JP2009051017A - Photocurable composition for photo-nanoimprint lithography and manufacturing method of substrate with pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition for photo-nanoimprint lithography, which excels in curability of the surface and the inside and can form a resist pattern excellent in exfoliation from a mold. <P>SOLUTION: The photocurable composition for the photo-nanoimprint lithography comprises (a) a polymerizable compound, (b) a photopolymerization initiator and (c) a surface-active photo polymerization initiator, and its viscosity at 25°C is ≥3 mPa s and ≤30 mPa s. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photocurable composition for optical nanoimprint lithography and a method for producing a patterned substrate.

  The nanoimprint lithography method is a method developed from an embossing technique that is well-known in optical disc production. The concave / convex pattern of a mold base (generally called a mold, stamper, template, etc.) on which a concave / convex pattern is formed. Is pressed onto a resist film, and the resist film is mechanically deformed to precisely transfer a fine pattern. Once a mold is made, it is economical because nanostructures can be easily and repeatedly molded, and it is a nano-processing technology that has few harmful wastes and emissions, so in recent years it has been expected to be applied in various fields. Yes.

  There are two main types of nanoimprint lithography methods: a technique using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1) and a technique using a photocurable composition (for example, see Non-Patent Document 2). It has been known. When a photocurable composition is used, the concave / convex pattern of the mold is pressed against the photocurable film (resist film) formed on the substrate, light is irradiated through the mold and / or the substrate, and the photocurable film is photocured. After that, the mold is peeled off to form a resist pattern.

  As a photocurable composition, a photosensitive composition containing a surface active photoinitiator capable of improving the surface strength of a formed cured film is known (for example, see Patent Documents 1 to 3). . On the other hand, a method using a curable material containing a polymerizable compound having a fluorine content of 40 to 70% by mass is known as a pattern forming method with good mold releasability in nanoimprint lithography (for example, Patent Documents). 4).

JP-T-2004-515611 JP-T-2004-522819 JP-T-2004-525994 JP 2006-114882 A S.Chou et al.:Appl.Phys.Lett.Vol.67,114,3314 (1995) M.Colbun et al,: Proc.SPIE, Vol.676,78 (1999)

  However, the photosensitive compositions described in Patent Documents 1 to 3 have insufficient strength inside the cured film and cannot be applied to optical nanoimprint lithography. Further, it has been clarified that the curable material described in Patent Document 4 has insufficient surface curing.

  The present invention has been made in view of the above, and for optical nanoimprint lithography capable of forming a resist pattern having excellent surface and internal curability and excellent mold releasability even when cured with a small exposure amount. It aims at providing the manufacturing method of the board | substrate with a pattern using the photocurable composition and the said photocurable composition for optical nanoimprint lithography, and makes it a subject to achieve this objective.

As a result of earnest study, the present inventor can achieve both the degree of cure inside the resist pattern formed and the degree of cure of the surface by using a photopolymerization initiator and a surface-active photopolymerization initiator in combination. The present inventors have obtained the knowledge that the releasability of the film can be improved, and have completed the present invention based on such knowledge.
That is, specific means for achieving the above-described problem are as follows.

<1> Light containing a (a) polymerizable compound, (b) a photopolymerization initiator, and (c) a surface-active photopolymerization initiator, and having a viscosity at 25 ° C. of 3 mPa · s to 30 mPa · s. It is a photocurable composition for nanoimprint lithography.
<2> The (c) surfactant photopolymerization initiator is an optionally substituted alkyl group having 3 to 30 carbon atoms, an optionally substituted siloxane group, and an optionally substituted fluorinated alkyl. It is a compound which has at least 1 sort (s) chosen from group, It is a photocurable composition for optical nanoimprint lithography as described in <1> characterized by the above-mentioned.

<3> The photocurable composition for optical nanoimprint lithography according to <1> or <2>, wherein a viscosity at 25 ° C. is 3 mPa · s or more and 18 mPa · s or less.
<4> Further, (d) any one of <1> to <3>, further comprising (d) at least one selected from a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant The photocurable composition for optical nanoimprint lithography according to any one of the above.

<5> A step of applying a photocurable composition for optical nanoimprint lithography according to any one of <1> to <4> on a substrate to form a photocurable layer, and a mold having an uneven pattern A step of deforming the photocurable layer by press-contacting the uneven pattern and the photocurable layer formed on the substrate; and a side of the substrate opposite to the side on which the photocurable layer is formed. And / or curing the deformed photocurable layer by irradiating the deformed photocurable layer with light from the opposite side of the mold that is in contact with the photocurable layer, and the substrate. The mold is peeled off, and a reverse pattern of the concavo-convex pattern is formed on the substrate.

<6> The method according to <5>, further comprising a step of etching the substrate using the reverse pattern formed on the substrate as a mask, and a step of peeling the reverse pattern from the substrate after etching. It is a manufacturing method of the board | substrate with a pattern of description.

  According to the present invention, even when cured with a small amount of exposure, the photocurable composition for optical nanoimprint lithography that can form a resist pattern having excellent surface and internal curability and excellent peelability from the mold, And the manufacturing method of the board | substrate with a pattern using the said photocurable composition for optical nanoimprint lithography can be provided.

≪Photocurable composition for optical nanoimprint lithography≫
The photocurable composition for optical nanoimprint lithography of the present invention (hereinafter also referred to as “photocurable composition of the present invention”) comprises (a) a polymerizable compound, (b) a photopolymerization initiator, and (c). And a surface active photopolymerization initiator, and the viscosity at 25 ° C. is 3 to 30 mPa · s.
By forming the photocurable composition as described above, when the resist pattern is formed using the photocurable composition, the surface and internal curability of the resist pattern can be maintained even when cured with a small exposure amount. This improves the releasability from the mold (hereinafter also referred to as “releasability from the mold” and “releasability”).
The reason why the above effect is obtained is not clear, but one of the reasons is estimated as follows.
That is, polymerization inside the pattern mainly proceeds by the component b). On the other hand, the component (c) can easily increase the concentration in the vicinity of the pattern surface after coating and drying, and thus can promote effective polymerization on the pattern surface and inside the pattern. It is presumed that the mold releasability is improved by the synergistic effect of the progress of curing of the pattern surface and the surface active function of the component (c).

In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Meta (acrylate) represents acrylate and methacrylate, meth (acryl) represents acryl and methacryl, and meth (acryloyl) represents acryloyl and methacryloyl. Moreover, in this specification, a monomer and a monomer are the same. The monomer in the present invention is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers.
The nanoimprint lithography referred to in the present invention is preferably pattern transfer having a size of about several μm to several tens of nm.

The photocurable composition of the present invention has a viscosity at 25 ° C. of 3 to 30 mPa · s. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified.
When the viscosity is greater than 30 mPa · s, when a mold having a fine uneven pattern is brought into close contact with the photocurable composition, the photocurable composition becomes difficult to flow into the cavity of the concave portion of the mold, and air is taken in. Since it becomes easy, it becomes easy to cause a bubble defect, and a residue tends to remain after photocuring in a mold convex part. Moreover, since the viscosity of the optical nanoimprint composition disclosed so far in the latest resist material handbook, P1, 103-104 (2005, published by the Information Organization) has a viscosity of about 50 mPa · s, bubble defects and photocuring Since there was a problem that residues were likely to remain in the recesses of the mold later, it could be applied only to limited applications. For example, it has been difficult to expand into microfabrication applications such as semiconductor integrated circuits and thin film transistors for liquid crystal displays. The photocurable composition of the present invention can be suitably applied to these applications, and other applications such as magnetic fields such as flat screens, microelectromechanical systems (MEMS), sensor elements, optical disks, and high-density memory disks. Recording media, optical components such as diffraction gratings and relief holograms, nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, microlens arrays, immunoassay chips, DNA separation chips, microreactors, It can be widely applied to the production of nanobio devices, optical waveguides, optical filters, photonic liquid crystals, and the like.

  If the viscosity is less than 3 mPa · s, problems of substrate coating suitability and mechanical strength of the film are reduced. Specifically, when the viscosity is too low, there is a problem that unevenness on the surface occurs during application of the composition, or the composition flows out of the substrate during application.

From the viewpoint of further suppressing the residue and further improving applicability, the viscosity of the photocurable composition at 25 ° C. is preferably 3 to 18 mPa · s, and more preferably 4 to 18 mPa · s.
Hereinafter, each component of the photocurable composition of the present invention will be described.

<(A) Polymerizable compound>
The photocurable composition of the present invention contains at least one polymerizable compound.
The polymerizable compound preferably contains a photo radical polymerizable unsaturated monomer and / or a photo cationic polymerizable unsaturated monomer.

  As a specific example of the photoradically polymerizable unsaturated monomer that can be used in the present invention, a monomer having an ethylenically unsaturated bond-containing group is preferably used.

  Examples of monomers having one ethylenically unsaturated bond-containing group include 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyl Roxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, aliphatic epoxy (Meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) Cresol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, Ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate Over DOO, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate,

Methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate,

Methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epi Chlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) ) Acrylate, polyethylene glycol-polypropylene glycol (meta Acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone Modified tetrahydrofurfuryl (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, trifluoroethyl (meth) acrylate, urethane mono (meth) acrylate, adamantyl ( (Meth) acrylate, 3-hydroxyadamantyl (meth) acrylate,

p-isopropenylphenol, 4-vinylpyridine, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-hydroxyethylacrylamide, N, N-dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, styrene, α-methylstyrene, acrylonitrile, vinylcaprolactam, vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, imide acrylate, vinyloxazoline and the like.

  Among these, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate N-vinyl-2-pyrrolidone, N-acryloylmorpholine and the like have low viscosity and excellent volatility, and are preferably used in the present invention.

  In addition, for the purpose of improving the releasability from the mold, the adhesion to the substrate, and the coating property, silicone compounds such as (meth) acryloyl-modified silicone, vinyl-modified silicone, and silicone hexaacrylate, and commercially available silicone acrylate (trade name) : Desolite Z7500 (manufactured by JSR), SHC200, SHC900, UVHC85XX series, UVHC11XX series (all manufactured by GE Toshiba Silicone), dimethylsiloxane monomethacrylate (FM0711, FM0721, FM0725 (all manufactured by Chisso Corporation)), dimethylsiloxane Dimethacrylate (DMS-V22 (manufactured by Chisso Corporation)) and Ebercryl-1360 (manufactured by Daicel Chemical Industries)) can also be used. Similarly, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl (meth) acrylate, (perfluorohexyl) ethyl (meth) A compound having a fluorine atom such as acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate can also be used.

  Further, in order to improve the adhesion to the substrate, for example, ethyl (meth) acrylate acid phosphate, 3-chloro-2-acid phosphoxypropyl (meth) acrylate, polyoxyethylene glycol (meth) acrylate acid phosphate, 2- Phosphoric acid-containing (meth) acrylic monomers such as hydroxyethyl (meth) acrylate acid phosphate and 2- (meth) acryloyloxyethyl caproate acid phosphate can also be used in the present invention.

