JP7514461B2 - Curable resin composition and cured product - Google Patents

Description

The present invention relates to a curable resin composition, a cured product, a concave-convex structure, and a method for producing the same.

Conventionally, curable resin compositions that are cured by applying energy rays such as light or heat to polymerize a polymerizable compound have been widely known. For example, there are curable compositions that use a polymerization initiator that generates an acid or the like to start the polymerization of the polymerizable compound.

The curing reaction of the curable composition is carried out, for example, by addition polymerization caused by an ethylenically unsaturated double bond in the compound, or by ring-opening polymerization caused by ring-opening of a glycidyl group in the compound. In the former case, for example, a polymerizable compound having an acryloyl group is generally known, and in the latter case, for example, a polymerizable compound having an epoxy ring is generally known. As a specific example, a compound having an oxirane ring such as pentaerythritol tetraglycidyl ether has been disclosed (for example, see Patent Documents 1 and 2).

On the other hand, curable compositions are used not only for producing molded bodies, but also as protective materials for imparting scratch resistance, processing materials for forming patterns, etc. Specific examples include curable compositions for forming a hard coat layer with high hardness that is resistant to scratches due to rubbing, and curable compositions for nanoimprint lithography (NIL) in which a resin is sandwiched between a mold and a substrate to transfer a nano-order pattern of the mold.
Among the NILs, UV nanoimprint lithography (UV-NIL) is a useful technique for mass production of films having an anti-reflective structure (ARS film). ARS films are widely used in electronic devices such as semiconductors, optical devices, recording media, etc., and are used by being attached to the surfaces of smartphones, tablets, touch panels, solar cells, LEDs, etc.

JP 2013-189504 A JP 2013-112649 A

Although various curable compositions have been provided and efforts have been made to improve performance such as curability, in recent years there has been a demand for further improvements in the durability of the cured product after curing, such as scratch resistance, shape retention, and abrasion resistance. In order to improve durability, it is effective to increase the hardness after curing.

The present disclosure has been made in view of the above.
An object of one embodiment of the present invention is to provide a curable resin composition that is excellent in reproducibility of fine structures such as a moth-eye structure and has a higher hardness than conventional ones, preferably a curable resin composition for imprinting.
Another object of the present invention is to provide a curable resin composition having excellent antifouling properties and significantly improved hardness compared to conventional compositions containing an antifouling agent, preferably for hard coating (i.e., formation of a hard coat layer).
Another object of the present invention is to provide a cured product having significantly improved hardness compared to conventional cured products.
Another object of the present invention is to provide a concave-convex structure having significantly improved hardness compared to conventional cured products, and a method for manufacturing the same.

The present inventors have found that a curable resin composition selectively using pentaerythritol tetraglycidyl ether, which is one of the polymerizable compounds that imparts polymerizability, has particularly high hardness and is suitable for, for example, hard coating applications and imprint applications. The curable resin composition and cured product of the present disclosure are based on this finding.
Furthermore, it has been believed that curable resin compositions containing a surfactant as an antifouling agent generally tend to have lower hardness than compositions that do not contain an antifouling agent. However, this reduction in hardness has been improved even in compositions that contain a surfactant as an antifouling agent, making it possible to produce cured products with higher hardness than before.

Specific means for solving the above problems include the following aspects.
<1> A curable resin composition containing pentaerythritol tetraglycidyl ether and a polymerization initiator, which is used for producing a concave-convex structure.
<2> A curable resin composition used for forming a hard coat layer, comprising pentaerythritol tetraglycidyl ether, a polymerization initiator, and a surfactant.
<3> The curable resin composition according to <2>, wherein the surfactant includes at least one selected from the group consisting of a fluorine compound and a siloxane compound.
<4> The curable resin composition according to <2> or <3>, wherein the surfactant includes at least one selected from the group consisting of a fluorinated acrylic compound and a fluorinated siloxane compound.
<5> The curable resin composition according to <1>, further comprising at least one selected from the group consisting of a fluorine compound and a siloxane compound.
<6> The curable resin composition according to any one of <1> to <5>, wherein the polymerization initiator is at least one compound selected from the group consisting of a photoacid generator, a thermal acid generator, and a photocation generator.
<7> The curable resin composition according to any one of <1> to <6>, further comprising at least one reactive compound selected from the group consisting of a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, an aliphatic epoxy compound, an olefin-oxidized epoxy compound, a silicone-modified compound, a fluorine-modified epoxy compound, and an oxetane compound.
<8> The curable resin composition according to any one of <1> to <7>, further comprising at least one sensitizer selected from the group consisting of an anthracene-based compound, an anthraquinone-based compound, a thioxanthone-based compound, a naphthalene-based compound, a phenanthrene-based compound, a chrysene-based compound, a perylene-based compound, and an acridine-based compound.
<9> The curable resin composition according to <8>, wherein the sensitizer contains a dialkoxyanthracene.
<10> The curable resin composition according to any one of <1> to <9>, wherein a content of the pentaerythritol tetraglycidyl ether is 45% by mass to 97% by mass with respect to a total mass of the curable resin composition.
<11> The curable resin composition according to any one of <1> to <10>, wherein the pentaerythritol tetraglycidyl ether has an epoxy equivalent of 90 to 150.
<12> The curable resin composition according to any one of <1> to <11>, wherein a content of the polymerization initiator is 3% by mass to 30% by mass with respect to the pentaerythritol tetraglycidyl ether.
<13> The curable resin composition according to any one of <1> to <12>, wherein a content of the polymerization initiator is 0.1% by mass to 10% by mass with respect to a total mass of the curable resin composition.
<14> The curable resin composition according to <1>, comprising the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, and a photoacid generator as the polymerization initiator.
<15> The curable resin composition according to <2>, comprising: the pentaerythritol tetraglycidyl ether; an alicyclic epoxy resin; a photoacid generator serving as the polymerization initiator; and the surfactant.
<16> The curable resin composition according to <14> or <15>, wherein a content of the pentaerythritol tetraglycidyl ether is 60% by mass to 85% by mass, a content of the alicyclic epoxy resin is 10% by mass to 30% by mass, and a content of the photoacid generator is 1% by mass to 6% by mass, based on a total mass of the curable resin composition.
<17> A cured product of the curable resin composition according to any one of <1> to <16>, wherein the cured product has a scratch pencil hardness of 7H or more in a flat film.
<18> A concave-convex structure which is a cured product of the curable resin composition according to <1> (including the curable resin compositions according to <5> to <16> not related to <2>), and has a concave-convex pattern with a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm.
<19> A method for producing a concave-convex structure, comprising the steps of forming a concave-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm using the curable resin composition according to <1> (including the curable resin compositions according to <5> to <16> not related to <2>), and curing the pattern.

According to one embodiment of the present invention, there is provided a curable resin composition that is excellent in reproducibility of fine structures such as a moth-eye structure and has a higher hardness than conventional curable resin compositions. Preferably, there is provided a curable resin composition for nanoimprinting.
According to another embodiment of the present invention, there is provided a curable resin composition having excellent antifouling properties and significantly improved hardness compared to conventional compositions containing an antifouling agent, preferably a curable resin composition for hard coating.
Furthermore, according to another embodiment of the present invention, there is provided a cured product having significantly improved hardness compared to conventional cured products.
Furthermore, according to another embodiment of the present invention, there is provided a concave-convex structure having significantly improved hardness compared to conventional cured products, and a method for producing the same.

1A to 1C are schematic diagrams showing an example of a manufacturing process for a protrusion-recess structure. FIG. 2 is a schematic cross-sectional view showing an example of a concave-convex structure manufactured by nanoimprinting. FIG. 1 is a process diagram showing a process for producing a moth-eye film using a curable resin composition containing a photoacid generator. FIG. 2 is a schematic diagram for explaining a method for evaluating scratch resistance using steel wool. 13 shows SEM images of the transfer surface of the moth-eye film of sample level 1 before and after a scratch resistance test. 13 shows SEM images of the transfer surface of the moth-eye film of sample level 2 before and after a scratch resistance test. 13 shows SEM images of the transfer surface of the moth-eye film of sample level 3 before and after a scratch resistance test. 1 is a graph showing the reflectance of the moth-eye films of sample levels 1 to 3. 1 is a graph showing the transmittance of the moth-eye films of sample levels 1 to 3. 1 is a graph showing the hardness of the moth-eye films of sample levels 1 to 2 and sample level 3. FIG. 1 is a process diagram showing a process for producing a moth-eye film using a curable resin composition containing a thermal acid generator. 1A is an SEM photograph showing the moth-eye structure of the cured film of sample level 27, and FIG. 1B is an SEM photograph showing the moth-eye structure of the cured film of sample level 28. 1 is a graph showing the reflectance of cured moth-eye films of sample levels 27 and 28. 1 is a SEM photograph showing the moth-eye structure of the cured film of Sample No. 27 before and after a scratch test. 1 is a SEM photograph showing the moth-eye structure of the cured film of Sample No. 36 before and after a scratch test. Photographs showing the state before and after artificial fingerprint liquid was dropped and then wiped off. The SEM images are taken before and after wiping off the artificial fingerprint liquid 20 times. 1 is a graph showing the change in reflectance before and after 20 wipes. 1 is a graph showing the change in transmittance before and after 20 wipings. 1A is an SEM photograph showing the moth-eye structure of the cured film of sample level 39, and FIG. 1B is an SEM photograph showing the moth-eye structure of the cured film of sample level 42.

