the droplets 102 of the curable composition (A) having a volume of 1.0 pL or more at a density of 150 droplets / mm 2 This can be obtained by arranging the layers at a density of 10 μm or less. In this embodiment, the average film thickness is preferably 10 μm or less, and more preferably 1 μm or less. If the average film thickness is greater than 10 μm, the stability of the pattern shape of the replica mold is low.

[0121] With reference to Fig. 2(a) to Fig. 2(d), the flow behavior of the droplets of the curable composition (A) placed on the mold substrate during the waiting process will be described. The droplets of the curable composition (A) are discretely placed on the mold substrate as shown in Fig. 2(a), and as shown in Fig. 2(b), each droplet gradually spreads on the mold substrate. Then, as shown in Fig. 2(c), the droplets of the curable composition (A) on the mold substrate begin to combine with each other to form a liquid film, and as shown in Fig. 2(d), it becomes a continuous liquid film (the surface of the mold substrate is covered with the curable composition (A) and there is no exposed surface). The state of the curable composition (A) as shown in Fig. 2(d) is called a "substantially continuous liquid film".

[0122] Furthermore, in the waiting step, as shown in Fig. 1(d), the solvent 105 (solvent (c)) contained in the liquid film 103 is volatilized. The amount of solvent (c) remaining in the liquid film 104 after the waiting step (e.g., at the start of the contacting step) is preferably 10% by volume or less, assuming that the total weight of the components other than solvent (c) is 100% by volume. If the amount of solvent (c) remaining is more than 10% by volume, the mechanical properties of the cured film may be reduced.

[0123] In the waiting step, in order to accelerate the evaporation of the solvent (c), a baking step may be performed in which the mold substrate 101 and the curable composition (A) are heated, or the atmospheric gas around the mold substrate 101 may be ventilated. The heating is performed, for example, at 30°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 110°C. The heating time may be 10 seconds or higher and 600 seconds or lower. The baking step may be performed using a known heater such as a hot plate or an oven.

[0124] The waiting step is, for example, 0.1 to 600 seconds, preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 seconds, the droplets of the curable composition (A) may not bond sufficiently to each other, and a substantially continuous liquid film may not be formed. If the waiting step exceeds 600 seconds, the productivity decreases. Therefore, in order to suppress the decrease in productivity, the mold base material after the arrangement step may be sequentially transferred to the waiting step, and the waiting step may be performed in parallel for a plurality of mold base materials, and the mold base material after the waiting step may be sequentially transferred to the contact step. In the prior art, it theoretically takes several thousand to several tens of thousands of seconds until a substantially continuous liquid film is formed, but in reality, the spread of the droplets of the curable composition stagnates due to the effect of volatilization, so that a continuous liquid film cannot be formed.

[0125] In the waiting step, when the solvent (c) evaporates, a composition consisting of the components (as), (af), (a), (b) and (d), i.e., a substantially continuous liquid film 104 of the curable composition (A'), remains. The average film thickness of the curable composition (A) from which the solvent (c) has been evaporated (removed), i.e., the substantially continuous liquid film 104 of the curable composition (A'), becomes thinner than the liquid film 103 by the amount of the solvent (c) that has been evaporated. The pattern formation region of the mold substrate 101 is maintained in a state of being covered with the substantially continuous liquid film 104 of the curable composition (A') over the entire region.

[0126] <Contact process> In the contact step, as shown in FIG. 1(e), the curable composition (A) from which the solvent (c) has been removed, i.e., a substantially continuous liquid film 104 of the curable composition (A'), is brought into contact with the master mold 106. The contact step includes a step of changing a state in which the curable composition (A') and the master mold 106 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. As a result, the liquid of the curable composition (A') is filled into the recesses of the fine pattern on the surface of the master mold 106, and the liquid becomes a liquid film that fills the fine pattern of the master mold 106.

[0127] In the waiting step, the solvent (c) is removed from the curable composition (A) and the curable composition (A') becomes a substantially continuous liquid film 104, so that the volume of gas trapped between the master mold 106 and the mold substrate 101 is reduced. Therefore, the spreading of the curable composition (A') in the contact step is quickly completed. A comparison (difference) between the contact step in the prior art disclosed in Japanese Patent No. 6584578 and the contact step in the present invention is shown in FIG. 4.

[0128] If the spreading and filling of the curable composition (A') is completed quickly in the contacting step, the time for which the master mold 106 is kept in contact with the curable composition (A') (the time required for the contacting step) can be shortened. The shortening of the time required for the contacting step leads to a shortening of the time required for pattern formation (film formation), thereby improving productivity. The contacting step is preferably from 0.1 to 3 seconds, and particularly preferably from 0.1 to 1 second. If the contacting step is shorter than 0.1 seconds, spreading and filling are insufficient, and defects called unfilled defects tend to occur frequently.