In order to improve the substrate adhesion of the photocurable composition of the present invention and the mechanical properties of the film, an isocyanate-based (meth) acrylate compound can also be included in the photocurable composition of the present invention.
Specific examples of the isocyanate-based (meth) acrylate compound include isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate n-propyl (meth) acrylate, isocyanate isopropyl (meth) acrylate, and isocyanate n-butyl (meth) ) Acrylate, isocyanate isobutyl (meth) acrylate, isocyanate sec-butyl (meth) acrylate, isocyanate alkyl (meth) acrylate such as isocyanate tert-butyl (meth) acrylate; (meth) acryloylmethyl isocyanate, (meth) acryloylethyl isocyanate, (Meth) acryloyl n-propyl isocyanate, (meth) acryloyl isopropyl isocyanate, (me ) Acryloyl n- butyl isocyanate, (meth) acryloyl Louis Seo-butyl isocyanate, (meth) acryloyl sec- butyl isocyanate, (meth) acryloyl tert- butyl isocyanate (meth) acryloyl alkyl isocyanate are exemplified.

Further, (meth) acrylate having a dioxolane skeleton can also be used in the photocurable composition of the present invention.
Specific examples of the (meth) acrylate having a dioxolane skeleton include 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3. -Dioxolane, 4-acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl -2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, and the like. .
Among them, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane and the like can be mentioned.

  Examples of monomers having two ethylenically unsaturated bond-containing groups that can be used in the present invention include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and di (meth). Acrylic isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexane Diol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di ( Meta) Acu Rate, EO-modified bisphenol F di (meth) acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, Propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate,

Poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol (di) acrylate, neopentyl glycol Modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di ( Data) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinyl ethylene urea, divinyl propylene urea and the like.

  Furthermore, in order to improve the adhesiveness with the substrate, a phosphoric acid-containing di (meth) acrylic monomer such as EO-modified phosphoric acid di (meth) acrylate can also be used in the present invention.

  Among these, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate and the like have a low viscosity among the bifunctional monomers and are preferably used in the present invention.

  Examples of polyfunctional monomers having three or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, penta Erythritol triacrylate, EO-modified phosphate triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meta) ) Acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate Dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Examples include pentaerythritol ethoxytetra (meth) acrylate and pentaerythritol tetra (meth) acrylate.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. have a low viscosity among the trifunctional or higher monomers, Preferably used.

  When using one having two or more photopolymerizable functional groups in one molecule, a large amount of photopolymerizable functional groups are introduced into the composition as described above, so that the crosslink density of the composition is very high. Therefore, the effect of improving various physical properties after curing is high. Among the various physical properties after curing, heat resistance and durability (abrasion resistance, chemical resistance, water resistance) are improved by increasing the crosslink density, and even when exposed to high heat, friction or solvent, Deformation, disappearance, and damage are less likely to occur.

  In the photocurable composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or polymer having a molecular weight higher than that of the polyfunctional monomer can be blended within a range that achieves the object of the present invention. . Polyfunctional oligomers having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, polyepoxy acrylate, oligomers having a bulky structure such as phosphazene skeleton, adamantane skeleton, cardo skeleton, norbornene skeleton, or Examples thereof include polymers.

As the polymerizable unsaturated monomer that can be used in the present invention, a compound having an oxirane ring can also be employed. Examples of the compound having an oxirane ring include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycol, Examples thereof include glycidyl ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds and epoxidized polybutadienes.
These compounds can be used alone or in combination of two or more thereof.

As an epoxy compound that can be used in the present invention, an epoxycyclohexyl group-containing compound and a glycidyl group-containing compound are preferable. The epoxycyclohexyl group-containing compound is excellent in cationic polymerizability. The glycidyl group compound imparts flexibility to the polymer, increases the mobility of the polymerization system, and further improves the curability.
In particular, alicyclic epoxy compounds are preferred because of their low viscosity and fast curing speed.

  Examples of the epoxycyclohexyl group-containing compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4- Epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4 '-Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate) ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ -Valerolactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1.2: 8,9 diepoxy limonene and the like can be exemplified.

  Among these components, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1.2: 8,9 diepoxy limonene is preferred.

  Commercially available products that can be suitably used as this component include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403 (above, manufactured by Daicel Chemical Industries, Ltd.), KRM -2100, KRM-2110, KRM-2199 (manufactured by Asahi Denka Kogyo Co., Ltd.). The said component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the glycidyl group-containing epoxy compound that can be preferably used include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, Brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ethers; Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; long aliphatic chains Diglycidyl esters of dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids Etc. can be illustrated.

  Among these components, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

  Examples of the polymerizable unsaturated monomer that can be used in the present invention include oxetane compounds. The oxetane compound is not particularly limited as long as it is a compound having an oxetane ring in the molecule. For example, the oxetane described in JP-A-8-143806, JP-A-2001-220526, and JP-A-2001-310937 is disclosed. A compound can be used conveniently. In addition, a silsesquioxane compound having an oxetanyl group or a fluorine compound having an oxetanyl group may be used to improve heat resistance, film hardness, and releasability.

  Examples of the compound having one oxetane ring in the molecule include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, and (3-ethyl-3-oxetanylmethoxy) methyl. Benzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3- Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl- 3-Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl) 3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether,

Dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3 -Ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl ( -Ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ) Ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3- (4-bromobutoxymethyl) -3-methyloxetane, (3-methyloxetane-3-yl) methylbenzoate and the like.

  Examples of compounds having two or more oxetane rings in the molecule include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanedii Rubis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] biphenyl, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane Tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane,

Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether,

Caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanyl) Methyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl- 3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether,

Poly (3- (4-bromobutoxymethyl) -3-methyloxetane), N-oxetan-2-ylmethoxymethylacrylamide, 3,5-bis (3-ethyl-3-oxetanylmethoxy) benzoic acid, 3,5 -Bis (3-ethyl-3-oxetanylmethoxy) benzoic acid methyl ester, 5- (3-ethyl-3-oxetanyl) isophthalic acid, 1,1,1-tris [4 (3-ethyl-3-oxetanylmethoxy) Phenyl] ethane and the like can be exemplified, and these can be used alone or in combination of two or more.

The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method. For example, Pattyson (DBPattison, J. Am. Chem. Soc., 3455, 79 (1957)) Discloses a method for synthesizing an oxetane ring from a diol.
In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included.

  Examples of commercially available oxetane compounds include OXT101 manufactured by Toa Gosei Co., Ltd. (3-ethyl-3-hydroxyoxetane, OXT221 manufactured by Toa Gosei Co., Ltd., di [1-ethyl (3-oxacenyl) methyl ether], manufactured by Toa Gosei Co., Ltd. 1 , 4-bis {[(3-ethyl-3-octacel) methoxymethyl] benzene, OXT211 (3-ethyl-3- (phenoxymethyl) octacene) manufactured by Toa Gosei Co., Ltd., MPO (3,3-dimethyl) produced by Toa Gosei Co., Ltd. -2- (p-methoxyphenyl) oxetane), UTE Kosan ETERNACOLL OXBP can be used.

  Among these, the number of oxetane rings in the molecule of the oxetane compound that can be suitably used as the constituent component of the photocurable composition of the present invention is preferably 1 to 10, and more preferably 1 to 4. Specifically, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis (3-ethyl-3- Oxetanylmethoxy) ethanetrimethylolpropanetris (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-oxetanylmethoxybenzene and the like.

A vinyl ether compound is mentioned as a polymeric compound which can be used by this invention.
The vinyl ether compound may be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, cyclohexane dimethanol monovinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol diester. Vinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, Trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexane All divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol Diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene Nyl ether, pentaerythritol tetraethylene vinyl ether, isobornyl vinyl ether, menthyl vinyl ether, cyclopentyl vinyl ether, 1,1,1-tris [4- (2-vinyloxyethoxy) phenyl] ethane, bisphenol A divinyloxy ethyl ether, etc. These vinyl ether compounds are useful in both radical polymerization and cationic polymerization, and are characterized by low viscosity.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

  A styrene derivative is mentioned as a polymeric compound which can be used by this invention. Examples of styrene derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p-hydroxy. Examples of the vinyl naphthalene derivative include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene, 4 Examples of N-vinyl compounds such as -methoxy-1-vinylnaphthalene include N-vinylcarbazole, N-vinylpyrrolidone, N-vinylindole, N-vinylpyrrole, N-vinylphenothiazine, N-vinylacetanilide, N -Vinylethylacetamide, N-vinylsuccinimide, - it can be exemplified vinyl phthalimide, N- vinyl caprolactam, the N- vinylimidazole like.

  As a polymerizable compound that can be used in the present invention, propenyl ether and butenyl ether can be blended. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbonene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) Decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene carbonate, and the like can be suitably applied.

  Various polyol compounds can be further blended in the photocurable composition of the present invention as necessary. Examples of polyols that can be suitably applied include ethylene glycol, glycerin, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, spiroglycol, various polyether polyols, various polyester polyols, and various caprolactone polyols. it can. The addition of such various polyols can improve the curing rate. Among these polyols, the hydroxyl group equivalent is small, and is excellent in compatibility with the epoxy compound and / or oxetane compound, which is the main reaction component of the photocationic curable composition, and the viscosity increase by addition is small, so ethylene glycol and trimethylolpropane Can be suitably applied in the present invention.

  The polyol preferably has 2 or more hydroxyl groups in one molecule, more preferably 2 to 6 hydroxyl groups in one molecule. When a polyol having two or more hydroxyl groups in one molecule is used, the effect of improving the photocurability is sufficiently obtained, and the mechanical properties of the resulting photocurable composition tend not to be lowered. On the other hand, the number of hydroxyl groups in one molecule of polyol is preferably 6 or less from the viewpoint of moisture resistance.

  Examples of such polyols include polyether polyols, polycaprolactone polyols, polyester polyols obtained by modification with a polyester composed of a dibasic acid and a diol.

  Of the above polyols, polyether polyols are preferred. For example, a polyether obtained by modifying a trihydric or higher polyhydric alcohol such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, and quadrol with a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Mention may be made of polyols. Specifically, EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerin, PO-modified glycerin, tetrahydrofuran-modified glycerin, EO-modified pentaerythritol, PO-modified pentaerythritol, tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO-modified quadrole, polyoxyethylene diol, polyoxypropylene diol, polyoxytetramethylene diol, polyoxybutylene diol, polyoxybutylene-oxy Examples include ethylene copolymer diol. Of these, EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerin, and PO-modified sorbitol are preferable.

  Commercially available polyether polyols include Sannix TP-400, Sannix GP-600, Sannix GP-1000, Sannix SP-750, Sannix GP-250, Sannix GP-400, Sannix GP-600 (Sanyo Kasei Co., Ltd.), TMP-3Glycol, PNT-4 Glycol, EDA-P-4, EDA-P-8 (Nippon Emulsifier Co., Ltd.), G-300, G-400, Examples thereof include G-700, T-400, EDP-450, SP-600, and SC-800 (manufactured by Asahi Denka Kogyo Co., Ltd.).

  Specific examples of the polycaprolactone polyol include caprolactone-modified trimethylolpropane, caprolactone-modified glycerin, caprolactone-modified pentaerythritol, and caprolactone-modified sorbitol.

  Examples of commercially available products of polycaprolactone polyol include TONE 0301, TONE 0305, and TONE 0310 (above, Union Carbide), and examples of polyester polyols that are available are Plaxel 303, Plaxel 305, Plaxel 308 (above, Daicel Chemical Industries, Ltd.), etc. Can be mentioned.

  Said polyol can be used individually by 1 type or in combination of 2 or more types. The molecular weight of the polyol used is preferably from 100 to 50,000, more preferably from 160 to 20,000. By using a polyol having a molecular weight within this range, a photocurable composition with better shape stability and physical property stability can be obtained, and the resulting photocurable composition has an excessively high viscosity. It tends to be able to prevent the elastic modulus from decreasing.