The curable resin composition and cured product of the present disclosure are described in detail below.

In this specification, a numerical range expressed using "to" means a range including the numerical values described before and after "to" as the lower and upper limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this disclosure, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
In this specification, the amount of each component in a composition means, when a plurality of substances corresponding to each component are present in the composition, the total amount of the plurality of substances present in the composition, unless otherwise specified.

In this specification, "(meth)acrylic" is a concept that includes both acrylic and methacrylic, and "(meth)acrylate" is a concept that includes both acrylate and methacrylate.

<Curable resin composition>
The curable resin composition of the first aspect of the present disclosure contains at least pentaerythritol tetraglycidyl ether and a polymerization initiator, and is used for producing a concave-convex structure. It preferably contains a reactive compound (hereinafter also referred to as a "reactive diluent"), an antifouling agent, a sensitizer, a silane coupling agent, and a filler, and may further contain an organic solvent and other additives as necessary.
The curable resin composition according to the second aspect of the present disclosure contains pentaerythritol tetraglycidyl ether, a polymerization initiator, and a surfactant (hereinafter, also referred to as an "antifouling agent"), and is used for forming a hard coat layer (hard coating). The curable resin composition preferably contains a reactive diluent, a sensitizer, a silane coupling agent, and a filler, and may further contain an organic solvent and/or other additives, as necessary.
Hereinafter, the curable resin compositions of the first and second aspects are collectively referred to simply as "curable resin compositions of the present disclosure." In addition, the "curable resin composition" may also be referred to as the "curable composition."

(Pentaerythritol tetraglycidyl ether)
The curable resin composition of the present disclosure contains pentaerythritol tetraglycidyl ether (hereinafter, sometimes abbreviated as "PETG") as a polymerizable compound. By selectively containing, among conventionally known polymerizable compounds, in particular, pentaerythritol tetraglycidyl ether, it is possible to obtain a cured product having improved hardness compared to conventional curable resin compositions.

As PETG, commercially available products may be used, for example, the Showfree (registered trademark) series manufactured by Showa Denko K.K.

Pentaerythritol tetraglycidyl ether (PETG) preferably has an epoxy equivalent of 90 to 150.
When the epoxy equivalent of PETG is 90 to 150, the purity of PETG is high (purity = 60% to 100%) and the density of epoxy groups that can participate in the polymerization reaction is high, so that the crosslinking density is further improved and the hardness after curing is further improved.
For the same reasons as above, the epoxy equivalent of PETG is more preferably 120 or less, further preferably 110 or less, and particularly preferably 100 or less. The lower limit of the epoxy equivalent of PETG may be 91 or more, or 92 or more.

The content of pentaerythritol tetraglycidyl ether (PETG) in the curable resin composition is preferably 15% by mass to 97% by mass, more preferably 45% by mass to 97% by mass, and still more preferably 60% by mass to 85% by mass, relative to the total mass of the curable resin composition.
When the content of PETG is 15% by mass or more, high hardness is easily obtained. In addition, the content of PETG is preferably 97% by mass or less in consideration of the contents of other components.

(Polymerization initiator)
The curable resin composition of the present disclosure contains at least one polymerization initiator. By containing the polymerization initiator, the curing reaction of PETG is started.

The polymerization initiator is preferably at least one compound selected from the group consisting of photoacid generators, thermal acid generators, and photocation generators.

- Photopolymerization initiator (photoacid generator) -
The photopolymerization initiator includes an onium salt compound.
Examples of the onium salt compound include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
The onium salt compound may have a halogen metal complex anion (BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B(6F5) ₄ ⁻ , etc.) and a special phosphorus compound such as (RF) _n PF _6-n as a counter ion.

Examples of onium salt compounds include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[(4-phenylthio)phenyl]sulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-bis[diphenylsulfonium]diphenylsulfide bishexafluorophosphate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and bis(4-tert-butylphenyl)iodonium. Examples of the inorganic phosphate compounds include hexafluoroantimonate, tri-p-tolylsulfonium hexafluorophosphate, and 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate.
The onium salt compound may be a commercially available product. Specific examples of commercially available products include OPTOMER SP-150, OPTOMER SP-152, OPTOMER SP-170, OPTOMER SP-172, and OPTOMER SP-300 manufactured by ADEKA CORPORATION; CPI-100P, CPI-100A, CPI-200K, CPI-210S, LW-S1, IK-1, IK-2, and HS-1 manufactured by San-Apro Ltd.; Irgacure 250, Irgacure 270, and Irgacure 290 manufactured by BASF; and WPI-113, WPI-116, WPI-170, and WPI-124 manufactured by Wako Pure Chemical Industries, Ltd.
In addition to the above, further examples of the cationic photopolymerization initiator include an ion association crystalline substance combining a metallocene represented by the formula [{ _C5 ( ^R1 ) _n } _{2mMm ] l} ⁺ [{B( ^R2 ) ₄ } ^- ] _l (wherein M is a central core transition metal; _C5 represents cyclopentadienyl; ^R1 is an electron donating substituent bonded to the carbon of the cyclopentadienyl; n is 4 or 5; m is 1 or 2; l is 1 or 2; ^R2 is a ligand coordinated to the boron atom (B), and the four ^R2s are the same) with a borate compound.

The content of the photopolymerization initiator is preferably 0.1% by mass to 10.0% by mass, and more preferably 1.0% by mass to 6.0% by mass, based on the total mass of the curable resin composition.
The photopolymerization initiators may be used alone or in combination of two or more.

- Thermal polymerization initiator (thermal acid generator) -
As the thermal acid generator, onium salts such as quaternary ammonium salts, sulfonium salts, iodonium salts and phosphonium salts can be used.
Examples of commercially available quaternary ammonium salts include K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE CXC-1733, K-PURE CXC-1742, K-PURE CXC-1821, K-PURE CXC-2689, K-PURE TAG-2678, K-PURE TAG-2689, and K-PURE TAG-2690 manufactured by King Industries.
Examples of commercially available sulfonium salts include San-Aid (registered trademark) SI-60, SI-60L, SI-80, SI-80L, SI-100, and SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.

The content of the thermal acid generator is preferably 0.1% by mass to 10.0% by mass, and more preferably 0.2% by mass to 5.0% by mass, based on the total mass of the curable resin composition.
The thermal polymerization initiators may be used alone or in combination of two or more.

The content of the polymerization initiator is preferably in the range of 3% by mass to 90% by mass, more preferably in the range of 3% by mass to 50% by mass, still more preferably in the range of 3% by mass to 30% by mass, and particularly preferably in the range of 3% by mass to 15% by mass, relative to the pentaerythritol tetraglycidyl ether.
A polymerization initiator content of 3% by mass or more is suitable for initiating the curing reaction of PETG, while a polymerization initiator content of 90% by mass or less is advantageous in terms of maintaining the storage stability of the composition after preparation and the physical property stability of the cured product.

The content of the polymerization initiator is preferably in the range of 0.1 mass% to 10 mass%, more preferably in the range of 1.0 mass% to 8.0 mass%, and particularly preferably in the range of 1.5 mass% to 6.0 mass%, relative to the total mass of the curable resin composition.
A polymerization initiator content of 0.1% by mass or more is suitable for promoting the initiation of the curing reaction of PETG, while a polymerization initiator content of 10% by mass or less is advantageous in terms of storage stability after preparation and retention of physical properties after curing.

(Anti-fouling agent)
The curable resin composition of the second aspect of the present disclosure contains at least one surfactant as an antifouling agent. The curable resin composition of the first aspect of the present disclosure may also contain at least one surfactant as an antifouling agent similar to that of the second aspect.
When the curable resin composition contains a surfactant, the cured product obtained by curing the composition is imparted with water repellency, oil repellency, hydrophilicity, lipophilicity, and the like, and can also be imparted with antifouling properties.

The surfactant in this disclosure is a compound that has a fluorine atom or a -SiO- structure in the molecule and can impart water repellency, oil repellency, hydrophilicity, or lipophilicity to the surface of the cured film after curing. Examples of such surfactants include fluorine compounds, silicone compounds, and silicone fluorine compounds.

