JPWO2018230725A1 - Curable resin composition, cured product, uneven structure and method for producing the same - Google Patents

Abstract

A curable resin composition and a cured product containing pentaerythritol tetraglycidyl ether and a polymerization initiator, which are used for producing an uneven structure, and an uneven structure and a method for producing the same.

Description

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

BACKGROUND ART Conventionally, a curable resin composition which is cured by polymerizing a polymerizable compound by applying an energy ray such as light or heat is widely known, and for example, polymerization of the polymerizable compound by generating an acid or the like. There is a curable composition using a polymerization initiator for initiating.

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

On the other hand, the curable composition is used not only for producing a molded product, but also as a protective material for imparting scratch resistance, a processing material for forming a pattern, and the like. As a specific example, a curable composition that forms a hard coat layer with high hardness that is unlikely to be scratched by abrasion, and a nano-order pattern of a mold by inserting a resin between the mold and the base material. There is known a curable composition for nanoimprint lithography (NIL), etc., for transferring the ink.
Among the NILs, UV nanoimprint lithography (UV-NIL) is a technique useful for mass production of a film (ARS film) having an antireflection structure. The ARS film is widely used for electronic devices such as semiconductors, optical devices, recording media, and the like, and is used by being attached to the surface of smartphones, tablets, touch panels, solar cells, LEDs, and the like.

Patent Document 1: JP 2013-189504 A Patent Document 2: JP 2013-112649 A

Conventionally, various curable compositions have been provided, and although improvements in performance such as curability have been attempted, in recent years, scratch resistance, shape retention, and abrasion resistance of cured products after curing have been achieved. Further improvement in durability is required. To improve the durability, it is effective to improve the hardness after curing.

The present disclosure has been made in view of the above. That is,
An object to be solved by one embodiment of the present invention is to provide a curable resin composition which is excellent in reproducibility of a fine structure such as a moth-eye structure and which can obtain higher hardness as compared with conventional ones. .. It is preferable to provide a curable resin composition for imprint.
The problem to be solved by another embodiment of the present invention is to provide a curable resin composition having excellent antifouling property and having significantly improved hardness as compared with the conventional composition containing an antifouling agent. is there. It is preferable to provide a curable resin composition for hard coating (that is, formation of a hard coat layer).
A problem to be solved by another embodiment of the present invention is to provide a cured product having a significantly improved hardness as compared with a conventional cured product.
Another problem to be solved by another embodiment of the present invention is to provide a concavo-convex structure body having significantly improved hardness as compared with a conventional cured product, and a method for manufacturing the same.

Among the polymerizable compounds that are one of the components imparting the polymerizability, the present inventors have found that a curable resin composition that selectively uses pentaerythritol tetraglycidyl ether has a particularly high hardness, for example, hard coating. It has been found that it is suitable for applications and imprint applications, and the curable resin composition and cured product of the present disclosure are based on such findings.
Further, a curable resin composition containing a surfactant as an antifouling agent has conventionally been generally considered to have a hardness lower than that of a composition not containing an antifouling agent, but as an antifouling agent, Even with a composition containing a surfactant, the decrease in hardness is improved, and it becomes possible to produce a cured product having a higher hardness than ever 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 an uneven structure.
<2> A curable resin composition containing pentaerythritol tetraglycidyl ether, a polymerization initiator, and a surfactant, which is used for forming a hard coat layer.
<3> The curable resin composition according to <2>, wherein the surfactant contains 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 contains at least one selected from the group consisting of a fluorine-containing acrylic compound and a fluorine-containing siloxane compound.
<5> The curable resin composition according to <1>, further including at least one selected from the group consisting of a fluorine compound and a siloxane compound.
<6> The polymerization initiator according to any one of <1> to <5>, which is at least one compound selected from the group consisting of a photoacid generator, a thermal acid generator, and a photocation generator. Curable resin composition.
<7> Furthermore, at least one type of reactivity selected from the group consisting of glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin oxide epoxy compounds, silicone modified compounds, fluorine modified epoxy compounds, and oxetane compounds. The curable resin composition according to any one of <1> to <6>, which contains a compound.
<8> Furthermore, at least one sensitizer selected from the group consisting of anthracene compounds, anthraquinone compounds, thioxanthone compounds, naphthalene compounds, phenanthrene compounds, chrysene compounds, perylene compounds, and acridine compounds. The curable resin composition according to any one of <1> to <7>.
<9> The curable resin composition according to <8>, in which the sensitizer contains dialkoxyanthracene.
<10> The curing according to any one of <1> to <9>, in which 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. Resin composition.
<11> The pentaerythritol tetraglycidyl ether is the curable resin composition according to any one of <1> to <10>, which has an epoxy equivalent of 90 to 150.
<12> The curable resin composition according to any one of <1> to <11>, in which the content of the polymerization initiator is 3% by mass to 30% by mass with respect to the pentaerythritol tetraglycidyl ether. It is a thing.
<13> The content of the polymerization initiator according to any one of <1> to <12>, which is 0.1% by mass to 10% by mass with respect to the total mass of the curable resin composition. It is a curable resin composition.
<14> The curable resin composition according to <1>, which contains the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, and a photoacid generator that is the polymerization initiator.
<15> The curable resin composition according to <2>, which contains the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, a photoacid generator that is the polymerization initiator, and the surfactant. Is.
<16> The content of the pentaerythritol tetraglycidyl ether is 60 mass% to 85 mass% with respect to the total mass of the curable resin composition, and the content of the alicyclic epoxy resin is the total mass of the curable resin composition. To 10% by mass to 30% by mass, and the content of the photoacid generator is 1% by mass to 6% by mass based on the total mass of the curable resin composition. <14> or <15> Curable resin composition.
<17> A cured product of the curable resin composition according to any one of <1> to <16>, wherein the flat film has a scratch pencil hardness of 7H or more.
<18> A cured product of the curable resin composition according to <1> (including the curable resin composition according to <5> to <16> not related to <2>) and having a height. Is 50 nm to 1000 nm and the pitch is 20 nm to 1000 nm.
<19> Using the curable resin composition according to <1> (including the curable resin composition according to <5> to <16> not related to <2>), the height is 50 nm to 1000 nm. It is a method for manufacturing a concavo-convex structure having a step of molding and curing a concavo-convex pattern having a pitch of 20 nm to 1000 nm.

According to one embodiment of the present invention, there is provided a curable resin composition that is excellent in reproducibility of a fine structure such as a moth-eye structure and has higher hardness than ever before. Preferably, a curable resin composition for nanoimprint is provided.
According to another embodiment of the present invention, there is provided a curable resin composition having excellent antifouling property and having significantly improved hardness as compared with a conventional composition containing an antifouling agent. Preferably, a curable resin composition for hard coating is provided.
Further, according to another embodiment of the present invention, there is provided a cured product having significantly improved hardness as compared with a conventional cured product.
Further, according to another embodiment of the present invention, there is provided a concavo-convex structure body having significantly improved hardness as compared with a conventional cured product, and a manufacturing method thereof.

