Photocurable resin composition for imprinting

Abstract

Provided is a photocurable resin composition for imprinting that contains an N-vinyloxazolidinone compound (A), a compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of from 100 to less than 700, and a photopolymerization initiator. The content of the N-vinyloxazolidinone compound (A) is 40 wt% or more with respect to 100 wt% of the photocurable resin composition for imprinting.

Description

Photocurable resin composition for imprinting

[0001] The present invention relates to a photocurable resin composition for imprinting and a resin mold obtained by curing the photocurable resin composition for imprinting.

[0002] Liquid crystal display devices are widely used as display devices for various electronic devices. In recent years, such electronic devices have become increasingly smaller, and there is a demand for smaller and lighter liquid crystal display devices as well.

[0003] Such liquid crystal display devices mainly use optical functional sheets that utilize the effects of reflection, refraction, scattering, etc., or sheets that combine these. As such optical functional sheets, shaped films formed by imparting a predetermined uneven shape to the surface of a resin film are known. Such shaped films are usually produced by press molding using a molded plate with the desired uneven shape, or by injection molding.

[0004] As another method for imparting a predetermined uneven shape to the surface of a resin film, for example, an imprinting method using a resin mold is proposed in Patent Document 1. In the technology described in Patent Document 1, a composition containing a fluorine compound or a silicon compound is used as a photocurable resin composition used in the resin mold from the viewpoint of improving the releasability and durability of the resin mold.

[0005] International Publication No. 2021 / 182049

[0006] However, compositions containing fluorine compounds or silicon compounds have problems such as high production costs and large adverse effects on the human body and the environment. Furthermore, compositions containing fluorine compounds or silicon compounds have poor handleability, and resin molds obtained by curing them may have problems such as insufficient transferability from a metal mold used in producing the resin mold, releasability from a resin to be transferred, transferability to a resin to be transferred, and durability.

[0007] An object of the present invention is to provide a photocurable resin composition for imprinting that can provide a resin mold excellent in transferability, releasability, and durability even when the content of a fluorine compound and a silicon compound is small or the composition is free of a fluorine compound and a silicon compound, a resin mold obtained using the photocurable resin composition for imprinting, and a resin mold laminate.

[0008] [1] According to Aspect 1 of the present invention, there is provided a photocurable resin composition for imprints, comprising: an N-vinyloxazolidinone compound (A); a compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700; and a photopolymerization initiator, wherein the content of the N-vinyloxazolidinone compound (A) is 40% by weight or more relative to 100% by weight of the photocurable resin composition for imprints.

[0009] [2] Aspect 2 of the present invention provides the photocurable resin composition for imprints of Aspect 1, wherein the content of the N-vinyloxazolidinone compound (A) relative to 100% by weight of the photocurable resin composition for imprints is 40% by weight or more and 80% by weight or less.

[0010] [3] A third aspect of the present invention provides the photocurable resin composition for imprints according to the first or second aspect, wherein the content of the compound (B) is 15% by weight or more and 55% by weight or less.

[0011] [4] A fourth aspect of the present invention provides the photocurable resin composition for imprints according to any one of the first to third aspects, in which the compound (B) is a compound containing 3 or more and 6 or less ethylenically unsaturated groups.

[0012] [5] A fifth aspect of the present invention provides the photocurable resin composition for imprints according to any one of the first to fourth aspects, wherein the content of the photopolymerization initiator relative to 100% by weight of the photocurable resin composition for imprints is 1% by weight or more and 5% by weight or less.

[0013] [6] According to a sixth aspect of the present invention, there is provided a resin mold having a fine pattern on its surface, which is obtained by curing the photocurable resin composition for imprints according to any one of the first to fifth aspects.

[0014] [7] According to the seventh aspect of the present invention, the hardness of the surface of the resin mold measured by a nanoindentation method at a temperature of 30°C is 50 N / mm ２ Above, 400N / mm ２ A resin mold according to Aspect 6 is provided as follows.

[0015] [8] According to aspect 8 of the present invention, there is provided a resin mold according to aspect 6 or 7, in which, when the surface of the resin mold is subjected to elemental analysis by X-ray photoelectron spectroscopy (XPS), the nitrogen concentration relative to the total amount of detected elements (100 atomic %) is 4.0 atomic % or more and 12.0 atomic % or less.

[0016] [9] According to a ninth aspect of the present invention, there is provided the resin mold of any one of the sixth to eighth aspects, wherein the elastic deformation rate of the surface of the resin mold measured by nanoindentation is 25% or more.

[0017]

[10] According to a tenth aspect of the present invention, there is provided the resin mold of any one of the sixth to ninth aspects, wherein the glass transition temperature (Tg) is 60° C. or higher and 250° C. or lower.

[0018]

[11] According to an eleventh aspect of the present invention, there is provided a resin mold laminate comprising a resin substrate and the resin mold of any one of aspects 6 to 10 provided on the resin substrate.

[0019]

[12] According to a twelfth aspect of the present invention, there is provided the resin molded laminate of the eleventh aspect, wherein the resin substrate is a polyester-based resin substrate.

[0020]

[13] According to Aspect 13 of the present invention, there is provided a method for producing a resin mold having a fine pattern on its surface, the method comprising the steps of: forming the photocurable resin composition for imprinting according to any one of Aspects 1 to 5 on the surface of a base material; pressing a mold having a reversal pattern of the fine pattern on its surface against the photocurable resin composition for imprinting so that the reversal pattern is in contact with the photocurable resin composition for imprinting; irradiating the photocurable resin composition for imprinting with light while the mold is pressed against the photocurable resin composition for imprinting to cure the photocurable resin composition for imprinting into a cured product; and separating the mold from the cured product to obtain a resin mold having the fine pattern formed on its surface.

[0021]

[14] According to aspect 14 of the present invention, there is provided a method for producing a shaped film, the method comprising the steps of: forming a photocurable resin composition to be transferred on the surface of a substrate; pressing a resin mold according to any one of aspects 6 to 10 against the photocurable resin composition to be transferred so that the fine pattern is in contact with the photocurable resin composition to be transferred; irradiating the photocurable resin composition to be transferred with light while the resin mold is pressed against the photocurable resin composition to harden the photocurable resin composition to form a hardened product; and separating the resin mold from the hardened product to obtain a shaped film having a concave-convex shape to which the fine pattern has been transferred.

[0022]

[15] According to aspect 15 of the present invention, there is provided a method for producing a shaped film, the method comprising the steps of: supplying a molten resin to the surface of a resin mold of any one of aspects 6 to 10; cooling and solidifying the molten resin to form a hardened product; and separating the resin mold from the hardened product to obtain a shaped film having a concave-convex shape formed by transferring the fine pattern.

[0023] According to the present invention, it is possible to provide a photocurable resin composition for imprints that can give a resin mold excellent in transferability, releasability, and durability, even when the content of a fluorine compound and a silicon compound is small or when the composition does not contain a fluorine compound or a silicon compound.

[0024] FIG. 1 is a diagram showing an example of a manufacturing apparatus for a shaped film using a resin mold according to an embodiment of the present invention. FIG. 2(A) is a cross-sectional view of a resin mold laminate according to an embodiment of the present invention, and FIG. 2(B) is an enlarged view of part IIB in FIG. 2(A). FIG. 3 is a diagram showing an example of a manufacturing apparatus for a resin mold according to an embodiment of the present invention. FIG. 4(A) is a plan view of a mold used in the examples, and FIG. 4(B) is a cross-sectional view of the prism shape of the mold, and an enlarged cross-sectional view showing the IVB-IVB' cross section of FIG. 4(A).

[0025] Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[0026] Fig. 1 is a diagram showing an example of a manufacturing apparatus for a shaped film using a resin mold in this embodiment, Fig. 2(A) is a cross-sectional view of a resin mold laminate in this embodiment, and Fig. 2(B) is an enlarged view of part IIB in Fig. 2(A). Note that the present invention is not particularly limited to the embodiment shown in Fig. 1.

[0027] <Method for manufacturing a shaped film> In the manufacturing apparatus shown in Fig. 1 , first, a substrate film 40 to be transferred is continuously unwound from a substrate unwind roll 10. After passing through a guide roll 11, a photocurable photocurable resin composition to be transferred is applied to the surface of the substrate film 40 in a T-die 20, thereby forming a photocurable resin composition layer to be transferred 50. The thickness of the photocurable resin composition layer to be transferred 50 is controlled by adjusting the clearance between the T-die 20 and the nip roll 12 and the unwinding speed of the substrate unwind roll 10.