As the polymerizable unsaturated compound that can be used in the present invention, as a photocationic polymerizable reactive component, the above-mentioned one having a cationic reactive single functional group such as an epoxy group, an oxetane group, or a vinyl group in one molecule. Not only compounds but also compounds having plural kinds of functional groups in the same molecule can be applied.
For example, a compound containing a vinyl ether group and an epoxy group in the same molecule or a reactive compound having a propenyl ether group and an epoxy group can be used.
Moreover, as a reactive component of photocationic polymerizable property and radical photopolymerizable property, 3-methyl-3-oxetanylmethyl acrylate (Osaka Organic Chemical Industries, Ltd., OXE-10), 3-methyl-3-oxetanylmethyl acrylate (Osaka) Organic Chemical Industry Co., Ltd., OXE-30), vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (manufactured by Daicel Chemical Industries, Celoxide 2000), (meth) acrylate compounds having an oxetane ring (Ube Industries, ETERNACOLL OXMA, etc.) ) Etc. can also be used.

The photocurable composition of the present invention may contain a hybrid with a reactive component having a radical curing mechanism, if necessary. Hybridization is performed by, for example, mixing a radical curable component such as an acroyl group-containing compound and a radical curing initiator as necessary with a cationic curable component containing an epoxy compound, an oxetane compound, a vinyl compound or the like as a reactive compound. can get. Preferred examples of the acroyl group-containing compound include compounds having a cationic polymerizable vinyl ether and a radical polymerizable acroyl group in the same molecule such as (meth) acrylic acid- (vinyloxy) ethyl.
Examples of commercially available hybrid compounds include 3-methyl-3-oxetanylmethyl acrylate (Osaka Organic Chemical Industry, OXE-10), 3-methyl-3-oxetanylmethyl acrylate (Osaka Organic Chemical Industry, OXE-30), (meth) acrylate compounds having an oxetane ring (Ube Industries, ETERNACOLL OXMA, etc.) 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (2-vinyloxyethoxy) ethyl methacrylate ( Nippon Shokubai Co., Ltd., VEEA), 3,4-epoxycyclohexyl (meth) acrylate (manufactured by Daicel Chemical Industries, Cyclomers A400, A100) and the like.

  Next, the preferable blend form of the photoradically polymerizable monomer in the photocurable composition of the present invention will be described. The photocurable composition of the present invention comprises a polymerizable unsaturated monomer having a viscosity of 30 mPa · s or less (preferably a monomer having one ethylenically unsaturated bond-containing group, a monomer having two, and A form in which one or more of the three monomers is included) and blended so as to include 50% by mass or more is preferable.

  In the present invention, the photoradically polymerizable monomer having one unsaturated bond-containing group is usually used as a reactive diluent, and is effective for lowering the viscosity of the photocurable composition of the present invention. The total polymerizable compound is preferably added in an amount of 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting the ratio of the monomer having one unsaturated bond-containing group to 80% by mass or less, the mechanical strength, etching resistance, and heat resistance of the cured film obtained by curing the photocurable composition of the present invention are improved. When it is used as a mold material for optical nanoimprint, it tends to be able to prevent the mold from swelling and deteriorating the mold, which is preferable. On the other hand, monomers having one and / or two unsaturated bond-containing groups are better as reactive diluents, so monomers having one or two unsaturated bond-containing groups are added. It is preferable.

  The monomer having two unsaturated bond-containing groups is preferably added in an amount of 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less of the total polymerizable compound. The proportion of the monomer having one and / or two unsaturated bond-containing groups is a total polymerizable compound, preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass. % Is added.

  The ratio of the polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably the total polymerizable unsaturated monomer. It is added in the range of 60% by mass or less. By setting the ratio of the polymerizable unsaturated monomer having 3 or more polymerizable unsaturated bond-containing groups to 80% by mass or less, the viscosity of the composition can be easily adjusted by the viscosity range of the present invention. .

  Furthermore, the preferable blend form of the photocationically polymerizable monomer in the photocurable composition of the present invention will be described. The range of the blend of the photocationic monomer is not particularly limited as long as it does not deviate from the range of the viscosity condition of the present invention.

  In the present invention, a cationically polymerizable monomer having one cationically polymerizable group is usually used as a reactive diluent and is effective in reducing the viscosity of the photocurable composition of the present invention. It is preferably added in an amount of 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less. By setting the ratio of the monomer having one cationic polymerizable group to 95% by mass or less, it is preferable because the mechanical strength, etching resistance, and heat resistance of the cured film tend to be kept better, Further, when an organic polymer is used as a mold material for optical nanoimprinting, there is a tendency that swelling of the mold can be suppressed and deterioration of the mold can be reduced. On the other hand, since a monomer having one and / or two cationically polymerizable groups is used as a reactive diluent, addition of a monomer having one or two cationically polymerizable groups is essential. The amount of the monomer is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

  As a polymeric compound in this invention, 50 mass% or more is preferable as content in all the polymeric compounds of the polymerizable unsaturated monomer whose viscosity in 25 degreeC is 30 mPa * s or less. Here, the content is preferably 60% by mass or more, and more preferably 75% by mass or more. An upper limit is not specifically limited, It is a numerical value from which the sum total with another essential component will be 100 mass%.

In general, in order to adjust the viscosity of the composition, it is possible to blend various monomers, oligomers, and polymers having different viscosities. In particular, the viscosity of the photocurable composition of the present invention is described above. From the viewpoint of preparing in a preferable range, it is preferable to contain 50% by mass or more of a polymerizable unsaturated monomer having a viscosity of 30 mPa · s or less.
That is, if the proportion of the polymerizable unsaturated monomer having a viscosity of 30 mPa · s or less is 50% by mass or more in the mass ratio in the total composition, bubble defects due to the air taken into the mold recesses, or photocuring It is possible to more effectively prevent the residue of the subsequent mold convex portion.

<(B) Photopolymerization initiator>
The photocurable composition of the present invention contains at least one photopolymerization initiator.
As the photopolymerization initiator in the present invention, one having activity with respect to the wavelength of the light source to be used can be blended, and an appropriate active species depending on the difference in reaction mode (for example, radical polymerization or cationic polymerization). The one that generates Moreover, only one type of photopolymerization initiator may be used, or two or more types may be used.

As the photopolymerization initiator in the present invention, a photoradical polymerization initiator can be used.
As the radical photopolymerization initiator, for example, a commercially available initiator can be used.
Examples of these include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1 available from Ciba Specialty Chemicals. -One, Irgacure (R) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (R) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (R) 651 (2,2-dimethoxy-1, 2-diphenylethane-1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl) -1 [4-Methylthiol Nyl] -2-morpholinopropan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4 Trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) ) Phenyl] -2- (O-benzoyloxy) Beam),

Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime),

Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) available from BASF, Lucirin TPO-L (2,4,6-trimethylbenzoylphenylethoxyphosphine oxide), ESACURE available from Sierra Hegner, ESACUR Japan 1001M (1- [4-Benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one,

Adekaoptomer (registered trademark) N-1414 (carbazole phenone series), Adekaoptomer (registered trademark) N-1717 (acridine series), Adekaoptomer (registered trademark) N-1606 (available from Asahi Denka Co., Ltd.) Triazine),

TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, TME- manufactured by Sanwa Chemical Triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine) (2- (4- Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine),

TAZ-113 manufactured by Midori Chemical (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 manufactured by Midori Chemical (2 -(3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine),

Benzophenone, 4,4′-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2- Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether , Benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, dietoxy Acetophenone and dibenzosuberone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (Methylphenylthio) phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1, 2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4 -(Dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, Tokishiechiru 4- (dimethylamino) benzoate, and the like.

As the photopolymerization initiator in the present invention, a photocationic polymerization initiator can also be used.
The cationic photopolymerization initiator may be a compound that generates a substance that initiates cationic photopolymerization by receiving energy rays such as ultraviolet rays, and is preferably an onium salt such as an arylsulfonium salt or an aryliodonium salt.

Specific examples of the onium salt include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenylsulfonium, diphenyl- 4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η ⁵ -2, 4- (cyclopentadienyl) [1,2,3,4,5,6-η]-(methylethyl) -benzene] ^-iron ( ¹⁺ ) and the like. Specific examples of anions include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl). ₆ ^-), perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonate ion _(CF 3 SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene Onium salts having other anions such as sulfonate anions can also be used.

  Among such onium salts, a particularly effective photocationic polymerization initiator is an aromatic onium salt. For example, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP-A52-30899, JP-A-56. Group VIA aromatic onium salts described in JP-A-55420, JP-A-55-125105, etc., Group VA aromatic onium salts described in JP-A-50-158698, etc., JP-A-56-8428 Oxosulfoxonium salts described in JP-A-56-149402 and JP-A-57-192429, aromatic diazonium salts described in JP-A-49-17040, US Pat. , 139,655, photoinitiates a hydrogen halide, a thiobililium salt, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator Halide, o- nitrobenzyl ester compounds, imide sulfonate compound, bissulfonyldiazomethane compounds, mention may be made of an oxime sulfonate compound.

  As the photocationic polymerization initiator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely used (edited by Organic Electronics Materials Research Group, “Organization for Imaging”). Materials, "Bunshin Publishing (1993), pages 187-192). These compounds are photoacid generators described in THE CHEMICAL SOCIETY OF JAPAN Voi.71 No.11, 1998, edited by Organic Electronics Materials Society, “Organic Materials for Imaging”, Bunshin Publishing (1993). Similarly, it can be easily synthesized by a known method.

  Commercially available photocationic polymerization initiators include UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide), Adekaoptomer SP-150, SP-151. , SP-170, SP-171, SP-172 (manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261, IRGACURE OXE01, IRGACURE CGI-1397, CGI-1325, CGI-1380, CGI-1311, CGI-263 CGI-268, CGI-1397, CGI-1325, CGI-1380, CGI-1311 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2638, CI-2064 ( Above, Nippon Soda Co., Ltd.), CD -1010, CD-1011, CD-1012 (manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 ( As described above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (manufactured by Nippon Kayaku Co., Ltd.), PHOTOINITIATOR 2074 (manufactured by Rhodia),

UR-1104, UR-1105, UR-1106, UR-1107, UR-1113, UR-1114, UR-1115, UR-1118, UR-1200, UR-1201, UR-1202, UR-1203, UR- 1204, UR-1205, UR-1207, UR-1401, UR-1402, UR-1403, UR-M1010, UR-M1011, UR-M10112, UR-SAIT01, UR-SAIT02, UR-SAIT03, UR-SAIT04, UR-SAIT05, UR-SAIT06, UR-SAIT07, UR-SAIT08, UR-SAIT09, UR-SAIT10, UR-SAIT11, UR-SAIT12, UR-SAIT13, UR-SAIT14, UR-SAIT15, UR-SAIT16, U -SAIT22, UR-SAIT30 (manufactured by URAY Co., Ltd.) and the like. Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-171, SP-172, CD-1012 and MPI-103 have higher photocuring sensitivity due to the composition containing them. Can be expressed.
Said photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

As content in the photocurable composition of the photoinitiator demonstrated above, 0.1-15 mass% is preferable, 0.2-12 mass% is more preferable, 0.3-10 mass% Is particularly preferred.
When the content is 0.1% by mass or more, sensitivity (fast curability), resolution, line edge roughness, and coating film strength (curability of the coating film) can be further improved. Moreover, light transmittance, coloring property, and handleability can be improved more as the said content is 15 mass% or less.