It is a schematic diagram showing an example of a manufacturing process of an uneven structure. It is a schematic sectional drawing which shows an example of the uneven structure manufactured by nanoimprint. It is process drawing which shows the process of producing a moth eye film using the curable resin composition containing a photo-acid generator. It is a schematic diagram for explaining a method of evaluating scratch resistance using steel wool. It is an SEM image before and after a scratch resistance test on the transfer surface of the moth-eye film of sample level 1. 3 is SEM images before and after a scratch resistance test on a transfer surface of a moth-eye film of sample level 2. It is an SEM image before and after a scratch resistance test on the transfer surface of the moth-eye film of sample level 3. It is a graph which shows the reflectance of the moth-eye film of sample levels 1-3. It is a graph which shows the transmittance|permeability of the moth-eye film of sample levels 1-3. It is a graph which shows the hardness of the moth-eye film of sample levels 1-2 and sample level 3. It is process drawing which shows the process of producing a moth eye film using the curable resin composition containing a thermal acid generator. (A) is an SEM photograph showing the moth-eye structure of the cured film of sample level 27, and (b) is an SEM photograph showing the moth-eye structure of the cured film of sample level 28. It is a graph which shows the reflectance in the cured film of the moth-eye film of sample level 27 and sample level 28. It is a SEM photograph which shows the moth-eye structure before and after the abrasion test of the cured film of sample level 27. It is a SEM photograph which shows the moth-eye structure before and after the abrasion test of the cured film of the sample level 36. It is a photograph showing a state before and after wiping after dropping an artificial fingerprint liquid. It is an SEM photograph before and after repeating 20 times of wiping off an artificial fingerprint liquid. It is a graph which shows the change of the reflectance before and after wiping 20 times. It is a graph which shows the change of the transmittance before and after 20 times of wiping. (A) is an SEM photograph showing the moth-eye structure of the cured film of sample level 39, and (b) is an SEM photograph showing the moth-eye structure of the cured film of sample level 42.

Hereinafter, the curable resin composition and the cured product of the present disclosure will be described in detail.

In the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value. In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition. Means

In the present 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 an uneven structure, and preferably a reactive compound (hereinafter, (Also referred to as "reactive diluent"), an antifouling agent, a sensitizer, a silane coupling agent, and a filler, and may further contain an organic solvent and other additives, if 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 “antifouling agent”), and forms a hard coat layer. It is used for (hard coating), preferably contains a reactive diluent, a sensitizer, a silane coupling agent, and a filler, and if necessary, further contains an organic solvent and/or other additives. You may contain an agent.
In the following, the curable resin composition of the first aspect and the second aspect is also generally simply referred to as “curable resin composition of the present disclosure”. 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. Among the conventionally known polymerizable compounds, by selectively containing pentaerythritol tetraglycidyl ether, it is possible to obtain a cured product having improved hardness as compared with the conventional curable resin composition. ..

As PETG, a commercially available commercially available product may be used, and for example, Showfree (registered trademark) series manufactured by Showa Denko KK can be used.

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 reaction during the polymerization reaction is high, so the crosslink density is further improved. However, the hardness after curing is further improved.
For the same reason 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, and 45% by mass to the total mass of the curable resin composition. It is more preferably 97% by mass, and further preferably 60% by mass to 85% by mass.
When the content of PETG is 15% by mass or more, high hardness is easily obtained. Further, 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)-
Examples of the photopolymerization initiator include onium salt compounds.
Examples of onium salt compounds include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and the like.
Onium salt compounds include halogen metal complex anions (BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B(6F5) ₄ ^−, etc.), and special phosphorus compounds such as (RF) _n PF _{6 −n} . May be used 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, bis(4-tert-butylphenyl)iodonium hexafluoroantimonate, tri-p-tolylsulfonium hexafluorophosphate, 4-isopropyl- 4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate and the like can be mentioned.
Further, as the onium salt compound, a commercially available commercially available product may be used, and specific examples of the commercially available product include Optomer SP-150, Optomer SP-152, Optomer SP-170 and Optomer SP-made by ADEKA CORPORATION. 172, Optomer SP-300, etc., CPI-100P, CPI-100A, CPI-200K, CPI-210S, LW-S1, IK-1, IK-2, HS-1, etc., manufactured by San Apro Co., Ltd., manufactured by BASF. Irgacure 250, Irgacure 270, Irgacure 290, and the like, WPI-113, WPI-116, WPI-170, WPI-124, and the like manufactured by Wako Pure Chemical Industries, Ltd. can be used.
In addition to the above, [{C ₅ (R ¹ ) _n } _2m M _m ] _l ⁺ [{B(R ² ) ₄ } ⁻ ] _l (wherein M is a central transition metal; C ₅ is Represents cyclopentadienyl; R ¹ is an electron donating substituent attached to the carbon of cyclopentadienyl; n is 4 or 5; m is 1 or 2; l is 1 or 2 R ² is a ligand that coordinates to a boron atom (B), and four R ² are the same.) Also, an ion-association crystalline substance obtained by combining a metallocene represented by the formula (4) and a borate compound can be used. It may be mentioned as a cationic polymerization initiator.

The content of the photopolymerization initiator is preferably 0.1% by mass to 10.0% by mass, more preferably 1.0% by mass to 6.0% by mass, based on the total mass of the curable resin composition. ..
Moreover, you may use a photoinitiator individually by 1 type or in combination of 2 or more types.

-Thermal polymerization initiator (thermal acid generator)-
As the thermal acid generator, onium salts such as quaternary ammonium salt, sulfonium salt, iodonium salt and phosphonium salt can be used.
As an example of the quaternary ammonium salt, commercially available products are K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE CXC-1733, K-PURE CXC-1742, and K, manufactured by King Industries. -PURE CXC-1821, K-PURE CXC-2689, K-PURE TAG-2678, K-PURE TAG-2689, K-PURE TAG-2690 etc. are mentioned.
As an example of the sulfonium salt, commercially available products include San-Aid (registered trademark) SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L and the like 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, more preferably 0.2% by mass to 5.0% by mass, based on the total mass of the curable resin composition. ..
Moreover, you may use a thermal-polymerization initiator individually by 1 type or in combination of 2 or more types.

As content of a polymerization initiator, the range of 3 mass%-90 mass% is preferable with respect to pentaerythritol tetraglycidyl ether, and the range of 3 mass%-50 mass% is more preferable, 3 mass%-30 mass%. Is more preferable, and the range of 3% by mass to 15% by mass is particularly preferable.
When the content of the polymerization initiator is 3% by mass or more, it is suitable for starting the curing reaction of PETG. Further, when the content of the polymerization initiator is 90% by mass or less, it is advantageous in maintaining the storage stability of the composition after preparation and the physical stability of the cured product.

As content of a polymerization initiator, the range of 0.1 mass%-10 mass% is preferable with respect to the total mass of curable resin composition, and the range of 1.0 mass%-8.0 mass% is more preferable. The range of 1.5% by mass to 6.0% by mass is particularly preferable.
When the content of the polymerization initiator is 0.1% by mass or more, it is suitable for promoting the initiation of the curing reaction of PETG. Further, when the content of the polymerization initiator is 10% by mass or less, it is advantageous in terms of storage stability after preparation and retention of physical properties after curing.

(Antifouling 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 similar to that of the second aspect as an antifouling agent.
When the curable resin composition contains a surfactant, the cured product obtained by curing is imparted with water repellency, oil repellency, hydrophilicity, lipophilicity and the like, and can be imparted with antifouling property.

The surfactant in the present disclosure is a compound having a fluorine atom or -SiO- structure in the molecule and capable of imparting water repellency, oil repellency, hydrophilicity or lipophilicity to the surface of the cured film after curing. There are, for example, fluorine compounds, silicone compounds, and silicone fluorine compounds.

Examples of the surfactant include fluorine compounds and siloxane compounds (including fluorine-containing siloxane compounds), and at least one selected from the group consisting of fluorine-containing acrylic compounds and fluorine-containing siloxane compounds is preferable.