[0129] When the curing step includes a light irradiation step, it is preferable to use a mold (die) made of a light-transmitting material as the master mold 106. As the material for the master mold 106, for example, glass, quartz, light-transmitting resin such as PMMA or polycarbonate resin, transparent metal deposition film, flexible film such as polydimethylsiloxane, light-cured film, metal film, etc. are preferable. However, when a light-transmitting resin is used as the material for the master mold 106, a resin that is not dissolved in the components contained in the curable composition is selected. Quartz is suitable as the material for the master mold 106 because it has a small thermal expansion coefficient and small pattern distortion.

[0130] The pattern formed on the surface of the master mold 106 has a height of, for example, 4 nm or more and 200 nm or less. The lower the height of the pattern of the master mold 106, the smaller the force for separating the master mold 106 from the cured film of the curable composition in the demolding process, i.e., the demolding force. Therefore, the number of demolding defects remaining on the master mold 106 due to the pattern of the curable composition being torn off can be reduced. In addition, the impact when the master mold 106 is demolded may cause the pattern of the curable composition to elastically deform, causing adjacent pattern elements to come into contact with each other, resulting in adhesion or damage. However, it is advantageous to have the height of the pattern element be about twice or less the width of the pattern element (aspect ratio 2 or less) in order to avoid such defects. On the other hand, if the height of the pattern element is too low, the processing accuracy of the mold substrate 101 will be reduced.

[0131] The master mold 106 may be subjected to a surface treatment before the contact step in order to improve the releasability of the master mold 106 with respect to the curable composition (A). For example, the surface treatment may involve applying a release agent to the surface of the master mold 106 to form a release agent layer. Examples of the release agent applied to the surface of the master mold 106 include silicon-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. For example, commercially available coating-type release agents such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also be suitably used. The release agent may be used alone or in combination of two or more types. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0132] In the contact step, when the master mold 106 is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is not particularly limited and is, for example, 0 MPa or more and 100 MPa or less. Note that, when the master mold 106 is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is preferably 0 MPa or more and 50 MPa or less. Furthermore, when the master mold 106 is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is more preferably 0 MPa or more and 30 MPa or less, and further preferably 0 MPa or more and 20 MPa or less.

[0133] The contact step can be carried out under any of the conditions of the air atmosphere, the reduced pressure atmosphere, and the inert gas atmosphere, but it is preferable to carry out the contact step under the reduced pressure atmosphere or the inert gas atmosphere, since it can prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas used when carrying out the contact step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various fluorocarbon gases, and the like, or mixed gases thereof. When carrying out the contact step under a specific gas atmosphere, including the air atmosphere, the preferred pressure is 0.0001 atm or more and 10 atm or less.

[0134] <Curing process> In the curing step, as shown in FIG. 1(f), the curable composition (A') is irradiated with irradiation light 107 as curing energy to cure the curable composition (A') and form a cured film. In the curing step, for example, the curable composition (A') is irradiated with irradiation light 107 through the master mold 106. More specifically, the curable composition (A') filled in the fine pattern of the master mold 106 is irradiated with irradiation light 107 through the master mold 106. As a result, the curable composition (A') filled in the fine pattern of the master mold 106 is cured to form a cured film 108 having a pattern.

[0135] The irradiation light 107 is selected according to the sensitivity wavelength of the curable composition (A). Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, or electron beams having a wavelength of 150 nm or more and 400 nm or less. It is particularly preferable that the irradiation light 107 is ultraviolet light. This is because many of the compounds commercially available as curing assistants (photopolymerization initiators) are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, Deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, the ultra-high-pressure mercury lamp is particularly preferable as the light source that emits ultraviolet light. The number of light sources may be one or more. The entire area of ​​the curable composition (A) filled in the fine pattern of the master mold may be irradiated with light, or only a part of the area (a limited area) may be irradiated with light. The light irradiation may be performed intermittently multiple times over the entire area of ​​the mold substrate, or may be performed continuously over the entire area of ​​the mold substrate. Furthermore, the first area of ​​the mold substrate may be irradiated with light in the first irradiation process, and the second area of ​​the mold substrate different from the first area may be irradiated with light in the second irradiation process.

[0136] <Mold release process> In the demolding step, as shown in FIG. 1(g), the master mold 106 is separated from the cured film 108. By separating the patterned cured film 108 from the master mold 106, the cured film 108 having a pattern that is an inversion of the fine pattern of the master mold 106 is obtained in a self-supporting state on the mold substrate. Here, the cured film remains in the recesses of the cured film 108 having a pattern corresponding to the pattern of the master mold 106. Such a film is called a residual film.