  Furthermore, in addition to the above-mentioned photopolymerization initiator, a photosensitizer can be added to the photocurable composition of the present invention to adjust the wavelength in the UV region. Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically, pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

  The content ratio of the photosensitizer in the photocurable composition of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less in the photocurable composition. preferable. Although the minimum of a photosensitizer content rate is not specifically limited, In order to express an effect, the minimum of a photosensitizer content rate is about 0.1 mass%.

  The light for initiating polymerization of the present invention includes not only light having a wavelength in the region of ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, infrared light, or electromagnetic waves, but also radiation. For example, microwave, electron beam, EUV, and X-ray are included. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light). The exposure can be multiple exposure, and it is also possible to further expose the entire surface after pattern formation for the purpose of increasing the film strength and etching resistance.

  The photopolymerization initiator used in the present invention needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization / exposure. Those that do not generate gas are preferable from the viewpoints that the mold is not easily contaminated, the frequency of cleaning the mold is reduced, and the photocurable composition is less likely to be deformed in the mold, so that the transfer pattern accuracy is less likely to deteriorate.

  In the above, (a) a polymerizable compound and (b) a photopolymerization initiator have been described. In the present invention, (a) a polymerizable compound, (b) a photopolymerization initiator, and other compositions known as other components are used. The component which comprises can also be used suitably. Known components include, for example, the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696, and the paragraph numbers [0027] to [0053] of JP-A-2006-64921. Of the ingredients.

<(C) Surface-active photopolymerization initiator>
The photocurable composition of the present invention contains at least one surface active photopolymerization initiator.
As the surface active photopolymerization initiator in the present invention, any compound having a surface active action and a photopolymerization initiating action can be used without particular limitation. For example, at least one substituent having a surface active action can be used. The compound which contains at least 1 sort (s) of the substituent which has a photoinitiation effect | action in the same molecule can be mentioned.
In the curable composition of the present invention, by further containing a surface active photopolymerization initiator in addition to the photopolymerization initiator, the surface properties of the cured film formed by the photocurable composition are improved, The peelability from the mold is improved. Thereby, for example, when a photo spacer constituting the display device is produced, a high degree of deformation recovery is exhibited. For example, when a light shielding layer, a colored layer, or a protective layer is manufactured, the surface strength of the cured film can be increased.

From the viewpoint of the surface characteristics of the cured film, the substituent having a surface active action may be an alkyl group having 3 to 30 carbon atoms that may be substituted, a siloxane group that may be substituted, and a substituent that may be substituted. It is preferably at least one selected from good fluorinated alkyl groups.
Examples of the substituent in the case where these groups have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, an amino group, and a cyano group. Can do.

  The alkyl group having 3 to 30 carbon atoms which may have the substituent is more preferably 4 to 20 carbon atoms. Specific examples include a hexyl group, octyl group, dodecyl group, octadecyl group, hexadecyl group and the like.

Moreover, as a siloxane group which may have the said substituent, it is preferable that the structural unit represented, for example by following General formula (1) is included.
Moreover, as a substituent in case a siloxane group has a substituent, a C1-C8 alkyl group, a C1-C8 alkoxy group, a halogen atom, an amino group, a cyano group etc. are mentioned, for example. be able to.

In the formula, R ³¹ represents a hydrogen atom, a hydrocarbon group or —OR ³³ , and R ³² represents a hydrogen atom, a hydrocarbon group or —OR ³⁴ . R ³³ and R ³⁴ each independently represent a hydrocarbon group. Examples of the hydrocarbon group represented by R ^{31 to} R ³⁴ include an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, and the like are preferable.
The number of repeating structural units represented by the general formula (1) is preferably 2 to 20 and more preferably 2 to 10 from the viewpoint of the surface properties of the cured film.

The fluorinated alkyl group which may have a substituent is preferably a fluorinated alkyl group having 1 to 16 carbon atoms, and preferably a fluorinated alkyl group having 3 to 12 carbon atoms. More preferred.
Examples of the substituent when the fluorinated alkyl group has a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, an amino group, and a cyano group. Can be mentioned.
In the present invention, a fluorinated alkyl group represented by the following general formula (2) is preferable.

In the formula, L ⁴ represents an oxygen atom or a single bond, i represents an integer of 0 to 8, and j represents an integer of 1 to 12. In the present invention, i is an integer of 0-6, j is preferably an integer of 1-10, i is an integer of 1-4, and j is an integer of 2-8. Is more preferable.
Specific examples include a perfluorohexyloxyethyl group and a perfluorooctylethyl group.

  Examples of the substituent having a photopolymerization initiating action include a substituent derived from the photopolymerization initiator described as the above (b) photopolymerization initiator. Among these, from the viewpoint of photopolymerization initiation activity, a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-aminoketone compound, an α-hydroxyketone compound, or the like is preferable.

  The (c) surface active photopolymerization initiator in the present invention may have a linking group between a substituent having a surface active action and a substituent having a photopolymerization start action. The linking group is not particularly limited, and examples thereof include an oxygen atom (—O—), a sulfur atom (—S—), a nitrogen atom, a carbonyl group, an amide bond, an ester bond, an alkylene group, an alkenylene group, an arylene group, and A linking group comprising these combinations can be exemplified. Moreover, not only a bivalent coupling group but a trivalent or more coupling group may be sufficient.

  As the (c) surface active photopolymerization initiator in the present invention, specifically, compounds described in JP-T-2004-515611, JP-A-2004-522819, JP-T-2004-525994, and the like, The following exemplary compounds 1-36 can be mentioned.

  As the (c) surface active photopolymerization initiator in the present invention, from the viewpoint of the surface properties of the cured film, a substituent having a surface active action may be a long chain alkyl group which may be substituted, or may be substituted. At least one selected from a siloxane group and an optionally substituted fluorinated alkyl group, the substituent having a photopolymerization initiating action is a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, α- It is preferable that the substituent is derived from an aminoketone compound or an α-hydroxyketone compound, and the substituent having a surface activity is a fluorinated alkyl group having 1 to 16 carbon atoms, a polymethylsiloxane group having 2 to 20 silicon atoms, Alternatively, the alkyl group having 4 to 20 carbon atoms and the substituent having a photopolymerization initiating action is a trihalomethyl-s-triazine compound. More preferably. Among these, the exemplified compounds 9, 30, 31 and the like are particularly preferable.

<(D) At least one selected from fluorine-based surfactants, silicone-based surfactants, and fluorine / silicone-based surfactants>
The photocurable composition of the present invention preferably contains at least one surfactant.
The surfactant is at least one selected from (d) a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant (hereinafter simply referred to as “(d) surfactant”). Preferably).
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, the photocurable composition of the present invention can be applied to a silicon wafer for manufacturing a semiconductor device, a glass square substrate for manufacturing a liquid crystal device, a chromium film, a molybdenum film, a molybdenum alloy film, or tantalum. Striations and scales that occur during coating, such as various films, such as films, tantalum alloy films, silicon nitride films, amorphous silicon films, tin oxide-doped indium oxide (ITO) films and tin oxide films The purpose of solving the problem of poor coating such as the pattern of the resist (unevenness of drying of resist film) and the fluidity of the photocurable composition into the cavity of the mold recess are improved, and the mold releasability between the mold and the resist is improved. In addition, the adhesion between the resist and the substrate can be improved, the viscosity of the photocurable composition can be lowered, and the like.
In particular, in the photocurable composition of the present invention, by adding the above-mentioned surfactant, the coating uniformity can be greatly improved, and in coating using a spin coater or slit scan coater, it is good regardless of the substrate size. Application suitability is obtained.

  Examples of the fluorosurfactant include trade name Fluorad FC-430, FC-431 (manufactured by Sumitomo 3M), trade name Surflon “S-382” (manufactured by Asahi Glass), EFTOP “EF-122A, 122B, 122C”. , EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products), product names PF-636, PF-6320, PF-656, PF-6520 (all OMNOVA), products Name aftergents FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), trade names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), product names Megafuck 171, 172 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of the silicone surfactant include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFac Paintad 31 (manufactured by Dainippon Ink and Chemicals), and KP-341 (manufactured by Shin-Etsu Chemical). It is done.

  Examples of fluorine / silicone surfactants that can be used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all of which are Shin-Etsu Chemical). Kogyo Kogyo Co., Ltd.), trade names Megafax R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

The amount of fluorine-based surfactant, silicone-based surfactant and fluorine-silicone-based surfactant is the total amount of these surfactants in the range of 0.001 to 5% by mass in the photocurable composition. It is preferable to mix | blend with, and it is more preferable to add in 0.01-3 mass%.
When the fluorine-based surfactant, the silicone-based surfactant, and the fluorine-silicone-based surfactant are 0.001% by mass or more in the photocurable composition, the coating uniformity can be further improved. When it is at most%, the releasability from the mold can be further improved.
The fluorine-based surfactant, silicone-based surfactant and fluorine-silicone-based surfactant used in the present invention may be used alone or in combination of two or more. In the present invention, it is preferable to include both a fluorine-based surfactant and a silicone-based surfactant, or a fluorine-silicone-based surfactant.
In particular, it is most preferable to contain a fluorine / silicone surfactant.

In addition to the above, other nonionic surfactants may be used in combination with the photocurable composition of the present invention for the purpose of improving the flexibility of the photocurable composition.
Examples of commercially available nonionic surfactants include polyoxy, such as D-3110, D-3120, D-3412, D-3440, D-3510, and D-3605 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene alkyl ethers such as ethylene alkylamine, D-1305, D-1315, D-1405, D-1420, D-1504, D-1508, and D-1518 of Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene monofatty acid esters such as D-2112-A, D-2112-C and D-2123-C of the Pionein series manufactured by Takemoto Yushi Co., Ltd. D- of the Pionein series manufactured by Takemoto Yushi Co., Ltd. Polyoxyethylene difatty acid esters such as 2405-A, D-2410-D, D-2110-D, etc., manufactured by Takemoto Yushi Co., Ltd. Onin series D-406, D-410, D-414, D-418 and other polyoxyethylene alkyl phenyl ethers, Nissin Chemical Industry's Surfinol series 104S, 420, 440, 465, 485, etc. And polyoxyethylenetetramethyldecynediol diether.

  Moreover, the reactive surfactant which has a polymerizable unsaturated group can also be used together with the surfactant used by this invention. For example, allyloxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PKE series), nonylphenoxy polyethylene glycol monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNE series), nonylphenoxy polypropylene glycol monometa. Acrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNP series), Nonylphenoxy poly (ethylene glycol-propylene glycol) monomethacrylate (Nippon Yushi Co., Ltd. trade name: Blenmer PNEP-600), Aqualon RN-10, RN- 20, RN-30, RN-50, RN-2025, HS-05, HS-10, HS-20 (Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

<Organic solvent>
The photocurable composition of the present invention may contain at least one organic solvent.
Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Monomethyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate;

Aromatic hydrocarbons such as toluene and xylene; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone; ethyl 2-hydroxypropionate, 2-hydroxy-2- Methyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Examples thereof include esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and lactate such as ethyl lactate.

Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.

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

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

Moreover, it is preferable that content of the organic solvent is 3 mass% or less in the photocurable composition of this invention in all the photocurable compositions.
That is, the photocurable composition of the present invention preferably dissolves the components of the photocurable composition of the present invention when a specific monofunctional or bifunctional monomer is included as a reactive diluent. Therefore, it is not always necessary to contain the organic solvent. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the photocurable composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained.