As the surfactant, a commercially available product 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, RS-90 manufactured by DIC Corporation, Neos Co., Ltd. Futgent 601AD, 602A, 650A, 710FL, 208G, 215M, FTX-218, FTX-601ADH, 730LM, NFX-552, etc., AGC Seimi Chemical Co., Ltd. Surflon S386, S651, manufactured by Shin-Etsu Chemical Co., Ltd. KY-164, KY-108, KY-1203, X-71-1206, ZX-058, ZX-101, ZX-104, ZX-105, ZX-106, ZX-108, ZX- manufactured by T&K TOKA CORPORATION. 109, ZX-022-U, ZX-201, ZX-202, ZX-203, ZX-212, ZX-401N, ZX-412 ZX-501, Daikin Industries, Ltd. OPTOOL DAC-HP, and the like. ..

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 1.0% by mass based on the total mass of the curable resin composition. % To 10% by mass is more preferable.
Moreover, you may use a surfactant individually or in combination of 2 or more types.

(Reactive diluent)
The curable resin composition of the present disclosure preferably further contains a reactive compound (reactive diluent) in addition to the above components. By containing a reactive diluent, adjustment or improvement of physical properties such as curability (hardness of cured film) and elongation of the curable resin composition, adjustment of viscosity, adhesion to substrate, addition of additives In this case, the compatibility can be improved.

As the reactive diluent, at least one selected from the group consisting of glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin oxide epoxy compounds, silicone modified compounds, fluorine modified epoxy compounds, and oxetane compounds. Suitable examples are reactive compounds.

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

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

-Epoxy compound-
Examples of epoxy compounds include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin oxide epoxy compounds, and modified products of these compounds.
Specific examples of the epoxy compound 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, spiro ring 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 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, 1,6 hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, tripropylene glycol diglycidyl ether Glycidyl 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, resorocinol diglycidyl ether , Diglycylol polyglycidyl ether, polyglycylol polyglycidyl ether, ethylene glycylol diglycidyl ether, styrene oxide, alcohol glycidyl ether, orthocresyl glycidyl ether, metaparacresyl glycidyl ether, glycidyl methacrylate, hexahydrophthalic acid diester Glycidyl ether, g Lipropylene glycol diglycidyl ether, bisphenol A tetraglycidyl ether, 3,4-epoxycyclohexanecarboxylic alydomethyl ester, 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), dicyclopentadiene dioxide ,3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane, 3',4'-epoxycyclohexylmethyl 3',4'- Examples thereof include epoxycyclohexanecarboxylate, ε-caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and 1,2-epoxy-4-vinylcyclohexane.

Of these, an alicyclic epoxy compound is preferable as the epoxy compound, and a compound represented by the following formula 1 is more preferable.

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.
The divalent hydrocarbon group for X may be linear or branched, and examples thereof 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. As the divalent alicyclic hydrocarbon group, for example, 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1, Examples thereof include cycloalkylene groups (including cycloalkylidene groups) such as 4-cyclohexylene and cyclohexylidene groups.
Further, X is preferably a linking group having an oxygen atom, and -CO-, -O-CO-O-, -COO-, -O-, -CONH-, or a group in which a plurality of these groups are linked or the like is used. Can be mentioned.

Specific examples of the alicyclic epoxy compound are shown below. However, the present disclosure is not limited thereto.

Further, as the epoxy compound, a commercially available commercially available product may be used, and specific examples of the commercially available product include the celoxide series which is an alicyclic epoxy resin manufactured by Daicel Corporation (eg: celoxide 8000, celoxide 2021P). , Celoxide 2081, Celoxide 8200, etc.) and the like.

-Silicone (siloxane) modified epoxy compound-
Examples of the epoxy compound having a silicon atom (silicone (siloxane) modified epoxy) include bis[2-(3,4-epoxycyclohexyl)ethyl]-tetramethyldisiloxane.
The silicone (siloxane)-modified epoxy may be a commercially available product on the market, and specific examples of the commercially available product include Shin-Etsu Chemical Co., Ltd. product names: X-40-2678, X-40-. 2670, X-40-2705, X-40-2669 and the like.

-Fluorine-modified epoxy compound-
Examples of the epoxy compound having a fluorine atom (fluorine-modified epoxy compound) include 3-(2,2,3,3-tetrafluoropropoxy)-1,2-epoxypropane and 3-(1H,1H,5H-octafluoropentyl. Roxy)-1,2-epoxypropane, 3-perfluorobutyl-1,2-epoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 1.4 bis(2,3-epoxypropyl)- Examples include perfluoro-n-butane and 1.6 bis(2,3-epoxypropyl)-perfluoro-n-hexane.
As the fluorine-modified epoxy compound, a commercially available product may be used, and specific examples of the commercially available product include product name: 1.3CHEP manufactured by Daikin Industries, Ltd.

-Oxetane compound-
Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, xylylenebisoxetane. , 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, 3-ethyl-3-(cyclohexyloxy)methyloxetane, 3-ethyl-3-(phenoxy)methyloxetane, 3-methyl- Examples include 3-oxetane methanol, 3-ethyl-3-oxetane methanol, allyloxyoxetane, bisphenol A bisoxetane, bisphenol F bisoxetane, and bisphenol S bisoxetane.
In addition, as the oxetane compound, a commercially available commercially available product may be used, and specific examples of the commercially available product include ETERNACOLL (registered trademark) series manufactured by Ube Industries, Ltd. (eg: ETERACOLLL OXBP, ETERACOLLL OXMA, etc.). To be Further, Toagosei Co., Ltd.'s OXT-101, OXT-212, OXT-121, and OXT-221 (product name), and OX-SQ TX made by Toagosei Co., Ltd., which is an oxetane compound having a silicon atom. -100, OX-SQ SI-20 (product name) (oxetanyl silsesquioxane or oxetanyl silicate) and the like.

-Other compounds-
Suitable examples of compounds other than the above-mentioned epoxy compound and oxetane compound include episulfide compounds.

When the physical properties of the curable resin composition are adjusted by containing the above reactive diluent, the content of the reactive diluent is 5% by mass with respect to the content of pentaerythritol tetraglycidyl ether (PETG). % To 90 mass% is preferable, 10 mass% to 50 mass% is more preferable, and 10 mass% to 30 mass% is more preferable.

Among the above, as the curable resin composition of the present disclosure, a composition containing PETG, a reactive diluent, and a polymerization initiator is one of the preferred embodiments, and PETG, the reactive diluent, and the polymerization initiator. A preferred embodiment in the case of containing: contains (1) PETG, an alicyclic epoxy resin (preferably a compound represented by the above formula 1), and a photoacid generator which is a photopolymerization initiator. Aspect, or an aspect containing PETG, an alicyclic epoxy resin (preferably a compound represented by the above formula 1), a photoacid generator which is a photopolymerization initiator, and a surfactant, Furthermore, (2) PETG 60 mass%-85 mass%, alicyclic epoxy resin (preferably the compound represented by the said Formula 1) 10 mass%-30 mass%, and a photo-acid generator 1 mass%-. The embodiment containing 6% by mass is more preferable.

(Sensitizer)
The curable resin composition of the present disclosure may further contain a sensitizer.
As the sensitizer, at least one sensitizer selected from the group consisting of anthracene compounds, anthraquinone compounds, thioxanthone compounds, naphthalene compounds, phenanthrene compounds, chrysene compounds, perylene compounds, and acridine compounds. It is preferable to contain

Specific examples of the sensitizer include anthracene, 1,2-benzanthracene, 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-nitroanthraquinone, 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-propane-1- On, thioxanthone, isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and the like.