[0137] The method of separating the master mold 106 from the cured film 108 having the pattern is not particularly limited as long as a part of the cured film 108 having the pattern is not physically damaged during the separation, and various conditions are not particularly limited. For example, the mold substrate 101 may be fixed, and the master mold 106 may be moved away from the mold substrate 101. Alternatively, the master mold 106 may be fixed, and the mold substrate 101 may be moved away from the master mold 106. The master mold 106 may be separated from the cured film 108 having the pattern by moving both the master mold 106 and the mold substrate 101 in opposite directions.

[0138] <Repeat> By a series of steps (manufacturing process) including the above-mentioned placement step through demolding step in this order, a cured film having a desired concave-convex pattern shape (a pattern shape that follows the concave-convex shape of the master mold 106) in a desired position can be obtained.

[0139] In the first pattern formation method, the repeating unit (shot) from the placement step to the demolding step can be repeated multiple times on the same mold substrate, and a cured film 108 having multiple desired patterns can be obtained at desired positions on the mold substrate.

[0140] [Second pattern formation method] The second pattern formation method of the present invention will be described with reference to Fig. 3(a) to Fig. 1(g). In the second pattern formation method, the member onto which droplets of the curable composition (A) are discretely dropped is a master mold.

[0141] Hereinafter, an example in which the film formation method of the present invention is applied to a second pattern formation method will be described. The second pattern formation method includes, for example, a preparation step, a placement step, a waiting step, a contact step, a curing step, and a demolding step. The placement step is performed after the preparation step, the waiting step is performed after the placement step, the contact step is performed after the waiting step, the curing step is performed after the contact step, and the demolding step is performed after the curing step.

[0142] <Placement process> In the disposing step, as shown diagrammatically in FIG. 3( a ), droplets 102 of the curable composition (A) are discretely disposed on a master mold 106 .

[0143] The inkjet method is particularly preferred as a method for arranging the droplets 102 of the curable composition (A) on the master mold. The droplets 102 of the curable composition (A) are arranged densely in regions where the recesses constituting the pattern of the master mold 106 are densely present, and arranged sparsely in regions where the recesses constituting the pattern of the master mold 106 are sparsely present. This allows the film (residual film) of the curable composition (A) described below to be formed on the mold substrate 101 to be controlled to a uniform thickness regardless of the density of the pattern of the master mold 106.

[0144] In order to define the volume of the curable composition (A) to be placed on the master mold, an index called the average liquid film thickness is defined. As described above, the average liquid film thickness is the value obtained by dividing the volume of the curable composition (A) (excluding the solvent (c)) placed in the placing step by the area of ​​the film-forming region of the master mold. The volume of the cured product or cured film of the curable composition (A) (excluding the solvent (c)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (c) has evaporated. According to this definition, even if the surface of the mold substrate is uneven, the average liquid film thickness can be defined regardless of the uneven state.

[0145] <Standby process> In the present invention, a waiting step is provided after the disposing step and before the contacting step (between the disposing step and the contacting step). Here, as described above, the average film thickness is defined as the value obtained by dividing the total volume of the droplets of the curable composition (A) dropped in one pattern formation by the total area of ​​the region (film formation region) where a pattern is formed in one pattern formation. In the waiting step, the droplets 102 of the curable composition (A) spread on the master mold 106 as shown in FIG. 3(b). As a result, the pattern formation region of the master mold 106 is covered with the curable composition (A) over the entire region. When the average film thickness is 130 nm or more, the droplets of the curable composition (A) bond with each other on the master mold to form a substantially continuous liquid film 103 as shown in FIG. 3(c). When the average film thickness is 150 nm or more, the surface of the liquid film 103 becomes flat.

[0146] The flow behavior of the droplets of the curable composition (A) placed on the master mold during the waiting step is similar to the flow behavior of the droplets of the curable composition (A) placed on the mold substrate during the waiting step described with reference to Figures 2(a) to 2(d). Specifically, the "mold substrate" can be replaced with the "master mold", and therefore a detailed description thereof will be omitted here.

[0147] Furthermore, in the waiting step, as shown in Fig. 3(d), the solvent 105 (solvent (c)) contained in the liquid film 103 is volatilized. The amount of solvent (c) remaining in the liquid film 104 after the waiting step (e.g., at the start of the contacting step) is preferably 10% by volume or less, assuming that the total weight of the components other than solvent (c) is 100% by volume. If the amount of solvent (c) remaining is more than 10% by volume, the mechanical properties of the cured film may be reduced.