[0028] In the manufacturing apparatus shown in FIG. 1 , a resin mold laminate 60 is continuously unwound from a resin mold unwind roll 13. A substrate film 40 on which a photocurable resin composition layer 50 is formed and the resin mold laminate 60 are superimposed by a laminating roll 15 and an upstream backup roll 16. Here, as shown in FIG. 2 , the resin mold laminate 60 includes a substrate film 70 and a resin mold 80. A predetermined uneven shape (fine pattern 81) is formed on the surface of the resin mold 80. Returning to FIG. 1 , the substrate film 40, the photocurable resin composition layer 50, and the resin mold laminate 60 are superimposed in this order, with the uneven surface of the resin mold laminate 60 in contact with the photocurable resin composition layer 50.

[0029] Next, the ultraviolet irradiation device 30 irradiates the photocurable resin composition layer 50 to be transferred from the side of the substrate film 40, thereby curing the curable resin material that constitutes the photocurable resin composition layer 50 to form a cured resin layer 51. At this time, the curable resin material is cured in a state in which the fine pattern 81 on the surface of the resin mold 80 is transferred. Therefore, the cured resin layer 51 has a desired uneven shape on its surface.

[0030] Next, the transferred substrate film 40, the cured resin layer 51, and the resin mold laminate 60, while stacked on one another, pass between the laminating roll 15 and the downstream backup roll 17. The resin mold laminate 60 is peeled off from the cured resin layer 51 by being taken up by the resin mold take-up roll 14. The cured resin layer 51 and the transferred substrate film 40 are taken up by the substrate take-up roll 19 via a guide roll 18.

[0031] In this manner, a shape-transfer film is continuously produced, which is formed by laminating the cured resin layer 51 and the transfer-receiving substrate film 40. A fine uneven shape is formed on the surface of the cured resin layer 51 by transferring the fine pattern 81 of the resin mold 80. For this reason, the shape-transfer film, which is formed by laminating the cured resin layer 51 and the transfer-receiving substrate film 40, is suitably used for various optical applications, for example, as an optical functional sheet that utilizes effects such as reflection, refraction, and scattering.

[0032] The manufacturing method and the configuration of the shaped film are not particularly limited to those described above. For example, instead of the photocurable resin composition for transfer containing a curable resin material, a molten resin may be used and the molten resin may be cured by cooling to obtain the cured resin layer 51.

[0033] The photocurable resin composition for imprinting of the present invention is suitably used as a constituent material of the resin mold 80 of the above-mentioned resin mold laminate 60. The photocurable resin composition for imprinting of the present invention will be described in detail below.

[0034] <Photocurable resin composition for imprinting> The photocurable resin composition for imprinting of the present invention comprises an N-vinyloxazolidinone compound (A), a compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700, and a photopolymerization initiator, and the content of the N-vinyloxazolidinone compound (A) relative to 100% by weight of the photocurable resin composition for imprinting is 40% by weight or more.

[0035] Examples of the N-vinyloxazolidinone compound (A) include N-vinyloxazolidinone (for example, "3-vinyloxazolidin-2-one" manufactured by Alfa Chemistry), and N-vinyl-5-methyloxazolidinone (for example, "VMOX" manufactured by BASF), with N-vinyl-5-methyloxazolidinone being preferred.

[0036] The content of the N-vinyloxazolidinone compound (A) in the photocurable resin composition for imprinting is 40% by weight or more, preferably 40% by weight or more and 80% by weight or less, more preferably 50% by weight or more and 75% by weight or less, and even more preferably 60% by weight or more and 70% by weight or less, based on 100% by weight of the photocurable resin composition for imprinting. By setting the content of the N-vinyloxazolidinone compound (A) within the above range, a resin mold made from the photocurable resin composition for imprinting can be made to have excellent transferability, releasability, and durability.

[0037] The compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700 may be any compound as long as it contains two or more ethylenically unsaturated groups, but preferably contains three or more and six or less ethylenically unsaturated groups. By using a compound (B) containing three or more and six or less ethylenically unsaturated groups as the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700, it is possible to provide a resin mold made from the photocurable resin composition for imprints with excellent transferability, releasability, and durability. Note that, as the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700, a compound containing two ethylenically unsaturated groups and a compound containing three or more and six or less ethylenically unsaturated groups may be used in combination.

[0038] The molecular weight of the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700 is 100 or more and less than 700, preferably 150 or more and 650 or less, and more preferably 250 or more and 600 or less.

[0039] The viscosity at 25° C. of the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700 is preferably 1 cps or more and 7,000 cps or less, more preferably 40 cps or more and 6,800 cps or less, and even more preferably 80 cps or more and 6,600 cps or less. The viscosity of the compound (B) can be measured using a B-type viscometer.

[0040] Examples of the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700 include compounds containing one or a combination of two or more of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a methallyl group, a styryl group, a maleimide group, and the like, and compounds containing two or more acryloyl groups, compounds containing two or more methacryloyl groups, and compounds containing two or more vinyl groups are preferred. Specific examples of the compound containing two or more acryloyl groups include 1,4-butanediol diacrylate (for example, "Viscoat #195" manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (for example, "HDDA" manufactured by Daicel Allnex Corporation), 1,9-nonanediol diacrylate (for example, "Light Acrylate 1.9ND-A" manufactured by Kyoeisha Chemical Co., Ltd.), 1,10-decanediol diacrylate (for example, "MIRAMER M2010" manufactured by MIWON Corporation), 3-methyl-1,5-pentanediol diacrylate (for example, "Light Acrylate MPD-A" manufactured by Kyoeisha Chemical Co., Ltd.), diethylene glycol diacrylate (for example, "SARTOMER SR230" manufactured by Arkema), triethylene glycol diacrylate (for example, "MIRAMER" manufactured by MIWON Corporation), "M232" and the like), tetraethylene glycol diacrylate (for example, "SARTOMER SR268" manufactured by Arkema, etc.), polyethylene glycol 400 diacrylate (for example, "MIRAMER M280" manufactured by MIWON, etc.), polyethylene glycol 600 diacrylate (for example, "MIRAMER M286" manufactured by MIWON, etc.), dipropylene glycol diacrylate (for example, "MIRAMER M222" manufactured by MIWON, etc.), tripropylene glycol diacrylate (for example, "MIRAMER M220" manufactured by MIWON, etc.), polypropylene glycol 400 diacrylate (for example, "MIRAMER M2040" manufactured by MIWON, etc.), 1,3-butylene glycol diacrylate (for example, "SARTOMER SR212" manufactured by Arkema, etc.), neopentyl glycol diacrylate (for example, "Light Acrylate NP-A" manufactured by Kyoeisha Chemical Co., Ltd., etc.), neopentyl glycol PO-modified diacrylate (for example, "MIRAMER M216" manufactured by MIWON, etc.), hydroxypivalic acid neopentyl glycol diacrylate (for example, "MIRAMER M210" manufactured by MIWON, etc.), 1,6-hexanediol EO-modified diacrylate (for example, MIWON's "MIRAMER M202"), glycerin diacrylate (for example, Toagosei's "M-920"), tricyclodecane dimethanol diacrylate (for example, MIWON's "MIRAMER M262"), bisphenol A EO-modified diacrylate (for example, Daicel-Allnex's "EBECRYL 150"), bisphenol F EO-modified diacrylate (for example, MIWON's "MIRAMER M290"), propoxylated (2) neopentyl glycol diacrylate (for example, Arkema's "SARTOMER SR9003"), NS" etc.), trimethylolpropane triacrylate (for example, "M-309" manufactured by Toagosei Co., Ltd., etc.), trimethylolpropane EO-modified triacrylate (for example, "MIRAMER M3130" manufactured by MIWON Co., Ltd., etc.), pentaerythritol triacrylate (for example, "MIRAMER M340" manufactured by MIWON Co., Ltd., etc.), tris(2-hydroxyethyl)isocyanurate triacrylate (for example, "SARTOMER SR368 NS" manufactured by Arkema, etc.), glycerin triacrylate (for example, "M-930" manufactured by Toagosei Co., Ltd., etc.), pentaerythritol tetraacrylate (for example, "Light Acrylate PE-4A" manufactured by Kyoeisha Chemical Co., Ltd., etc.), pentaerythritol EO-modified tetraacrylate (for example, "MIRAMER M3130" manufactured by MIWON Co., Ltd., etc.), Examples of the compound containing two or more methacryloyl groups include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 110, 111, 112, 113, 114, 115, 120, 121, 122, 123, 124, 125, 130, 131, 132, 136-hexanediol dimethacrylate (e.g., MIWON's "MIRAMER M201"), ethylene glycol dimethacrylate (e.g., MIWON's "MIRAMER M221"), diethylene glycol dimethacrylate (e.g., MIWON's "MIRAMER M231"), triethylene glycol dimethacrylate (e.g., MIWON's "MIRAMER M233"), tetraethylene glycol dimethacrylate (e.g., MIWON's "MIRAMER M235"), 1,4-butanediol dimethacrylate (e.g., MIWON's "MIRAMER M205"), polyethylene glycol dimethacrylate (e.g., MIWON's "MIRAMER M283"), bisphenol A Examples of suitable compounds include EO-modified dimethacrylates (e.g., MIRAMER M245 manufactured by MIWON Corporation), polysiloxane dimethacrylates (e.g., FM-7711 manufactured by JNC Corporation), and trimethylolpropane trimethacrylates (e.g., MIRAMER M301 manufactured by MIWON Corporation). Specific examples of compounds containing two or more vinyl groups include α-allyloxymethyl acrylic acid esters (e.g., AOMA manufactured by Nippon Shokubai Co., Ltd.). Among these, compounds containing two or more acryloyl groups are preferred, and compounds containing three or more acryloyl groups are more preferred. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. These compounds may be used alone or in combination of two or more. ,