  As described above, the photocurable composition of the present invention does not necessarily contain an organic solvent. However, the reactive diluent does not dissolve a compound that does not dissolve in the photocurable composition of the present invention or has a viscosity. It can be added arbitrarily, for example, when finely adjusting. The organic solvent that can be preferably used in the photocurable composition of the present invention is a solvent generally used in a photocurable composition or a photoresist, and dissolves and uniformly disperses the compound used in the present invention. Any material can be used as long as it does not react with these components.

<Other ingredients>
In addition to the above components, the photocurable composition of the present invention may include a release agent, a silane coupling agent, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiaging agent, and a plasticizer as necessary. , Adhesion promoters, thermal polymerization initiators, colorants, inorganic particles, elastomer particles, antioxidants, photoacid multipliers, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants, etc. These components may be contained.

(Release agent)
For the purpose of further improving the releasability, a release agent can be arbitrarily blended in the photocurable composition of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the photocurable composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate. Examples of the release agent include conventionally known release agents, for example, silicone-type release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-type, phosphate ester-type compounds, etc. Can also be used. Moreover, these mold release agents can be attached to the mold.

  Silicone release agents have particularly good release properties from the mold when combined with the above-mentioned photocurable resin used in the present invention, and the phenomenon of taking a plate hardly occurs. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, and silicone acrylic resin.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more of the above-described modification methods can be performed on one polysiloxane molecule.

  The modified silicone oil preferably has moderate compatibility with the photocurable composition component. In particular, when using a reactive silicone oil that is reactive with other coating-forming components blended in the photocurable composition as necessary, the photocurable composition of the present invention was cured. Since they are fixed in the cured film by chemical bonding, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone, vinyl-modified silicone, etc., since it crosslinks with the photocurable composition of the present invention, it has excellent properties after curing. .

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeding out on the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
The said mold release agent can be added only in 1 type or in combination of 2 or more types.

  When adding a mold release agent to the photocurable composition of the present invention, it is preferable to add 0.001 to 10% by mass in the total amount of the photocurable composition, and a range of 0.01 to 5% by mass. It is more preferable to add at. When the ratio of the release agent is 0.01% by mass or more, the effect of improving the mold release between the mold and the photocurable composition layer is sufficient. On the other hand, if the ratio of the release agent is within the above range of 10% by mass, the problem of surface roughness of the coating film due to repelling during the application of the photocurable composition hardly occurs, and the substrate itself and the proximity in the product. It is preferable in that the adhesion of the layer, for example, the vapor deposition layer is hardly hindered and the film is not easily broken during transfer (the film strength is too weak).

(Organic metal coupling agent)
In the photocurable composition of the present invention, an organic metal coupling agent may be blended in order to increase the heat resistance, strength, or adhesion of the surface structure having a fine uneven pattern to the metal deposition layer. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

  Examples of the silane coupling agent used in the photocurable composition of the present invention include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyl Acrylic silanes such as trimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldi Epoxy silanes such as ethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N -Phenyl -Aminosilane such as γ-aminopropyltrimethoxysilane; and other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, and the like. .

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

  The said organometallic coupling agent can be arbitrarily mix | blended in the ratio of 0.001-10 mass% in solid content whole quantity of a photocurable composition. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective in improving heat resistance, strength, and adhesion with the vapor deposition layer. On the other hand, it is preferable that the ratio of the organometallic coupling agent is 10% by mass or less because the stability of the photocurable composition and the deficiency in film formability can be suppressed.

(Polymerization inhibitor)
The photocurable composition of the present invention may contain a polymerization inhibitor in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like. The polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the photocurable composition.

(Antioxidant)
Examples of commercially available antioxidants include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Antigene P, 3C, FR, and Sumilyzer S (manufactured by Sumitomo Chemical Co., Ltd.). The antioxidant is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the photocurable composition.

(UV absorber)
Commercially available UV absorbers include Tinuvin P, 234, 320, 326, 32
7, 328, 213 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (above, manufactured by Sumitomo Chemical Co., Ltd.), etc. Is mentioned. It is preferable to mix | blend a ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of a photocurable composition.

Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) Etc. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the photocurable composition.

Commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, and RD-G.
, FR, AW (above, manufactured by Sumitomo Chemical Co., Ltd.) and the like. The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the photocurable composition.

(Plasticizer)
A plasticizer can be added to the photocurable composition of the present invention in order to adjust adhesion to the substrate, flexibility of the film, hardness, and the like. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate, There are di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the photocurable composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.

(Adhesion promoter)
An adhesion promoter may be added to the photocurable composition of the present invention in order to adjust adhesion to the substrate. Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2′-bipyridine derivatives, benzotriazoles, organic phosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used. The adhesion promoter is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less in the photocurable composition. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain the effect.

(Thermal polymerization initiator)
When hardening the photocurable composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

(Photobase generator)
The photocurable composition of the present invention may contain a photobase generator as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitro Benzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5- Diacetyl-4 (2'-nitrophenyl)
Preferred examples include -1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine.

(Coloring agent)
For the purpose of improving the visibility of the coating film, a colorant may be optionally added to the photocurable composition of the present invention. As the colorant, pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired. As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And metal complex oxides.
As organic pigments, CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150 , 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36, 37, CIPigment Brown 25 28, CIPigment Black 1, 7 and carbon black.

(Filler)
For the purpose of improving the heat resistance, mechanical strength, tackiness, etc. of the coating film, fillers such as inorganic fine particles and elastomer particles may be added as optional components to the photocurable composition of the present invention. .
As the inorganic fine particles, those having an ultrafine particle size can be used. Here, “ultrafine particle” means a particle of submicron order, and generally means a particle having a particle size smaller than a particle having a particle size of several μm to several 100 μm, which is generally called “fine particle”. ing. The specific size of the inorganic fine particles used in the present invention varies depending on the use and grade of the optical article to which the photocurable composition is applied, but generally the primary particle size is in the range of 1 nm to 300 nm. When the primary particle size is preferably 1 nm or more, the moldability, shape maintenance and releasability of the photocurable composition can be sufficiently improved, while if the primary particle size is 300 nm or less, The transparency necessary for curing the resin can be maintained, which is preferable in terms of transparency.

Specific examples of the inorganic fine particles include metal oxide fine particles such as SiO ₂ , TiO ₂ , ZrO ₂ , SnO ₂ , and Al ₂ O ₃ , among which colloidal dispersion is possible as described above. In addition, it is preferable to select and use a particle having a particle size on the order of submicron, and particularly, it is preferable to use colloidal silica (SiO ₂ ) fine particles.

  The inorganic fine particles are preferably blended in a proportion of 1 to 70% by mass and particularly preferably in a proportion of 1 to 50% by mass in the total solid content of the photocurable composition. By setting the proportion of the inorganic fine particles to 1% by mass or more, the moldability, shape maintaining property and releasability of the photocurable composition of the present invention can be sufficiently improved, and the proportion of the inorganic fine particles is set to 70% by mass. % Or less is preferable in terms of strength and surface hardness after exposure and curing.

In the photocurable composition of the present invention, elastomer particles may be added as an optional component for the purpose of improving mechanical strength, flexibility and the like.
The elastomer particles that can be added as an optional component to the photocurable composition of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / Particles of elastomer such as polyene copolymer, acrylic rubber, butadiene / (meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

  Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resinas Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.

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

(Antioxidant)
The photocurable composition of the present invention can contain a known antioxidant. The antioxidant suppresses fading caused by light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like.

(Basic compound)
A basic compound may be optionally added to the photocurable composition of the present invention for the purpose of suppressing curing shrinkage and improving thermal stability. Examples of the basic compound include amines and nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.

(Acid growth agent)
In the present invention, the cationic polymerization initiator that generates acid by energy rays is combined with a substance (hereinafter referred to as an acid proliferation agent) that newly generates an acid by the action of the generated acid to improve the curing rate. It can also be made. Examples of the acid proliferating agent include compounds disclosed in JP-A-08-248561, JP-A-10-1508 and JP-A-3106640, specifically 1,4-bis (p-toluenesulfonyloxy). ) Cyclohexane, 1,4-bis (p-toluenesulfonyloxy) cyclohexane, cis-3- (p-toluenesulfonyloxy) -2-pinanol, cis-3- (p-octanesulfonyloxy) -2-pinanol It is done. Examples of commercially available compounds include ACPRESS 11M (manufactured by Nippon Chemix Co., Ltd.).

<Preferable combination of the photocurable composition of the present invention>
About each component of the photocurable composition of this invention, by optimizing the combination of a kind and content, the surface and internal sclerosis | hardenability, and the peelability from a mold can further be improved.

  From the viewpoint of obtaining the above effect more effectively, as a preferable combination of (b) a photopolymerization initiator and (c) a surface-active photopolymerization initiator, (b) a photopolymerization initiator is 2, 4 -Bis- (trichloroethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine, Irgacure-184, Irgacure-651, Irgacure-369, Irgacure -907, Darocure-1173, Lucirin TPO, Lucirin TPO-L, MP-triazine, TAZ-108, bis (4-methylphenyl) iodonium, diphenyl-4-thiophenoxyphenylsulfonium, etc., (c) surface activity Whether the photopolymerization initiator is a trihalomethyl-s-triazine compound A compound having a group derived from the above and a fluorinated alkyl group having 1 to 16 carbon atoms, a polymethylsiloxane group having 2 to 20 silicon atoms, or an alkyl group having 4 to 20 carbon atoms (for example, Exemplified Compounds 9, 30) And (b) the photopolymerization initiator is 2,4-bis- (trichloroethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethylamino) -3 ′. -Bromophenyl] -s-triazine, Lucirin TPO, Darocure-1173, Irgacure-651, Irgacure-369, Irgacure-907, Lucirin TPO-L, (c) the surfactant photopolymerization initiator is trihalomethyl- A compound having a group derived from an s-triazine compound and a fluorinated alkyl group having 1 to 16 carbon atoms A combination that is (for example, exemplified compound 30) is more preferable.

  From the viewpoint of obtaining the above effect more effectively, the content ratio [((c) surfactant photopolymerization initiator) / ((b) photopolymerization initiator)] (mass ratio) is 0.1. -1.0 is preferred.

  Moreover, from the viewpoint of obtaining the above effect more effectively, as a preferable combination of (c) a surfactant photopolymerization initiator and (d) a surfactant, (c) a surfactant photopolymerization initiator is A compound having a group derived from a trihalomethyl-s-triazine compound and a fluorinated alkyl group having 1 to 16 carbon atoms, a polymethylsiloxane group having 2 to 20 silicon atoms, or an alkyl group having 4 to 20 carbon atoms ( For example, a combination in which (d) the surfactant is at least one selected from a fluorine-based surfactant and a silicone-based surfactant is preferable, and (c) an interface A compound in which the active photopolymerization initiator has a group derived from a trihalomethyl-s-triazine compound and a fluorinated alkyl group having 1 to 16 carbon atoms (for example, exemplified compound 30) There are, (d) surfactant combination is at least one selected from fluorine-based surfactants and silicone-based surfactants are more preferable.

  From the viewpoint of obtaining the above effect more effectively, the content ratio [((d) surfactant) / ((c) surfactant photopolymerization initiator)] (mass ratio) is 0.1 to 0.1%. 1.0 is preferred.