Among the above, the preferable sensitizer is preferably dialkoxyanthracene, and particularly preferably 2-ethyl-9,10-dimethoxyanthracene and 9,10-dibutoxyanthracene, in terms of excellent curability improving effect.

When performing the curing reaction of the curable resin composition utilizing visible light, a known sensitizer of coumarin type, thiazine type, azine type, acridine type, xanthene type, titanocene type sensitizers which are dye type sensitizing substances. You may use.

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 include a coupling agent. By containing the coupling agent, the adhesiveness between the curable resin composition and the substrate can be further enhanced.

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

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl. Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 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-ureidopropyltrialkoxy Examples include silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatepropyltriethoxysilane.

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 nano-order nanoparticles, depending on the application.
The nanoparticles refer to particles of an organic material or an inorganic material having an average primary particle diameter of 1 nm to 1000 nm. The average primary particle diameter is a value obtained by a laser analysis type particle size distribution meter.

The nanoparticles may be any particles as long as they do not inhibit the polymerization reaction of the curable resin composition.
Examples of the nanoparticles include carbon, organic fillers such as diamond, graphene, graphene oxide, fullerene, polyethylene, polypropylene and polystyrene. Examples of the inorganic filler include 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 and the like.
Also, particles in which the surface of the nanoparticles is coated or chemically modified with a reactive group are preferable.

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

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.
Moreover, you may use a filler individually by 1 type or in combination of 2 or more types.

(Organic solvent)
The curable resin composition of the present disclosure may be prepared in a diluted form by 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.

As the organic solvent, for example, toluene, xylene, hexane, cyclohexane, styrene, octanedecane, 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, propylene glycol monomethyl ether and the like.
The organic solvent may be used alone or in combination of two or more.

(Other additives)
The curable resin composition of the present disclosure is further, if necessary, an antioxidant, an antioxidant, a colorant, a viscosity modifier, a flame retardant, an ultraviolet absorber, a discoloration inhibitor, an antibacterial agent, an antistatic agent, Additives such as a plasticizer, a lubricant, a defoaming agent, a thickener, a thixotropic agent, a leveling agent, and a release agent can be contained.

Examples of the colorant include dyes, carbon black, titanium oxide, zinc oxide, iron oxide, anthraquinone type and phthalocyanine type.
Examples of stabilizers such as antiaging agents and antioxidants include hindered phenol compounds, phosphorus compounds, benzophenone compounds, hydrazine compounds, and the like.

-Curing method of curable resin composition-
Curing of the curable resin composition can be performed by applying an active energy ray of 200 nm to 1300 nm (light such as ultraviolet rays) or heat of 50° C. to 250° C., or by applying both of these. Above all, the curable resin composition can be cured by irradiating with an active energy ray of 200 nm to 850 nm (preferably 250 nm to 560 nm) or by heating at a temperature of 80°C to 180°C.

Examples of active energy rays include α rays, γ rays, X rays, ultraviolet rays, visible rays, infrared rays, and electron rays.
Further, as the curable resin composition of the present disclosure, a photocurable composition that is cured by light such as ultraviolet rays, visible rays, and infrared rays is preferable, and among them, a photocurable composition that is cured by ultraviolet rays is preferable.

When the curable resin composition is cured by irradiation with active energy rays, it is preferable to use an ultraviolet irradiation device as an exposure device and irradiate the curable resin composition with active energy rays.
As the ultraviolet 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, and an LED can be used. Moreover, when irradiating with ultraviolet rays to cure, 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. Is.

Further, when the curable resin composition is cured by heating, a heating device such as an infrared heating device or an electric furnace that heats an object with infrared rays is used, and a temperature of 80° C. to 180° C. with respect to the curable resin composition. It is preferable to heat for 1 minute to 120 minutes.

The curable resin composition according to the first aspect of the present disclosure is used for producing (imprinting) an uneven structure. An uneven structure is obtained by curing the curable resin composition to form an uneven structure (particularly a moth-eye structure) on the substrate. Since the curable resin composition of the present disclosure is used, it is possible to manufacture an uneven structure having high hardness and excellent antireflection properties.
The uneven structure is preferably an uneven structure having a nanoscale fine uneven pattern. The uneven pattern preferably has 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 effect of molding using the curable resin composition of the present disclosure can be favorably obtained, and a concave-convex structure having excellent antireflection properties can be produced. can do.

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 of the second aspect of the present disclosure has a curing performance of selectively including PETG and curing. Conventionally, there was a problem that curability is reduced when containing an antifouling component, in the curable resin composition of the second aspect of the present disclosure, a high hardness is obtained even if it contains an antifouling component, At the same time, excellent antifouling property can be imparted.
Therefore, when a hard coat layer is provided on the surface of a member or the like used in a field requiring high strength by using the curable resin composition of the second aspect of the present disclosure, strength resistance to external force and stain resistance. Can be compatible.

<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 7H or more in a flat film. With the curable resin composition of the present disclosure, a cured product having improved hardness can be obtained as compared with conventional curable resin compositions.

Scratch pencil hardness is based on JIS-K5600 5-4 mechanical method, and has two wheels on one side and a hand-held pencil scratch hardness with a cylindrical hole in the center for inserting a pencil with an angle of 45°±1°. Testing machine No. It is a value measured using a 553-S (manufactured by Yasuda Seiki Co., Ltd.) with a load of 750±10 g.
The scratch pencil hardness of 7 H or more in the flat film indicates that the hardness is higher and the durability is superior to the conventional one. The scratch pencil hardness is preferably as close to 9H as possible, and above all, 8H or higher is preferable, and 9H or higher is more preferable.

<Rough structure and method for manufacturing the same>
The concavo-convex structure body of the present disclosure is a cured product of the curable resin composition of the first aspect described above, and has a concavo-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm. Since the uneven structure of the present disclosure uses the curable resin composition of the above-described first aspect, the surface hardness after curing is high, and a fine structure is easily obtained, and therefore the height: 50 nm to 1000 nm. , Pitch: suitable for producing a fine uneven pattern of 20 nm to 1000 nm.
From this point of view, the curable resin composition of the above-mentioned first aspect is suitable for production (imprint) of a concavo-convex structure body, a fine concavo-convex structure (particularly moth-eye structure) structure can be obtained with good reproducibility, and For example, a structure (cured product) such as a replica mold formed by using a master mold has excellent hardness. Since the replica mold is cheaper than the master mold and suitable for mass production, the replica mold is widely used.However, the replica mold having the moth-eye structure using the curable resin composition of the present disclosure has high hardness. It has excellent wear resistance and durability.

The concavo-convex structure body of the present disclosure may be produced by any method as long as it is a method using the curable resin composition of the first aspect described above. In the production of the uneven structure of the present disclosure, it is preferable to use the curable resin composition of the above-described first aspect to form an uneven pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm. It is carried out by a method having a step of molding and curing.

Specifically, it may be produced by the following method. That is,
For the production of the uneven structure, a mold having an uneven pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm and a base material coated with the curable resin composition are prepared, and the curability is set. The resin composition is brought into contact with the uneven pattern and pressed, an introducing step of introducing a curable resin composition into the uneven pattern, a curing step of curing the introduced curable resin composition, and a curable resin composition. You may perform by the method which has the mold release process which mold-releases the said base material provided with the uneven structure obtained by hardening.