[0041] The content of the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700 in the photocurable resin composition for imprints is preferably 15% by weight or more and 55% by weight or less, more preferably 20% by weight or more and 45% by weight or less, and even more preferably 25% by weight or more and 35% by weight or less, based on 100% by weight of the photocurable resin composition for imprints.

[0042] The photocurable resin composition for imprints may contain, in addition to the N-vinyloxazolidinone compound (A) and the compound (B), a compound (C) containing one or more ethylenically unsaturated groups. Examples of the compound (C) containing one or more ethylenically unsaturated groups include aliphatic (meth)acrylates, alicyclic (meth)acrylates, aromatic (meth)acrylates, (meth)acrylamides, vinyl compounds, fluorine-containing (meth)acrylates, silicon-containing (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, and polyester (meth)acrylates, all of which contain one or more ethylenically unsaturated groups. Specific examples of aliphatic (meth)acrylates containing one or more ethylenically unsaturated groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate. Examples of alicyclic (meth)acrylates containing one or more ethylenically unsaturated groups include cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 1-ethylcyclopentyl (meth)acrylate,Examples of aromatic (meth)acrylates containing one or more ethylenically unsaturated groups include phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, biphenylmethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, benzyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, and phenoxy polyethylene glycol (meth)acrylate. Examples of (meth)acrylamides containing one or more ethylenically unsaturated groups include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methylol(meth)acrylamide, and (meth)acryloylmorpholine. Examples of vinyl compounds containing one or more ethylenically unsaturated groups include N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcarbazole, N-vinylmorpholine, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylformamide, etc. Examples of fluorine-containing (meth)acrylates containing one or more ethylenically unsaturated groups include 2,2,2-trifluoroethyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, etc. Examples of silicon-containing acrylates containing one or more ethylenically unsaturated groups include polysiloxane(meth)acrylate, polysiloxanepropyl(meth)acrylate, 3-{tris[(trimethylsilyl)oxy]silyl}propyl(meth)acrylate, silicone di(meth)acrylate, etc. Examples of urethane(meth)acrylates containing one or more ethylenically unsaturated groups include "KRM9276", "KRM9465", "EBECRYL 230", "EBECRYL 270", "EBECRYL 4858", "EBECRYL 8402", "EBECRYL 8409", "EBECRYL 8804", "EBECRYL 8807", etc., all manufactured by Daicel-Allnex Corporation."EBECRYL 9270", "KRM2000", "KRM8191", "EBECRYL 4513", "EBECRYL 4738", "EBECRYL 4740", "EBECRYL 8311", "EBECRYL 8465", "EBECRYL 9260", "EBECRYL 8701", "KRM8667", "KRM8296", "EBECRYL 4265", "EBECRYL 4587", "EBECRYL 4666", "EBECRYL 8210", "EBECRYL 8606", "EBECRYL 1290", "EBECRYL 5129", "EBECRYL 8301R", "KRM8200", "KRM8904", "KRM8452", "EBECRYL 210", "EBECRYL 220", Arkema's "CN929", "CN962", "CN963", "CN964", "CN965", "CN968", "CN980", "CN981", "CN982", "CN983", "CN996", "CN9001", "CN9002", "CN9788", "CN9893", "CN971", "CN972", "CN975", "CN978" "," "CN9782," "CN9783," Toagosei's "M-1100," "M-1200," Negami Chemical Industrial's "Art Resin UN-2601," "Art Resin UN-6206," "Art Resin UN-7700," "Art Resin UN-5500," "Art Resin UN-3320HA," "Art Resin UN-901T," "Art Resin UN-952," -Resin UN-905, -Resin UN-908, -Resin UN-909, and Mitsubishi Chemical's UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV-7650B, UV-6630B, and UV- 7000B", "UV-7510B", "UV-2000B", "UV-2750B", "UV-3000B", "UV-3200B", "UV-3300B", "UV-3310B", "UV-3700B", "UV-6640B", Shin-Nakamura Chemical Co., Ltd.'s "UA-4200", "UA-160TM", "UA-290TM", "UA-7100", "UA-W2A",Examples of epoxy (meth)acrylates containing one or more ethylenically unsaturated groups include "UA-4400", "UA-122P", "U-200PA", "UA-1100H", "U-6LPA", "UA-33H", "U-10HA", "U-10PA", and "U-15HA" manufactured by Kyoeisha Chemical Co., Ltd., and "AH-600", "UA-306H", "UA-306T", "UA-306I", "UA-510H", "UF-8001G", and "DAUA-167" manufactured by Kyoeisha Chemical Co., Ltd. Examples of epoxy (meth)acrylates containing one or more ethylenically unsaturated groups include "EBECRYL 3605", "EBECRYL 3701", "EBECRYL 3702", "EBECRYL 3703", "EBECRYL 3708", and "EBECRYL 860", Arkema's "CN104", "CN111", "CN115", "CN116", "CN118", "CN120", "CN124", "CN151", and "CNUVE151", and Kyoeisha Chemical's "Epoxy Ester M-600A", "Epoxy Ester 40EM", "Epoxy Ester 70PA", "Epoxy Ester 200PA", "Epoxy Ester 80MFA", "Epoxy Ester 3002M(N)", "Epoxy Ester 3002A(N)", "Epoxy Ester 3000MK", and "Epoxy Ester 3000A". Examples of polyester (meth)acrylates containing one or more ethylenically unsaturated groups include "EBECRYL 524," "EBECRYL 525," "EBECRYL 571," "EBECRYL 851," "EBECRYL 436," "EBECRYL 438," "EBECRYL 811," "EBECRYL 852," "EBECRYL 853," "EBECRYL 884," "EBECRYL 812," "EBECRYL 888," "EBECRYL 893," "EBECRYL 800," "EBECRYL 810," "EBECRYL 450," "EBECRYL 820," "EBECRYL 846," "EBECRYL 870," and "EBECRYL 893," all manufactured by Daicel Allnex Corporation. 1830", "EBECRYL LEO10801", Arkema's "CN2285", "CN2203 NS", "CN2254 NS", "CN2271", "CN2273", "CN2279", "CN2281", "CN2283 NS",Examples include "CN8201 NS", "CN7001 NS", "CN2259", "CN2261 NS", "CN292", "CN294", "CN299", "CN2282", "CN2295", "CN293", "CN296", "CN2267", "CN2303", "CN2302", and "CN2304", as well as "M-6100", "M-6250", "M-6500", "M-7100", "M-7300K", "M-8030", "M-8060", "M-8100", "M-8530", "M-8560", and "M-9050" manufactured by Toagosei Co., Ltd. These may be used alone or in combination of two or more. In the present invention and this specification, "(meth)acrylate" means acrylate or methacrylate, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0043] The content of the compound (C) having one or more ethylenically unsaturated groups in the photocurable resin composition for imprints is preferably 20% by weight or less, and more preferably 10% by weight or less, based on 100% by weight of the photocurable resin composition for imprints. It is further preferable that the photocurable resin composition for imprints is substantially free of the compound (C) having one or more ethylenically unsaturated groups.