The surfactant may be a fluorine compound or a siloxane compound (including a fluorine-containing siloxane compound), and preferably at least one selected from the group consisting of a fluorine-containing acrylic compound and a fluorine-containing siloxane compound.

As the surfactant, commercially available products on the market may be used. Examples of commercially available products include Megafac RS-90, RS-55, RS-72-K, RS-75, RS-76-E, RS-78, and RS-90 manufactured by DIC Corporation, Futergent 601AD, 602A, 650A, 710FL, 208G, 215M, FTX-218, FTX-601ADH, 730LM, and NFX-552 manufactured by Neos Co., Ltd., Surflon S386 and S651 manufactured by AGC Seimi Chemical Co., Ltd., KY-164, KY-108, KY-1203, and X-71-1206 manufactured by Shin-Etsu Chemical Co., Ltd., and T&K Corporation. Examples include TOKA's ZX-058, ZX-101, ZX-104, ZX-105, ZX-106, ZX-108, ZX-109, ZX-022-U, ZX-201, ZX-202, ZX-203, ZX-212, ZX-401N, ZX-412 ZX-501, and Daikin Industries' Optool DAC-HP.

The content of the surfactant is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and still more preferably 1.0% by mass to 10% by mass, based on the total mass of the curable resin composition.
The surfactants may be used alone or in combination of two or more.

(Reactive Diluent)
In addition to the above components, the curable resin composition of the present disclosure preferably further contains a reactive compound (reactive diluent). By containing a reactive diluent, it is possible to adjust or improve the physical properties such as the curability (hardness of the cured film) and elongation of the curable resin composition, adjust the viscosity, improve the adhesion to the substrate, and improve the compatibility when an additive is added.

The reactive diluent is preferably at least one reactive compound selected from the group consisting of glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin-oxidized epoxy compounds, silicone-modified compounds, fluorine-modified epoxy compounds, and oxetane compounds.

As the reactive diluent, from the viewpoint of adjusting the physical properties of pentaerythritol tetraglycidyl ether (PETG), a cyclic ether compound or a cyclic sulfide is preferable.
Preferred examples of the cyclic ether compound include epoxy compounds and modified epoxy compounds (for example, silicone (siloxane) modified epoxy compounds, fluorine modified epoxy compounds), oxetane compounds, and episulfide compounds.

When a reactive diluent is used, the cyclic ether compound may be contained alone or in combination of two or more kinds.
Furthermore, any of the embodiments in which two or more kinds of epoxy compounds are used in combination, or the embodiments in which at least two kinds selected from epoxy compounds, oxetane compounds, silicone (siloxane)-modified epoxy compounds, fluorine-modified epoxy compounds, episulfide compounds, and compounds other than these, etc. are used in combination may be used.

-Epoxy compounds-
Examples of the epoxy compound include a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, an aliphatic epoxy compound, an olefin oxide epoxy compound, and modified products of these compounds.
Specific examples of epoxy compounds include bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, bisphenol S type epoxy, brominated bisphenol A type epoxy, biphenyl type epoxy, naphthalene type epoxy, fluorene type epoxy, spirocyclic type epoxy, phenol novolac type epoxy, orthocresol novolac type epoxy, brominated cresol novolac type epoxy, tetraphenylolethane type epoxy fatty acid modified epoxy, toluidine type epoxy, aniline type epoxy, aminophenol type epoxy diphenyl ether type epoxy, dicyclopentadiene type epoxy, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ether, urethane modified epoxy, NBR modified epoxy, CTBN modified epoxy, limonene oxide, limonene dioxide, butyl glycidyl ether, phenyl glycidyl ether, 1.4 butanediol diglycidyl ether, and 1,6 hexanediol. Diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadienyl diglycidyl ether, bis[2-(3,4-epoxycyclohexyl)ethyl]-tetramethyldisiloxane, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, p-tetrabutylphenyl glycidyl ether, dibromophenyl glycidyl ether, lauryl alcohol glycidyl ether, resorcinol diglycidyl ether, diglycidyl polyglycidyl ether, polyglycidyl polyglycidyl ether, ethylene glycidyl ether, styrene glycidyl ether, oxide, alcohol glycidyl ether, orthocresyl glycidyl ether, meta-para-cresyl glycidyl ether, glycidyl methacrylate, hexahydrophthalic acid diglycidyl ether, tripropylene glycol diglycidyl ether, bisphenol A tetraglycidyl ether, 3,4-epoxycyclohexane carboxylic aldo methyl ester, 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexane carboxylate), dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane, 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinylcyclohexane, and the like.

Among these, the epoxy compound is preferably an alicyclic epoxy compound, and more preferably a compound represented by the following formula 1:

In the following formula 1, X represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these groups are linked together.
The divalent hydrocarbon group for X may be linear or branched, and examples of the divalent hydrocarbon group include an alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. Examples of the alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene groups.
Furthermore, X is preferably a linking group having an oxygen atom, and examples thereof include --CO--, --O--CO--O--, --COO--, --O--, --CONH--, and groups in which a plurality of these groups are linked together.

Specific examples of alicyclic epoxy compounds are shown below. However, this disclosure is not limited to these.

The epoxy compound may be a commercially available product. Specific examples of commercially available products include the Celloxide series (e.g., Celloxide 8000, Celloxide 2021P, Celloxide 2081, Celloxide 8200, etc.), which are alicyclic epoxy resins manufactured by Daicel Corporation.

- Silicone (siloxane) modified epoxy compound -
Examples of epoxy compounds having silicon atoms (silicone (siloxane) modified epoxy) include bis[2-(3,4-epoxycyclohexyl)ethyl]-tetramethyldisiloxane.
In addition, the silicone (siloxane) modified epoxy may be a commercially available product. Specific examples of commercially available products include those manufactured by Shin-Etsu Chemical Co., Ltd. under the product names X-40-2678, X-40-2670, X-40-2705, and X-40-2669.

- Fluorine-modified epoxy compound -
Examples of epoxy compounds having fluorine atoms (fluorine-modified epoxy compounds) include 3-(2,2,3,3-tetrafluoropropoxy)-1,2-epoxypropane, 3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane, 3-perfluorobutyl-1,2-epoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 1.4 bis(2,3-epoxypropyl)-perfluoro-n-butane, and 1.6 bis(2,3-epoxypropyl)-perfluoro-n-hexane.
Furthermore, the fluorine-modified epoxy compound may be a commercially available product. A specific example of a commercially available product is 1.3CHEP, a product manufactured by Daikin Industries, Ltd.

-Oxetane compounds-
Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, xylylene bisoxetane, 1,3 bis[(3-ethyloxetan-3-yl)methoxy]benzene, 3-ethyl-3-(cyclohexyloxy)methyloxetane, 3-ethyl-3-(phenoxy)methyloxetane, 3-methyl-3-oxetanemethanol, 3-ethyl-3-oxetanemethanol, allyloxyoxetane, bisphenol A bisoxetane, bisphenol F bisoxetane, and bisphenol S bisoxetane.
The oxetane compound may be a commercially available product on the market, and specific examples of commercially available products include the ETERNACOLL (registered trademark) series (e.g., ETERNACOLL OXBP, ETERNACOLL OXMA, etc.) manufactured by Ube Industries, Ltd. Further examples include OXT-101, OXT-212, OXT-121, and OXT-221 (product names) manufactured by Toagosei Co., Ltd., and OX-SQ TX-100 and OX-SQ SI-20 (product names) (oxetanyl silsesquioxane or oxetanyl silicate), which are oxetane compounds having silicon atoms, manufactured by Toagosei Co., Ltd.

-Other compounds-
As a compound other than the above-mentioned epoxy compound and oxetane compound, for example, an episulfide compound is preferably mentioned.

When the physical properties of the curable resin composition are adjusted by adding the reactive diluent, the content of the reactive diluent is preferably in the range of 5% by mass to 90% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 10% by mass to 30% by mass, relative to the content of pentaerythritol tetraglycidyl ether (PETG).

Among the above, a composition containing PETG, a reactive diluent, and a polymerization initiator is one of the preferred embodiments of the curable resin composition of the present disclosure. When the composition contains PETG, a reactive diluent, and a polymerization initiator, the preferred embodiment is (1) an embodiment containing PETG, an alicyclic epoxy resin (preferably a compound represented by the above formula 1), and a photoacid generator that is a photopolymerization initiator, or an embodiment containing PETG, an alicyclic epoxy resin (preferably a compound represented by the above formula 1), a photoacid generator that is a photopolymerization initiator, and a surfactant. Furthermore, an embodiment containing (2) 60% to 85% by mass of PETG, 10% to 30% by mass of an alicyclic epoxy resin (preferably a compound represented by the above formula 1), and 1% to 6% by mass of a photoacid generator is more preferred.