Hereinafter, each step in the method for manufacturing the concavo-convex structure product of the present embodiment will be described with reference to FIG. FIG. 1 is a schematic view showing the manufacturing process of the uneven structure.

As shown in FIG. 1A, the imprint apparatus 100 includes a stage 5, a push jig 6, a feeding roller 7 and a winding roller 8. The imprint apparatus 100 is an apparatus for manufacturing the concavo-convex structure 10 (base material 1 having the concavo-convex structure).

The stage 5 is a stand for placing and fixing the mold 2. As shown in FIG. 1A, the mold 2 is fixed to the stage 5 so that the concavo-convex pattern and the substrate 1 coated with the curable resin composition 3 face each other.

The push jig 6 is for moving the stage 5 up and down, and by fixing the mold 2 on the stage 5, the mold 2 is moved up and down.
By raising the stage 5 to which the mold 2 is fixed, the base material 1 coated with the curable resin composition 3 and the concavo-convex pattern of the mold 2 can be brought into contact with each other. The resin composition 3 can be introduced into the uneven pattern.
Further, by lowering the stage 5 to which the mold 2 is fixed, the base material 1 having the concavo-convex structure can be released from the mold 2 as described later.

As shown in the figure, the sheet-shaped base material 1 is wound around the feed roller 7 and the take-up roller 8.
The delivery roller 7 is a roller for delivering the wound sheet-shaped base material 1 to the stage 5 side to which the mold 2 is fixed, and the take-up roller 8 molds the wound sheet-shaped base material 1 into the mold 2 Is a roller for winding from the fixed stage 5 side.

[Introduction process]
In this step, as shown in FIG. 1( b ), the base material 1 coated with the curable resin composition 3 and the mold 2 having the concavo-convex pattern are pressed against the curable resin composition 3 by contacting the concavo-convex pattern. Then, the curable resin composition 3 is introduced into the uneven pattern.
The curable resin composition is applied to the base material 1 before the introducing step. The method of applying the curable resin composition is not particularly limited.

In the introducing step, the stage 5 to which the mold 2 is fixed is raised at a constant speed to bring the base material 1 coated with the curable resin composition 3 into contact with the concavo-convex pattern of the mold 2, and then the curable resin composition. The substrate 1 on which the object 3 is applied and the mold 2 having the concavo-convex pattern are pressed with a constant pressure.

In the introducing step, the mold and the base material 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, and more preferably at a pressure of 0.01 MPa to 0.03 MPa. Pressing is more preferable, and pressing with a pressure of 0.01 MPa to 0.02 MPa is particularly preferable. By pressing with a pressure of 0.005 MPa or more, a sufficient amount of the curable resin composition can be introduced into the concavo-convex pattern, and as a result, a concavo-convex structure having excellent functions in terms of transparency and antireflection can be obtained. can get. Further, by pressing with a pressure of 1 MPa or less, the amount of the curable resin composition introduced into the concavo-convex pattern can be adjusted appropriately.

[Curing process]
In this step, as shown in FIG. 1C, the curable resin composition 3 introduced into the uneven pattern is cured.
Here, the light-transmitting base material 1 and the photocurable composition are used, and the base material 1 is irradiated with ultraviolet rays (UV) from the side opposite to the side where the mold 2 is fixed. Since the base material 1 has a light-transmitting property, the ultraviolet light applied to the base material 1 passes through the base material 1 and is applied to the curable resin composition 3. As a result, the curable resin composition 3 introduced into the concavo-convex pattern is cured, so that the cured concavo-convex structure is formed on the substrate 1.
It should be noted that the irradiation time and irradiation amount when irradiating the curable resin composition 3 with ultraviolet rays are not particularly limited as long as they are sufficient to cure the curable resin composition 3 introduced into the uneven pattern.

[Release process]
In this step, as shown in FIG. 1D, the base material 1 having the concave-convex structure obtained by curing the curable resin composition 3 is released from the mold 2.
In the releasing step, the stage 5 having the mold 2 fixed thereon is lowered at a constant speed to release the contact between the concavo-convex structure obtained by curing the curable resin composition and the concavo-convex pattern of the mold 2.
At this time, as shown in FIG. 2, since the contact area between the concave-convex structure and the concave-convex pattern of the mold 2 is large, a large releasing force is applied when releasing the contact between the concave-convex structure and the concave-convex pattern of the mold 2. Will be required. Therefore, the tip of the concavo-convex structure is likely to be broken and remain on the bottom of the mold, which easily causes a problem of shortening the life of the mold.
However, in the method for manufacturing a concavo-convex structure product of the present disclosure, since the hardness of the cured product after curing is high, the tip of the concavo-convex structure is less likely to be damaged, and mold release capable of reproducing a fine structure pattern is possible. Thus, the uneven structure obtained by the method for manufacturing an uneven structure of the present disclosure is superior in antireflection property and water repellency as compared with the uneven structure 40 obtained by the conventional nanoimprint, and is, for example, an uneven structure. The mold will have a long life.

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

(Example 1)
-Sample level 1-
-Preparation of curable composition-
A brown glass wide-mouth standard bottle (Sansho Co., Ltd., glass wide-mouth standard bottle 1K, full volume: 14 ml), pentaerythritol tetraglycidyl ether (PETG; trade name: Showfree (registered trademark), Showa Denko KK) 9 0.5 g of triallyl sulfonium salt (photo acid generator; trade name: CPI210S, manufactured by San-Apro Co., Ltd.) was mixed, and a hand homogenizer (MH-1000, manufactured by As One Co., Ltd.) and a test tube mixer ( VXRS1, manufactured by IKA Co., Ltd.) was mixed with stirring to prepare a curable composition.
The viscosity (23° C.) of the curable composition was measured and found to be 159 mPa·s.
The viscosity was measured by using an E-type viscometer (cone plate type) EVT-25L manufactured by Toki Sangyo Co., Ltd. while keeping the curable composition at 23°C. The same is true for the sample levels shown below.

-Formation of hard coat layer-
The prepared curable composition was applied on a glass slide (S1214, manufactured by Matsunami Glass Industry Co., Ltd.) having a size of 76 mm×26 mm, which had been degreased with acetone in advance to have a thickness of about 50 μm. : ECS5-015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.), and the curable composition is cured by irradiation with ultraviolet rays under the conditions of an irradiation amount of 9,000 mJ/cm ² and an illuminance of 100 mW/cm ^2. Then, a cured layer (hard coat layer), which is a cured product, was formed on the slide glass.
As described above, a test piece having a hard coat layer was produced.

-Evaluation 1a-
The following evaluation was performed on the test piece having the hard coat layer. 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 1 day. According to JIS-K5600 5-4 Mechanical Method, the test piece after being left has two wheels on one side, and a cylindrical hole into which a pencil with an angle of 45°±1° is inserted at the center. Hand-held pencil scratch hardness tester No. Using 553-S (manufactured by Yasuda Seiki Co., Ltd.), a load of 750±10 g was applied to measure the scratch pencil hardness of the hard coat layer.
The scratch pencil hardness is evaluated in the range of 6B to 9H, and the closer to 9H, the harder the property.

(Scratch resistance)
Using a test piece having a hard coat layer in the same manner as described above, as shown in FIG. 4, with respect to the surface of the hard coat layer of the test piece, a steel wool having a count: extra fine #0000 (center diameter: about 0.012 mm) (#0000, manufactured by Trusco Nakayama Co., Ltd.) is placed in contact with 34 and a container containing water is placed thereon, and the operation of rubbing the hard coat layer in one direction under a load of 500 g is repeated 10 times. The presence or absence of scratches on the surface was evaluated.