[0148] In the waiting step, in order to accelerate the evaporation of the solvent (c), a baking step may be performed in which the master mold 106 and the curable composition (A) are heated, or the atmospheric gas around the master mold 106 may be ventilated. The heating is performed, for example, at a temperature of 30° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower, and particularly preferably 90° C. or higher and 110° C. The heating time may be 10 seconds or higher and 600 seconds or lower. The baking step may be performed using a known heater such as a hot plate or an oven.

[0149] The waiting step is, for example, 0.1 to 600 seconds, preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 seconds, the droplets of the curable composition (A) may not bond sufficiently to each other, and a substantially continuous liquid film may not be formed. If the waiting step exceeds 600 seconds, the productivity decreases. Therefore, in order to suppress the decrease in productivity, the master molds that have completed the arrangement step may be sequentially transferred to the waiting step, and the waiting step may be performed in parallel for a plurality of master molds, and the master molds that have completed the waiting step may be sequentially transferred to the contact step.

[0150] In the waiting step, when the solvent (c) evaporates, a composition consisting of the components (as), (af), (a), (b) and (d), i.e., a substantially continuous liquid film 104 of the curable composition (A'), remains. The average film thickness of the curable composition (A) from which the solvent (c) has been evaporated (removed), i.e., the substantially continuous liquid film 104 of the curable composition (A'), becomes thinner than the liquid film 103 by the amount of the solvent (c) that has been evaporated. The pattern formation region of the master mold 106 is maintained in a state of being covered with the substantially continuous liquid film 104 of the curable composition (A') over the entire region.

[0151] <Contact process> 3(e), the contacting step is to bring the curable composition (A) from which the solvent (c) has been removed, i.e., a substantially continuous liquid film 104 of the curable composition (A'), into contact with the mold substrate 101. The contacting step includes a step of changing a state in which the curable composition (A') and the mold substrate 101 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other.

[0152] In the waiting step, the solvent (c) is removed from the curable composition (A) and the curable composition (A') becomes a substantially continuous liquid film 104 of the curable composition (A'), so that the volume of the gas entrapped between the master mold 106 and the mold substrate 101 decreases. Therefore, the spreading of the curable composition (A') in the contact step is quickly completed.

[0153] When the curing step includes a light irradiation step, it is preferable to use a substrate made of a light-transmitting material as the mold substrate 101. As the material for the mold substrate 101, for example, a light-transmitting resin such as glass, quartz, PMMA, or polycarbonate resin, a transparent metal deposition film, a flexible film such as polydimethylsiloxane, a photocured film, or a metal film is preferable. However, when a light-transmitting resin is used as the material for the mold substrate 101, a resin that is not dissolved in the components contained in the curable composition is selected. Quartz is suitable as a material for the mold substrate 101 because it has a small thermal expansion coefficient and small pattern distortion.

[0154] In the contact step, the pressure applied to the curable composition (A) when the mold substrate 101 is brought into contact with the curable composition (A) is not particularly limited, and is, for example, 0 MPa or more and 100 MPa or less. The pressure applied to the curable composition (A) when the mold substrate 101 is brought into contact with the curable composition (A) is preferably 0 MPa or more and 50 MPa or less. The pressure applied to the curable composition (A) when the mold substrate 101 is brought into contact with the curable composition (A) is more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0155] <Curing process> In the curing step, as shown in FIG. 3(f), the curable composition (A') is irradiated with irradiation light 107 as curing energy to cure the curable composition (A') and form a cured film. In the curing step, for example, the curable composition (A') is irradiated with irradiation light 107 through the mold substrate 101. More specifically, the curable composition (A') filled in the fine pattern of the master mold 106 is irradiated with irradiation light 107 through the mold substrate 101. As a result, the curable composition (A') filled in the fine pattern of the master mold 106 is cured to form a cured film 108 having a pattern.

[0156] In the irradiation step, the entire area of ​​the curable composition (A) filled in the fine pattern of the master mold may be irradiated with light, or only a part of the area (a limited area) may be irradiated with light. The light irradiation may be performed intermittently multiple times over the entire area of ​​the master mold, or may be performed continuously over the entire area of ​​the master mold. Furthermore, a first area of ​​the master mold may be irradiated with light in a first irradiation process, and a second area different from the first area of ​​the master mold may be irradiated with light in a second irradiation process.

[0157] <Mold release process> In the demolding step, as shown in schematic form in Fig. 3(g), the master mold 106 is separated from the cured film 108. By separating the patterned cured film 108 from the master mold 106, the cured film 108 having a pattern that is an inversion of the fine pattern of the master mold 106 is obtained in a self-supporting state on the mold substrate. Here, the cured film, i.e., the residual film, remains in the recesses of the cured film 108 having a pattern corresponding to the pattern of the master mold 106.