(Sensitizer)
The curable resin composition of the present disclosure may further contain a sensitizer.
The sensitizer preferably contains at least one sensitizer selected from the group consisting of anthracene-based compounds, anthraquinone-based compounds, thioxanthone-based compounds, naphthalene-based compounds, phenanthrene-based compounds, chrysene-based compounds, perylene-based compounds, and acridine-based compounds.

Specific examples of sensitizers include anthracene, 1,2-benzoanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diglycidyloxyanthracene, 9,10-bis(phenylethyl)anthracene, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, hydroxyanthraquinone, aminoanthraquinone, anthraquinonesulfonic acid, 1-nitroan ... Examples include dianthraquinone, 1,2-benzanthraquinone, acetophenone, diethoxyacetophenone, 2-ethoxy-2-phenylacetophenone, 4-methoxyacetophenone, 4,4-dimethoxyacetophenone, 4-phenylacetophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, thioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone.

Among the above, the preferred sensitizers are dialkoxyanthracenes, which have excellent effects in improving curing properties, and 2-ethyl-9,10-dimethoxyanthracene and 9,10-dibutoxyanthracene are particularly preferred.

When the curing reaction of the curable resin composition is carried out using visible light, known dye-based sensitizers such as coumarin, thiazine, azine, acridine, xanthene, and titanocene sensitizers may be used.

The content of the sensitizer is preferably 0.1% by mass to 10% by mass, and more preferably 0.3% by mass to 5% by mass, based on the total mass of the curable resin composition.
The sensitizers may be used alone or in combination of two or more.

(Coupling Agent)
The curable resin composition of the present disclosure may contain a coupling agent. By containing a coupling agent, it is possible to further increase the adhesion between the curable resin composition and a substrate.

Examples of the coupling agent include various coupling agents such as silane-based, titanate-based, or aluminate-based coupling agents.
As the coupling agent, for example, a silane coupling agent represented by "X ₃ -Si(CH ₂ ) _n -Y" is suitable. Here, X represents a chlorine atom, a methoxy group, an ethoxy group, a methoxyethoxy group, an acetoxy group, or the like, and may contain a methyl group. n is an integer from 0 to 3. Examples of Y include a vinyl group, an epoxy group, a methacryloyloxy group, an acryl group, an amino group, a sulfide group, a ureido group, an isocyanate group, an isocyanurate group, a styryl group, and a mercapto group.

Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc.

The content of the coupling agent is preferably 0.1% by mass to 10.0% by mass, and more preferably 0.5% by mass to 5.0% by mass, based on the total mass of the curable resin composition.
The coupling agents may be used alone or in combination of two or more.

(Filler)
The curable resin composition of the present disclosure may further contain a filler such as nanoparticles of the nano-order depending on the application, etc.
Nanoparticles refer to particles of organic or inorganic materials with an average primary particle diameter of 1 nm to 1000 nm. The average primary particle diameter is a value determined by a laser analysis type particle size distribution analyzer.

The nanoparticles may be any particles as long as they do not inhibit the polymerization reaction of the curable resin composition.
Examples of nanoparticles include particles of diamond, graphene, graphene oxide, fullerene, polyethylene, polypropylene, polystyrene, etc., which are carbon or organic material fillers, and particles of gold, silver, silicon, indium tin oxide, silica, zirconia, alumina, silicon nitride, carbon nitride, aluminum nitride, boron nitride, zinc oxide, titanium oxide, silicon carbide, etc., which are inorganic material fillers.
Also preferred are nanoparticles whose surfaces are coated or chemically modified with reactive groups.

The nanoparticles may be commercially available products. Examples of commercially available products include silica particles with an average primary particle size of 10 nm to 100 nm, such as Admanano (registered trademark) YA010C, YA050C, YC100C, YA010-SM1, YA010-SV1, YA050-SM1, YA050-SV6, YA050C-SV2, YA010-SP3, YA050C-SP3, and YC100C-SP3 manufactured by Admatechs Co., Ltd. In addition, examples of zirconia particles include Zircostar AX-ZP-153-A manufactured by Nippon Shokubai Co., Ltd., and PCS, PCS-90, and PCS-60 manufactured by Nippon Denko Co., Ltd.

The content of the filler is preferably 0.1% by mass to 80% by mass, and more preferably 10% by mass to 50% by mass, based on the total mass of the curable resin composition.
The fillers may be used alone or in combination of two or more.

(Organic solvent)
The curable resin composition of the present disclosure may be prepared in a diluted form containing an organic solvent.
Examples of the organic solvent include solvents selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ether acetal esters, ketones, and nitrogen compounds.

Examples of organic solvents include toluene, xylene, hexane, cyclohexane, styrene, octane decane, petroleum ether, petroleum naphtha, ethyl alcohol, isopropyl alcohol, propanol, ethylene glycol, propylene glycol, γ-butyrolactone, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether.
The organic solvents may be used alone or in combination of two or more kinds.

(Other additives)
The curable resin composition of the present disclosure may further contain additives, such as an antiaging agent, an antioxidant, a colorant, a viscosity modifier, a flame retardant, an ultraviolet absorber, a discoloration inhibitor, an antibacterial agent, an antistatic agent, a plasticizer, a lubricant, an antifoaming agent, a thickener, a thixotropy imparting agent, a leveling agent, and a mold release agent, as necessary.

Examples of the colorant include dyes, carbon black, titanium oxide, zinc oxide, iron oxide, anthraquinones, and phthalocyanines.
Examples of the antioxidants and antioxidants that serve as stabilizers include hindered phenol compounds, phosphorus compounds, benzophenone compounds, and hydrazine compounds.

~Method for curing curable resin composition~
The curable resin composition can be cured by applying active energy rays (light such as ultraviolet rays) of 200 nm to 1,300 nm or heat of 50° C. to 250° C., or by applying both of these. In particular, the curable resin composition can be cured by irradiating it with active energy rays of 200 nm to 850 nm (preferably 250 nm to 560 nm) or by heating it at a temperature of 80° C. to 180° C.

Examples of the active energy rays include α rays, γ rays, X-rays, ultraviolet rays, visible light rays, infrared rays, and electron beams.
Furthermore, the curable resin composition of the present disclosure is preferably a photocurable composition that is cured by light such as ultraviolet light, visible light, or infrared light, and among these, a photocurable composition that is cured by ultraviolet light is preferred.

When the curable resin composition is cured by irradiation with active energy rays, it is preferable to use an ultraviolet ray irradiation device as the exposure device and irradiate the curable resin composition with active energy rays.
As the ultraviolet ray irradiation device, for example, an exposure device equipped with a light source such as a metal halide lamp, a high pressure mercury lamp, a laser exposure device, an LED, etc. When curing by irradiation with ultraviolet rays, the irradiation amount of ultraviolet rays is preferably 1,000 mJ/cm ² to 40,000 mJ/cm ² , and more preferably 3,000 mJ/cm ² to 9,000 mJ/cm ² .

When the curable resin composition is cured by heating, it is preferable to use an infrared heating device that heats the object with infrared rays, an electric furnace, or other heating device, and heat the curable resin composition at a temperature of 80°C to 180°C for 1 to 120 minutes.

The curable resin composition according to the first aspect of the present disclosure is used for the manufacture (imprinting) of a concave-convex structure. The concave-convex structure is obtained by curing the curable resin composition to form a concave-convex structure (particularly, a moth-eye structure) on a substrate. Since the curable resin composition according to the present disclosure is used, it is possible to manufacture a concave-convex structure having high hardness and excellent antireflection properties.
The concave-convex structure is preferably a concave-convex structure having a nanoscale fine concave-convex pattern, preferably having a height of 50 nm to 1000 nm (preferably 100 nm to 300 nm) and a pitch of 20 nm to 1000 nm (preferably 50 nm to 150 nm).
When the height and pitch of the concave-convex pattern of the mold are within the above ranges, the effects can be obtained well when molding using the curable resin composition of the present disclosure, and a concave-convex structure with excellent anti-reflection properties can be produced.

The curable resin composition according to the second aspect of the present disclosure is used for forming a hard coating, that is, a hard coat layer.
The curable resin composition according to the second aspect of the present disclosure has a curing performance of selectively containing and curing PETG. Conventionally, when an antifouling component is contained, there is a problem that the curability is reduced. In contrast, the curable resin composition according to the second aspect of the present disclosure can obtain high hardness and also impart excellent antifouling properties even when the antifouling component is contained.
Therefore, when a hard coat layer is provided on the surface of a member or the like used in a field requiring high strength using the curable resin composition of the second aspect of the present disclosure, it is possible to achieve both strength resistance to external forces and antifouling properties.