-Production of GC moth-eye mold-
First, glassy carbon (GC, Tokai Carbon Co., Ltd.) that had been mirror-polished on both sides was irradiated with an oxygen ion beam using an electron cyclotron resonance (ECR) type ion shower device, and oxygen ion beam etching was performed. After that, a vacuum vapor deposition machine (VPC-260F, ULVAC Kiko Co., Ltd.) was used to perform vacuum vapor deposition on the processed GC surface to form a Cr vapor deposition film having a thickness of 30 nm. After that, a mold release treatment (fluorine-based mold release agent; coated with OPTOOL DSX manufactured by Daikin Industries, Ltd.) was performed to prepare a GC moth-eye mold having a width of 20 mm and having an antireflection structure called a moth-eye structure.
The processing conditions of GC are as follows.

For the ion beam irradiation, an electron cyclotron resonance (ECR) ion shower device EIG-210ER (manufactured by Elionix Inc.) was used. For details on the fabrication of GC moth-eye molds, see NB 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).

-Production of moth-eye film-
Next, as shown in FIG. 3, the curable composition 14 is applied to the processed surface of the manufactured GC moth-eye mold 12 at a coating amount of 1.25 g/m ² to form a coating film 14, A polyester film (Cosmoshine (registered trademark) A4300; PET film) 16 manufactured by Toyobo Co., Ltd. was placed on the film 14. Using a UV irradiation device (model: Aicure UP50 manufactured by Panasonic Corporation), the coating film 14 is irradiated with ultraviolet rays through a PET film (irradiation amount of sample levels 1 to 3: 10,000 mJ/cm ² , sample levels 1 to 3). Illuminance: 50 mW/cm ² ) was used as 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 following evaluation was performed on the moth-eye film obtained above. The evaluation results are shown in FIGS. 5, 8A, 8B and 9.

(Scratch resistance)
As shown in FIG. 4, steel wool (#0000, manufactured by Trusco Nakayama Co., Ltd.) 34 of count: extra fine #0000 (center diameter: about 0.012 mm) is brought into contact with the surface of the cured film 24 of the moth-eye film 18. Then, a container 32 containing water is placed, and a test of rubbing the cured film 24 with the PET film 16 in one direction under a load of 100 g is repeated 10 times, and the presence or absence of scratches on the surface of the cured film 24 is determined as follows. An evaluation was made.
I. Image Evaluation The surface of the cured film 24 of the moth-eye film before and after the rubbing test was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix), and the presence or absence of scratches due to rubbing was evaluated by 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 before and after the scratch test were measured. ..
C. Hardness (Martens hardness)
The hardness of the surface of the cured film 24 of the moth-eye film was measured from the load and displacement when the triangular pyramid indenter was pushed into the cured film using a dynamic ultra-micro hardness meter (DUH-211, Shimadzu Corporation).

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

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

Details of the components in Table 2 are as follows.
-Celoxide 8000: Alicyclic epoxy compound manufactured by Daicel Corporation-EPICLON EXA-830-CRP: Bisphenol F type epoxy resin, manufactured by DIC Corporation-CPI210S: triallyl sulfonium salt (photo acid generator; trade name: CPI210S, Made by San-Apro Co.
KY-1203: One terminal (meth)acryl-modified perfluoropolyether compound (fluorine-based antifouling additive, manufactured by Shin-Etsu Chemical Co., Ltd.)

As shown in Table 2, in the sample levels 1 and 2 containing PETG, the hardness was dramatically improved as compared with the comparative examples containing other epoxy compounds which were not PETG, and the rubbing test using steel wool was performed. However, the occurrence of scratches was not recognized, and the result was excellent in scratch resistance.
Further, in the moth-eye film produced by using the curable compositions of Sample Levels 1 and 2, as shown in FIGS. 5 to 6, no scratches due to the scratch test were observed. On the other hand, in the moth-eye film produced by using the curable composition of Sample Level 3, as shown in FIG. 7, the scratches due to the scratch test are remarkably observed, and it is understood that the scratch resistance is poor. The reflectance and transmittance of the moth-eye films of sample levels 1 to 2 and sample level 3 before and after rubbing are shown in FIGS. 8A and 8B. As shown in FIGS. 8A and 8B, in the sample levels 1 and 2, the changes in the reflectance and the transmittance due to the scratch test are small, and in the sample level 3, the increase in the reflectance and the decrease in the transmittance after the scratch test are observed. It can be seen that it appears remarkably. That is, it was proved that the moth-eye film of sample level 3 had a larger change in shape due to scratching than the moth-eye film of sample levels 1-2. This shows that the surface hardness (Martens hardness) 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 8-20-
A test piece having a hard coat layer was prepared in the same manner as in Sample Level 1 except that the composition of Sample Level 1 was changed as shown in Table 3 below.
Among the prepared test pieces, some of the test pieces were measured and evaluated in the same manner as in the sample level 1. Then, another part of the test piece was placed in a thermostatic chamber (SAFETY OVEN SPH-201, manufactured by Espec Corporation) having an ambient temperature of 85° C. and left for 30 minutes, and the sample level 1 was applied to the test piece after the standing. Measurements and evaluations similar to the above were performed. The results of measurement and evaluation are shown in Table 3.

Table 3 shows the influence of the reactive diluent type and the content concentration in the sample levels 8 to 20.
As shown in Table 3, the steel wool scratch resistance could be improved by containing PETG and the epoxy compound which is a reactive diluent. As is clear from the above, the concentration of the reactive diluent is preferably less than 30% by mass.
In addition, when a moth-eye film was produced, as in Sample Levels 1 and 2, scars due to a scratch test were less likely to occur, and the hardness (Martens hardness) of the surface of the cured film was high, so that the reflectance and transmittance by a scratch test were high. The change in the rate is also considered to be small.

(Example 3)
-Sample levels 21-26-
In Sample Level 1, 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 4 below, and measurement and evaluation were performed. Table 4 shows the results of measurement and evaluation.

Table 4 shows the influence of the type of the polymerization initiator in the sample levels 21 to 26.
As shown in Table 4, the effect of changing the type of the polymerization initiator was small, and the hardness obtained by using PETG together with PETG was excellent.
In addition, when a moth-eye film was produced, as in Sample Levels 1 and 2, scars due to a scratch test were less likely to occur, and the hardness (Martens hardness) of the surface of the cured film was high, so that the reflectance and transmittance by a scratch test were high. The change in the rate is also considered to be small.

(Example 4)
-Sample levels 27-28-
-Preparation of curable composition-
A curable composition 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 5 below.

-Formation of hard coat layer-
The prepared curable composition was applied on a slide glass (S1214, manufactured by Matsunami Glass Industry Co., Ltd.) having a size of 76 mm×26 mm, which had been degreased in advance with acetone, to have a thickness of about 50 μm. The sample was placed in a constant temperature bath (Drying Oven DV41, manufactured by Yamato Scientific Co., Ltd.) adjusted to °C, heated for 15 minutes, taken out from the constant temperature bath, and left at room temperature (25°C) for 1 day. By thus curing the curable composition, a cured layer (hard coat layer), which is a cured product, was formed on the slide glass.
As described above, a test piece having a hard coat layer was produced.
Then, the test piece prepared above was measured and evaluated in the same manner as in the sample level 1. The results of measurement and evaluation are shown in Table 5.