[0158] The method of separating the master mold 106 from the cured film 108 having the pattern is not particularly limited as long as a part of the cured film 108 having the pattern is not physically damaged during the separation, and various conditions are not particularly limited. For example, the mold substrate 101 may be fixed, and the master mold 106 may be moved away from the mold substrate 101. Alternatively, the master mold 106 may be fixed, and the mold substrate 101 may be moved away from the master mold 106. The master mold 106 may be separated from the cured film 108 having the pattern by moving both the master mold 106 and the mold substrate 101 in opposite directions.

[0159] When the glass transition temperature of the cured product of the curable composition is sufficiently higher than the temperature at the time of demolding, the cured product at the time of demolding is in a strong glass state, i.e., exhibits high mechanical strength, so that the pattern is less likely to collapse or be damaged by the impact of demolding. Therefore, when the demolding step is carried out at room temperature, the glass transition temperature of the cured product is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0160] As a method for measuring the glass transition temperature of a cured product, a method using a differential scanning calorimetry (DSC) or a dynamic viscoelasticity device can be applied. For example, consider the case where the glass transition temperature is measured using DSC. In this case, a straight line is obtained by extending the low-temperature side baseline (the DSC curve part in the temperature range where the test piece does not undergo transition or reaction) of the DSC curve of the cured product to the high-temperature side, and a tangent line is drawn at the point where the gradient of the curve of the stepwise change part of the glass transition is maximum. Then, the extrapolated glass transition onset temperature (Tig) is obtained from the intersection point of the straight line and the tangent line, and this can be determined as the glass transition temperature. The main device is STA-6000 (manufactured by Perkin Eimer), etc. On the other hand, when the glass transition temperature is measured using a dynamic viscoelasticity device, the temperature at which the loss sine (tan δ) of the cured product is maximum is defined as the glass transition temperature. The main device for measuring dynamic viscoelasticity is MCR301 (manufactured by Anton Paar), etc.

[0161] [Example] To supplement the above-described embodiment, a more specific example will be described.

[0162] <Conditions for obtaining a substantially continuous liquid film> Droplets of the curable composition (A) with a surface tension of 24 mN / m, a viscosity of 30 mPa·s, and a volume of 1 pL were dropped (arranged) on a flat substrate (mold substrate) in a square array at a predetermined interval. The behavior of each droplet of the curable composition (A) spreading on the substrate was calculated by a numerical calculation based on the Navier-Stokes equations approximated as a thin film with a free surface (lubrication theory). The thicknesses of the liquid film at the center of the drop position (thickest part of the liquid film on the substrate) and at the center of the square formed by the four droplets arranged in a square array (thinnest part of the liquid film on the substrate) 300 seconds after the drop of the curable composition (A) was dropped are shown in Table 1 below. It is assumed that the contact angle of the droplet of the curable composition (A) with respect to the substrate is 0°, and that the solvent (c) does not evaporate within 300 seconds after the drop of the curable composition (A) was dropped.

[0163] [Table 1]

[0164] Referring to Table 1, it can be seen that the entire substrate is covered with the curable composition (A) in Examples 1 to 5, in which the average film thickness is 130 nm or more, and furthermore, it can be seen that a flat liquid film is formed in which the thickness of the thickest part and the thickness of the thinnest part are approximately 0 nm in Examples 1 to 3, in which the average film thickness is 150 nm or more.

[0165] <Verification of controllability of average film thickness> The volume of the droplets of the curable composition (A) and the pitch of the square arrangement may be changed, but the thickness of the liquid film before the solvent (c) evaporates is 130 nm even in the minimum region, as described above. The thickness of the liquid film remaining after the solvent (c) evaporates is calculated from the state in which a substantially continuous liquid film is formed. The minimum value of the pitch of the square arrangement of the droplets of the curable composition (A) dropped on the substrate was set to 35 μm, and the maximum value of the thickness before the mold (master mold) was contacted was calculated. Since the minimum value of the thickness of the liquid film before the solvent (c) evaporates, in which a substantially continuous liquid film is formed, was calculated to be 130 nm as described above, the minimum value of the thickness of the liquid film before the mold is contacted can be calculated as the main component concentration (volume %) × 130 nm. Here, the main component concentration (volume %) was determined to be the value obtained by subtracting the volume % of the solvent (c) from 100 volume %. The case where the droplet volume of the curable composition (A) is 1.0 pL is shown in Table 2 below, and the case where the droplet volume of the curable composition (A) is 3.0 pL is shown in Table 3 below.

[0166] [Table 2]

[0167] [Table 3]

[0168] For example, in a photolithography process for manufacturing a semiconductor device, the film thickness required for film formation including pattern formation (or planarization) is 30 nm to 200 nm. With reference to Tables 2 and 3, when the main component concentration is 10 volume % or more, a film (thick film) having a thickness of 200 nm or more can be formed, and when the main component concentration is 20 volume % or less, a film (thin film) having a thickness of 30 nm or less can be formed.