<Cured Product>
The cured product of the present disclosure is a cured product of the curable resin composition of the present disclosure described above, and has a scratch pencil hardness of 7 H or more in a flat film. The curable resin composition of the present disclosure can provide a cured product with improved hardness compared to conventional curable resin compositions.

The scratch pencil hardness is a value measured in accordance with JIS-K5600 5-4 Machine Method using a manual pencil scratch hardness tester No. 553-S (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) having two wheels on one side and a cylindrical hole in the center into which a pencil is inserted at an angle of 45°±1°, with a load of 750±10 g applied.
A scratch pencil hardness of 7H or more for a flat film indicates higher hardness and superior durability compared to conventional films. The closer to 9H the scratch pencil hardness is, the more preferable, and among these, 8H or more is preferable, and 9H or more is more preferable.

<Protrusion-recess structure and method for producing same>
The concave-convex structure of the present disclosure is a cured product of the curable resin composition of the first embodiment described above, and has a concave-convex pattern with a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm. Since the concave-convex structure of the present disclosure uses the curable resin composition of the first embodiment described above, the surface hardness after curing is high and a fine structure can be easily obtained, so that the concave-convex structure is suitable for producing a fine concave-convex pattern with a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm.
From this viewpoint, the curable resin composition of the first aspect described above is suitable for the production (imprinting) of a concave-convex structure, and a fine concave-convex structure (particularly a moth-eye structure) can be obtained with good reproducibility, and a structure (cured product) such as a replica mold molded using the master mold, for example, has excellent hardness. Since replica molds are cheaper than master molds and suitable for mass production, replica molds are widely used, but a replica mold having, for example, a moth-eye structure using the curable resin composition of the present disclosure has high hardness, excellent wear resistance, and excellent durability.

The concave-convex structure of the present disclosure may be produced by any method using the curable resin composition of the first embodiment described above. The concave-convex structure of the present disclosure is preferably produced by a method using the curable resin composition of the first embodiment described above, the method including a step of forming a concave-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm, and curing the pattern.

Specifically, the film may be prepared by the following method.
The concave-convex structure may be manufactured by a method including the steps of: preparing a mold having a concave-convex pattern with a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm; and a substrate coated with a curable resin composition; bringing the concave-convex pattern into contact with the curable resin composition and pressing it against the curable resin composition to introduce the curable resin composition into the concave-convex pattern; curing the introduced curable resin composition; and releasing the substrate having the concave-convex structure obtained by curing the curable resin composition from the mold.

Hereinafter, each step in the manufacturing method of the concave-convex structure of this embodiment will be described with reference to FIG. 1. FIG. 1 is a schematic diagram showing the manufacturing process of the concave-convex structure.

As shown in FIG. 1(a), the imprinting apparatus 100 includes a stage 5, a push jig 6, a feed roller 7, and a take-up roller 8. The imprinting apparatus 100 is an apparatus for manufacturing a concave-convex structure 10 (a substrate 1 having a concave-convex structure).

The stage 5 is a platform on which the mold 2 is placed and fixed. As shown in FIG. 1(a), the mold 2 is fixed to the stage 5 so that the concave-convex pattern faces the substrate 1 on which the curable resin composition 3 is applied.

The push jig 6 is used to raise and lower the stage 5, and by fixing the mold 2 onto the stage 5, the mold 2 is raised and lowered.
By raising the stage 5 to which the mold 2 is fixed, the substrate 1 to which the curable resin composition 3 has been applied can be brought into contact with the concave-convex pattern of the mold 2, and by further raising it, the curable resin composition 3 can be introduced into the concave-convex pattern.
Furthermore, by lowering the stage 5 to which the mold 2 is fixed, the substrate 1 having the concave-convex structure can be released from the mold 2, as described below.

As shown in the figure, a sheet-like substrate 1 is wound around a feed roller 7 and a take-up roller 8 .
The feed roller 7 is a roller for sending the wound sheet-like substrate 1 to the side of the stage 5 to which the mold 2 is fixed, and the winding roller 8 is a roller for winding the wound sheet-like substrate 1 from the side of the stage 5 to which the mold 2 is fixed.

[Introduction process]
In this process, as shown in FIG. 1(b), a substrate 1 to which a curable resin composition 3 has been applied and a mold 2 having a concave-convex pattern are brought into contact with the curable resin composition 3 and pressed against the concave-convex pattern, thereby introducing the curable resin composition 3 into the concave-convex pattern.
Before the introducing step, the curable resin composition is applied to the substrate 1. The method for applying the curable resin composition is not particularly limited.

In the introduction process, the stage 5 to which the mold 2 is fixed is raised at a constant speed to bring the substrate 1 to which the curable resin composition 3 is applied into contact with the uneven pattern of the mold 2, and then the substrate 1 to which the curable resin composition 3 is applied and the mold 2 having the uneven pattern are pressed together with a constant pressure.

In the introduction step, the mold and the substrate are preferably pressed at a pressure of 0.005 MPa to 1 MPa, more preferably at a pressure of 0.01 MPa to 0.2 MPa, even more preferably at a pressure of 0.01 MPa to 0.03 MPa, and particularly preferably at a pressure of 0.01 MPa to 0.02 MPa. By pressing at a pressure of 0.005 MPa or more, a sufficient amount of the curable resin composition can be introduced into the concave-convex pattern, resulting in a concave-convex structure having excellent functions in terms of transparency and anti-reflection properties. In addition, by pressing at a pressure of 1 MPa or less, the amount of the curable resin composition introduced into the concave-convex pattern can be suitably adjusted.

[Curing process]
In this step, as shown in FIG. 1(c), the curable resin composition 3 introduced into the concave-convex pattern is cured.
Here, a light-transmitting substrate 1 and a photocurable composition are used, and ultraviolet (UV) rays are irradiated onto the substrate 1 from the side opposite to the side on which the mold 2 is fixed. Since the substrate 1 is light-transmitting, the ultraviolet rays irradiated onto the substrate 1 pass through the substrate 1 and are irradiated onto the curable resin composition 3. As a result, the curable resin composition 3 introduced into the concave-convex pattern is cured, and a cured concave-convex structure is formed on the substrate 1.
The irradiation time and amount of ultraviolet light when irradiating the curable resin composition 3 are not particularly limited as long as they are sufficient to cure the curable resin composition 3 introduced into the concave-convex pattern.

[Mold release process]
In this step, as shown in FIG. 1( d ), the substrate 1 having the concave-convex structure obtained by curing the curable resin composition 3 is released from the mold 2 .
In the demolding step, the stage 5 to which the mold 2 is fixed is lowered at a constant speed, thereby releasing the contact between the concave-convex structure obtained by curing the curable resin composition and the concave-convex pattern of the mold 2 .
2, the contact area between the concave-convex structure and the concave-convex pattern of the mold 2 is large, so a large demolding force is required to release the contact between the concave-convex structure and the concave-convex pattern of the mold 2 and release the mold. Therefore, the tip of the concave-convex structure is likely to break off and remain on the bottom of the mold, which can cause a problem of shortening the life of the mold.
However, in the method for producing a concave-convex structure according to the present disclosure, the hardness of the cured product is high, so that the tips of the concave-convex structure are less likely to break, and it is possible to release the structure while reproducing a fine structural pattern. As a result, the concave-convex structure produced by the method for producing a concave-convex structure according to the present disclosure has superior anti-reflection and water repellency compared to the concave-convex structure 40 produced by conventional nanoimprinting, and the concave-convex structure, for example a mold, has a long life.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the following examples, the curable resin composition of the present disclosure is also simply referred to as the "curable composition".
In addition, "-" in each table below indicates that the corresponding component is not contained.

Example 1
-Sample level 1-
--Preparation of curable composition--
Into a brown wide-mouth standard glass bottle (Sansho Co., Ltd., wide-mouth standard glass bottle 1K, full capacity: 14 ml), 9.5 g of pentaerythritol tetraglycidyl ether (PETG; product name: Showfree (registered trademark), manufactured by Showa Denko K.K.) and 0.5 g of triallylsulfonium salt (photoacid generator; product name: CPI210S, manufactured by San-Apro Co., Ltd.) were mixed and stirred using a hand homogenizer (MH-1000, manufactured by AS ONE Corporation) and a test tube mixer (VXRS1, manufactured by IKA Corporation) to prepare a curable composition.
The viscosity of the curable composition (23° C.) was measured and found to be 159 mPa·s.
The viscosity was measured using an E-type viscometer (cone plate type) EVT-25L manufactured by Toki Sangyo Co., Ltd., while the curable composition was kept at 23° C. The same applies to the sample levels shown below.