<Method for Preparing Photocurable Composition of the Present Invention>
The photocurable composition of the present invention can be prepared as a solution by, for example, filtering with a filter having a pore diameter of 0.05 μm to 5.0 μm after mixing the above-described components. Mixing and dissolution of the photocurable composition is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

  The photocurable composition of the present invention includes a semiconductor integrated circuit, a flat screen, a micro electro mechanical system (MEMS), a sensor element, an optical disk, a magnetic recording medium such as a high-density memory disk, an optical component such as a diffraction grating or a relief hologram, Nano devices, optical devices, optical films and polarizing elements for flat panel display fabrication, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillar materials, rib materials for liquid crystal alignment, microlens arrays, immunoassays It can be used as an optical nanoimprint resist composition for forming a fine pattern when producing a chip, a DNA separation chip, a microreactor, a nanobiodevice, an optical waveguide, an optical filter, a photonic liquid crystal, or the like.

≪Pattern manufacturing method≫
The method for producing a patterned substrate of the present invention includes:
(1) A step of applying the photocurable composition of the present invention described above on a substrate to form a photocurable layer (hereinafter, also referred to as “photocurable layer forming step”);
(2) A step of pressing the concavo-convex pattern of the mold having the concavo-convex pattern and the photocurable layer formed on the substrate to deform the photocurable layer (hereinafter also referred to as “pressure-contacting step”). )When,
(3) From the opposite side of the substrate on which the photocurable layer is formed (hereinafter also referred to as “substrate back side”) and / or on the opposite side of the mold in contact with the photocurable layer. (Hereinafter, also referred to as “mold back side”), the step of irradiating the deformed photocurable layer with light to cure the deformed photocurable layer (hereinafter, also referred to as “exposure step”),
(4) A step of peeling the mold from the substrate and forming an inverted pattern of the concave-convex pattern on the substrate (hereinafter, also referred to as “mold peeling step”);
It is comprised.

  The method for producing a substrate with a pattern of the present invention uses the photocurable composition of the present invention to form a resist pattern that is a reversal pattern of the concave and convex pattern of the mold. The curability of the surface and the inside of the pattern is improved, and the peelability of the resist pattern from the mold is improved.

The “pattern” in the “patterned substrate” is:
(A) A pattern formed by further curing the resist pattern formed on the substrate by post-exposure or heat treatment, if necessary,
And / or
(B) A pattern formed by etching using a resist pattern formed on the substrate as a mask, and comprising a substrate surface, a metal film, a semiconductor film, an insulator film (which may be an organic film or an inorganic film, and the same shall apply hereinafter). .
Specific examples of (A) include, for example, a photo spacer pattern, an alignment control projection pattern, a partition wall (for example, black matrix) pattern, a colored pixel pattern, and the like in a display device.
Specific examples of (B) include, for example, a wiring pattern, an electrode pattern, a semiconductor pattern, an insulating film pattern, a groove pattern used in a polishing process such as CMP in a semiconductor device, a display device, a printed wiring board, and the like. Can be mentioned.

The method for forming the pattern (B) is not particularly limited,
(5) Etching a substrate (including a metal film, a semiconductor film, and an insulator film formed on the substrate in addition to the substrate itself) using a resist pattern formed using the photocurable composition of the present invention as a mask A process (hereinafter also referred to as an “etching process”),
(6) If necessary, a step of peeling the resist pattern (hereinafter also referred to as “resist pattern peeling step”);
The form which has is mentioned.
In this embodiment, the surface and internal curability of the formed resist pattern and the releasability from the mold are improved, so that the etching property of the substrate is improved.

Hereinafter, each step will be described.
<(1) Photocurable layer forming step>
The photocurable layer forming step is a step of forming the photocurable layer by applying the photocurable composition of the present invention described above on a substrate.
As the substrate, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate (Ni, Cu, Cr, Fe, etc.), paper, SOG, polymer substrate (polyester film, polycarbonate film, Polyimide film, etc.), TFT array substrate, PDP electrode plate, glass substrate, transparent plastic substrate, conductive substrate (ITO, metal, etc.), insulating substrate, semiconductor fabrication substrate (silicon, silicon nitride, polysilicon, oxidation) There are no particular restrictions. The shape of the substrate may be a plate shape or a roll shape.

As a coating method for coating the photocurable composition of the present invention on a substrate, generally well-known coating methods such as dip coating, air knife coating, curtain coating, wire bar coating, and gravure coating are used. Further, an extrusion coating method, a spin coating method, a slit scanning method, a slit & spin method and the like can be used.
Although the layer thickness of the photocurable layer formed by applying the photocurable composition of the present invention varies depending on the intended use, it is preferably 0.05 μm to 30 μm. In addition, the photocurable composition of the present invention may be applied multiple times.

<(2) Pressure welding process>
The press-contacting step is a step of deforming the photocurable layer by press-contacting the concave-convex pattern of the mold having the concave-convex pattern and the photocurable layer formed on the substrate.

(mold)
As a mold in the present invention, a mold having an uneven pattern to be transferred onto a substrate on at least one surface is used.
The concavo-convex pattern can be formed according to desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
Examples of the mold in the present invention include a light transmissive mold and a non-light transmissive mold.

  The material of the light transmissive mold used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film are exemplified.

  The non-light-transmitting mold is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. There are no particular restrictions. The shape may be either a plate mold or a roll mold. The roll mold is applied particularly when continuous transfer productivity is required.

  The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the peelability between the photocurable composition and the mold. Products that have been treated with a silane coupling agent such as silicone or fluorine, such as Daikin Industries: trade name Optool DSX or Sumitomo 3M: trade name Novec EGC-1720, etc. Can do.

(Pressing condition)
There is no particular limitation on the pressure contact condition (mold pressure) when pressing the concave-convex pattern of the mold and the photocurable layer on the substrate, but 10 atm or less is preferable.
It is preferable to set the mold pressure to 10 atm or less because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and because the pressure is low, the apparatus can be reduced. The mold pressure is preferably selected in a region where the uniformity of mold transfer can be ensured within a range in which the residual film of the photocurable composition on the mold convex portion is reduced.

<(3) Exposure process>
In the exposure step, light is irradiated (ie, exposed) from the back side of the substrate and / or from the back side of the mold to the laminate formed of the substrate and the mold formed by the pressure contact step, and the deformation This is a step of curing the photocurable layer (that is, the portion of the photocurable layer located in the concave portion of the concave / convex pattern of the mold).

In the case of irradiating light from the back side of the substrate, it is preferable to use a light transmissive substrate among the aforementioned substrates. On the other hand, when irradiating light from the back side of the mold, it is preferable to use a light-transmitting mold among the aforementioned molds.
Here, “light transmittance” refers to a property that the transmittance of light to be irradiated (transmittance at the exposure wavelength) is 90% or more (preferably 95% or more).

Although it does not specifically limit as light irradiated in an exposure process, The light or radiation of the wavelength of area | regions, such as high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, and infrared, is mentioned.
As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used.
Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The radiation includes, for example, microwaves and EUV.
Also, laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser light can be suitably used in the present invention.
These lights may be monochromatic lights, or may be lights having different wavelengths (mixed lights).

In the present invention, the light irradiation amount may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing can be determined by examining the consumption of unsaturated bonds of the photocurable composition and the tackiness of the cured film.
At this time, in order to expose the photocurable layer formed using the photocurable composition of the present invention described above, even when cured with a small amount of exposure, the surface and internal curability is excellent, and from the mold. It is possible to form a resist pattern having excellent releasability.
In addition, the substrate temperature during light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase reactivity.
As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the photocurable composition. May be. In the present invention, a preferable degree of vacuum is in the range of 10 ⁻¹ Pa to normal pressure.

<(4) Mold peeling process>
The mold peeling step is a step of peeling a mold from the substrate after light irradiation (specifically, a photocurable layer on the substrate), and forming a resist pattern on the substrate as an inverted pattern of the concavo-convex pattern.
At this time, since the mold is peeled off from the photocurable layer formed using the photocurable composition of the present invention described above, a phenomenon in which an uncured product remains in the mold even when cured with a small exposure amount. Can be effectively prevented, and the releasability from the mold can be improved.

<(5) Etching process>
The etching process is performed using a resist pattern formed using the photocurable composition of the present invention as a mask (not limited to the substrate itself, but a metal film, a semiconductor film, or an insulator film formed on the substrate). Or may be etched).
When providing an etching process in the substrate with a pattern of this invention, the resist pattern formed including the process of said (1)-(4) can function as an etching resist.

The etching method can be performed by a method appropriately selected from known etching methods, and is performed for removing a base portion not covered with a resist pattern to obtain a pattern.
As the etching, either a treatment with an etching solution (wet etching) or a treatment in which a reactive gas is activated by plasma discharge under reduced pressure (dry etching) is performed.
The etching process may be a batch system in which an appropriate number of sheets are processed together, or a single wafer process in which each sheet is processed.

(Wet etching)
As etching solutions for wet etching, many etching solutions have been developed and used, with ferric chloride / hydrochloric acid systems, hydrochloric acid / nitric acid systems, hydrobromic acid systems and the like as representative examples.
For Cr, mixed solution of cerium ammonium nitrate or cerium nitrate / hydrogen peroxide solution, for Ti, diluted hydrofluoric acid, hydrofluoric acid / nitric acid mixed solution, for Ta, mixed solution of ammonium solution and hydrogen peroxide solution For Mo, hydrogen peroxide solution, a mixture of ammonia water and hydrogen peroxide solution, a mixture solution of phosphoric acid and nitric acid, and for MoW and Al, a mixture solution of phosphoric acid and nitric acid, a mixture solution of hydrofluoric acid and nitric acid, phosphoric acid Nitric acid / acetic acid mixed solution For ITO, diluted aqua regia, ferric chloride solution, hydrogen iodide water, SiNx and SiO ₂ are buffered hydrofluoric acid, hydrofluoric acid / ammonium fluoride mixed solution, Si, poly Si Is a mixture of hydrofluoric acid, nitric acid and acetic acid, W is a mixture of ammonia water and hydrogen peroxide, PSG is a mixture of nitric acid and hydrofluoric acid, and BSG is a mixture of hydrofluoric acid and ammonium fluoride. used.

Wet etching may be either a shower method or a dip method, but the etching rate, in-plane uniformity, and wiring width accuracy largely depend on the processing temperature, so the conditions are optimal according to the substrate type, application, and line width. It is necessary to make it. Moreover, when performing the said wet etching, it is desirable to perform a post-bake in order to prevent the undercut by the penetration | penetration of etching liquid.
Here, the post-baking refers to a process of heating and further curing the resist pattern formed including the steps (1) to (4).
Usually, post-baking is performed at about 90 ° C. to 140 ° C., but is not necessarily limited thereto.

(Dry etching)
The dry etching basically uses a parallel plate type dry etching apparatus having a pair of electrodes arranged in parallel in a vacuum apparatus and setting a substrate on one of the electrodes.
Reactive ion etching (RIE) mode in which ions are mainly involved and radicals are mainly involved depending on whether the high-frequency power source for generating plasma is connected to the electrode on the side where the substrate is installed or to the opposite electrode The plasma etching (PE) mode is classified.
As an etchant gas used in the dry etching, an etchant gas suitable for each film type is used. Carbon tetrafluoride (chlorine) + oxygen, carbon tetrafluoride (sulfur hexafluoride) + hydrogen chloride (chlorine) for a-Si / n ⁺ and s-Si, carbon tetrafluoride for a-SiNx + Oxygen, carbon tetrafluoride + oxygen for a-SiOx, carbon trifluoride + oxygen, carbon tetrafluoride (sulfur hexafluoride) + oxygen for Ta, carbon tetrafluoride for MoTa / MoW For chlorine + oxygen for + oxygen and Cr, boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide and the like for Al. In the dry etching process, the resist structure may be greatly altered by ion bombardment or heat, which also affects the peelability.