[0044] The photocurable resin composition for imprints may contain an acrylic resin in addition to the N-vinyloxazolidinone compound (A), the compound (B), and the compound (C). Specific examples of acrylic resins include "EBECRYL 1710" (acrylic resin diluted with 1,6-hexanediol diacrylate (HDDA)) manufactured by Daicel Allnex Co., Ltd., "MIRAMER SC9213" (acrylic resin diluted with 1,6-hexanediol diacrylate (HDDA)) manufactured by MIWON Co., Ltd., "DIANAL BR-50", "DIANAL BR-80", "DIANAL BR-105", "DIANAL BR-106", "DIANAL BR-107", "DIANAL BR-115", "DIANAL MB-2539", "DIANAL MB-2660", and "DIANAL MB-7497" manufactured by Mitsubishi Chemical Corporation, and "DEGALAN LP64 / 12", "DEGALAN PM381N", and "DEGALAN These may be used alone or in combination of two or more.

[0045] The content of the acrylic resin in the photocurable resin composition for imprinting is preferably 20% by weight or less, and more preferably 10% by weight or less, relative to 100% by weight of the photocurable resin composition for imprinting. It is further preferable that the photocurable resin composition for imprinting is substantially free of acrylic resin.

[0046] The photocurable resin composition for imprinting contains a photopolymerization initiator, such as an α-hydroxyketone compound, an acylphosphine oxide compound, an α-aminoketone compound, an oxime ester compound, or an intramolecular hydrogen abstraction compound. Specific examples of the α-hydroxyketone compound include 2-hydroxy-2-methylpropiophenone (for example, "Omnirad 1173" manufactured by IGM Resins, and "2-Hydroxy-2-methylpropiophenone" manufactured by Tokyo Chemical Industry Co., Ltd.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (for example, "Omnirad 127" manufactured by IGM Resins), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (for example, "Omnirad 2959" manufactured by IGM Resins), and 1-hydroxycyclohexylphenyl ketone (for example, "Omnirad 1173" manufactured by IGM Resins). 184), oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} (for example, "ESACURE ONE" manufactured by IGM Resins), and the like. Specific examples of the acylphosphine oxide compound include bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (for example, "Omnirad TPO" manufactured by IGM Resins), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (for example, "Omnirad 819" manufactured by IGM Resins), and ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (for example, "Omnirad TPO-L" manufactured by IGM Resins).Specific examples of the α-aminoketone compound include 2-methyl-4′-methylthio-2-morpholinopropiophenone (for example, “Omnirad 907” manufactured by IGM Resins), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (for example, “Omnirad 369” manufactured by IGM Resins), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (for example, “Omnirad 379EG” manufactured by IGM Resins). Specific examples of the oxime ester compound include 1-[4-(phenylthio)-2-(O-benzoyloxime)] (for example, "Irgacure OXE01" manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (for example, "Irgacure OXE02" manufactured by BASF), "Irgacure OXE03" and "Irgacure OXE04" manufactured by BASF, and the like. Specific examples of intramolecular hydrogen abstraction compounds include phenyl glyoxylic acid methyl ester (for example, "Omnirad MBF" manufactured by IGM Resins), bis(η5-2,4-cyclopentadiene-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyltitanium] (for example, "Omnirad 784" manufactured by IGM Resins), and 2,2-dimethoxy-1,2-diphenylethan-1-one (for example, "Omnirad 651" manufactured by IGM Resins). Among these, α-hydroxyketone compounds and acylphosphine oxide compounds are preferred. These compounds may be used alone or in combination of two or more.

[0047] The content of the photopolymerization initiator is preferably 1% by weight or more and 5% by weight or less, and more preferably 1.5% by weight or more and 4% by weight or less, relative to 100% by weight of the entire photocurable resin composition for imprints. By setting the content of the photopolymerization initiator within this range, the curability of the photocurable resin composition for imprints can be made sufficient.

[0048] The photocurable resin composition for imprints of the present invention may further contain additives such as antioxidants, light stabilizers, and polymerization inhibitors, within limits that do not impair the effects of the present invention.

[0049] Specific examples of the antioxidant include pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate] (e.g., "IRGANOX 1010" manufactured by BASF, "ADEKA STAB AO-60" manufactured by ADEKA, etc.), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (e.g., "IRGANOX 1035" manufactured by BASF, etc.), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., "IRGANOX 1076" manufactured by BASF, "ADEKA STAB AO-50" manufactured by ADEKA, etc.), octyl 3-[4-hydroxy-3,5-bis(propan-2-yl)phenyl]propanoate (for example, "IRGANOX 1135" manufactured by BASF), 4,4',4' '-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(2,6-di-tert-butylphenol) (for example, "IRGANOX 1330" manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (for example, "IRGANOX 1520L" manufactured by BASF), 4,6-bis(dodecylthiomethyl)-o-cresol (for example, "IRGANOX 1726" manufactured by BASF), 3,6-dioxaoctane-1,8-diol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate] (for example, "IRGANOX 245" manufactured by BASF), and the like), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (for example, "IRGANOX 259" manufactured by BASF, etc.), 1,3,5-tris[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (for example, "IRGANOX 3114" manufactured by BASF, "ADEKA STAB AO-20" manufactured by ADEKA, etc.), 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g., "IRGANOX 3790" manufactured by BASF, etc.), bis[4-(1,1,3,3-tetramethylbutyl)phenyl]amine (e.g., "IRGANOX 5057" manufactured by BASF, etc.), 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol (e.g., "IRGANOX 565" manufactured by BASF, etc.), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (e.g., "ADEKA STAB AO-30" manufactured by ADEKA, etc.), 4,4'-butylidenebis(6-tert-butyl-m-cresol) (for example, "ADEKA STAB AO-40" manufactured by ADEKA Corporation), 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (for example, "ADEKA STAB AO-80" manufactured by ADEKA Corporation), 2,6-di(tert-butyl)-4-methylphenol (for example, "SUMIRAIZER BHT" manufactured by Sumitomo Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

[0050] Specific examples of the light stabilizer include N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine (for example, "TINUVIN 111FDL" manufactured by BASF), decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, and a mixture of a reaction product of 1,1-dimethylethyl hydroperoxide and octane, and a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (for example, "TINUVIN 111FDL" manufactured by BASF). 123" and the like), bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate (for example, "TINUVIN 144" manufactured by BASF, etc.), 2-[[4,6-bis[butyl[1-(cyclohexyloxy)-2,2,6,6-tetramethylpiperidin-4-yl]amino]-1,3,5-triazin-2-yl]amino]ethanol (for example, "TINUVIN 152" manufactured by BASF, etc.), a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (for example, "TINUVIN 152" manufactured by BASF, etc.), 292" and the like), 1-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidino)ethyl] butanedioate (for example, "TINUVIN 622" manufactured by BASF, etc.), bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate (for example, "TINUVIN 770" manufactured by BASF, etc.), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)=1,2,3,4-butanetetracarboxylate (for example, "ADEKA STAB LA-52" manufactured by ADEKA, etc.), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) (for example, "ADEKA STAB LA-57" manufactured by ADEKA Corporation), "ADEKA STAB LA63P" manufactured by ADEKA Corporation, "ADEKA STAB LA-68" manufactured by ADEKA Corporation, "ADEKA STAB LA72" manufactured by ADEKA Corporation, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (for example, "ADEKA STAB LA- 77Y" and the like), "ADEKA STAB 81" manufactured by ADEKA Corporation, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (for example, "ADEKA STAB LA-82" manufactured by ADEKA Corporation), 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (for example, "ADEKA STAB LA-87" manufactured by ADEKA Corporation), "TINUVIN 765", "TINUVIN 780", "TINUVIN 905", "TINUVIN 5100", "TINUVIN 5050", "TINUVIN 5060", "TINUVIN 5151", "CHIMASSORB 119FL", "CHIMASSORB 944FL", "CHIMASSORB 944LD" and the like manufactured by BASF Corporation. These may be used alone or in combination of two or more.