- Formation of hard coat layer -
The prepared curable composition was applied to a thickness of about 50 μm on a slide glass (S1214: manufactured by Matsunami Glass Industrial Co., Ltd.) measuring 76 mm × 26 mm, which had been degreased in advance with acetone, to form a test piece. The test piece was irradiated with ultraviolet light using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by iGraphics Co., Ltd.) under conditions of an irradiation amount of 9,000 mJ/ ^cm2 and an illuminance of 100 mW/ ^cm2 to cure the curable composition and form a cured layer (hard coat layer) as a cured product on the slide glass.
In this manner, a test piece having a hard coat layer was prepared.

-Evaluation 1a-
The test pieces having the above hard coat layer were subjected to the following evaluations. The evaluation results are shown in Table 2 below.

(Pencil hardness)
The test piece having the hard coat layer was left at room temperature for one day. After the test piece was left, the scratch pencil hardness of the hard coat layer was measured by applying a load of 750±10 g using a manual pencil scratch hardness tester No. 553-S (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) having two wheels on one side and a cylindrical hole in the center for inserting a pencil at an angle of 45°±1° in accordance with JIS-K5600 5-4 Machine Method.
The scratch pencil hardness is rated in the range of 6B to 9H, with the closer to 9H the harder the material is.

(Scratch resistance)
As in the above, a test piece having a hard coat layer was used, and as shown in FIG. 4, a steel wool (#0000, manufactured by TRUSCO NAKAYAMA CORPORATION) 34 having a fine number of #0000 (center diameter: about 0.012 mm) was brought into contact with the surface of the hard coat layer of the test piece, a container containing water was placed on it, and the hard coat layer was rubbed in one direction with a load of 500 g. This operation was repeated 10 times to evaluate the presence or absence of scratches on the surface of the hard coat layer.

- Creation of GC moth-eye mold -
First, a double-sided mirror-polished glassy carbon (GC, Tokai Carbon Co., Ltd.) was irradiated with an oxygen ion beam using an electron cyclotron resonance (ECR) type ion shower device, and oxygen ion beam etching was performed. Then, a vacuum deposition machine (VPC-260F, ULVAC Kiko Co., Ltd.) was used to perform vacuum deposition on the processed GC surface to form a Cr deposition film with a thickness of 30 nm. Then, a mold release treatment (a fluorine-based mold release agent; Optool DSX manufactured by Daikin Industries, Ltd. was applied) was performed to produce a GC moth-eye mold with a width of 20 mm having an anti-reflection structure called a moth-eye structure.
The processing conditions for GC are as follows:

For ion beam irradiation, an electron cyclotron resonance (ECR) ion shower device, EIG-210ER (Elionix, Inc.), was used. Details of the fabrication of the GC moth-eye mold are described in N. B. Abu Talip[a]Yusofand J. Taniguchi, Microelectron. Eng. 110, 163 (2013). and J. Taniguchi, Y. Kamiya, and N. Unno, J. Photopolym. Sci. Technol. 1, 24 (2011).

- Creation of Moth Eye Film -
3, the above-mentioned curable composition 14 was applied in an amount of 1.25 g/ ^m2 onto the processed surface of the prepared GC moth-eye mold 12 to form a coating film 14, and a polyester film (Cosmoshine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.; PET film) 16 was placed on the coating film 14. Using an ultraviolet irradiation device (model: Aicure UP50, manufactured by Panasonic Corporation), ultraviolet light was irradiated onto the coating film 14 through the PET film (irradiation amount for sample levels 1 to 3: 10,000 mJ/ ^cm2 , illuminance for sample levels 1 to 3: 50 mW/ ^cm2 ) to form a cured film, and the cured film 24 was released together with the PET film 16 to produce a moth-eye film to which the moth-eye structure was transferred.
That is, a moth-eye film was produced by nanoimprint lithography (NIL, UV-NIL) using a curable resin.

-Evaluation 1b-
The moth-eye film obtained above was subjected to the following evaluations. The evaluation results are shown in Fig. 5, Fig. 8A, Fig. 8B, and Fig. 9.

(Scratch resistance)
As shown in FIG. 4 , a test was performed in which steel wool (#0000, manufactured by TRUSCO NAKAYAMA CORPORATION) 34 having a fine count of #0000 (center diameter: about 0.012 mm) was brought into contact with the surface of the cured film 24 of the moth-eye film 18, a container 32 containing water was placed on top of the steel wool, and the cured film 24 was rubbed together with the PET film 16 in one direction under a load of 100 g. The test was repeated 10 times, and the presence or absence of scratches on the surface of the cured film 24 was evaluated as follows.
A. Image Evaluation The surface of the cured film 24 of the moth-eye film was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix) before and after the abrasion test, and the presence or absence of scratches due to abrasion was evaluated from the SEM photographs.
B. Measurement of Reflectance and Transmittance Using an ultraviolet-visible-near infrared spectrophotometer (SolidSpec-3700, Shimadzu Corporation), the reflectance and transmittance of the surface of the cured film 24 of the moth-eye film were measured before and after the abrasion test.
C. Hardness (Martens hardness)
The surface hardness of the cured film 24 of the moth-eye film was measured using a dynamic ultra-microhardness tester (DUH-211, Shimadzu Corporation) based on the load and displacement when a triangular pyramidal indenter was pressed into the cured film.

-Sample level 2-
A test piece having a hard coat layer and a moth-eye film were prepared in the same manner as in Sample Level 1, except that the composition in Sample Level 1 was changed as shown in Table 2 below, and further measurement and evaluation were performed. The results of the measurement and evaluation are shown in Table 2 and Figs. 6, 8A, 8B, and 9.

-Sample level 3 to 7-
A test piece having a hard coat layer and a moth-eye film were prepared in the same manner as in Sample Level 1, except that the composition in Sample Level 1 was changed as shown in Table 2 below, and further measurement and evaluation were performed. The results of the measurement and evaluation are shown in Table 2 and Figs. 7 to 9.

Details of the components in Table 2 are as follows.
CELLOXIDE 8000: alicyclic epoxy compound manufactured by Daicel Corporation EPICLON EXA-830-CRP: bisphenol F type epoxy resin manufactured by DIC Corporation CPI210S: triallylsulfonium salt (photoacid generator; product name: CPI210S, manufactured by San-Apro Ltd.)
KY-1203: One-terminated (meth)acrylic modified perfluoropolyether compound (fluorine-based antifouling additive, manufactured by Shin-Etsu Chemical Co., Ltd.)

As shown in Table 2, in the samples 1 and 2 containing PETG, the hardness was dramatically improved compared to the comparative examples containing epoxy compounds other than PETG, and no scratches were observed in the abrasion test using steel wool, indicating excellent scratch resistance.
In addition, in the moth-eye films prepared using the curable compositions of sample levels 1 and 2, no scars were observed due to the scratch test, as shown in FIG. 5 and FIG. 6. In contrast, in the moth-eye films prepared using the curable compositions of sample level 3, as shown in FIG. 7, the scars due to the scratch test were prominent, and it can be seen that the resistance to scratching is poor. The reflectance and transmittance before and after scratching of the moth-eye films of sample levels 1 and 2 and sample level 3 are shown in FIG. 8A and FIG. 8B. As shown in FIG. 8A and FIG. 8B, in sample levels 1 and 2, the change in reflectance and transmittance due to the scratch test was small, and in sample level 3, the increase in reflectance and the decrease in transmittance after the scratch test were significant. That is, it was confirmed that the moth-eye film of sample level 3 had a larger change in shape due to scratching than the moth-eye films of sample levels 1 and 2. This is shown in FIG. 9, which shows that the hardness (Martens hardness) of the surface of the cured film of the moth-eye films of sample levels 1 and 2 is higher than that of the comparative example.

Example 2
-Sample level 8 to 20-
Test pieces having a hard coat layer were prepared in the same manner as in Sample Level 1, except that the composition in Sample Level 1 was changed as shown in Table 3 below.
Of the prepared test pieces, some of the test pieces were subjected to the same measurement and evaluation as Sample Level 1. Next, the other part of the test pieces was placed in a thermostatic chamber (SAFETY OVEN SPH-201, manufactured by ESPEC CORPORATION) at an atmospheric temperature of 85° C. and left for 30 minutes, and the test pieces after being left were subjected to the same measurement and evaluation as Sample Level 1. The results of the measurement and evaluation are shown in Table 3.

Table 3 shows the effect of the type and concentration of reactive diluent on sample levels 8 to 20.
As shown in Table 3, the steel wool abrasion resistance could be improved by containing PETG and an epoxy compound as a reactive diluent. As is clear from the above, when a reactive diluent is contained, the concentration is preferably in the range of less than 30 mass%.
Furthermore, when a moth-eye film was produced, similarly to sample levels 1 and 2, scratches due to the scratch test were unlikely to occur, and the surface hardness (Martens hardness) of the cured film was high, and it is considered that changes in reflectance and transmittance due to the scratch test were also small.