[0169] <Evaluation of inkjet ejection and filling properties> According to Table 4 below, the curable composition (A) was mixed so that the total of the components (as), (a), (b) and (c) was 100% by weight, and the curable composition (A) was also mixed without using the components (a) and (c). The viscosity of these curable compositions (A) at 23°C was measured, and the results are shown in Table 5 below. The abbreviations shown in Table 4 are as follows. "Component (as)" TM-0701T: 3-methacryloxypropyltris(trimethylsiloxy)silane (manufactured by JNC) AC-SQ TA-100: Silsesquioxane derivative with acrylate group (manufactured by Toagosei) "Ingredients (af)" Viscoat 8F: 1H,1H,5H-octafluoropentyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) "Component (a)" IBXA: Isobornyl acrylate (Osaka Organic Chemical) DCP-A: Dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical) "Component (b)" Omnirad819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (IGM Resin) "Component (c)" tBuG-tBu: Ethylene glycol di-tert-butyl ether (manufactured by Nippon Nyukazai Co., Ltd.) (boiling point: 165°C) MDG-tBu: Diethylene glycol methyl-tert-butyl ether (manufactured by Nippon Nyukazai Co., Ltd.) (boiling point: 185°C) MFDG-tBu: 3,10,12,12-tetramethyl-2,5,8,11-tetraoxatridecane (manufactured by Nippon Nyukazai Co., Ltd.) (boiling point: 201°C) EOFP: Ethyl 5H-octafluorovalerate (Tokyo Chemical Industry Co., Ltd.) (boiling point: 142°C) PFEI: 2-perfluorohexylethyl iodide (manufactured by Daikin Industries, Ltd.) (boiling point: 180°C) PGMEA: Propylene glycol monomethyl ether acetate (Kanto Chemical) (boiling point: 146°C) 2-Trifluoromethyl-3-ethoxydodecafluorohexane (Fujifilm Wako Pure Chemical Industries, Ltd.) (boiling point: 130°C)

[0170] [Table 4]

[0171] [Table 5]

[0172] <Evaluation of inkjet ejection speed> The inkjet ejection speed was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). The curable compositions of Examples 12 to 29 and Comparative Examples 4 to 6 shown in Table 4 were filled into cartridges (1 pL). The ejection of droplets was observed with a built-in ejection observation camera, and the inkjet ejection speed was evaluated according to the following evaluation criteria. (Evaluation Criteria) AAA: At ejection speeds (flight speeds) of 6 m / sec or more, no deviation (distortion) in the impact position was observed. AA: At ejection speeds of 6 m / sec or more, a very slight deviation in the impact position was observed that had no practical effect. A: At ejection speeds of 4 m / sec or more, a very slight deviation in the impact position was observed that had no practical effect. B: No discharge.

[0173] <Evaluation of intermittent ejection of inkjet> The intermittent ejection property of the inkjet was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). The curable compositions of Examples 12 to 29 and Comparative Examples 4 to 6 shown in Table 4 were filled into a cartridge (1 pL). Then, droplets were ejected from all (12) nozzles at a frequency of 40 kHz for 1 second, and after a predetermined pause, one droplet was ejected from each nozzle. The state of ejection was observed with a built-in ejection observation camera, and the intermittent ejection property of the inkjet was evaluated according to the following evaluation criteria. (Evaluation Criteria) AAA: Even after a 10-second break, more than half of the nozzles were able to eject ink. AA: Even after a 5-second break, more than half of the nozzles were able to eject ink. A: Even after a 3-second break, more than half of the nozzles were able to eject. B: After a 3-second break, more than half of the nozzles were unable to eject.

[0174] <Evaluation of filling ability> Under conditions where the thickness of the liquid film before the solvent (c) volatilizes is 130 nm, the curable compositions (A) of Examples 12 to 29 and Comparative Examples 4 to 6 shown in Table 4 were discretely dropped (placed) on a silicon substrate. Then, the time until a substantially continuous liquid film was formed was measured, and the filling property was evaluated according to the following evaluation criteria. (Evaluation Criteria) AAA: A substantially continuous liquid film was formed within less than 100 seconds. AA: A substantially continuous liquid film was formed within 100 seconds or more and less than 200 seconds. A: A substantially continuous liquid film was formed within a time period of 200 seconds or more and less than 300 seconds. B: No substantial continuous liquid film was formed even after 300 seconds.

[0175] The evaluation results to date are shown in Table 6 below.