[0051] Specific examples of the polymerization inhibitor include quinones such as hydroquinone, parabenzoquinone, and 2,5-di-tert-butylbenzoquinone; phenols such as 4-methoxyphenol, 6-tert-butyl-2,4-xylenol, and 4-tert-butylcatechol; sulfur-containing compounds such as phenothiazine, thiourea, and sodium N,N-diethyldithiocarbamate; nitroso compounds such as N-nitrosodiphenylamine and N-nitrosophenylhydroxylamine aluminum salt; and 4-hydroxy-2,2,6,6-tetramethylpiperidine. phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; and phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite, tris(2-ethylhexyl)phosphite, and bis(decyl)pentaerythritol diphosphite. These may be used alone or in combination of two or more.

[0052] The content of additives such as antioxidants, light stabilizers, and polymerization inhibitors is preferably 0.001 wt % or more and 3 wt % or less, more preferably 0.01 wt % or less and 1.5 wt % or less, still more preferably 0.02 wt % or more and 1 wt % or less, and most preferably 0.03 wt % or more and 0.3 wt % or less, based on 100 wt % of the total weight of the photocurable resin composition for imprints.

[0053] The types and contents of the above components in the photocurable resin composition for imprints of the present invention can be confirmed by analysis using GC-MS, NMR, or the like.

[0054] The molecular weights of the components in the photocurable resin composition for imprints of the present invention are identified by mass spectrometry (MS) for those having a molecular weight of less than 1,000, and are weight-average molecular weights (Mw) calculated in terms of standard polystyrene by gel permeation chromatography (GPC) for those having a molecular weight of 1,000 or more. The weight-average molecular weight (Mw) can be measured, for example, using a GPC apparatus (product name "HLC-8320 GPC with built-in RI detector / UV-8320" manufactured by Tosoh Corporation) under the following conditions: analytical column: two TSKgel SuperMultiporeHZ-M columns, reference column: two TSKgel SuperHM-H columns, detector: RI detector, sample injection amount: 10 μL, sample concentration: 0.1 w / v %, eluent: chloroform, measurement temperature: 40° C., and flow rate: 0.35 mL / min. The calibration curve can be created, for example, by plotting the elution time and molecular weight value of each peak from the measured standard polystyrene using a standard polystyrene of known molecular weight (product name "PStQuick MP-M", manufactured by Tosoh Corporation), and performing cubic approximation.

[0055] The photocurable resin composition for imprinting of the present invention preferably further has the following characteristic: The photocurable resin composition for imprinting is applied to a first substrate having a total light transmittance of 80% or more at a wavelength of 365 nm to form a coating film, a second substrate is laminated onto the coating film, and an illuminance of 100 mW / cm at a wavelength of 365 nm is obtained using a metal halide lamp. ２ , the cumulative light amount at a wavelength of 365 nm is 1000 mJ / cm ２ When a cured product having a thickness of 15 μm is obtained by irradiating the coating film with light through the first substrate under the conditions of (a) above, the hardness of the surface of the cured product that is revealed by peeling off the second substrate, as measured by nanoindentation at a temperature of 30° C., is 50 N / mm ２ Above, 400N / mm ２ Preferably, it is 80 N / mm or less. ２ Above, 380N / mm ２ More preferably, it is 120 N / mm or less. ２ Above, 360N / mm ２ More preferably, it is 150 N / mm or less.２ Above, 320N / mm ２ It is particularly preferable that the following is true. The first substrate and the second substrate are not particularly limited, but those made of a resin material can be suitably used. Examples of the resin material constituting the first substrate and the second substrate include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylic resins such as polymethyl methacrylate (PMMA), carbonate resins such as polycarbonate (PC), amide resins such as nylon 6, cyclic olefin resin (COP), ethylene vinyl alcohol copolymer (EVOH), polyphenylene sulfide (PPS), etc. The first substrate and the second substrate may be made of the same resin material or different resin materials. The photocurable resin composition for imprints has a hardness of 50 N / mm when measured by nanoindentation of a cured product obtained under the above conditions. ２ Above, 400N / mm ２ By satisfying the following, the resin mold 80 obtained can be made to have better transferability, releasability, and durability.

[0056] The photocurable resin composition for imprinting of the present invention can be prepared by appropriately mixing the above-mentioned components by a known method. The photocurable resin composition for imprinting of the present invention can provide a resin mold 80 that is excellent in transferability, releasability, and durability, even when the resin composition contains a small amount of fluorine compound and silicon compound, or when the resin composition does not contain a fluorine compound or a silicon compound. The phrase "containing a small amount of fluorine compound and silicon compound" means that, when a cured product of the photocurable resin composition for imprinting is subjected to elemental analysis by X-ray photoelectron spectroscopy (XPS), the fluorine concentration and silicon concentration are both less than 1 atomic % relative to 100 atomic % of the total amount of detected elements.

[0057] <Resin Mold 80> The resin mold 80 is made of a cured product of the photocurable resin composition for imprinting described above. As shown in FIG. 2(A), the resin mold 80 has a micropattern 81 with a concave-convex shape formed on its surface. As shown in FIG. 2(B), the cross section C of the micropattern 81 is triangular. That is, the micropattern 81 has a structure in which a plurality of prism shapes (triangular prisms) are arranged side by side. The height H of the micropattern 81 is preferably 1 μm or more and 100 μm or less, and more preferably 3 μm or more and 50 μm or less. The height H of the micropattern 81 is the length from the apex to the base of the triangular cross section C in FIG. 2(B). That is, the height H of the micropattern 81 is the difference in height between the highest and lowest points of the cross section of the concave-convex shape of the micropattern 81. The height H of the micropattern 81 can be determined by observing the cross section of the resin mold 80 with a laser microscope or the like. The method for forming the fine pattern 81 on the surface of the resin mold 80 is not particularly limited, but an example thereof includes a method, as described below, in which a die (mold) engraved with a fine concave-convex shape is pressed against the photocurable resin composition for imprinting before curing, the photocurable resin composition for imprinting is irradiated with ultraviolet light to cure it, and then the mold is peeled off. The resin mold 80 is made of a cured product of the photocurable resin composition for imprinting of the present invention, and therefore has an excellent transfer rate from the die.

[0058] The uneven shape of the micropattern 81 is not particularly limited, and examples thereof include a micropattern in which the convex portions form a triangle, a rectangle, a trapezoid, or the like in the cross-sectional view of the resin mold laminate shown in FIG. 2 . The length of each side of the uneven shape and the interior angle of each vertex may or may not be equal. The height H of the micropattern 81 can be determined as the difference between the highest and lowest points of the uneven shape in the cross section. By using the photocurable resin composition for imprinting of the present invention, it is possible to produce a micropattern having a triangular uneven shape that is resistant to deformation and folding.

[0059] The thickness of the resin mold 80 is not particularly limited, but is preferably 1 μm or more and 120 μm or less, more preferably 3 μm or more and 100 μm or less, and even more preferably 5 μm or more and 50 μm or less. In the embodiment shown in FIG. 2(A), the thickness of the resin mold 80 is defined as the length from the boundary between the resin mold 80 and the base film 70 to the upper end of the fine pattern 81 of the resin mold 80.

[0060] The glass transition temperature (Tg) of the resin mold 80 is preferably 60° C. or higher and 250° C. or lower, and more preferably 100° C. or higher and 200° C. or lower.

[0061] The resin mold 80 has a hardness of 50 N / mm when measured by nanoindentation on the surface of the resin mold 80 at a temperature of 30°C. ２ Above, 400N / mm ２ Preferably, it is 80 N / mm or less. ２ Above, 380N / mm ２ More preferably, it is 120 N / mm or less. ２ Above, 360N / mm ２ More preferably, it is 150 N / mm or less. ２ Above, 320N / mm ２ It is particularly preferred that:

[0062] The resin mold 80 preferably has an elastic deformation rate of 25% or more, and more preferably 30% or more, measured by nanoindentation on the surface of the resin mold 80 at a temperature of 30°C.