Example 3
--Sample levels 21 to 26--
A test piece having a hard coat layer was prepared in the same manner as in sample level 1, except that the composition in sample level 1 was changed as shown in Table 4 below, and further measurement and evaluation were performed. The results of the measurement and evaluation are shown in Table 4.

Table 4 shows the effect of the type of polymerization initiator on sample levels 21 to 26.
As shown in Table 4, the effect of changing the type of polymerization initiator was small, and the hardness obtained by using any polymerization initiator in combination with PETG was excellent.
Furthermore, when a moth-eye film was produced, similarly to sample levels 1 and 2, scratches due to the scratch test were unlikely to occur, and the surface hardness (Martens hardness) of the cured film was high, and it is considered that changes in reflectance and transmittance due to the scratch test were also small.

Example 4
--Sample level 27 to 28--
--Preparation of curable composition--
Curable compositions were prepared in the same manner as in Sample Level 1, except that the composition in Sample Level 1 was changed as shown in Table 5 below.

- Formation of hard coat layer -
The prepared curable composition was applied to a thickness of about 50 μm on a slide glass (Matsunami Glass Industrial Co., Ltd.: S1214) of 76 mm × 26 mm that had been degreased with acetone in advance, and the test piece was placed in a thermostatic chamber (Drying Oven DV41, Yamato Scientific Co., Ltd.) with the temperature inside the chamber adjusted to 130 ° C., heated for 15 minutes, removed from the thermostatic chamber, and left at room temperature (25 ° C.) for 1 day. In this way, the curable composition was cured to form a cured layer (hard coat layer) on the slide glass.
In this manner, a test piece having a hard coat layer was prepared.
Next, the test pieces prepared above were measured and evaluated in the same manner as in Sample Level 1. The results of the measurements and evaluations are shown in Table 5.

Table 5 shows the effect of the type of polymerization initiator on sample levels 27 and 28.
As shown in Table 5, the effect of using a thermal acid generator as a polymerization initiator to form a thermosetting system was small, and even when a thermal acid generator was used in combination with PETG, the hardness obtained was excellent.

- Creation of Moth Eye Film -
10 , the above-mentioned curable composition 14 was applied in an amount of 1.25 g/ ^m2 onto the processed surface of a GC moth-eye mold 12 prepared in the same manner as in Sample Level 1 to form a coating film 14, and a glass substrate 26 having a thickness of 150 μm was placed on the coating film 14. Next, the GC moth-eye mold was placed on a heater 30 and heated under heating conditions of a temperature of 130° C., a load of 1500 N, and a load time of 900 seconds to form a cured film, and the cured film 24 was released together with the glass substrate 26 to produce a moth-eye sheet to which the moth-eye structure was transferred.

The surface of the cured film 24 of the moth-eye sheet obtained above was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix Corporation). As a result, it was visually confirmed that a good moth-eye structure was transferred and formed in all of the moth-eye sheets produced using the curable compositions of sample levels 27 to 28, as shown in FIG.
Furthermore, the reflectance of the surface of the cured moth-eye film was measured using an ultraviolet-visible-near infrared spectrophotometer (SolidSpec-3700, Shimadzu Corporation), and the results are shown in FIG.

Example 5
--Sample level 29 to 36--
A test piece having a hard coat layer was prepared in the same manner as in Sample Level 1, except that the composition was changed as shown in Table 6 below. Measurements and evaluations were then carried out. Furthermore, the antifouling property was evaluated by the following method.
The results of the measurements and evaluations are shown in Table 6 below.

- Antifouling properties -
The stain resistance was evaluated by the oil-based marker wiping test described below.
The prepared curable composition was applied onto a glass slide measuring 76 mm x 26 mm using a No. 22 bar coater, and irradiated with ultraviolet light using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by iGraphics Co., Ltd.) under conditions of an irradiation amount of 6,000 mJ/ ^cm2 and an illuminance of 50 mW/ ^cm2 to cure the coating film, which was then left for one day. A spiral pattern was drawn on the surface of the cured film of the test piece thus obtained using an oil-based marker PM-41 (manufactured by Kokuyo Co., Ltd.), and the operation of wiping off the oil-based ink with Kimwipe S-200 (manufactured by Nippon Paper Crecia Co., Ltd.) was repeated, and the number of times that it was possible to wipe off was recorded.

In sample levels 29 to 36, the compositions containing antifouling components are shown in Table 6.
As shown in Table 6, by including the antifouling component, it was possible to provide wiping properties while maintaining high hardness and scratch resistance. In contrast, in sample level 36, which contains the antifouling component but does not contain PETG, good wiping properties were obtained, but it was impossible to achieve both hardness and scratch resistance at the same time.

- Creation of Moth Eye Film -
Next, moth-eye films were prepared using the curable compositions of sample level 32 and sample level 36, and the moth-eye structure and wiping properties were evaluated.
3, the above-mentioned curable composition 14 was applied in an amount of 1.25 g/ ^m2 onto the processed surface of the prepared GC moth-eye mold 12 to form a coating film 14, and a polyester film (Cosmoshine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.; PET film) 16 was placed on the coating film 14. Using an ultraviolet irradiation device (model: Aicure UP50, manufactured by Panasonic Corporation), ultraviolet light was irradiated onto the coating film 14 through the PET film (irradiation amount: 10,000 mJ/ ^cm2 , illuminance: 50 mW/ ^cm2 ) to form a cured film, and the cured film 24 was released together with the PET film 16 to produce a moth-eye film to which the moth-eye structure was transferred.

Next, as shown in FIG. 4, the scratch test was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was evaluated as follows.
A. Image Evaluation The surface of the cured moth-eye film before and after the abrasion test was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix), and the presence or absence of scratches due to abrasion was evaluated from the SEM photographs.
B. Contact angle The water contact angle on the transferred surface of the moth-eye structure of the moth-eye film was measured using a fully automatic contact angle meter (DM-701, Kyowa Interface Science Co., Ltd.).
C. Wipeability: An artificial fingerprint liquid was dropped onto the transfer surface of the moth-eye structure of the moth-eye film, and the oil-based ink was repeatedly wiped off with Kimwipe S-200 (manufactured by Nippon Paper Crecia Co., Ltd.), and the number of times that the ink could be wiped off was recorded.

When the surface of the cured film 24 of the moth-eye film obtained above was observed with an SEM, no scars from the scratch test were observed in the moth-eye film produced using the curable composition of sample level 32, as shown in FIG. 13. Therefore, the change in the water contact angle before and after scratching was small. In contrast, in the moth-eye film produced using the curable composition of sample level 36, as shown in FIG. 14, the scars from the scratch test were more noticeable than in sample level 32 using PETG, and the moth-eye structure was destroyed, resulting in a large change in the water contact angle. Thus, it can be seen that there is a significant difference in resistance to scratching between sample level 32 and sample level 36.

Furthermore, the moth-eye film of sample level 32 was subjected to a wiping test after being heat-treated under the following conditions.
<Conditions>
Heating temperature: 85°C
Heating time: 30 minutes Test cloth: Kimwipe Test liquid: Artificial fingerprint liquid [Artificial fingerprint liquid]
The artificial fingerprint liquid used here was prepared by adding 0.1 mass % of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., CAS. No. 81-88-9) to the following composition described in JIS K2246 (2007) Rust Preventive Oil.
<Composition> Purified water: 500mL
Methanol: 500 mL
Sodium chloride: 7g
・Urea: 1g
Lactic acid: 4g

As a result, as shown in FIG. 15, the artificial fingerprint liquid could be successfully wiped off.
Next, Fig. 16 shows an SEM photograph when the artificial fingerprint liquid was wiped off 20 times. As can be seen from Fig. 16, there was no change in the moth-eye structure even after wiping off 20 times. In addition, the change in the contact angle was also small. Furthermore, Figs. 17A and 17B show the changes in reflectance and transmittance before and after wiping off 20 times. As shown in Figs. 17A and 17B, the decrease was less than 1%.

Example 6
--Sample level 37 to 38--
A test piece having a hard coat layer was prepared in the same manner as in Sample Level 1, except that the composition in Sample Level 1 was changed as shown in Table 7 below, and further measurements and evaluations were carried out. Furthermore, the adhesive strength was evaluated as an index of the sensitizing effect by the following method.
The results of the measurements and evaluations are shown in Table 7 below.