Table 5 shows the influence of the type of the polymerization initiator in the sample levels 27 to 28.
As shown in Table 5, the effect of constituting a thermosetting system using a thermal acid generator as a polymerization initiator is small, and even if a thermal acid generator is used, the hardness obtained in combination with PETG is excellent. Was there.

-Production of moth-eye film-
Then, as shown in FIG. 10, the curable composition 14 was applied at a coating amount of 1.25 g/m ^{2 on} the processed surface of the GC moth-eye mold 12 produced in the same manner as in Sample Level 1. The film 14 was formed, and the glass substrate 26 having a thickness of 150 μm was placed on the coating film 14. Then, it is placed on the heater 30, and the GC moth-eye mold is heated under a heating condition 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 is released from the glass base material 26. Thus, a moth-eye sheet having a moth-eye structure transferred was produced.

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). As a result, it was visually confirmed that good moth-eye structures were transferred and formed on the moth-eye sheets produced using the curable compositions of Sample Levels 27 to 28, as shown in FIG.
Further, the reflectance of the surface of the cured film of the moth-eye film was measured using an ultraviolet-visible near-infrared spectrophotometer (SolidSpec-3700, Shimadzu Corporation). The result is shown in FIG.

(Example 5)
-Sample levels 29-36-
In Sample Level 1, 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, and further measured and evaluated. Furthermore, the antifouling property was evaluated by the following method.
The results of measurement and evaluation are shown in Table 6 below.

− Antifouling property −
Antifouling property was evaluated by the following oily magic wiping test.
The prepared curable composition was applied onto a glass slide of size 76 mm x 26 mm with a No22 bar coater, and an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.) was used. The coating film was cured by irradiating it with ultraviolet rays under the conditions of an irradiation amount of 6,000 mJ/cm ² and an illuminance of 50 mW/cm ² , and left for 1 day. An operation in which a spiral pattern is drawn on the surface of the cured film of the test piece thus obtained using the oil-based marker PM-41 (manufactured by KOKUYO) and the oil-based ink is wiped off with Kimwipe S-200 (manufactured by Nippon Paper Crecia). Was repeated, and the number of times it could be wiped off was recorded.

Table 6 shows the compositions containing antifouling components in sample levels 29 to 36.
As shown in Table 6, by containing the antifouling component, it was possible to impart wiping property while maintaining high hardness and scratch resistance. On the other hand, with the sample level 36 containing the antifouling component but not PETG, good results were obtained in terms of wiping property, but it was impossible to achieve both hardness and scratch resistance.

-Production of moth-eye film-
Next, a moth-eye film was produced using the curable compositions of Sample Level 32 and Sample Level 36, and the moth-eye structure and wiping property were evaluated.
First, as shown in FIG. 3, the curable composition 14 is applied to the processed surface of the manufactured GC moth-eye mold 12 at a coating amount of 1.25 g/m ² to form a coating film 14, A polyester film (Cosmoshine (registered trademark) A4300; PET film) 16 manufactured by Toyobo Co., Ltd. was placed on the film 14. Using a UV irradiation device (model: Aicure UP50 manufactured by Panasonic Corporation), the coating film 14 is irradiated with UV rays through a PET film (irradiation amount: 10000 mJ/cm ² , illuminance: 50 mW/cm ² ) to obtain a cured film. By releasing the cured film 24 together with the PET film 16, a moth-eye film having the moth-eye structure transferred was produced.

Then, as shown in FIG. 4, the rubbing test was repeated 10 times, and the following evaluations were made regarding the presence or absence of scratches on the surface of the cured film.
I. Image Evaluation The surface of the cured film of the moth-eye film before and after the rubbing test was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix), and the presence or absence of scratches due to rubbing was evaluated by SEM photographs.
B. Contact Angle Using a fully automatic contact angle meter (DM-701, Kyowa Interface Science Co., Ltd.), the water contact angle on the transfer surface of the moth-eye structure of the moth-eye film was measured.
C. Wipeability The artificial fingerprint liquid was dropped on the transfer surface of the moth-eye structure of the moth-eye film, 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 it was able to be wiped off was recorded.

When the surface of the cured film 24 of the moth-eye film obtained above was observed by SEM, the moth-eye film produced using the curable composition of Sample Level 32 showed no scratches due to a scratch test as shown in FIG. .. Therefore, the change in water contact angle before and after rubbing was small. On the other hand, in the moth-eye film produced using the curable composition of sample level 36, as shown in FIG. 14, scratches due to the abrasion test are more prominent than those of the sample level 32 using PETG. The structure was broken and the water contact angle changed significantly. As described above, it can be seen that the sample level 32 and the sample level 36 have a marked difference in resistance to scratching.

Further, the moth-eye film of sample level 32 was heat-treated under the following conditions, and then a wiping test was conducted.
<Condition>
・Heating temperature: 85℃
・Heating time: 30 minutes ・Test cloth: Kimwipe ・Test solution: Artificial fingerprint solution [Artificial fingerprint solution]
The artificial fingerprint liquid used here has the following composition described in JIS K2246 (2007) rust preventive oil and rhodamine B (manufactured by Tokyo Kasei Kogyo Co., Ltd., CAS.NO81-88-9). It was prepared by adding 0.1% by mass to
<Composition>-Purified water: 500 mL
・Methanol: 500 mL
・Sodium chloride: 7 g
・Urea: lg
・Lactic acid: 4g

As a result, as shown in FIG. 15, the artificial fingerprint liquid could be wiped off well.
Next, FIG. 16 shows an SEM photograph when the wiping of the artificial fingerprint liquid was repeated 20 times. As can be seen from FIG. 16, there was no change in the moth-eye structure even after wiping 20 times. Also, the change in contact angle was small. Further, changes in reflectance and transmittance before and after wiping 20 times are shown in FIGS. 17A and 17B. As shown in FIGS. 17A and 17B, the reduction width was less than 1%.

(Example 6)
-Sample levels 37-38-
In Sample Level 1, 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 7 below, and measurement and evaluation were performed. Further, the adhesive strength was evaluated as an index of the sensitizing effect by the following method.
The results of measurement and evaluation are shown in Table 7 below.

-Adhesiveness-
By the following method, the adhesive strength was measured and the adhesiveness was evaluated using a test body that does not transmit 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.) is degreased with acetone, and then the degreased surface is coated with a curable composition at a constant coating thickness. As a spacer, a mending tape (MP-18, manufactured by Sumitomo 3M Limited) was attached.
Next, the curable composition is applied to the surface of the epoxy glass plate on which the mending tape is attached, and the two epoxy glass plates are attached alternately so that the application area of the curable composition is 26 mm×3 mm. A test piece was produced by pressing with a drumstick clip (Kuri-44, manufactured by KOKUYO CORPORATION). Thereafter, using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.), the curable composition of the test body was irradiated with an irradiation amount of 9000 mJ/cm ^{2 and} an illuminance of 100 mW/ The curable composition was cured by irradiating with ultraviolet rays at cm ² .
Then, the irradiated test body was left at room temperature (25° C.) for 1 day. The test piece after standing was pulled by using Autograph AG-5KNXplus (manufactured by Shimadzu Corporation) at two glass plates at a pulling speed of 50 mm/min to measure the shear adhesive strength.

Table 7 shows the compositions containing the sensitizers in the sample levels 37 to 38.
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 the sensitizer, so that the absorption wavelength of the sensitizer is 350 nm to 400 nm. When irradiated with ultraviolet rays in the wavelength range, the polymerization initiator was sensitive and could be cured. That is, it can be said that a composition containing a polymerization initiator and a sensitizer is also effective as a method for curing PETG.
In addition, when a moth-eye film was produced, as in Sample Levels 1 and 2, scars due to a scratch test were less likely to occur, and the hardness (Martens hardness) of the surface of the cured film was high, so that the reflectance and transmittance by a scratch test were high. The change in the rate is also considered to be small.