[0063] Furthermore, when the surface of the resin mold 80 is subjected to elemental analysis by X-ray photoelectron spectroscopy (XPS), the nitrogen concentration relative to 100 atomic % of the total amount of detected elements is preferably 4.0 atomic % or more and 12.0 atomic % or less, more preferably 6.0 atomic % or more and 10.5 atomic % or less, and even more preferably 7.1 atomic % or more and 9.3 atomic % or less. The nitrogen concentration on the surface of the resin mold 80 obtained by XPS can be controlled by adjusting the content of the N-vinyloxazolidinone compound (A) in the photocurable resin composition for imprints. Furthermore, when the surface of the resin mold 80 is subjected to elemental analysis by X-ray photoelectron spectroscopy (XPS), the silicon concentration relative to 100 atomic % of the total amount of detected elements is preferably less than 1 atomic %, and the fluorine concentration relative to 100 atomic % of the total amount of detected elements is preferably less than 1 atomic %.

[0064] <Substrate Film 70> The substrate film 70 constituting the resin mold laminate 60 is preferably made of a resin material. Examples of resin materials constituting the substrate film 70 include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylic resins such as polymethyl methacrylate (PMMA), carbonate resins such as polycarbonate (PC), amide resins such as nylon 6, cyclic olefin resin (COP), ethylene vinyl alcohol copolymer (EVOH), polyphenylene sulfide (PPS), and the like. Among these, polyethylene terephthalate (PET) is preferred. The surface of the substrate film 70 may be subjected to an easy-adhesion treatment such as a primer treatment.

[0065] Although not particularly limited, the base film 70 preferably has a total light transmittance at a wavelength of 365 nm of 80% or more, and more preferably 85% or more.

[0066] <Method for Manufacturing Resin Mold 80 and Resin Mold Laminate 60> FIG. 3 is a diagram showing an example of an apparatus for manufacturing the resin mold 80 in this embodiment. The resin mold 80 and the resin mold laminate 60 can be manufactured as follows. As shown in FIG. 3 , first, a substrate film 70 is fed from a substrate feed roll 10a, and a photocurable resin composition for imprinting 801 is applied to the surface of the substrate film 70 using a T-die 20a. Next, while a mold 100 having a fine unevenness (a reversal pattern of the fine pattern 81) formed on its surface is pressed against the photocurable resin composition for imprinting 801 applied to the substrate film 70, the photocurable resin composition for imprinting 801 is irradiated with ultraviolet light using an ultraviolet irradiation device 30a. This cures the photocurable resin composition for imprinting 801, yielding a resin mold 80. Furthermore, a resin mold laminate 60 is obtained in which the resin mold 80 and the substrate film 70 are laminated together. As described above, the manufacturing apparatus shown in Fig. 3 continuously produces the resin mold 80 and the resin mold laminate 60. A fine pattern 81 is formed on the surface of the resin mold 80 produced in this manner by transferring the concave-convex shape of the metal mold 100. Note that, in manufacturing the resin mold laminate 60 of the present invention, it is not necessary to perform a mold release treatment on the metal mold 100.

[0067] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. Furthermore, hereinafter, the N-vinyloxazolidinone compound (A), the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700, and the compound (C) containing one or more ethylenically unsaturated groups in the photocurable resin composition for imprints will also be referred to simply as component (A), component (B), and component (C), respectively.

[0068] <Viscosity> The viscosity of the photocurable resin composition for imprints was measured using a Brookfield viscometer (analog viscosity system LVT, manufactured by Eiko Seiki Co., Ltd.) at a temperature of 25°C using a small-volume sample adapter (sample chamber SC4-13R(P)) and a spindle SC4-18 at a rotation speed of 30 to 60 rpm.

[0069] <Tg> A cured product of the photocurable resin composition for imprints was measured for viscoelasticity using a viscoelasticity measuring device (DMA7100, manufactured by Hitachi High-Technologies Corporation) at a temperature rise rate of 5°C / min and a frequency of 1 Hz, and the peak temperature of tan δ was taken as Tg.

[0070] <Nanoindentation hardness and elastic deformation rate> A loading / unloading test was performed on the surface of the cured product of the photocurable resin composition for imprinting using an ultra-microhardness tester (ENT-1100a, manufactured by ELIONIX) at a surface temperature of 30°C using a Berkovich indenter under an indentation load of 0.1 mN and a loading rate of 0.010 mN / sec, to measure the nanoindentation hardness and elastic deformation rate.

[0071] <Element Concentration> A wide scan analysis was performed on the surface of the cured product of the photocurable resin composition for imprinting using an X-ray photoelectron spectrometer (K-Alpha, manufactured by Thermo Fisher Scientific), and a narrow scan analysis was performed on each detected element. Each obtained spectrum was subjected to charge correction based on the C1s peak position (284.8 eV) using analysis software (Avantage, manufactured by Thermo Fisher Scientific), background removal was performed using the smart background function, and normalized peak areas were calculated using Scofield relative sensitivity coefficient correction. The atomic % of each element was calculated from the ratio of the normalized peak area of ​​each element to the total normalized peak area of ​​each element. The measurement was performed under the following conditions: X-ray source: monochromated Al Kα (1486.6 eV); X-ray spot diameter: 400 μm; Neutralization gun: on; Vacuum level: <5×10 －５ Pa Wide scan: pass energy 200 eV, energy step 1 eV, dwell time 10 ms Narrow scan: pass energy 50 eV, energy step 0.1 eV, dwell time 50 ms

[0072] Example 1 A photocurable resin composition for imprinting having the following formulation was prepared: The viscosity of this photocurable resin composition for imprinting was measured by the method described above. N-vinyl-5-methyloxazolidinone (product name "VMOX", manufactured by BASF, component (A)) 50 parts by weight Trimethylolpropane triacrylate (product name "M-309", manufactured by Toagosei Co., Ltd., component (B)) 20 parts by weight Dipentaerythritol hexaacrylate (product name "DPHA", manufactured by Daicel-Allnex Corporation, also containing dipentaerythritol pentaacrylate as a by-product, component (B)) 20 parts by weight Trifluoroethyl acrylate (product name "Viscoat 3F", manufactured by Osaka Organic Chemical Industry Ltd., component (C)) 10 parts by weight HMPP: 2-hydroxy-2-methylpropiophenone (product name "2-Hydroxy-2-methylpropiophenone", manufactured by Tokyo Chemical Industry Co., Ltd., α-hydroxyketone-based photopolymerization initiator) 5 parts by weight

[0073] (Preparation and Evaluation of Cured Product) A curable resin composition for imprinting was applied to the adhesion-treated surface of a PET film with an adhesion-enhancing layer (product name "Panaclear AC-M", manufactured by Panac Corporation, total light transmittance at a wavelength of 365 nm of 82%, thickness of 72 μm), and a smooth PET film (product name "Emblet S-25", manufactured by Unitika Ltd., total light transmittance at a wavelength of 365 nm of 84%, thickness of 25 μm) was laminated on the photocurable resin composition for imprinting. Next, using a metal halide lamp, illuminance at a wavelength of 365 nm: 100 mW / cm ２ , integrated light amount at wavelength 365 nm: 1000 mJ / cm ２The photocurable resin composition for imprinting was irradiated with light through the PET film with the easy-adhesion layer under the conditions above, and the photocurable resin composition for imprinting was cured to obtain a cured product with a thickness of 15 μm. The surface of the cured product revealed by peeling off the smooth PET film was analyzed by X-ray photoelectron spectroscopy (XPS), and the results were a C concentration of 70.3 atomic%, an O concentration of 22.9 atomic%, an N concentration of 6.1 atomic%, an Si concentration of 0.0 atomic%, and an F concentration of 0.8 atomic%. The surface of the cured product of the photocurable resin composition for imprinting obtained in this manner was evaluated for nanoindentation hardness and elastic deformation rate using the methods described above. A cured product was also prepared in the same manner as described above, except that the PET film with the easy-adhesion layer was replaced with a smooth PET film and the thickness of the cured product was changed to 50 μm. The two smooth PET films were then peeled off, and the glass transition temperature of the cured product was evaluated.

[0074] (Production and Evaluation of Resin Mold 80) Fig. 4(A) is a plan view of the mold 100 used in the examples, and Fig. 4(B) is a cross-sectional view of the prism shape 300 of the mold 100, and is an enlarged cross-sectional view showing the IVB-IVB' cross section of Fig. 4(A). First, NiP plating was applied to a roll 200 having a roll width (length) of 350 mm and a roll diameter of φ250 mm, and the NiP plating was cut along the longitudinal direction of the roll 200 to obtain a mold 100 having prism shapes 300 formed on the surface, as shown in Figs. 4(A) and 4(B). The prism height H of the prism shape 300 was ０ is 9 μm, prism width W ０ is 18.5 μm, and the prism angle θ ０ is 100°, prism spacing D ０ The line segment 310 in FIG. 4A represents the ridge line of the prism shape 300.