-Adhesiveness-
The adhesive strength was measured and the adhesiveness was evaluated by the following method using a test piece that was opaque to the absorption wavelength of the polymerization initiator. The evaluation results are shown in Table 7 below.
One surface of an epoxy glass plate (KEL-GE (10 mm × 250 mm, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) was degreased with acetone, and then a mending tape (MP-18, manufactured by Sumitomo 3M Limited) was attached to the degreased surface as a spacer for making the coating thickness of the curable composition uniform.
Next, a curable composition was applied to the surface of the epoxy glass plate to which the mending tape was attached, and two epoxy glass plates were alternately attached so that the application area of the curable composition was 26 mm × 3 mm, and a test specimen was prepared by pressing with a drumstick-shaped clip (CREE-44, manufactured by KOKUYO Co., Ltd.). Thereafter, using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by iGraphics Co., Ltd.), the curable composition of the test specimen was irradiated with ultraviolet light at an irradiation dose of 9,000 mJ/ ^cm2 and an illuminance of 100 mW/ ^cm2 to cure the curable composition.
The irradiated test specimen was then left for one day at room temperature (25° C.) After leaving the test specimen, the two glass plates were pulled at a pulling speed of 50 mm/min using an Autograph AG-5KNXplus (manufactured by Shimadzu Corporation) to measure the shear adhesive strength.

In sample levels 37 and 38, the compositions containing sensitizers are shown in Table 7.
The epoxy glass plate used does not transmit the absorption wavelength of the polymerization initiator, but the curable compositions of sample levels 37 to 38 contain a sensitizer, so that the polymerization initiator reacts and cures when irradiated with ultraviolet light in the wavelength range of 350 nm to 400 nm, which is the absorption wavelength of the sensitizer. In other words, it can be said that a composition containing a polymerization initiator and a sensitizer is also effective as a method for curing PETG.
Furthermore, when a moth-eye film was produced, similarly to sample levels 1 and 2, scratches due to the scratch test were unlikely to occur, and the surface hardness (Martens hardness) of the cured film was high, and it is considered that changes in reflectance and transmittance due to the scratch test were also small.

(Example 7)
--Sample level 39 to 42--
A test piece having a hard coat layer was prepared in the same manner as in sample level 1, except that the composition in sample level 1 was changed as shown in Table 8 below, and further measurement and evaluation were performed. The results of the measurement and evaluation are shown in Table 8.

Table 8 shows the results for sample levels 39 to 42, which were compositions containing filler.
As shown in Table 8, the compositions containing the filler also provided excellent hardness when used in combination with PETG.

- Creation of Moth Eye Film -
Next, moth-eye films were prepared using the curable compositions of sample levels 39 and 42, and the moth-eye structure was evaluated.
3, the above-mentioned curable composition 14 was applied in an amount of 1.25 g/ ^m2 onto the processed surface of the prepared GC moth-eye mold 12 to form a coating film 14, and a polyester film (Cosmoshine (registered trademark) A4300, manufactured by Toyobo Co., Ltd.; PET film) 16 was placed on the coating film 14. Using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by i-Graphics Co., Ltd.), ultraviolet light was irradiated onto the coating film 14 through the PET film (irradiation amount: 10,000 mJ/ ^cm2 , illuminance: 50 mW/ ^cm2 ) to form a cured film, and the cured film 24 was released together with the PET film 16 to produce a moth-eye film to which the moth-eye structure was transferred.

The surface of the cured moth-eye film obtained above was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix). As a result, it was confirmed by visual inspection that a good moth-eye structure was transferred to the moth-eye films produced using the curable compositions of sample levels 39 and 42, as shown in Figure 18.

(Example 8)
--Sample level 43 to 44--
A test piece having a hard coat layer was prepared in the same manner as in Sample Level 1, except that the composition was changed as shown in Table 9 below. Further, the adhesive strength was measured as an index for evaluating the adhesiveness by the following method.
The results of the measurements and evaluations are shown in Table 9 below.

-Adhesiveness-
One surface of a slide glass (S1214, manufactured by Matsunami Glass Industry Co., Ltd.) measuring 76 mm × 26 mm was degreased with acetone, and then a mending tape (MP-18, manufactured by Sumitomo 3M Limited) was attached to the degreased surface as a spacer for keeping the coating thickness of the curable composition constant.
Next, the curable composition was applied to the surface of the slide glass plate to which the mending tape was attached, and two epoxy glass plates were alternately attached so that the application area of the curable composition was 26 mm × 3 mm, and a test specimen was prepared by pressing with a drumstick-shaped clip (CREE-44, manufactured by KOKUYO Co., Ltd.). Thereafter, using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by iGraphics Co., Ltd.), the curable composition of the test specimen was irradiated with ultraviolet light at an irradiation dose of 9,000 mJ/ ^cm2 and an illuminance of 100 mW/ ^cm2 to cure the curable composition.
The irradiated test specimen was then left for one day at room temperature (25° C.) After leaving the test specimen, the two glass plates were pulled at a pulling speed of 50 mm/min using an Autograph AG-5KNXplus (manufactured by Shimadzu Corporation) to measure the shear adhesive strength.
Separately from the above, the shear adhesive strength was measured in the same manner, except that the slide glass plate was replaced with an acrylic plate or a polycarbonate plate (PC plate).
The measurement results are shown in Table 9 below.

Table 9 shows the results for sample levels 43 and 44, which were compositions containing a silane coupling agent.
As shown in Table 9, even in the compositions containing a silane coupling agent, the hardness obtained when used in combination with PETG was excellent.
Furthermore, when a moth-eye film was produced, similarly to sample levels 1 and 2, scratches due to the scratch test were unlikely to occur, and the surface hardness (Martens hardness) of the cured film was high, and it is considered that changes in reflectance and transmittance due to the scratch test were also small.

The curable resin composition of the present disclosure is suitable for various applications requiring high hardness, and is preferably used in the fields of antireflection, diffraction gratings (optical elements), LSI (integrated circuit wiring), polarizing plates, and nanoimprinting. In the field of nanoimprinting, it is suitable for forming various patterns such as moth-eye patterns such as cones or polygonal pyramids, pillar structures, hole structures, microlens array structures, honeycomb structures, lattice structures, line and space structures, and replica molds.

The disclosure of Japanese Patent Application No. 2017-117642, filed on June 15, 2017, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

(Explanation of symbols)
1: Sheet-like substrate 2: Mold 3, 14: Curable resin composition (curable composition)
5... Stage 7... Feed-out roller 8... Take-up roller 10... Protrusion-recess structure 12... Coating film 16... Polyester film 18... Moth-eye film 24... Cured film 26... Glass substrate 30... Heater 32... Container 34... Steel wool 100... Imprinting device

Claims (10)

The composition contains pentaerythritol tetraglycidyl ether having an epoxy equivalent of 90 to 150, a polymerization initiator, and a surfactant, the surfactant containing at least one selected from the group consisting of a fluorine compound and a siloxane compound,
The content of the pentaerythritol tetraglycidyl ether is 45% by mass to 97% by mass based on the total mass of the curable resin composition ,
The content of the polymerization initiator is 0.1% by mass to 10% by mass based on the total mass of the curable resin composition,
The content of the surfactant is 0.1% by mass to 30% by mass based on the total mass of the curable resin composition.
A curable resin composition used to form a hard coat layer. The curable resin composition according to claim 1, wherein the surfactant comprises at least one selected from the group consisting of a fluorine-containing acrylic compound and a fluorine-containing siloxane compound. The curable resin composition according to claim 1 or 2, wherein the polymerization initiator is at least one compound selected from the group consisting of a photoacid generator, a thermal acid generator, and a photocation generator. The curable resin composition according to any one of claims 1 to 3, further comprising at least one reactive compound selected from the group consisting of a glycidyl ether compound other than pentaerythritol tetraglycidyl ether having an epoxy equivalent of 90 to 150, a glycidyl ester compound, a glycidyl amine compound, an aliphatic epoxy compound, an olefin-oxidized epoxy compound, a silicone-modified epoxy compound, a fluorine-modified epoxy compound, and an oxetane compound. The curable resin composition according to any one of claims 1 to 4 further contains at least one sensitizer selected from the group consisting of anthracene-based compounds, anthraquinone-based compounds, thioxanthone-based compounds, naphthalene-based compounds, phenanthrene-based compounds, chrysene-based compounds, perylene-based compounds, and acridine-based compounds. The curable resin composition according to claim 5, wherein the sensitizer comprises a dialkoxyanthracene. The curable resin composition according to claim 1, which contains pentaerythritol tetraglycidyl ether having an epoxy equivalent of 90 to 150, an alicyclic epoxy resin, a photoacid generator as the polymerization initiator, and the surfactant. The curable resin composition according to claim 7, wherein the content of the pentaerythritol tetraglycidyl ether having an epoxy equivalent of 90 to 150 is 60% by mass to 85% by mass relative to the total mass of the curable resin composition, the content of the alicyclic epoxy resin is 10% by mass to 30% by mass relative to the total mass of the curable resin composition, and the content of the photoacid generator is 1% by mass to 6% by mass relative to the total mass of the curable resin composition. A cured product of the curable resin composition according to any one of claims 1 to 8, the cured product having a scratch pencil hardness of 7H or more in a flat film. The cured product according to claim 9, which does not contain a filler.