<(6) Resist stripping step>
The resist stripping step is a step of stripping the resist pattern from the etched substrate.
The resist pattern is stripped (hereinafter also referred to as “resist stripping”) by removing it with a liquid (wet stripping) or by oxidizing it with a plasma discharge of oxygen gas under reduced pressure to remove it (dry stripping / The resist can be removed by several stripping methods, such as ashing) or oxidized by ozone and UV light to remove it in a gaseous state (dry stripping / UV ashing).

  As a stripping solution used for wet stripping, an aqueous solution system such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide or ozone-dissolved water and an organic solvent system such as a mixture of amine, dimethyl sulfoxide or N-methylpyrrolidone are generally known. It has been. As an example of the latter, a monoethanolamine / dimethyl sulfoxide mixture (mass mixing ratio = 7/3) is well known.

  The resist stripping rate is greatly influenced by temperature, liquid amount, time, pressure, etc., and can be optimized depending on the substrate type and application. In the present invention, it is preferable to immerse the substrate (from several minutes to several tens of minutes) in the temperature range of room temperature to 100 ° C., and perform rinsing with butyl acetate or the like and washing with water. From the viewpoint of improving the rinsing properties, particle removability, and corrosion resistance of the stripper itself, only water rinsing may be used. A preferable example is a pure water shower for washing and an air knife drying for drying. When the amorphous silicone is exposed on the substrate, an oxide film is formed in the presence of water and air. Therefore, it is preferable to block air.

  Moreover, you may apply the method of using together ashing (ashing) and peeling by a chemical | medical solution. Examples of ashing include plasma ashing, downflow ashing, ashing using ozone, and UV / ozone ashing. For example, when an Al substrate is processed by dry etching, a chlorine-based gas is generally used, but aluminum chloride, which is a product of chlorine and Al, may corrode Al. In order to prevent these, a stripping solution containing a preservative may be used.

<Other processes>
The manufacturing method of the board | substrate with a pattern of this invention may have other processes other than the process of (1)-(6) demonstrated above.
There is no restriction | limiting in particular as said other process, Selecting suitably from the processes in well-known pattern formation is mentioned.
For example, a hardening process process etc. are mentioned.
These may be used alone or in combination of two or more. There is no restriction | limiting in particular as a hardening process, Although it can select suitably according to the objective, For example, a whole surface heat processing, a whole surface exposure process, etc. are mentioned suitably.

  Examples of the method for the entire surface heat treatment include a method for heating the formed pattern. By heating the entire surface, the film strength on the surface of the pattern is increased. As heating temperature in whole surface heating, 80-200 degreeC is preferable and 90-180 degreeC is more preferable. When the heating temperature is 80 ° C. or higher, the film strength by heat treatment tends to be further improved, and when it is 200 ° C. or lower, the components in the photocurable composition are decomposed and the film quality is weak and brittle. Can be more effectively deterred. There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned. Moreover, when using a hot plate, in order to heat uniformly, it is desirable to carry out by lifting the substrate on which the pattern is formed from the plate.

  Examples of the entire surface exposure processing method include a method of exposing the entire surface of the formed pattern. The entire surface exposure promotes curing in the photocurable composition for forming the photosensitive layer and the surface of the pattern is cured, so that etching resistance can be increased. There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

  Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]
≪Preparation of substrate with resist pattern≫
<Preparation of photocurable composition>
As a polymerizable compound, 9.799 g of benzyl acrylate (R-01), 78.392 g of tripropylene glycol diacrylate (R-11), 9.799 g of ethylene oxide-modified trimethylolpropane triacrylate (R-12), a photopolymerization initiator 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) (P-1) 2.00 g, 0.5 g of the exemplified compound 30 as a surface active photopolymerization initiator, As a surfactant, 0.01 g of EFTOP EF-122A (fluorine-based, W-1) is precisely weighed and mixed at room temperature for 24 hours to obtain a photocurable composition (coating liquid) A-1 as a uniform solution. It was.
In the obtained photocurable composition A-1, the ratio of the polymerizable compound having a viscosity of 30 mPa · s or less was 90% by mass, and the viscosity of the photocurable composition A-1 was 18 mPa · s.

Here, the viscosity of the polymerizable compound and the photocurable composition was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotational speed at the time of measurement is 0.5 rpm to less than 5 mPa · s is 100 rpm, 5 mPa · s to less than 10 mPa · s is 50 rpm, 10 mPa · s to less than 30 mPa · s is 20 rpm, 30 mPa · s to less than 60 mPa · s. Was 10 rpm, 60 mPa · s or more and less than 120 mPa · s was 5 rpm, and 120 mPa · s or more was 1 rpm or 0.5 rpm.

<Formation of resist pattern>
The light prepared above on a color filter layer (having R (red), G (green), and B (blue) pixels) formed on a glass substrate (size 350 mm × 400 mm) having a thickness of 1 mm. The photocurable layer was formed by spin coating the curable composition A-1 to a thickness of 6.0 μm.

The substrate with a photocurable layer obtained by spin coating as described above was set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source.
In this nanoimprint apparatus, a mold made of polydimethylsiloxane (manufactured by Dow Corning Toray Co., Ltd., cured SILPOT184 at 80 ° C. for 60 minutes) is set. On one side of the mold, a 10 μm line / space pattern (groove depth of 5.0 μm) is provided as an uneven pattern.
In addition, the said board | substrate with a photocurable layer and the said mold were set with the arrangement | positioning in which the photocurable layer on a board | substrate and the uneven | corrugated pattern on a mold face each other.

Next, the photocurable layer and the concavo-convex pattern of the mold were pressed against each other at a soft mold pressure of 0.8 kN, and the photocurable layer was deformed into an inverted pattern with respect to the concavo-convex pattern of the mold.
The photocurable layer deformed by the pressure contact was exposed from the back side of the mold under the condition of 100 mJ / cm ² to cure the photocurable layer. The degree of vacuum during exposure was 10 Torr.
After the exposure, the mold was peeled from the substrate to obtain a resist pattern.
The resist pattern was formed as an inverted pattern with respect to the concave / convex pattern of the mold.

≪Evaluation≫
The following evaluation was performed about the obtained photocurable composition or resist pattern. The evaluation results are shown in Table 2.

<Peelability from mold>
Evaluation of the peelability of the resist pattern from the mold was performed as follows.
When the mold was peeled after the exposure, whether or not the uncured product of the photocurable layer remained in the mold was observed with an optical microscope (300 times magnification), and evaluated according to the following criteria.
In the following criteria, if it is A or B, it is practically acceptable.
~Judgment criteria~
A: No residue at all.
B: There is a little residue (less than 30% with respect to the contact area between the mold and the photocurable layer).
C: About half of the residue (30% or more and less than 90% with respect to the contact area between the mold and the photocurable layer).
D: Large amount of residue (90% or more with respect to the contact area between the mold and the photocurable layer.

<Photocurability> ... Curability inside resist pattern As an evaluation of curability inside the resist pattern, photocurability was evaluated as follows.
Using the high pressure mercury lamp as the light source for the photocurable composition, the change in the absorption at 810 cm ⁻¹ of the monomer (polymerizable compound) was measured using a Fourier transform infrared spectrometer (FT-IR). (Monomer consumption rate) was performed in real time.
Based on the measurement results, the photocurability of the photocurable composition was evaluated according to the following criteria.
In the following criteria, if it is A, it is practically acceptable.
~Judgment criteria~
A: The curing reaction rate is 0.5 / second or more.
B: Curing reaction rate is 0.2 / second or more and less than 0.5 / second.
C: Curing reaction rate is less than 0.2 / second.

<Adhesiveness> ... Curability of resist pattern surface As an evaluation of curability of the resist pattern surface, photocurability was evaluated as follows.
When the tape was affixed to the surface of the obtained resist pattern and peeled off, it was judged by visual observation whether or not a photocured resist pattern photocured on the tape side was adhered, and evaluated according to the following criteria.
In the following criteria, if it is A, it is practically acceptable.
~Judgment criteria~
A: There is no pattern adhesion on the tape side.
B: Although it is very thin on the tape side (the area where the pattern is attached is less than 10% of the area of the tape), the adhesion of the pattern is recognized.
C: Pattern adhesion is clearly observed on the tape side (the pattern adhesion area is 10% or more of the tape area).

<Observation of residual film properties and pattern shape>
About the formed resist pattern, the pattern shape and the residue of the pattern were observed with a scanning electron microscope (magnification 300 times), and the remaining film property and the pattern shape were evaluated according to the following criteria.

-Judgment criteria for residual film properties-
A: A residue is not observed.
B: A little residue is observed.
C: Many residues are observed.

~ Judgment criteria for pattern shape ~
A: It is almost the same as the pattern of the original plate from which the pattern shape of the mold is based.
B: There is a part (a range of less than 20% with respect to the film thickness of the original pattern) that is partly different from the original pattern shape of the mold pattern.
C: The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.

<Spin coating suitability> ... coating property (I)
The photocurable composition of the present invention was spin-coated on a 4-inch square 0.7 mm-thick glass substrate on which an aluminum (Al) film having a thickness of 400 nm was formed so as to have a thickness of 6.0 μm. Then, this glass substrate was left still for 1 minute, surface shape observation was performed, and the following judgment criteria evaluated.
~Judgment criteria~
A: No repelling or coating streaks are observed.
B: A few application stripes were observed.
C: Repelling or coating streaks were strongly observed.

<Slit application suitability> ... Applicability (II)
An aluminum (Al) film having a film thickness of 400 nm was formed on the photocurable composition of the present invention by using a slit coater resist coating apparatus (head coater system manufactured by Hirata Kiko Co., Ltd.) for coating a large substrate. The coating was applied on a 7 mm thick glass substrate (550 mm × 650 mm) to form a resist film having a thickness of 2.0 μm, and the presence or absence of streaky irregularities extending vertically and horizontally was observed and evaluated according to the following criteria.
~Judgment criteria~
A: Striped unevenness was not observed.
B: Streaky unevenness was weakly observed.
C: Streaky unevenness was strongly observed or repelling was observed on the resist film.

[Example 2]
As a polymerizable compound, phenoxyethyl acrylate (R-02) 29.39 g, hydroxypivalic acid neopentyl glycol diacrylate (R-09) 48.98 g, tripropylene glycol diacrylate (R-11) 9.795 g, propylene oxide 9.9595 g of modified trimethylolpropane triacrylate (R-13), 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L manufactured by BASF) (P-1) 2 as a photopolymerization initiator 0.0 g, 0.5 g of Exemplified Compound 9 as a surfactant initiator, and 0.05 g of Mega-Fac Painted 31 (silicone-based, W-2) as a surfactant are precisely weighed and mixed at room temperature for 24 hours. As a solution, a photocurable composition (coating solution) A-2 was obtained.
In the photocurable composition A-2 obtained above, the ratio of the polymerizable compound having a viscosity of 30 mPa · s or less was 90% by mass, and the viscosity of the photocurable composition A-2 was 18 mPa · s. It was.
The viscosity was measured by the same method as in Example 1.
Using the photocurable composition A-2 obtained above, a resist pattern was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

Example 3
A photocurable composition A-3 was prepared in the same manner as in Example 1 except that the exemplified compound 30 used as the surface active photopolymerization initiator in Example 1 was changed to the exemplified compound 31.
About the photocurable composition A-3 obtained above, it carried out similarly to Example 1, and measured the viscosity. Moreover, the resist pattern was formed like Example 1 using the photocurable composition A-3 obtained above, and evaluation similar to Example 1 was performed.