[0075] The curable resin composition for imprinting was applied onto a PET film with an easy-adhesion layer as the base film 70. Next, the mold 100 was pressed against the photocurable resin composition for imprinting so that the prism shapes 300 of the mold 100 were in contact with the photocurable resin composition for imprinting. Next, with the mold 100 pressed against the photocurable resin composition, a metal halide lamp was used to illuminate the composition at a wavelength of 365 nm with an illuminance of 100 mW / cm. ２ , integrated light amount at wavelength 365 nm: 1000 mJ / cm ２ The photocurable resin composition for imprinting was irradiated with light under the conditions above to cure the photocurable resin composition for imprinting. This resulted in a resin mold 80 having a fine pattern 81 on its surface, and a resin mold laminate 60 formed by laminating the resin mold 80 and a substrate film 70. The thickness of the resin mold 80 was 16 μm. The transfer rate from the metal mold 100 of this resin mold 80 was evaluated by the following method.

[0076] <Transfer rate from mold 100 to resin mold 80> Using a laser microscope (controller unit: VK-X3000, head unit: VK-X3100, manufactured by Keyence Corporation), the height H of the fine pattern 81 on the resin mold 80 was measured under the condition of an objective lens of 150x magnification. The transfer rate from the mold 100 to the resin mold 80 was calculated based on the following formula. The transfer rate was evaluated as follows: Transfer rate from mold 100 to resin mold 80 = height H of the fine pattern 81 on the resin mold 80 / height H of the prism shape 300 on the mold 100 ０ × 100 (%) Excellent: Transfer rate to resin mold 80 is 95% or more. Passable: Transfer rate to resin mold 80 is 90% or more but less than 95%. Failable: Transfer rate to resin mold 80 is less than 90%.

[0077] (Transfer to Receiving Resin and Evaluation) A photocurable resin composition (a) to be transferred was applied to the easy-adhesion layer side of an acrylic resin film (product name "Fine Cast Film", manufactured by Toyo Kohan Co., Ltd.) with an easy-adhesion layer on one side as a receiving substrate film. The composition of the photocurable resin composition (a) to be transferred was shown in Table 6. The resin mold 80 was pressed against the photocurable resin composition to be transferred so that the fine pattern 81 of the resin mold 80 was in contact with the photocurable resin composition to be transferred. While the resin mold 80 was pressed against the photocurable resin composition to be transferred, light was irradiated onto the photocurable resin composition to cure the photocurable resin composition to obtain a transferee in which the transferee cured layer and the resin mold 80 were laminated on the transferee substrate. As a result, a fine pattern in which the fine pattern 81 was transferred to the surface of the transferee cured layer was formed. Using this transferee, the 90-degree peel strength and transfer rate were evaluated by the following methods.

[0078] <90-degree peel strength of resin mold 80 from transfer resin> A sample measuring 25 mm wide x 150 mm long was prepared from the transfer object, and the surface of the transfer substrate was attached to a test plate using double-sided tape. Next, a tensile tester ("Tensilon Universal Material Tester RTC-1210A", manufactured by ORIENTEC Co., Ltd.) was used to clamp the end of the resin mold 80 and perform a 90-degree peel test at a pulling rate of 200 mm / min, and the 90-degree peel strength [unit: N / 25 mm] of the contact surface between the resin mold 80 and the transfer cured layer was measured. The smaller the 90-degree peel strength value, the better the resin mold 80's peelability from the transfer resin can be determined to be.

[0079] <Transfer rate from resin mold 80 to the transferee resin> The resin mold 80 was peeled off and separated from the transferee. The transfer rate from the resin mold 80 to the transferee resin was calculated based on the following formula. The transfer rate was evaluated as follows. The closer the transfer rate expressed by the formula below is to 100%, the better the resin mold 80 is judged to be at transferring to the transferee resin. The height of the fine pattern of the transferee resin was measured in the same manner as the height H of the fine pattern 81 of the resin mold 80. Transfer rate from the resin mold 80 to the transferee resin = height of the fine pattern of the transferee resin / height H' of the fine pattern 81 of the resin mold 80 after transfer × 100 (%) Excellent: transfer rate to the transferee resin of 95% or more Fair: transfer rate to the transferee resin of 90% or more but less than 95% Poor: transfer rate to the transferee resin of less than 90%

[0080] <Retention rate of prism shape of resin mold 80> The resin mold 80 was peeled off and separated from the transfer target object. The retention rate of the prism shape of the resin mold 80 was calculated based on the following formula. The retention rate of the prism shape was evaluated as follows. The closer the retention rate of the prism shape expressed by the formula below is to 100%, the more excellent the durability of the resin mold 80 can be judged to be. Retention rate of prism shape of resin mold 80 = Height H' of the fine pattern 81 of the resin mold 80 after separation / Height H of the prism shape 300 of the metal mold 100 ０ × 100 (%) Excellent: The retention rate of the prism shape of the resin mold 80 is 95% or more. Passable: The retention rate of the prism shape of the resin mold 80 is 90% or more but less than 95%. Failable: The retention rate of the prism shape of the resin mold 80 is less than 90%.

[0081] Examples 2 to 8, 10 to 12, 16 to 23, 27 to 29 Except for using photocurable resin compositions for imprinting having the formulations shown in Tables 1 to 3, cured products, resin molds 80, resin mold laminates 60, and recipients were obtained and evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0082] Example 9 The conditions for the cumulative light intensity at a wavelength of 365 nm in the production of a cured product of a photocurable resin composition for imprinting and the production of a resin mold 80 were set to 2000 mJ / cm ２A cured product, a resin mold 80, a resin mold laminate 60, and a transfer target were obtained in the same manner as in Example 8, except that the above-mentioned procedure was changed to the above-mentioned procedure, and the evaluations were similarly carried out.

[0083] Examples 13 to 15 A cured product, a resin mold 80, a resin mold laminate 60, and an object to be transferred were obtained and evaluated in the same manner as in Example 12, except that the photocurable resin composition for transfer had the formulation shown in Table 6. The results are shown in Table 2.

[0084] Examples 24 to 26 A cured product, a resin mold 80, a resin mold laminate 60, and an object to be transferred were obtained and evaluated in the same manner as in Example 23, except that the photocurable resin composition for transfer had the formulation shown in Table 6. The results are shown in Table 3.

[0085] Comparative Examples 1 to 19 A cured product, a resin mold 80, a resin mold laminate 60, and an object to be transferred were obtained and evaluated in the same manner as in Example 1, except that the photocurable resin compositions for imprinting were used with the formulations shown in Tables 4 and 5. The results are shown in Tables 4 and 5.