[0176] [Table 6]

[0177] It can be seen that when the viscosity of the curable composition at 23°C is 1.3 mPa·s or more and 60 mPa·s or less, inkjet ejection is good, and a viscosity of 5 mPa·s or more and 30 mPa·s or less is preferable, and a viscosity of 5 mPa·s or more and 15 mPa·s or less is even more preferable.

[0178] It can be seen that if the boiling point of the solvent contained in the curable composition is 135°C or higher, the intermittent ejection properties of the inkjet are good, and a boiling point of 145°C or higher and 250°C or lower is preferable, and a boiling point of 150°C or higher and 200°C or lower is further preferable.

[0179] If the surface tension of the non-volatile components excluding the solvent at 23°C is γ1 [mN / m] and the surface tension of the solvent at 23°C is γ2 [mN / m], it can be seen that the filling property is good if γ1 is 30 or less, γ2 is 24 or less, and γ1 is greater than γ2. It can also be seen that it is preferable that γ1-γ2>0.1, and more preferably that γ1-γ>1.

[0180] The disclosure of the present specification includes the following curable compositions, film-forming methods, and manufacturing methods.

[0181] (Item 1) A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), The curable composition has a viscosity of 1.3 mPa s or more and 60 mPa s or less at 23° C. and 1 atmospheric pressure, The content of the solvent (c) relative to the entire curable composition is 5% by volume or more and 95% by volume or less, The boiling point of the solvent (c) is 135° C. or higher at 1 atmospheric pressure; When the surface tension of a composition obtained by removing the solvent (c) from the curable composition at 1 atmospheric pressure is γ1 [mN / m], and the surface tension of the solvent (c) at 23°C at 1 atmospheric pressure is γ2 [mN / m], γ1 is 30 or less, γ2 is 24 or less, and γ1 is greater than γ2; A curable composition comprising:

[0182] (Item 2) 2. The curable composition according to item 1, wherein γ1-γ2>0.1 [mN / m].

[0183] (Item 3) 2. The curable composition according to item 1, wherein γ1-γ2>1 [mN / m].

[0184] (Item 4) 4. The curable composition according to any one of items 1 to 3, wherein the solvent (c) contains silicon atoms or fluorine atoms in an amount of 10 at % or less.

[0185] (Item 5) 5. The curable composition according to any one of items 1 to 4, wherein the polymerizable compound (a) includes a compound containing a silicon atom or a fluorine atom.

[0186] (Item 6) 6. The curable composition according to any one of items 1 to 5, wherein the boiling point of the solvent (c) is 130° C. or higher and lower than 250° C. at 1 atmospheric pressure.

[0187] (Item 7) 7. The curable composition according to any one of items 1 to 6, wherein the solvent (c) contains a polyhydric alcohol ether in which all of the hydroxyl groups of a polyhydric alcohol are alkyl-etherified.

[0188] (Item 8) 7. The curable composition according to any one of items 1 to 6, wherein the solvent (c) contains ethylene glycol di-tert-butyl ether or diethylene glycol methyl tert-butyl ether.

[0189] (Item 9) A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), The curable composition has a viscosity of 1.3 mPa s or more and 60 mPa s or less at 23° C. and 1 atmospheric pressure, The content of the solvent (c) relative to the entire curable composition is 5% by volume or more and 95% by volume or less, The solvent (c) includes ethylene glycol di-tert-butyl ether or diethylene glycol methyl tert-butyl ether. A curable composition comprising:

[0190] (Item 10) A film forming method for forming a film of a curable composition in a space between a mold and a substrate, comprising the steps of: A disposing step of disposing a plurality of droplets of the curable composition according to any one of items 1 to 9 discretely on the substrate or the mold; a waiting step of waiting until each of the plurality of droplets combines with an adjacent droplet to form a liquid film; a contacting step of contacting the mold with the liquid film after the waiting step; A film forming method comprising the steps of:

[0191] (Item 11) Item 11. The film forming method according to item 10, wherein in the waiting step, the process waits until the solvent contained in the liquid film evaporates and the content of the solvent becomes 10 volume % or less with respect to the entire liquid film.

[0192] (Item 12) 12. The film forming method according to item 10 or 11, wherein in the waiting step, the substrate is heated under conditions of 30° C. or higher and 200° C. or lower for 10 seconds or higher and 600 seconds or lower.

[0193] (Item 13) In the disposing step, droplets of the curable composition having a volume of 1.0 pL or more are placed at 130 droplets / mm 2 13. The method for forming a film according to any one of items 10 to 12, wherein the particles are arranged at a density of at least 100 nm.

[0194] (Item 14) 14. The method for forming a film according to any one of items 10 to 13, wherein an average film thickness, which is a value obtained by dividing the volume of the curable composition remaining after the waiting step by an area of ​​a film-forming region where the film is to be formed, is 10 μm or less.