(Example 7)
-Sample levels 39-42-
In Sample Level 1, 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 8 below, and further measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 8.

Table 8 shows the results when the compositions containing the fillers in the sample levels 39 to 42 were used.
As shown in Table 8, even in the composition containing the filler, the hardness obtained in combination with PETG was excellent.

-Production of moth-eye film-
Next, a moth-eye film was produced using the curable compositions of Sample Levels 39 and 42, and the moth-eye structure was evaluated.
First, as shown in FIG. 3, the curable composition 14 is applied to the processed surface of the manufactured GC moth-eye mold 12 at a coating amount of 1.25 g/m ² to form a coating film 14, A polyester film (Cosmoshine (registered trademark) A4300; PET film) 16 manufactured by Toyobo Co., Ltd. was placed on the film 14. Using a UV irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.), the coating film 14 is irradiated with ultraviolet rays through a PET film (irradiation amount: 10000 mJ/cm ² , illuminance: 50 mW/cm ² ) to form a cured film, and the cured film 24 is released together with the PET film 16 to produce a moth-eye film to which the moth-eye structure is transferred.

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

(Example 8)
-Sample levels 43-44-
In Sample Level 1, 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, and further measurement and evaluation were performed. Further, the adhesive strength was measured as an index for evaluating the adhesiveness by the following method.
The results of measurement and evaluation are shown in Table 9 below.

-Adhesiveness-
A spacer for degreasing one surface of a glass slide (S1214, manufactured by Matsunami Glass Industry Co., Ltd.) having a size of 76 mm×26 mm with acetone, and then applying a constant thickness to the curable composition on the degreased surface. As a result, a mending tape (MP-18, manufactured by Sumitomo 3M Limited) was attached.
Next, the curable composition is applied to the surface of the slide glass plate on which the mending tape is attached, and the two epoxy glass plates are alternately laminated so that the application area of the curable composition is 26 mm×3 mm. A test piece was produced by pressing with a mold clip (Kuri-44, manufactured by KOKUYO CORPORATION). Thereafter, using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.), the curable composition of the test body was irradiated with an irradiation amount of 9000 mJ/cm ^{2 and} an illuminance of 100 mW/ The curable composition was cured by irradiating with ultraviolet rays at cm ² .
Then, the irradiated test body was left at room temperature (25° C.) for 1 day. The test piece after standing was pulled by using Autograph AG-5KNXplus (manufactured by Shimadzu Corporation) at two glass plates at a pulling speed of 50 mm/min to measure the shear adhesive strength.
Separately from the above, the slide glass plate was replaced with an acrylic plate or a polycarbonate plate (PC plate), and the shear adhesive strength was measured by the same method.
The measurement results are shown in Table 9 below.

Table 9 shows the results when the compositions containing the silane coupling agent were used in the sample levels 43 to 44.
As shown in Table 9, even in the composition containing the silane coupling agent, the hardness obtained in combination with PETG was excellent.
In addition, when a moth-eye film was produced, as in Sample Levels 1 and 2, scars due to a scratch test were less likely to occur, and the hardness (Martens hardness) of the surface of the cured film was high, so that the reflectance and transmittance by a scratch test were high. The change in the rate is also considered to be 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 grating (optical element), LSI (integrated circuit wiring), polarizing plate, and nanoimprint. Further, in the field of nanoimprint, it is suitable for forming various patterns such as a conical or polygonal pyramid moth-eye pattern, a pillar structure, a hole structure, a microlens array structure, a honeycomb structure, a lattice structure, a line & space structure, and a replica mold.

The disclosure of Japanese Patent Application 2017-117642 filed on Jun. 15, 2017 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference, Incorporated herein by reference.

(Explanation of symbols)
1... Sheet-shaped base material 2... Mold 3, 14... Curable resin composition (curable composition)
5... Stage 7... Delivery roller 8... Winding roller 10... Concavo-convex structure 12... Coating film 16... Polyester film 18... Moth eye film 24... Cured film 26・・・Glass substrate 30 ・・・Heating device 32 ・・・Container 34 ・・・Steel wool 100 ・・・Imprinting device

Claims (19)

A curable resin composition containing pentaerythritol tetraglycidyl ether and a polymerization initiator, which is used for producing an uneven structure. A curable resin composition containing pentaerythritol tetraglycidyl ether, a polymerization initiator, and a surfactant, which is used for forming a hard coat layer. The curable resin composition according to claim 2, wherein the surfactant contains at least one selected from the group consisting of a fluorine compound and a siloxane compound. The curable resin composition according to claim 2 or 3, wherein the surfactant contains 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, further comprising at least one selected from the group consisting of a fluorine compound and a siloxane compound. The curability according to any one of claims 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. Resin composition. Further, it contains at least one reactive compound selected from the group consisting of glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin oxide epoxy compounds, silicone modified compounds, fluorine modified epoxy compounds, and oxetane compounds. The curable resin composition according to any one of claims 1 to 6. Further, containing at least one sensitizer selected from the group consisting of anthracene compounds, anthraquinone compounds, thioxanthone compounds, naphthalene compounds, phenanthrene compounds, chrysene compounds, perylene compounds, and acridine compounds. The curable resin composition according to any one of claims 1 to 7. The curable resin composition according to claim 8, wherein the sensitizer contains dialkoxyanthracene. Content of the said pentaerythritol tetraglycidyl ether is 45 mass%-97 mass% with respect to curable resin composition total mass, The curable resin composition of any one of Claims 1-9. Stuff. The curable resin composition according to any one of claims 1 to 10, wherein the pentaerythritol tetraglycidyl ether has an epoxy equivalent of 90 to 150. Content of the said polymerization initiator is 3 mass%-30 mass% with respect to the said pentaerythritol tetraglycidyl ether, The curable resin composition of any one of Claims 1-11. Content of the said polymerization initiator is 0.1 mass%-10 mass% with respect to the total mass of curable resin composition, The curable resin of any one of Claims 1-12. Composition. The curable resin composition according to claim 1, comprising the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, and a photoacid generator that is the polymerization initiator. The curable resin composition according to claim 2, which contains the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, a photoacid generator that is the polymerization initiator, and the surfactant. The content of the pentaerythritol tetraglycidyl ether is 60 mass% to 85 mass% based on the total mass of the curable resin composition, and the content of the alicyclic epoxy resin is based on the total mass of the curable resin composition. It is 10 mass%-30 mass %, and the content of the said photo-acid generator is 1 mass%-6 mass% with respect to curable resin composition total mass, The curability of Claim 14 or Claim 15. Resin composition. A cured product of the curable resin composition according to any one of claims 1 to 16, wherein the flat film has a scratch pencil hardness of 7H or more. A cured product of the curable resin composition used in the production of the concavo-convex structure, of the curable resin composition according to any one of claims 1, 5, 14 and 16. And, a concavo-convex structure body having a concavo-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm. Among the curable resin compositions according to any one of claims 1, 5, 14 and 16, a curable resin composition used for producing the concavo-convex structure is used, and a height is used. Is 50 nm to 1000 nm, and a method for producing a concavo-convex structure having a step of molding and curing a concavo-convex pattern having a pitch of 20 nm to 1000 nm.