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092] The compounds used in each example and each comparative example are as follows: VMOX: N-vinyl-5-methyloxazolidinone (product name "VMOX", manufactured by BASF Corporation, viscosity at 25°C: 3 cps) HDDA: 1,6-hexanediol diacrylate (product name "HDDA", manufactured by Daicel Allnex Corporation, viscosity at 25°C: 6 cps) DPGDA: dipropylene glycol diacrylate (product name "MIRAMER M222", manufactured by MIWON Corporation, viscosity at 25°C: 8 cps) TCDDA: tricyclodecane dimethanol diacrylate (product name "MIRAMER M262", manufactured by MIWON Corporation, viscosity at 25°C: 145 cps) 1,9-NDDA: 1,9-nonanediol diacrylate (product name "Light Acrylate 1.9ND-A", manufactured by Kyoeisha Chemical Co., Ltd., viscosity at 25°C: 10 cps) TPGDA: tripropylene glycol diacrylate (product name "M-220", manufactured by Toagosei Co., Ltd., viscosity at 25°C: 13 cps) PEG600DA: polyethylene glycol 600 diacrylate (product name "MIRAMER M286", manufactured by MIWON Co., Ltd., viscosity at 25°C: 104 cps) TMPTA: trimethylolpropane triacrylate (product name "M-309", manufactured by Toagosei Co., Ltd., viscosity at 25°C: 99 cps) PETTA: pentaerythritol tetraacrylate (product name "Light Acrylate PE-4A", manufactured by Kyoeisha Chemical Co., Ltd., viscosity at 25°C: 880 cps) DPE-6A: dipentaerythritol hexaacrylate (product name "Light Acrylate DPE-6A", manufactured by Kyoeisha Chemical Co., Ltd., also contains dipentaerythritol pentaacrylate as a by-product, viscosity at 25°C: 4000 to 6500 cps) DPHA: dipentaerythritol hexaacrylate (product name "DPHA", manufactured by Daicel Allnex Corporation, also contains dipentaerythritol pentaacrylate as a by-product, viscosity at 25°C: 6900 cps) tBA: t-butyl acrylate (product name "tert-butyl acrylate", manufactured by Tokyo Chemical Industry Co., Ltd., viscosity at 25°C: 1 cps) TFEA: 2,2,2-trifluoroethyl acrylate (product name "Viscoat 3F", manufactured by Osaka Organic Chemical Industry Ltd., viscosity at 25°C: 1 cps) TFOA: 1H,1H,2H,2H-tridecafluorooctyl acrylate (product name "Viscoat 13F", manufactured by Osaka Organic Chemical Industry Co., Ltd., viscosity at 25°C: 4 cps) EBECRYL8402: urethane acrylate (product name "EBECRYL8402", manufactured by Daicel-Allnex Corporation, viscosity at 25°C: 12,500 cps) EBECRYL350: silicone diacrylate (product name "EBECRYL350", manufactured by Daicel-Allnex Corporation, viscosity at 25°C: 350 cps) EBECRYL1710: acrylic resin diluted with 1,6-hexanediol diacrylate (HDDA) (60 wt%) (product name "EBECRYL1710", manufactured by Daicel-Allnex Corporation, viscosity at 25°C: 25,700 cps) HCPK: 1-hydroxycyclohexylphenyl ketone (product name "Omnirad 184", manufactured by IGM Resins, α-hydroxyketone-based photopolymerization initiator) HMPP: 2-hydroxy-2-methylpropiophenone (product name "2-Hydroxy-2-methylpropiophenone", manufactured by Tokyo Chemical Industry Co., Ltd., α-hydroxyketone-based photopolymerization initiator) TPO-L: ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omnirad TPO-L", manufactured by IGM Resins, acylphosphine oxide-based photopolymerization initiator) BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins) Resins Co., Ltd., an acylphosphine oxide-based photopolymerization initiator),

[0093] As shown in Tables 1 to 3, when the photocurable resin composition for imprinting contained an N-vinyloxazolidinone compound (A), a compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700, and a photopolymerization initiator, and the content of the N-vinyloxazolidinone compound (A) relative to 100% by weight of the photocurable resin composition for imprinting was 40% by weight or more, the resin mold 80 obtained by curing the photocurable resin composition for imprinting was excellent in transferability from the mold, releasability from a resin to be transferred, transferability to a resin to be transferred, and durability (Examples 1 to 29).

[0094] On the other hand, when the photocurable resin composition for imprinting did not contain the compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700, the durability of the resin mold 80 was poor, or the transfer rate was poor (Comparative Examples 1, 7, and 18). Furthermore, when the content of the N-vinyloxazolidinone compound (A) in the photocurable resin composition for imprinting was less than 40% by weight, the releasability and durability of the resin mold 80 were poor, or the cured resin to be transferred could not be separated from the resin mold 80 (Comparative Examples 6, and 8 to 17). Furthermore, when the photocurable resin composition for imprinting did not contain the N-vinyloxazolidinone compound (A), the cured resin to be transferred could not be separated from the resin mold 80 (Comparative Examples 2 to 5). When the photocurable resin composition for imprinting was composed only of the N-vinyloxazolidinone compound (A), the resin composition could not be sufficiently cured, and as a result, a resin mold 80 could not be obtained (Comparative Example 19).

[0095] DESCRIPTION OF SYMBOLS 10, 10a... Substrate payout roll 11, 11a, 18, 18a... Guide roll 12, 12a... Nip roll 13... Resin mold payout roll 14... Resin mold take-up roll 15... Laminating roll 16, 16a... Upstream backup roll 17, 17a... Downstream backup roll 19, 19a... Substrate take-up roll 20, 20a... T-die 30, 30a... Ultraviolet irradiation device 40... Transferred substrate film 50... Transferred photocurable resin composition layer 51... Cured resin layer 60... Resin mold laminate 70... Substrate film 80... Resin mold 81... Fine pattern 801... Photocurable resin composition for imprinting 100... Mold 200... Roll 300... Prism shape 310... Ridge line

Claims

1. A photocurable resin composition for imprinting, comprising: an N-vinyloxazolidinone compound (A); a compound (B) containing two or more ethylenically unsaturated groups and having a molecular weight of 100 or more and less than 700; and a photopolymerization initiator, wherein the content of the N-vinyloxazolidinone compound (A) relative to 100% by weight of the photocurable resin composition for imprinting is 40% by weight or more.

2. The photocurable resin composition for imprinting according to claim 1, wherein the content of the N-vinyloxazolidinone compound (A) is 40% by weight or more and 80% by weight or less relative to 100% by weight of the photocurable resin composition for imprinting.

3. The photocurable resin composition for imprinting according to claim 1 or 2, wherein the content of the compound (B) is 15% by weight or more and 55% by weight or less.

4. The photocurable resin composition for imprinting according to any one of claims 1 to 3, wherein the compound (B) is a compound containing 3 or more and 6 or less ethylenically unsaturated groups.

5. The photocurable resin composition for imprinting according to any one of claims 1 to 4, wherein the content of the photopolymerization initiator relative to 100% by weight of the photocurable resin composition for imprinting is 1% by weight or more and 5% by weight or less.

6. A resin mold having a fine pattern on its surface, obtained by curing the photocurable resin composition for imprinting according to any one of claims 1 to 5.

7. The hardness of the surface of the resin mold measured by nanoindentation at a temperature of 30°C is 50 N / mm ２ Above, 400N / mm ２ The resin mold according to claim 6, wherein:

8. A resin mold according to claim 6 or 7, wherein when the surface of the resin mold is subjected to elemental analysis by X-ray photoelectron spectroscopy (XPS), the nitrogen concentration relative to the total amount of detected elements (100 atomic %) is 4.0 atomic % or more and 12.0 atomic % or less.

9. A resin mold according to any one of claims 6 to 8, wherein the elastic deformation rate of the surface of the resin mold measured by nanoindentation method is 25% or more.

10. The resin mold according to any one of claims 6 to 9, which has a glass transition temperature (Tg) of 60°C or higher and 250°C or lower.

11. A resin mold laminate comprising a resin substrate and the resin mold according to any one of claims 6 to 10 provided on the resin substrate.

12. The resin molded laminate according to claim 11, wherein the resin substrate is a polyester-based resin substrate.

13. A method for manufacturing a resin mold having a fine pattern on its surface, comprising the steps of: forming the photocurable resin composition for imprinting according to any one of claims 1 to 5 on the surface of a substrate; pressing a mold having a reverse pattern of the fine pattern on its surface against the photocurable resin composition for imprinting so that the reverse pattern is in contact with the photocurable resin composition for imprinting; irradiating the photocurable resin composition for imprinting with light while the mold is pressed against the photocurable resin composition for imprinting, thereby curing the photocurable resin composition for imprinting to form a cured product; and separating the mold from the cured product to obtain a resin mold having the fine pattern formed on its surface.

14. A method for producing a shaped film, comprising the steps of: forming a photocurable resin composition to be transferred on the surface of a substrate; pressing a resin mold according to any one of claims 6 to 10 against the photocurable resin composition to be transferred so that the fine pattern is in contact with the photocurable resin composition to be transferred; irradiating the photocurable resin composition to be transferred with light while the resin mold is pressed against the photocurable resin composition to harden the photocurable resin composition to form a hardened product; and separating the resin mold from the hardened product to obtain a shaped film having a concave-convex shape to which the fine pattern has been transferred.

15. A method for producing a shaped film, comprising the steps of: supplying molten resin to the surface of a resin mold described in any one of claims 6 to 10; cooling and solidifying the molten resin to form a hardened product; and separating the resin mold from the hardened product to obtain a shaped film having a concave-convex shape formed by transferring the fine pattern.

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