[0195] (Item 15) the mold comprises a master mold; The substrate includes a mold base material. 15. The film forming method according to any one of items 10 to 14,

[0196] (Item 16) the master mold includes a pattern; The method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a pattern corresponding to the pattern of the master mold. Item 16. The film forming method according to item 15,

[0197] (Item 17) 17. The film forming method according to any one of items 10 to 16, wherein in the disposing step, the plurality of droplets are discretely disposed by using an inkjet method.

[0198] (Item 18) Item 17. A method for producing a replica mold, comprising the step of forming a cured film having a pattern corresponding to the pattern of the master mold on a mold substrate by using the film formation method according to item 16.

[0199] The invention is not limited to the above-described embodiments, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention. [Explanation of symbols]

[0200] 101: Mold substrate 102: Liquid droplet 103: Liquid film 104: Liquid film 105: Solvent 106: Master mold 107: Irradiation light 108: Cured film

Claims

1. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), The curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23° C. and 1 atmosphere, The content of the solvent (c) relative to the entire curable composition is 5 vol% or more and 95 vol% or less, The boiling point of the solvent (c) is 135° C. or higher at 1 atmospheric pressure; When the surface tension of a composition obtained by removing the solvent (c) from the curable composition at 1 atmospheric pressure is γ1 [mN / m], and the surface tension of the solvent (c) at 23° C. and 1 atmospheric pressure is γ2 [mN / m], γ1 is 30 or less, γ2 is 24 or less, and γ1 is greater than γ2; A curable composition comprising:

2. The curable composition according to claim 1, characterized in that γ1-γ2>0.1 [mN / m].

3. The curable composition according to claim 1, characterized in that γ1-γ2>1 [mN / m].

4. 2. The curable composition according to claim 1, wherein the solvent (c) contains silicon atoms or fluorine atoms in an amount of 10 at % or less.

5. The curable composition according to claim 1 , wherein the polymerizable compound (a) comprises a compound containing a silicon atom or a fluorine atom.

6. 2. The curable composition according to claim 1, wherein the boiling point of the solvent (c) is 130° C. or higher and lower than 250° C. at 1 atmospheric pressure.

7. 2. The curable composition according to claim 1, wherein the solvent (c) contains a polyhydric alcohol ether in which all of the hydroxyl groups of a polyhydric alcohol have been alkyl-etherified.

8. The curable composition according to claim 1 , wherein the solvent (c) comprises ethylene glycol di-tert-butyl ether or diethylene glycol methyl tert-butyl ether.

9. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), The curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23° C. and 1 atmosphere, The content of the solvent (c) relative to the entire curable composition is 5 vol% or more and 95 vol% or less, The solvent (c) includes ethylene glycol di-tert-butyl ether or diethylene glycol methyl tert-butyl ether; A curable composition comprising:

10. A film forming method for forming a film of a curable composition in a space between a mold and a substrate, comprising the steps of: A disposing step of disposing a plurality of droplets of the curable composition according to claim 1 or 9 discretely on the substrate or the mold; a waiting step of waiting until each of the plurality of droplets combines with an adjacent droplet to form a liquid film; a contacting step of contacting the mold with the liquid film after the waiting step; A film forming method comprising the steps of:

11. 11. The film forming method according to claim 10, wherein the waiting step waits until the solvent contained in the liquid film volatilizes and the content of the solvent becomes 10% by volume or less with respect to the entire liquid film.

12. 11. The film forming method according to claim 10, wherein in the waiting step, the substrate is heated at a temperature of 30° C. or more and 200° C. or less for a period of 10 seconds or more and 600 seconds or less.

13. In the disposing step, droplets of the curable composition having a volume of 1.0 pL or more are placed at 130 droplets / mm ２ 11. The film forming method according to claim 10, wherein the particles are arranged at a density of at least 100 nm.

14. 11. The film forming method according to claim 10, wherein an average film thickness, which is a value obtained by dividing the volume of the curable composition remaining after the waiting step by an area of ​​the film formation region where the film is formed, is 10 μm or less.

15. the mold comprises a master mold; The substrate includes a mold base material. The film forming method according to claim 10 .

16. the master mold includes a pattern; The method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a pattern corresponding to the pattern of the master mold. The film forming method according to claim 15 .

17. 11. The film forming method according to claim 10, wherein in the disposing step, the plurality of droplets are discretely disposed by using an inkjet method.

18. A manufacturing method, comprising the step of forming a cured film having a pattern corresponding to a pattern of a master mold on a mold substrate by using the film formation method according to claim 16 to manufacture a replica mold.

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