Example 4
In Example 3, Photocurable Composition A-4 was prepared in the same manner as Example 3 except that EFTOP EF-122A (fluorine-based, W-1) used as the surfactant was omitted.
About the obtained photocurable composition A-4, it carried out similarly to Example 1, and measured the viscosity. Moreover, the resist pattern was formed like Example 1 using the photocurable composition A-4 obtained above, and evaluation similar to Example 1 was performed.

Example 5
In Example 3, except that EFTOP EF-122A (fluorine type, W-1) used as the surfactant was changed to MegaFac R-08 (fluorine / silicone type, W-3), as in Example 3. Thus, a photocurable composition A-5 was prepared.
About the obtained photocurable composition A-5, it carried out similarly to Example 1, and measured the viscosity. Moreover, the resist pattern was formed like Example 1 using the photocurable composition A-5 obtained above, and evaluation similar to Example 1 was performed.

[Examples 6 to 10]
In Examples 1 to 5, a resist pattern was formed in the same manner as in Examples 1 to 5 except that the exposure amount from the back side of the mold was changed to a condition of 50 mJ / cm ² , and the same evaluation as in Example 1 was performed. Went.

Example 11
As a polymerizable compound, hydroxypivalate neopentyl glycol diacrylate (R-09) 46.2 g, ethylene oxide-modified trimethylolpropane triacrylate (R-12) 46.2 g, ethylene oxide-modified phosphate dimethacrylate (R-16) ) 0.1 g, as photopolymerization initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 manufactured by Ciba Specialty Chemicals) (P-2) 7.5 g, surface activity 0.5 g of Exemplified Compound 31 as an initiator and 0.05 g of EFTOP EF-122A (fluorine-based, W-1) as a surfactant are precisely weighed, mixed at room temperature for 24 hours, and made into a uniform solution as photocurable. Composition (coating solution) A-6 was obtained.
In the photocurable composition A-6 obtained above, the ratio of the polymerizable compound having a viscosity of 30 mPa · s or less was 60% by mass, and the viscosity of the photocurable composition A-6 was 28 mPa · s. It was.
The viscosity was measured by the same method as in Example 1.
Using the photocurable composition A-6 obtained above, a resist pattern was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

[Comparative Examples 1-4]
In Examples 1 to 4, photocurable compositions N-1 to N-4 were respectively prepared in the same manner as in Examples 1 to 4, except that the surfactant photopolymerization initiator was not added.
About each obtained photocurable composition, it carried out similarly to Example 1, and measured the viscosity. Moreover, the resist pattern was formed like Example 1 using each photocurable composition obtained above, and evaluation similar to Example 1 was performed.

[Comparative Example 5]
In Example 1, a photocurable composition N-5 was prepared in the same manner as in Example 1 except that no photopolymerization initiator was added.
About the obtained photocurable composition N-5, it carried out similarly to Example 1, and measured the viscosity. Further, using the obtained photocurable composition N-5, a resist pattern was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

[Comparative Examples 6 to 10]
In Comparative Examples 1 to 5, a resist pattern was formed in the same manner as Comparative Examples 1 to 5 except that the exposure amount from the back side of the mold was changed to the condition of 50 mJ / cm ^2. Went.

[Comparative Example 11]
As a polymerizable compound, 28.6 g of tripropylene glycol diacrylate (R-11), 62 g of ethylene oxide-modified trimethylolpropane triacrylate (R-12), 4.77 g of neopentyl glycol diacrylate (R-22), photopolymerization As an initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 manufactured by Ciba Specialty Chemicals) (P-2) 4.58 g, and exemplified compound 31 as a surfactant initiator 0.5 g, EFTOP EF-122A (fluorine-based, W-1) 0.05 g as a surfactant is precisely weighed and mixed at room temperature for 24 hours. As a uniform solution, a photocurable composition (coating liquid) N -6 was obtained.
In the photocurable composition N-6 obtained above, the proportion of the polymerizable compound having a viscosity of 30 mPa · s or less was 30% by mass, and the viscosity of the photocurable composition N-6 was 33 mPa · s. It was.
The viscosity was measured by the same method as in Example 1.
Using the photocurable composition N-6 obtained above, a resist pattern was formed in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

The compositions of the photocurable compositions in Examples 1 to 5 and 11 and Comparative Examples 1 to 5 and 11 are shown in Table 1 below.
The evaluation results of Examples 1 to 11 and Comparative Examples 1 to 11 are shown in Table 2 below.

<Explanation of symbols in Table 1>
-(A) Polymerizable compound-
R-01: benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)
R-02: Phenoxyethyl acrylate (Light acrylate PO-A: manufactured by Kyoeisha Yushi Co., Ltd.)
R-09: Hydroxypivalic acid neopentyl glycol diacrylate (Kalayad MANDA: manufactured by Nippon Kayaku Co., Ltd.)
R-11: Tripropylene glycol diacrylate (Kalayad TPGDA: manufactured by Nippon Kayaku Co., Ltd.)
R-12: Ethylene oxide modified trimethylolpropane triacrylate (SR-454: manufactured by Kayaku Sartomer)
R-13: Propylene oxide-modified trimethylolpropane triacrylate (New Frontier TMP-3P: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
R-16: Ethylene oxide-modified phosphate dimethacrylate (Kayamer PM-21: Nippon Kayaku Co., Ltd.)
R-22: Neopentyl glycol diacrylate (SR-351: Kayaku Sartomer)

-(B) Photopolymerization initiator-
P-1: 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF)
P-2: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173: manufactured by Ciba Specialty Chemicals)

~ (C) Surfactant ~
W-1: EFTOP EF-122A (manufactured by Tochem Products: fluorinated surfactant)
W-2: Megafuck Paintad 31 (Dainippon Ink & Chemicals, Inc .: silicone surfactant)
W-3: Mega-Fac R-08 (Dainippon Ink Chemical Industries, Ltd .: fluorine / silicone surfactant)

As shown in Table 2, the peelability from the mold was good in Examples 1 to 5 and 11 containing at least a surface-active photopolymerization initiator, but Comparative Examples 1 to 4 not containing a surface-active photopolymerization initiator. In particular, the peelability from the mold was not satisfactory.
In addition, while Examples 6 to 10 in which the exposure amount was halved maintained good performance, Comparative Examples 6 to 10 were not able to obtain satisfactory performance.
Furthermore, Comparative Example 11 having a viscosity exceeding 30 mPa · s could not obtain satisfactory coating properties and performance.

Example 12
≪Preparation of substrate with Al electrode pattern≫
<Formation of resist pattern>
The thickness of the photocurable composition A-1 prepared above is 6.0 μm on an aluminum (Al) film having a thickness of 400 nm formed on a 4 inch square glass substrate having a thickness of 1 mm. The photocurable layer was formed on the Al film by spin coating as described above.

Next, a resist pattern was formed on the Al film by the same method as in Example 1.
The resist pattern was formed as an inverted pattern with respect to the concave / convex pattern of the mold.

<Formation of Al electrode pattern>
Next, wet etching of the Al film was performed using the obtained resist pattern as a mask.
That is, an aluminum (Al) portion not covered with the resist pattern was removed with a phosphoric nitrate etchant to form an aluminum (Al) electrode pattern (hereinafter also referred to as “Al electrode pattern”).
Further, the resist was stripped by immersion for 3 minutes at 80 ° C. using a mixed stripping solution of monoethanolamine / dimethyl sulfoxide.
As a result, an Al electrode-patterned substrate was obtained.

≪Evaluation≫
Evaluation similar to Example 1 was performed about the said photocurable composition and the said resist pattern.
Furthermore, the following etching property was evaluated about the said Al electrode pattern.
The evaluation results are shown in Table 3.

<Etching property>
The Al electrode pattern after resist peeling was observed visually and with an optical microscope (magnification 500 times). Observation was performed for 5 points in the substrate and evaluated according to the following criteria.
~Judgment criteria~
A: An aluminum line having a line width of 10 ± 2.0 μm was obtained.
B: Variation in line width The line exceeded ± 2.0 μm.
C: Line missing portions existed or lines were connected.

[Examples 13 to 16]
In Example 12, Example 12 except that the photocurable composition A-1 prepared in Example 1 was changed to the photocurable compositions A-2 to A-5 prepared in Examples 2 to 5. Similarly, a resist pattern and an Al electrode pattern were formed. Evaluation similar to Example 12 was performed about the said photocurable composition, the said resist pattern, and the said Al electrode pattern, respectively.
The evaluation results are shown in Table 3.

[Comparative Examples 12 to 16]
In Examples 12-16, except having changed photocurable composition A-1 to A-5 into the above-mentioned photocurable composition N-1 to N-5, it is the same as that of Examples 12-16, A resist pattern and an Al electrode pattern were respectively formed. Evaluation similar to Example 12 was performed about the said photocurable composition, the said resist pattern, and the said Al electrode pattern, respectively.
The evaluation results are shown in Table 3.

  As shown in Table 3, Examples 12 to 16 containing at least a surfactant initiator compound exhibited good mold releasability and etching properties, but Comparative Examples 12 to 15 containing no surfactant initiator compound. The composition and the composition of Comparative Example 16 that did not contain a photopolymerization initiator were not particularly satisfactory in the releasability from the mold and the etching property.

Claims (6)

For optical nanoimprint lithography, comprising (a) a polymerizable compound, (b) a photopolymerization initiator, and (c) a surface-active photopolymerization initiator, and having a viscosity at 25 ° C. of 3 mPa · s to 30 mPa · s. Photocurable composition.   The (c) surfactant photopolymerization initiator is selected from an optionally substituted alkyl group having 3 to 30 carbon atoms, an optionally substituted siloxane group, and an optionally substituted fluorinated alkyl group. The photocurable composition for optical nanoimprint lithography according to claim 1, wherein the photocurable composition is a compound having at least one kind.   3. The photocurable composition for photo-nanoimprint lithography according to claim 1, wherein the viscosity at 25 ° C. is 3 mPa · s or more and 18 mPa · s or less.   Furthermore, (d) At least 1 sort (s) chosen from a fluorine-type surfactant, a silicone type surfactant, and a fluorine-silicone type surfactant is included, The any one of Claims 1-3 characterized by the above-mentioned. The photocurable composition for photo-nanoimprint lithography described in 1. The process of apply | coating the photocurable composition for optical nanoimprint lithography of any one of Claims 1-4 on a board | substrate, and forming a photocurable layer,
Deforming the photocurable layer by pressing the concave / convex pattern of the mold having the concave / convex pattern and the photocurable layer formed on the substrate;
The deformed photocurable layer is irradiated with light from the opposite side of the substrate on which the photocurable layer is formed and / or from the opposite side of the mold in contact with the photocurable layer. Curing the deformed photocurable layer,
Peeling the mold from the substrate and forming a reversal pattern of the concavo-convex pattern on the substrate;
A method for manufacturing a substrate with a pattern. Furthermore,
Etching the substrate using the reverse pattern formed on the substrate as a mask;
Peeling the reverse pattern from the etched substrate;
The method for producing a substrate with a pattern according to claim 5, wherein: