Photocurable composition for film formation

Abstract

[Problem] To provide a photocurable composition that can be applied to a film. [Solution] A photocurable composition comprising the following components (a) to (d), wherein the content of component (a) is 80-99 parts by mass per 100 parts by mass of the total content of components (a) to (d), and the viscosity at 25.0°C is 1-50 mPa·s. (a) At least one monofunctional or polyfunctional (meth)acrylate having one or more (meth)acryloyloxy groups per molecule (excluding component (d) below); (b) a photoradical initiator; (c) silica particles that are surface-modified with at least one silane coupling agent and have a primary particle size of 1-100 nm; and (d) a polyrotaxane having a (meth)acryloyloxy group.

Description

Photocurable composition for thin film formation

[0001] The present invention relates to a photocurable composition comprising a monofunctional or polyfunctional (meth)acrylate having one or more (meth)acryloyloxy groups per molecule, a photoradical initiator, silica particles surface-modified with a specific silane coupling agent, and a polyrotaxane having a (meth)acryloyloxy group. The photocurable composition has a low viscosity, allowing for thin film application by spin coating or the like, while the cured product and molded article obtained from the photocurable composition can be patterned by imprinting, and also has high transparency and a viscosity similar to that of glass. ５５０ = 1.50.

[0002] The imprinting method is a technology in which a mold (commonly called a stamper or template) with engraved irregularities measuring tens to hundreds of nanometers is pressed against a resin material, mechanically deforming it to precisely transfer the fine pattern of the mold.Once the mold is made, nano-sized fine structures can be easily and repeatedly molded, making it more economical than conventional pattern formation techniques that use lithography and etching.

[0003] Imprinting methods are broadly divided into two types based on the technique used. One is called thermal imprinting, which uses a thermoplastic resin as disclosed in Patent Document 1, and the other is called photoimprinting, which uses a photocurable resin as disclosed in Patent Document 2. In particular, photoimprinting uses an uncured material when pressing, which shortens the manufacturing time, and does not require high pressure or high temperature heating, so it is a technique that can be used with heat-sensitive materials. Due to this high yield, photoimprinting is widely used in the creation of optical materials.

[0004] In order to improve the yield of imprinting by the photoimprinting method, it is common to apply a low-viscosity curable composition to a substrate. This allows the curable composition to be sufficiently filled into the mold. As shown in Patent Documents 3 and 4, known methods such as spin coating, dip coating, and inkjet printing can be used to apply the curable composition to a substrate.

[0005] An example of an invention using these techniques is a curable composition for imprints, as disclosed in Patent Document 5, which has low viscosity and causes little volatilization of components on a substrate when applied.

[0006] On the other hand, a technique of combining inorganic fine particles such as silica particles or zirconia particles with an organic resin is widely known as a method for improving the heat resistance, adhesion, optical properties, etc. of a cured product. In an example shown in Patent Document 6, it is reported that the transmittance of a cured product and a molded article obtained from a curable composition was improved by blending a specific polyfunctional polymerizable monomer, silica particles surface-modified with a specific silane coupling agent, and a polyfunctional thiol in a predetermined amount into the curable composition.

[0007] US Patent No. 5,772,905 US Patent No. 6,334,960 Japanese Patent No. 5,348,433 Japanese Patent No. 5,671,377 JP 2014-170949 WO 2020 / 129902

[0008] In Patent Document 5, when evaluating volatility, the residual rate of one type of polymerizable monomer alone is evaluated, and therefore the level of volatility of a curable composition containing two or more types of polymerizable monomers is unknown. Furthermore, the viscosity of the curable composition described in Patent Document 6 is very high, and when applied to a substrate using a method such as spin coating, there is a problem in that the uniformity of the film surface is significantly reduced. There has yet to be a particle-added resin composition that has high transparency suitable for use as an optical material and can be applied to a thin film with uniformity using a method such as spin coating, and its development has been desired. The present invention has been made in consideration of these circumstances, and an object of the present invention is to provide a curable composition that solves the above-mentioned problems.

[0009] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that by blending a specific monofunctional or polyfunctional (meth)acrylate in a predetermined amount into a photocurable composition, the photocurable composition can be made to have a composition that can be applied as a thin film by spin coating, etc. Furthermore, the present inventors have found that a pattern can be formed by imprinting on a cured product and a molded article obtained from this photocurable composition.

[0010] That is, a first aspect of the present invention is a photocurable composition comprising the following components (a) to (d), wherein the content of component (a) is 80 to 99 parts by mass per 100 parts by mass of the sum of components (a), (b), and (c), and the composition has a viscosity of 1 mPa·s to 50 mPa·s at 25.0°C: (a): at least two types of monofunctional or polyfunctional (meth)acrylates having one or more (meth)acryloyloxy groups per molecule (excluding component (d) below), (b): a photoradical initiator, and (c): silica particles having a primary particle size of 1 nm to 100 nm and surface-modified with at least one silane coupling agent represented by the following formula (1): (In the formula, X １ represents a hydrogen atom or a (meth)acryloyloxy group, R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, m represents an integer of 1 to 14, and n represents an integer of 0 to 2. (d): Polyrotaxane having a (meth)acryloyloxy group

[0011] The photocurable composition of the present invention may further contain the following component (e): (e): a polyfunctional thiol represented by the following formula (2): (In the formula, R ３ represents a single bond, a linear alkylene group having 1 to 6 carbon atoms, or a branched alkylene group having 3 to 6 carbon atoms; X ２ represents a single bond, an ester bond or an ether bond, and Q １ represents an organic group having 2 to 12 carbon atoms which may contain at least one heteroatom or no heteroatom, or a heteroatom, and p represents an integer of 2 to 6. The heteroatom represents an atom other than carbon and hydrogen, such as nitrogen, oxygen, or sulfur.

[0012] The photocurable composition of the present invention may further contain the following component (f) and / or component (g): (f): a phenol-based antioxidant, and (g): a sulfide-based antioxidant.

[0013] The component (a) is, for example, selected from the group consisting of the following components (a1), (a2), and (a3): (a1): monofunctional (meth)acrylate, (a2): bifunctional urethane (meth)acrylate, and (a3): bifunctional (meth)acrylate represented by the following formula (3): (In the formula, R ４ represents a hydrogen atom or a methyl group, and Q ２ represents a linear or branched alkylene group having 4 to 10 carbon atoms.

[0014] The component (c) is, for example, X in the formula (1). １ are silica particles whose surfaces have been modified with a silane coupling agent having a (meth)acryloyloxy group.

[0015] A second aspect of the present invention is a cured product of the photocurable composition, having a film thickness of 1.0 μm to 10.0 μm.

[0016] A third aspect of the present invention is a method for producing a molded article, comprising a step of imprint molding the photocurable composition.

[0017] A fourth aspect of the present invention is a method for producing a molded product from a photocurable composition, the method comprising: a step of supplying the photocurable composition onto a substrate; an imprinting step of bringing the photocurable composition into contact with a mold having a reverse pattern of the shape of a desired molded product; a photocuring step of exposing the photocurable composition through the mold after the imprinting step to form a photocured portion; and a demolding step of separating the photocured portion from the mold.

[0018] The step of supplying the photocurable composition is a step of applying the photocurable composition by a spin coating method, a slit scanning method, or an ink jet method.

[0019] The method may further include a step of heating the photocuring section after the photocuring step, before, during or after the demolding step.

[0020] The molded article is, for example, an optical film for a flat panel display.

[0021] The photocurable composition of the present invention contains the components (a) to (d) as essential components, optionally contains the component (e), and optionally contains the component (f) and / or the component (g). The presence of the components (a) and (b) allows a three-dimensional crosslinked product to be formed when the photocurable composition is exposed to light, resulting in a cured product. It has also been found that the component (a) reduces the viscosity of the composition, enabling thin film application by spin coating or the like, while also enabling pattern formation by imprinting.

[0022] Furthermore, by using, as the component (c), a silane coupling agent as represented by the formula (1), i.e., silica particles surface-modified with a silane coupling agent having a hydrocarbon group having 1 to 14 carbon atoms, the affinity and adhesion between the surface of the silica particles and the organic resin is improved, thereby increasing the dispersibility of the silica particles and increasing the transparency of the cured product and molded article.

[0023] FIG. 1 is a field emission scanning electron microscope (FE-SEM) photograph showing a molded article formed on a glass substrate using the photocurable composition prepared in Example 11.

[0024] The photocurable composition of the present invention has a viscosity at 25.0°C of 1 mPa·s to 70 mPa·s, preferably 1 mPa·s to 50 mPa·s, more preferably 1 mPa·s to 45 mPa·s. Each component of the photocurable composition of the present invention will be described in more detail. In the present invention, the (meth)acryloyloxy group means a group having a structure such as "CH ２ =C(CH ３ )-C(=O)O-" or a methacryloyloxy group represented by "CH ２ ═CH—C(═O)O—” is an acryloyloxy group.

[0025] [Component (a): At Least Two Monofunctional or Polyfunctional (meth)acrylates Having One or More (meth)acryloyloxy Groups in the Molecule] In this specification, of the monofunctional or polyfunctional (meth)acrylates having one or more (meth)acryloyloxy groups in the molecule that can be used as component (a) in the photocurable composition of the present invention, a monofunctional (meth)acrylate is referred to as component (a1), a compound having at least one urethane bond represented by "-NH-C(=O)O-" [bifunctional urethane (meth)acrylate] is referred to as component (a2), and a bifunctional (meth)acrylate represented by formula (3) is referred to as component (a3). When the photocurable composition of the present invention contains component (a2), cured products and molded articles obtained from the photocurable composition have excellent adhesion to substrates. When the photocurable composition of the present invention contains the component (a3), the cured product and molded article obtained from the photocurable composition have excellent flexibility and excellent compatibility with the polyrotaxane having a (meth)acryloyloxy group described below. The component (a) of the photocurable composition of the present invention excludes the component (d) described below.

[0026] [Component (a1): Monofunctional (meth)acrylate] Examples of the component (a1) include 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ... hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylic acid dimer, benzyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, butanediol mono(meth)acrylate, butoxyethyl (meth)acrylate, butyl (meth)acrylate, cetyl (meth)acrylate, ethylene oxide-modified (hereinafter referred to as "EO-modified")) cresol (meth)acrylate, dipropylene glycol (meth)acrylate, ethoxylated phenyl (meth)acrylate, ethyl (meth)acrylate, isoamyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methyl (meth)acrylate, neopentyl glycol benzoate (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate acrylate, nonylphenoxy polypropylene glycol (meth)acrylate, octyl (meth)acrylate, paracumylphenoxy ethylene glycol (meth)acrylate, epichlorohydrin-modified phenoxy acrylate, phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth)acrylate, phenoxy hexaethylene glycol (meth)acrylate, phenoxy tetraethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, stearyl (meth)acrylate, EO-modified succinic acid (meth)acrylate, tert-butyl (meth)acrylate, tribromophenyl (meth)acrylate, EO-modified tribromophenyl (meth)acrylate, and tridodecyl (meth)acrylate.

[0027] [Component (a2): Bifunctional Urethane (Meth)acrylate] Examples of the component (a2) include U-2PPA, U-200PA, U-160TM, U-290TM, UA-4200, UA-4400, UA-122P, and UA-W2A (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, and UF-8001G (all manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL (registered trademark) 210, 230, 270, 280 / 15IB, 284, 4491, 4683, 4858, 8307, 8402, 8411, 8413, 8804, 8807, 9270, and 246 / 2 0HEMA, 1271, 286, 4859, 8409, 8809, 8810, 8811, KRM (registered trademark) 7735, 8961, 8191 (all manufactured by Daicel Allnex Co., Ltd.), M-1100, M-1200 (all manufactured by Toagosei Co., Ltd.), UV-2000B, UV-3000B, UV-3200B, UV-3300B, UV-3310B, UV-3500BA, UV-3520EA, UV-3700B, UV-6640B and UV-6630B (all manufactured by Mitsubishi Chemical Corporation).

[0028] The component (a2) may be used alone or in combination of two or more.

[0029] [Component (a3): Bifunctional (meth)acrylate represented by the formula (3)] Examples of the component (a3) ​​include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 2-ethyl-1,3-hexanedi ...1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth) Sandiol di(meth)acrylate, 1,8-nonanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,4,4-trimethyl-1,6-hexanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-decanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate.

[0030] Commercially available products may be used as the component (a3). Specific examples include Viscoat #195, Viscoat #230, and Viscoat #260 (all manufactured by Osaka Organic Chemical Industry Ltd.), BD, NPG, A-NPG, HD-N, A-HD-N, NOD-N, A-NOD-N, A-IND, DOD-N, and A-DOD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.), and FA-121M, FA-124M, FA-125M, and FA-129AS (all manufactured by Showa Denko Materials Co., Ltd.). Examples of such acrylates include Light Ester 1.4BG, Light Ester NP, Light Ester 1.6HX, Light Ester 1.9ND, Light Acrylate 1.6HX-A, Light Acrylate 1.9ND-A, Light Acrylate NP-A, and Light Acrylate MPD-A (all manufactured by Kyoeisha Chemical Co., Ltd.), HDDA (all manufactured by Daicel Allnex Co., Ltd.), HDDA, L-C9A, and ND-DA (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0031] The component (a3) ​​may be used alone or in combination of two or more.

[0032] Among the polyfunctional (meth)acrylates, examples of bifunctional (meth)acrylates that do not fall under either the component (a2) or the component (a3) ​​include cyclohexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, Examples of the di(meth)acrylate include ethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, propylene oxide-modified (hereinafter referred to as "PO-modified") neopentyl glycol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, EO-modified hydrogenated bisphenol A di(meth)acrylate, and hydroxypivalic acid neopentyl glycol di(meth)acrylate.

[0033] Commercially available products may be used as the bifunctional (meth)acrylate that does not correspond to either the component (a2) or the component (a3). Specific examples include Viscoat #310HP and Viscoat #335HP (both manufactured by Osaka Organic Chemical Industry Ltd.), DCP, A-DCP, A-DOG, 2G, 3G, 4G, 9G, 14G, 23G, A-200, A-400, and A-60. 0, A-1000, APG-100, APG-200, APG-400, APG-700, 3PG, 9PG, A-1206PE, A-0612PE, A-0412PE, A -1000PER, A-3000PER, A-PTMG-65, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP- 3 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-222A, FA-220M, FA-240M, FA-240A, FA-P240A, FA-P270A, FA-023M, FA-PTG9M, FA-PTG9A, FA-320M, FA-321M, FA-3218M, FA-321A, FA-324A (all manufactured by Showa Denko Materials Co., Ltd.), Light Ester 2EG, 3EG, 4EG, 9EG, 14EG, BP-2EMK, Light Acrylate (registered trademark) DCP-A, 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, BP-4EAL, BP-4PA, HPP-A (all manufactured by Kyoeisha Chemical Co., Ltd.), DPGDA, TPGDA, IRR 214-K, EBECRYL (registered trademark) 11, 130, 145, and 150 (all manufactured by Daicel Allnex Co., Ltd.), PE-200, PE-300, PE-400, PE-600, PEM-1000, BPEM-4, BPE-4, BPEM-10, BPE-10, BPE-20, HBPE-4, HBPEM-10, and HPN (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0034] The bifunctional (meth)acrylates that do not fall under either the component (a2) or the component (a3) ​​can be used alone or in combination of two or more.

[0035] Among the polyfunctional (meth)acrylates, examples of trifunctional or higher (meth)acrylates include U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA-53H, UA-33H, and UA-7100 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, and UA-510H ( The above are manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL (registered trademark) 220, 8800, 294 / 25HD, 4220, 4513, 4738, 4740, 4820, 8311, 9260, 8701, 4265, 4587, 4666, 4680, 8210, 8405, 1290, 5129, 8301R, KRM 4501, KRM 2221, KRM 8465, KRM 1258, KRM 4101, KRM 4201, KRM 8209, KRM 1291, KRM 8602, KRM 225, KRM (registered trademark) 8667, KRM 8296, KRM 8528, KRM 8200, KRM 8200AE, KRM 8530, KRM 8904, KRM 8531BA, KRM 8452 (all manufactured by Daicel Allnex Co., Ltd.), UV-275 0B, UV-7000B, UV-7510B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, and UV-7650B (all manufactured by Mitsubishi Chemical Corporation).

[0036] Other examples of the tri- or higher functional (meth)acrylates include Viscoat #295, #300, and #802 (all manufactured by Osaka Organic Chemical Industry Ltd.), A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, TMPT, A-TMPT, AD-TMP, and ATM. -35E, A-TMMT, A-9550, A-DPH (all manufactured by Shin-Nakamura Chemical Co., Ltd.), FANCRYL (registered trademark) FA-731A, FA-137M (all manufactured by Hitachi Chemical Co., Ltd.), Light Ester TMP, Light Acrylate (registered trademark) TMP-A, PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), PETI A, PETRA, TMPTA, OTA480, EBECRYL (registered trademark) 160S, EBECRYL 40, EBECRYL (registered trademark) 140, EBECRYL 1142, PETA, DPHA (all manufactured by Daicel Allnex Co., Ltd.), TMPTM, TMPT, TMP-2P, TMP-3P, TMP-3, PET-3, PETA-4, TEICA, MF-001, M F-101 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-350, M-360, M-400, M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-460 and M-471 (all manufactured by Toagosei Co., Ltd.).

[0037] The tri- or higher functional (meth)acrylates may be used singly or in combination of two or more.

[0038] The content of component (a) in the photocurable composition of the present invention is 80 to 99 parts by mass, preferably 83.5 to 98 parts by mass, and more preferably 87 to 97 parts by mass, relative to 100 parts by mass of the total of components (a), (b), (c), and (d) contained in the photocurable composition. If the content of component (a) is less than 80 parts by mass, the composition may not be spin-coatable. Furthermore, cured products and molded articles obtained from the photocurable composition may not form an organic resin matrix with sufficient crosslink density, and the cured products and molded articles may become brittle due to their low crosslink density.

[0039] When the component (a) includes a component selected from the group consisting of the component (a1), the component (a2), and the component (a3), the content thereof, relative to 100 parts by mass of the total of the components (a), (b), (c), and (d) contained in the photocurable composition of the present invention, satisfies all of the relationships represented by the following formulas (4) to (6) or (4), (5), and (7), preferably satisfies all of the relationships represented by the following formulas (4') to (6') or (4'), (5'), and (7'), more preferably satisfies all of the relationships represented by the following formulas (4") to (6") or (4", (5"), and (7"): Here, the content of the component (a1) is defined as X parts by mass, the content of the component (a2) is defined as Y parts by mass, and the content of the component (a3) ​​is defined as Z parts by mass. Formula (4): 80 parts by mass ≦ ​​(X + Y + Z) ≦ 99 parts by mass Formula (5): 0 parts by mass ≦ ​​Y ≦ 30 parts by mass Formula (6): 80 parts by mass ≦ ​​(X + Y) ≦ 99 parts by mass Formula (7): 86 parts by mass ≦ ​​(Y + Z) Formula (4'): 83.5 parts by mass ≦ ​​(X + Y + Z) ≦ 98 parts by mass Formula (5'): 0 parts by mass ≦ ​​Y ≦ 20 parts by mass Formula (6'): 83.5 parts by mass ≦ ​​(X + Y) ≦ 98 parts by mass Formula (7'): 87 parts by mass ≦ ​​(Y + Z) Formula (4''): 87 parts by mass ≦ ​​(X + Y + Z) ≦ 97 parts by mass Formula (5''): 0 parts by mass ≦ ​​Y ≦ 10 parts by mass Formula (6''): 87 parts by mass ≦ ​​(X + Y) ≦ 97 parts by mass Formula (7''): 88 parts by mass ≦ ​​(Y + Z)

[0040] If the content of the component (a2) is more than 30 parts by mass, there is a risk that the uniformity of the film surface cannot be maintained when the composition is spin-coated.

[0041] [Component (b): Photoradical Initiator] Examples of photoradical initiators that can be used as component (b) of the photocurable composition of the present invention include alkylphenones, benzophenones, dibenzoyls, anthraquinones, acylphosphine oxides, benzoylbenzoates, oxime esters, and thioxanthones, and intramolecular cleavage-type photoradical polymerization initiators are particularly preferred. Commercially available products may be used as the photoradical initiator. For example, OMNIRAD (registered trademark) 127, 184, 369, 369E, 379EG, 500, 651, 819, 784, 907, 1173, 2959, and TPO H (all manufactured by IGM Resins), IRGACURE (registered trademark) OXE01, OXE02, OXE03, OXE04, CGI1700, CGI1750, CGI1850, and CG24-61 (all manufactured by BASF Japan Ltd.), and ESACURE Examples include KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46 and KIP75 (all manufactured by Lamberti).

[0042] The content of component (b) in the photocurable composition of the present invention is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total of components (a), (c), and (d) contained in the photocurable composition. If the content of component (b) is less than 0.1 part by mass, the strength of the cured product and molded article obtained from the photocurable composition may be reduced. If the content of component (b) is more than 5 parts by mass, the heat resistance of the cured product and molded article may be reduced.

[0043] The component (b) may be used alone or in combination of two or more.

[0044] [Component (c): Silica particles having a primary particle diameter of 1 nm to 100 nm and surface-modified with at least one silane coupling agent represented by formula (1)] The silane coupling agent represented by formula (1) that modifies the surface of the silica particles (component (c)) of the photocurable composition of the present invention is characterized in that m in formula (1) is an integer of 1 to 14, i.e., has a linear hydrocarbon group of 1 to 14 carbon atoms in the molecule. Specifically, it is an alkoxysilane compound in which a linear alkyl group of 1 to 14 carbon atoms is bonded to a silicon atom, or an alkoxysilane compound in which a (meth)acryloyloxy group is bonded to a silicon atom via a linear alkylene group of 1 to 14 carbon atoms. In the case of a silane coupling agent in which m in formula (1) is 15 or more, the crystallinity of the linear hydrocarbon group becomes significant, and there is a risk of the silica particles surface-modified with the silane coupling agent agglomerating.

[0045] Examples of the silane coupling agent represented by the formula (1) include methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxy ... Acryloyloxypropyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, 3-(meth)acryloyloxypropyldimethylmethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldimethoxysilane, n-octyl Ethyldimethoxysilane, n-octylmethyldiethoxysilane, n-octylethyldiethoxysilane, n-octyldimethylmethoxysilane, n-octyldiethylmethoxysilane, n-octyldimethylethoxysilane, n-octyldiethylethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-tetradecyltrimethoxysilane, n-tetradecyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane , 8-(meth)acryloyloxyoctyltriethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxyoctylethyldimethoxysilane, 8-(meth)acryloyloxyoctylmethyldiethoxysilane, 8-(meth)acryloyloxyoctylethyldiethoxysilane, 8-(meth)acryloyloxyoctyldimethylmethoxysilane, 8-(meth)acryloyloxyoctyldiethylmethoxysilane, 8-(meth)acryloyloxyoctyldimethylethoxysilane,Examples of such silanes include 8-(meth)acryloyloxyoctyldiethylethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 10-(meth)acryloyloxydecyltriethoxysilane, 12-(meth)acryloyloxydodecyltrimethoxysilane, 12-(meth)acryloyloxydodecyltriethoxysilane, 14-(meth)acryloyloxytetradecyltrimethoxysilane, and 14-(meth)acryloyloxytetradecyltriethoxysilane.

[0046] As the silane coupling agent represented by the formula (1), a commercially available product may be used, and specific examples thereof include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-13, KBE-13, KBM-22, KBE-22, KBM-3033, KBE-3033, KBM-3063, KBE-3063, KBM-5803, KBM-3103C and KBE-3083 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0047] The silane coupling agents represented by the formula (1) can be used alone or in combination of two or more.

[0048] Furthermore, the silane coupling agent represented by the formula (1) may be used in combination with other silane coupling agents not represented by the formula (1). Examples of the other silane coupling agents include isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, isooctyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, p-tolyltrimethoxysilane, p-styryltrimethoxysilane, benzyltrimethoxysilane, 1-naphthyltrimethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 8-(2-aminoethylamino)octyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, isopropyltriethoxysilane, isobutyltriethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane trialkoxysilanes such as triethoxysilane, isooctyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, phenyltriethoxysilane, p-tolyltriethoxysilane, p-styryltriethoxysilane, benzyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, and tris[3-(triethoxysilyl)propyl]isocyanurate; diisobutyldimethoxysilane; cyclopentyltriethoxysilane; dimethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, di-p-tolyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, diisobutyldiethoxysilane, cyclopentylmethyldiethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldiethoxysilane, vinylmethyldiethoxy Examples of suitable silanes include dialkoxysilanes such as silane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, di-p-tolyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-mercaptopropylmethyldiethoxysilane; monoalkoxysilanes such as vinyldimethylmethoxysilane, phenyldimethylmethoxysilane, diphenylmethylmethoxysilane, and triphenylmethoxysilane; and polyfunctional silane coupling agents.

[0049] As the other silane coupling agents, commercially available products may be used, specifically, KBM-1003, KBE-1003, KBM-1403, KBM-602, KBM-603, KBM-903, KBE-903, KBM-573, KBM-6803, KBE-9007, KBM-9659, KBE-9659, KBM-802, KBM-803, KBM- 103, KBE-103, KBM-202SS, X-12-1048, X-12-1050, X-12-1154, X-12-1156, X-12-972F, X-12-1159L, X-40-9296, KR-503, KR-511, KR-513, KR-518, KR-519 and KPN-3504 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0050] The other silane coupling agents may be used alone or in combination of two or more.

[0051] When the silane coupling agent represented by the formula (1) is used and, optionally, other silane coupling agents not represented by the formula (1) are used in combination to surface modify silica particles, the amounts of these silane coupling agents used per 1 g of the silica particles satisfy all of the relationships represented by the following formulas (8) and (9), preferably all of the relationships represented by the following formulas (8') and (9'), and more preferably all of the relationships represented by the following formulas (8") and (9"). Here, the amount of the silane coupling agent represented by the formula (1) used is y millimoles, and the amount of the other silane coupling agent not represented by the formula (1) used is z millimoles. Formula (8): 0.1 mmol≦(y+z)≦2 mmol Formula (9): 0.1 mmol≦y Formula (8′): 0.2 mmol≦(y+z)≦1.5 mmol Formula (9′): 0.2 mmol≦y Formula (8″): 0.3 mmol≦(y+z)≦1 mmol Formula (9″): 0.3 mmol≦y

[0052] If the amount of the silane coupling agent represented by formula (1) used is less than 0.1 millimoles, the affinity and adhesion between the surface of silica particles and organic resin are insufficient, and the transmittance of the cured product and molded article obtained from the photocurable composition of the present invention may decrease.If the total amount of the silane coupling agent represented by formula (1) and other silane coupling agents not represented by formula (1) used is more than 2 millimoles, the silane coupling agent becomes excessive relative to the silica particles, and the silane coupling agent that is not consumed for surface modification of the silica particles is significantly generated, and this may cause the storage stability and mechanical properties of the cured product and molded article to deteriorate.

[0053] The silica particles of component (c) of the photocurable composition of the present invention have a primary particle diameter of 1 nm to 100 nm. Here, primary particles are particles that constitute a powder, and particles formed by aggregation of these primary particles are called secondary particles. The primary particle diameter can be calculated from the relationship D = 6 / (ρS) that holds between the specific surface area (surface area per unit mass) S of the silica particles measured by gas adsorption (BET) method, the density ρ of the silica particles, and the primary particle diameter D. The primary particle diameter calculated from the relationship is the average particle diameter, i.e., the diameter of the primary particles. If the primary particle diameter is smaller than 1 nm, the silica particles are likely to aggregate, which may result in poor storage stability. If the primary particle diameter is larger than 100 nm, the transparency of the cured product and molded article may be impaired.

[0054] The silica particles of component (c) can be obtained by reacting surface-unmodified silica particles with the silane coupling agent by various known methods.As the surface-unmodified silica particles, for example, it is preferable to use the silica particles dispersed in an organic solvent (organosilica sol).

[0055] Commercially available organosilica sols may be used, and examples thereof include CHO-ST-M, DMAC-ST, DMAC-ST-ZL, EAC-ST, EG-ST, EG-ST-ZL, EG-ST-XL30, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, methanol silica sol, MA-ST-M, MA-ST-L, MA-ST-ZL, MA-ST-UP, MEK-ST, MEK-ST-40, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-ST-L, NMP-ST, NPC-ST-30, PMA-ST, PGM-ST, PGM-ST, PGM-ST-UP, and TOL-ST (all manufactured by Nissan Chemical Industries, Ltd.).

[0056] The organosilica sol may be a commercially available water-dispersed silica sol in which the water is replaced with an organic solvent by a known method such as vacuum distillation or ultrafiltration, or a commercially available powdered silica particle dispersed in an organic solvent.

[0057] The silica solid content concentration in the organosilica sol is not particularly limited, but is generally preferably 60% by mass or less.

[0058] The content of component (c) in the photocurable composition of the present invention is 0.5 to 13 parts by mass, preferably 1 to 11.5 parts by mass, and more preferably 1.5 to 10 parts by mass, per 100 parts by mass of the total of components (a), (b), (c), and (d) contained in the photocurable composition. If the content of component (c) is less than 0.5 parts by mass, the adhesion and heat resistance of the cured product and molded article obtained from the photocurable composition may be reduced. If the content of component (c) is more than 13 parts by mass, haze may occur in the cured product and molded article, and the transmittance may be reduced.

[0059] The component (c) may be used singly or in combination of two or more. For example, a plurality of silica particles having different primary particle sizes may be combined, or a plurality of silica particles having different types or amounts of silane coupling agents used for surface modification may be combined.

[0060] [Component (d): Polyrotaxane Having a (Meth)acryloyloxy Group] A polyrotaxane having a (meth)acryloyloxy group that can be used as component (d) of the photocurable composition of the present invention has a pseudo-polyrotaxane in which the openings of cyclic molecules are pierced and enclosed by linear molecules, and blocking groups are arranged at both ends of the pseudo-polyrotaxane to prevent the cyclic molecules from being detached, and the cyclic molecules have (meth)acryloyloxy groups. The cyclic molecules, linear molecules, and blocking groups, which are the components of the polyrotaxane, will now be described.

[0061] <d-1. Cyclic Molecules> The cyclic molecules of the polyrotaxane are not particularly limited as long as they are cyclic, have an opening, and are skewered and included by the linear molecules. The (meth)acryloyloxy group may be bonded directly to the cyclic molecule or via a spacer. The spacer is not particularly limited, but examples thereof include one or a combination of two or more selected from the group consisting of an alkylene group, a (poly)alkylene glycol group, a hydroxyalkylene group, a urethane bond [—NH—C(═O)O—], an ester bond [—C(═O)O—], and a carbonate bond [—O—C(═O)O—]. The cyclic molecule is preferably selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0062] <d-2. Linear Molecule> The linear molecule of the polyrotaxane is not particularly limited as long as it can be included in the opening of the cyclic molecule to be used in a skewered manner. As the linear molecule, for example, a polymer selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether is preferred, and polyethylene glycol is particularly preferred.

[0063] The linear molecule has a weight-average molecular weight of 1,000 or more, preferably 3,000 to 100,000, and more preferably 6,000 to 50,000. In the polyrotaxane, the combination of (cyclic molecule, linear molecule) is particularly preferably (α-cyclodextrin-derived, polyethylene glycol-derived).

[0064] <d-3. Blocking Group> The blocking groups of the polyrotaxane are not particularly limited, as long as they are located at both ends of the pseudopolyrotaxane and act to prevent the cyclic molecules used from being detached. Examples of the blocking groups include those selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantyl groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, and more preferably adamantyl groups or cyclodextrins. The blocking groups are bonded to the linear molecules via, for example, [—NH—C(═O)—].

[0065] Commercially available products may be used as the polyrotaxane, and specific examples include CELUM (registered trademark) Super Polymer SA1305P, SA1303P, SA1305P-10, SA2403P, SA2405P-10, SA3403P, SM1303P, SM2403P, and 3403P (all manufactured by ASM Corporation (formerly Advanced Soft Materials Co., Ltd.)).

[0066] When the photocurable composition of the present invention contains component (d), the content thereof is 0.5 to 7 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the total of components (a), (b), (c), and (d) contained in the photocurable composition. By incorporating component (d), toughness can be imparted to cured products and molded articles obtained from the photocurable composition, and mechanical properties and thermal shock resistance can be improved.

[0067] The component (d) may be used alone or in combination of two or more.

[0068] [Component (e): Polyfunctional Thiol Represented by Formula (2)] Examples of polyfunctional thiols represented by Formula (2) that can be used as Component (e) of the photocurable composition of the present invention include 1,2-ethanedithiol, 1,3-propanedithiol, bis(2-mercaptoethyl)ether, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate). trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and pentaerythritol tris(3-mercaptopropyl)ether.

[0069] As the polyfunctional thiol compound represented by formula (2), commercially available products may be used, and examples thereof include Karenz MT (registered trademark) PE1, Karenz MT NR1, Karenz MT BD1, TPMB, and TEMB (all manufactured by Showa Denko K.K.), TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, and PEPT (all manufactured by SC Organic Chemical Co., Ltd.).

[0070] The content of component (e) in the photocurable composition of the present invention is 0 to 4 parts by mass, preferably 0.2 to 3 parts by mass, per 100 parts by mass of the total of components (a), (b), (c), and (d) contained in the photocurable composition. The incorporation of component (e) reduces polymerization inhibition by oxygen during photocuring of the photocurable composition, thereby improving radical reaction efficiency. Furthermore, the transmittance of the cured product and molded article obtained from the photocurable composition can be improved. If the content of component (e) is greater than 4 parts by mass, the cured product and molded article may develop haze when exposed to a high-humidity, high-temperature environment, potentially reducing reliability.

[0071] The component (e) may be used alone or in combination of two or more.

[0072] [Component (f): Phenolic Antioxidant] Examples of phenolic antioxidants that can be used as component (f) in the photocurable composition of the present invention include IRGANOX (registered trademark) 245, 1010, 1035, 1076, and 1135 (all manufactured by BASF Japan Ltd.), SUMILIZER (registered trademark) GA-80, GP, MDP-S, BBM-S, and WX-R (all manufactured by Sumitomo Chemical Co., Ltd.), and Adekastab (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 (all manufactured by ADEKA Corporation).

[0073] When the photocurable composition of the present invention contains component (f), the content thereof is 0.05 to 3 parts by mass, and preferably 0.1 to 1 part by mass, per 100 parts by mass of the total of components (a), (b), (c), and (d) contained in the photocurable composition.

[0074] The component (f) may be used alone or in combination of two or more.

[0075] [Component (g): Sulfide-Based Antioxidant] Examples of sulfide-based antioxidants that can be used as the component (g) in the photocurable composition of the present invention include ADK STAB (registered trademark) AO-412S and AO-503 (both manufactured by ADEKA Corporation), IRGANOX (registered trademark) PS802 and IRGANOX PS800 (both manufactured by BASF Japan Ltd.), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).

[0076] When the photocurable composition of the present invention contains the component (g), the content thereof is 0.2 to 1 part by mass, and preferably 0.5 to 0.7 parts by mass, per 100 parts by mass of the total of the components (a), (b), (c), and (d) contained in the photocurable composition.

[0077] The component (g) may be used alone or in combination of two or more.

[0078] <Other Additives> The photocurable composition of the present invention may further contain additives such as a chain transfer agent, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology modifier, an adhesion aid such as a silane coupling agent, a pigment, a dye, or an antifoaming agent, as needed, as long as the effects of the present invention are not impaired.

[0079] <Method for Preparing Photocurable Composition> The method for preparing the photocurable composition of the present invention is not particularly limited. Examples of the preparation method include mixing components (a), (b), (c), and (d), and optionally components (e), (f), and / or (g), in predetermined proportions to prepare a homogeneous solution.

[0080] The photocurable composition of the present invention prepared as a solution is preferably used after being filtered using a filter having a pore size of 0.1 μm to 10 μm.

[0081] <Cured Product> The photocurable composition of the present invention can be exposed (photocured) to obtain a cured product, and the present invention also covers such cured products. The light used for exposure is not particularly limited as long as it can obtain the cured product, and examples thereof include ultraviolet light, electron beams, and X-rays. Examples of light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. After exposure, the cured product may be post-baked to stabilize its physical properties. The post-baking method is not particularly limited, and is typically performed using a hot plate, oven, or the like at 50°C to 260°C for 1 minute to 24 hours.

[0082] The cured product obtained by photocuring the photocurable composition of the present invention has a high transmittance of at least 90% at a wavelength of 410 nm, making the photocurable composition of the present invention suitable for use as an optical film for flat panel displays.

[0083] <Molded Article> The photocurable composition of the present invention can be used to easily produce various molded articles (patterns) in parallel with the formation of a cured product, for example, by using an imprint method. The process for producing the molded article will be described in detail below.

[0084] <Coating Step> The method for producing a molded article of the present invention includes a step of supplying (preferably applying, more preferably coating) the photocurable composition of the present invention onto a substrate to form a coating layer (pattern-forming layer). Examples of the coating method for supplying the photocurable composition of the present invention onto a substrate by coating include commonly known coating methods, such as spin coating, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, and extrusion coating; slit scanning; and inkjet methods.

[0085] The film thickness of the coating layer made of the photocurable composition of the present invention varies depending on the application, but is approximately 0.05 μm to 10 μm. The photocurable composition of the present invention may be applied by multiple coating. Furthermore, another organic layer, such as a planarizing layer, may be formed between the substrate and the coating layer made of the photocurable composition of the present invention. This prevents direct contact between the coating layer and the substrate, thereby preventing dust from adhering to the substrate and damage to the substrate. Furthermore, the molded article (pattern) formed from the photocurable composition of the present invention has excellent adhesion to the organic layer, even when an organic layer is provided on the substrate.

[0086] In the method for producing a molded article using the photocurable composition of the present invention, among the above-mentioned coating methods, a coating method in which the surface area per a given volume of the composition (specific surface area) increases significantly during coating is preferred because the effects of the present invention are more pronounced. Preferred coating methods include spin coating, slit scanning, and inkjet coating. In the method for producing a molded article of the present invention, the method for supplying the photocurable composition onto a substrate is more preferably spin coating or inkjet coating.

[0087] Examples of the substrate include a semiconductor substrate such as silicon coated with a silicon oxide film, a semiconductor substrate such as silicon coated with a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), and a glass substrate on which an ITO film is formed.

[0088] <Imprinting Step> The method for producing a molded article of the present invention includes an imprinting step in which a mold is pressed against the surface of a coating layer to transfer a pattern to the coating layer (pattern-forming layer). This allows a fine pattern previously formed on the pressing surface of the mold to be transferred to the coating layer. The material of the mold is not limited as long as it is a material that transmits light such as ultraviolet light used in the photocuring step described below, and examples thereof include (meth)acrylic resins such as polymethyl methacrylate, cycloolefin polymer (COP) resins, quartz, borosilicate glass, and calcium fluoride. When the mold material is a resin, it may be either a non-photosensitive resin or a photosensitive resin. Examples of the photosensitive resin include the imprint replica mold material disclosed in International Publication No. 2019 / 031359. The mold may also have a light-shielding film. The material of the light-shielding film is not limited as long as it is a material that does not transmit light such as ultraviolet light used in the photocuring step described below, and examples thereof include aluminum, chromium, nickel, cobalt, titanium, tantalum, tungsten, and molybdenum.

[0089] For the demolding step described below, the mold is preferably used after being subjected to a demolding treatment by applying a demolding agent and drying it. The release agent is commercially available, and examples thereof include Novec (registered trademark) 1700, 1710, and 1720 (all manufactured by 3M Japan Ltd.), Fluorosurf (registered trademark) FG-5084 and FG-5093 (all manufactured by Fluorotechnology Co., Ltd.), Durasurf (registered trademark) DP-500, DP-200, DS-5400, DH-100, DH-405TH, DH-610, DS-5800, and DS-5935 (all manufactured by Harves Co., Ltd.), and Polyflon (registered trademark) PTFE TC-7105GN, PTFE TC-7109BK, PTFE TC-7113LB, PTFE TC-7400CR, and PTFE TC-7113B. PTFE TC-7405GN, PTFE TC-7408GY, PTFE TC-7409BK, PTFE TC-7609M1, PTFE TC-7808GY, PTFE TC-7809BK, PTFE TD-7139BD, OPTOOL (registered trademark) DAC-HP, OPTOOL DSX-E, OPTACE (registered trademark) WP-140, DAIFREE (registered trademark) GW-4000, GW-4010, GW-4500, GW-4510, GW-8000, GW-8500, MS-175, GF-700, GF-750, MS-600, GA-3000, GA-970 0, Megafac (registered trademark) GA-9750 (all manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-553, F-555, F-558, F-561 (all manufactured by DIC Corporation), SFE-DP02H, SNF-DP20H, SFE-B002H, SNF-B200A, SCV-X008, SFEX008, SNF-X800, SR-4000A, S-680, S-685, MR F-6441-AL, MR F-6711-AL, MR F-6758-AL, MR F-6811-AL, and MR EF-6521-AL (all manufactured by AGC Seimi Chemical Co., Ltd.). In addition to the commercially available products, examples of the release agent include mold release agents disclosed in WO 2019 / 031312.

[0090] <Photocuring Step> The method for producing a molded article of the present invention includes a photocuring step in which, after the imprinting step, the photocurable composition is exposed to light through the mold to form a photocured portion. The light used for exposure is not particularly limited as long as it can form the photocured portion, and examples thereof include ultraviolet light, electron beams, and X-rays. Examples of light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. The film thickness of the photocured portion is typically 1 μm to 10 μm, preferably 1.5 μm to 8 μm, and more preferably 2 μm to 6 μm. When the mold is made of a material that transmits light such as ultraviolet light and has a light-shielding film that does not transmit light such as ultraviolet light, it is used as a mask in this step.

[0091] <Heating Step> In the method for producing a molded article of the present invention, a heating step is preferably included after the photocuring step and before the demolding step described below. By including this heating step, the effects of the present invention are more pronounced. The heating temperature is preferably 30°C to 150°C, more preferably 40°C to 120°C, and even more preferably 50°C to 110°C. The heating time is preferably 10 seconds to 5 minutes, more preferably 20 seconds to 3 minutes, and even more preferably 30 seconds to 2 minutes.

[0092] <Mold-releasing step> The method for producing a molded article of the present invention includes a mold-releasing step of separating the photocured portion from the mold. The mold-releasing method is not particularly limited as long as the photocured portion can be completely separated from the mold without being damaged or deformed. The mold is subjected to a release treatment in which the release agent is applied and dried, making it easy to separate the photocured portion from the mold. After the photocuring step, the method may further include a step of heating the photocured portion before, during, or after this mold-releasing step. In this case, the heating conditions for the photocured portion are appropriately selected from the ranges of, for example, 50°C to 260°C and 1 minute to 24 hours. The heating means is not particularly limited, but examples include a hot plate and an oven.

[0093] <Anti-Reflection Film Forming Step> The method for producing a molded article of the present invention may further include a step of forming an anti-reflection film on the surface of the photo-cured part after the demolding step. The anti-reflection film is formed on the surface of the photo-cured product to suppress reflection of light incident on the photo-cured product and improve transmittance. Examples of methods for forming the anti-reflection film include vacuum deposition, sputtering, CVD, mist deposition, spin coating, dip coating, and spray coating. Examples of the anti-reflection film include inorganic films such as magnesium fluoride and silicon dioxide, and organic films such as organopolysiloxane.

[0094] The molded article (pattern) produced by such a method can be suitably used for interlayer insulating films, gate insulating films, spacers, protective films of semiconductor elements, polarizers of liquid crystal display elements, optical members, and the like.

[0095] 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. In the following examples and comparative examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

[0096] (1) Stirring and degassing equipment: Thinky Corporation's Awatori Rentaro (registered trademark) mixer (2) Viscosity measurement equipment: Toki Sangyo Co., Ltd.'s E-type viscometer TVE-22L (3) Film thickness measurement equipment: Filmetrics Corporation's film thickness measuring instrument F-20 (n=1.50) (4) UV exposure and imprinting equipment: Meisho Kiko Co., Ltd.'s thermal / UV curing compatible hybrid nanoimprinter NM-0801HB (wavelength 365 nm) (5) Transmittance measurement equipment: JASCO Corporation's UV-visible-near-infrared spectrophotometer V-670 Reference: Air (6) Refractive index measurement equipment: Metricon's Prism Coupler MODEL2010 / M (7) Imprintability evaluation equipment: Hitachi High-Tech Corporation Field emission scanning electron microscope S-4800

[0097] The compounds used in each of the Preparation Examples, Examples and Comparative Examples were supplied by the following sources. APG-100: manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester APG-100 UA-4200: manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Oligo UA-4200 V#150: manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Viscoat #150 V#160: manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Viscoat #160 V#190: manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Viscoat #190 V#230: manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Viscoat #230 V#260: manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Viscoat #260 I184: manufactured by IGM Resins, trade name: OMNIRAD (registered trademark) 184 MOTMS: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-5803 Silica sol i: manufactured by Nissan Chemical Industries, Ltd., trade name: MA-ST-M PEPT: manufactured by SC Organic Chemicals Co., Ltd., trade name: PEPT SA1305P: manufactured by ASM Corporation (formerly Advanced Soft Materials Co., Ltd.), trade name: Selm (registered trademark) Super Polymer SA1305P I245: manufactured by BASF Japan Ltd., trade name: IRGANOX (registered trademark) 245

[0098] V#150, V#160, and V#190 are monofunctional (meth)acrylates having one (meth)acryloyloxy group per molecule that can be used as the component (a1).

[0099] APG-100, UA-4200, V#230, and V#260 are polyfunctional (meth)acrylates having two or more (meth)acryloyloxy groups per molecule that can be used as the component (a). All of these are bifunctional (meth)acrylates having two (meth)acryloyloxy groups per molecule. Furthermore, among these, UA-4200 is a bifunctional urethane (meth)acrylate of the component (a2), and V#230 and V#260 are bifunctional (meth)acrylates represented by the formula (3) of the component (a3).

[0100] I184 is a photoradical initiator that can be used as the component (b).

[0101] The MOTMS is a silane coupling agent represented by the formula (1) that modifies the surface of the silica particles of the component (c).

[0102] Silica sol i (methanol-dispersed silica sol, primary particle diameter of 20 nm to 25 nm, silica particle concentration of 40 mass %) is an organosilica sol containing surface-unmodified silica particles having a primary particle diameter of 1 nm to 100 nm, which are the raw material for the silica particles of component (c).

[0103] SA1305P (an ethyl acetate dispersion of a polyrotaxane comprising cyclodextrin cyclic molecules, polyethylene glycol chains, and adamantyl groups as blocking groups, the polyrotaxane having acryloyloxy groups attached via spacers to the side chains of the cyclic molecules, solids concentration: 50% by mass) is a polyrotaxane having a (meth)acryloyloxy group that can be used as the component (d).

[0104] PEPT is a polyfunctional thiol represented by the formula (2) that can be used as the component (e).

[0105] I245 is a phenolic antioxidant that can be used as the component (f).

[0106] [Production Example 1] 50 g of silica sol i and 5 g of MOTMS (0.8 mmol per 1 g of silica particles) were weighed into a 100 mL recovery flask, and a hydrolysis and condensation reaction was carried out for a total of 6 hours in an oil bath at 65° C. Subsequently, 40 g of the obtained methanol dispersion of MOTMS-modified silica particles (solid content concentration 45% by mass) and 15 g of UA-4200 were weighed into a 200 mL recovery flask, and the mixture was stirred to homogenize. Then, the methanol was distilled off using an evaporator at 60° C. and a reduced pressure of 133.3 Pa or less to obtain a UA-4200 dispersion of MOTMS-modified silica particles (concentration of the MOTMS-modified silica particles 55% by mass).

[0107] [Production Example 2] 20 g of V#260 and 40 g of SA1305P were weighed into a 100 mL recovery flask and stirred to homogenize. Then, using an evaporator, ethyl acetate was distilled off at 50°C and a reduced pressure of 133.3 Pa or less, thereby obtaining a V#260 dispersion of the polyrotaxane (concentration of the polyrotaxane: 50% by mass).

[0108] In preparing the photocurable compositions of the Examples and Comparative Examples described below, when the surface-modified silica particles of component (c) were blended, they were blended as the UA-4200 dispersion obtained in Production Example 1, and when the polyrotaxane of component (d) was blended, they were blended as the V#260 dispersion obtained in Production Example 2.

[0109] Example 1 0.7 g of UA-4200 and 3.6 g of V#260 were blended as the component (a), 0.05 g of I184 as the component (b), 0.45 g of the UA-4200 dispersion obtained in Production Example 1 as the component (c) (0.25 g in terms of MOTMS-modified silica particles), and 0.25 g of the V#260 dispersion obtained in Production Example 2 as the component (d) (0.13 g in terms of polyrotaxane), and the mixture was mixed by shaking at 25.0°C for 15 hours, and then stirred and defoamed for 10 minutes using the stirring defoamer, to prepare photocurable composition 1.

[0110] Example 2 Photocurable composition 2 was prepared in the same manner as in Example 1, except that 0.1 g of UA-4200 and 4.2 g of V#260 were used as the component (a), 0.55 g of the UA-4200 dispersion obtained in Production Example 1 (0.30 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.15 g of the V#260 dispersion obtained in Production Example 2 (0.075 g in terms of polyrotaxane) was used as the component (d).

[0111] Example 3 Photocurable composition 3 was prepared in the same manner as in Example 1, except that 0.04 g of UA-4200 and 4.7 g of V#260 were used as the component (a), 0.18 g of the UA-4200 dispersion obtained in Production Example 1 (0.099 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.05 g of the V#260 dispersion obtained in Production Example 2 (0.025 g in terms of polyrotaxane) was used as the component (d).

[0112] Example 4 Photocurable composition 4 was prepared in the same manner as in Example 1, except that 1.1 g of UA-4200 and 2.8 g of V#160 were used as the component (a), 0.73 g of the UA-4200 dispersion obtained in Production Example 1 (0.40 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.39 g of the V#260 dispersion obtained in Production Example 2 (0.20 g in terms of polyrotaxane) was used as the component (d).

[0113] Example 5 Photocurable composition 5 was prepared in the same manner as in Example 1, except that 1.1 g of UA-4200 and 2.8 g of V#190 were used as the component (a), 0.73 g of the UA-4200 dispersion obtained in Production Example 1 (0.40 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.39 g of the V#260 dispersion obtained in Production Example 2 (0.20 g in terms of polyrotaxane) was used as the component (d).

[0114] Example 6 Photocurable composition 6 was prepared in the same manner as in Example 1, except that 0.4 g of UA-4200 and 4.2 g of V#190 were used as the component (a), 0.27 g of the UA-4200 dispersion obtained in Production Example 1 (0.15 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.15 g of the V#260 dispersion obtained in Production Example 2 (0.075 g in terms of polyrotaxane) was used as the component (d).

[0115] Example 7 Photocurable composition 7 was prepared in the same manner as in Example 1, except that 0.1 g of UA-4200 and 4.7 g of V#190 were used as the component (a), 0.09 g of the UA-4200 dispersion obtained in Production Example 1 (0.050 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.05 g of the V#260 dispersion obtained in Production Example 2 (0.025 g in terms of polyrotaxane) was used as the component (d).

[0116] Example 8 0.03 g of UA-4200 and 4.1 g of V#260 as the component (a), 0.05 g of I184 as the component (b), 0.54 g of the UA-4200 dispersion obtained in Production Example 1 as the component (c) (0.30 g in terms of MOTMS-modified silica particles), 0.23 g of the V#260 dispersion obtained in Production Example 2 as the component (d) (0.12 g in terms of polyrotaxane), and 0.04 g of I245 as the component (f) were blended and mixed by shaking at 25.0°C for 15 hours, and then 0.06 g of PEPT was added as the component (e), and the mixture was stirred and defoamed for 10 minutes using the stirring defoamer, thereby preparing photocurable composition 8.

[0117] Example 9 Photocurable composition 9 was prepared in the same manner as in Example 8, except that 0.05 g of UA-4200 and 3.6 g of V#260 were used as the component (a), 0.90 g of the UA-4200 dispersion obtained in Production Example 1 (0.50 g in terms of MOTMS-modified silica particles) as the component (c), and 0.38 g of the V#260 dispersion obtained in Production Example 2 (0.19 g in terms of polyrotaxane) as the component (d) were used, and then the solutions were mixed in the same manner as in Example 8, and 0.10 g of PEPT was added as the component (e).

[0118] Example 10 A photocurable composition 10 was prepared in the same manner as in Example 8, except that 0.02 g of UA-4200 and 4.4 g of V#260 were used as the component (a), 0.36 g of the UA-4200 dispersion obtained in Production Example 1 (0.20 g in terms of MOTMS-modified silica particles) as the component (c), and 0.15 g of the V#260 dispersion obtained in Production Example 2 (0.075 g in terms of polyrotaxane) as the component (d) were used, and the solutions were mixed together in the same manner as in Example 8, and then 0.04 g of PEPT was added as the component (e).

[0119] Example 11 Photocurable composition 8 was prepared in the same manner as in Example 10, except that 0.01 g of UA-4200 and 4.7 g of V#260 were used as the component (a), 0.17 g of the UA-4200 dispersion obtained in Production Example 1 (0.094 g in terms of MOTMS-modified silica particles) as the component (c), and 0.07 g of the V#260 dispersion obtained in Production Example 2 (0.035 g in terms of polyrotaxane) as the component (d) were used, and the solutions were mixed together in the same manner as in Example 8, and then 0.02 g of PEPT was added as the component (e).

[0120] Example 12 Photocurable composition 12 was prepared in the same manner as in Example 8, except that 0.02 g of UA-4200 and 4.4 g of V#150 were used as the component (a), 0.36 g of the UA-4200 dispersion obtained in Production Example 1 (0.20 g in terms of MOTMS-modified silica particles) as the component (c), and 0.15 g of the V#260 dispersion obtained in Production Example 2 (0.075 g in terms of polyrotaxane) as the component (d) were used, and the solutions were mixed together in the same manner as in Example 8, and then 0.04 g of PEPT was added as the component (e).

[0121] Comparative Example 1 A photocurable composition 13 was prepared in the same manner as in Example 1, except that 2.0 g of UA-4200 and 0.9 g of V#260 were used as the component (a), 1.36 g of the UA-4200 dispersion obtained in Production Example 1 (0.75 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.74 g of the V#260 dispersion obtained in Production Example 2 (0.37 g in terms of polyrotaxane) was used as the component (d).

[0122] Comparative Example 2 A photocurable composition 14 was prepared in the same manner as in Example 1, except that 1.3 g of UA-4200 and 2.3 g of V#260 were used as the component (a), 0.91 g of the UA-4200 dispersion obtained in Production Example 1 (0.50 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.49 g of the V#260 dispersion obtained in Production Example 2 (0.25 g in terms of polyrotaxane) was used as the component (d).

[0123] Comparative Example 3 A photocurable composition 15 was prepared in the same manner as in Example 1, except that 1.1 g of UA-4200 and 2.8 g of APG-100 were used as the component (a), 0.73 g of the UA-4200 dispersion obtained in Production Example 1 was used as the component (c) (0.40 g in terms of MOTMS-modified silica particles), and 0.39 g of the V#260 dispersion obtained in Production Example 2 was used as the component (d) (0.20 g in terms of polyrotaxane).

[0124] Comparative Example 4 A photocurable composition 16 was prepared in the same manner as in Example 1, except that 1.1 g of UA-4200 and 2.8 g of V#230 were used as the component (a), 0.73 g of the UA-4200 dispersion obtained in Production Example 1 was used as the component (c) (0.40 g in terms of MOTMS-modified silica particles), and 0.39 g of the V#260 dispersion obtained in Production Example 2 was used as the component (d) (0.20 g in terms of polyrotaxane).

[0125] Comparative Example 5 Photocurable composition 17 was prepared in the same manner as in Example 8, except that 0.09 g of UA-4200 and 2.1 g of V#260 were used as the component (a), 1.80 g of the UA-4200 dispersion obtained in Production Example 1 (0.99 g in terms of MOTMS-modified silica particles) as the component (c), and 0.76 g of the V#260 dispersion obtained in Production Example 2 (0.38 g in terms of polyrotaxane) as the component (d) were used, and the solutions were mixed together in the same manner as in Example 8, and then 0.20 g of PEPT was added as the component (e).

[0126] Comparative Example 6 Photocurable composition 18 was prepared in the same manner as in Example 8, except that 0.09 g of UA-4200 and 2.1 g of V#150 were used as the component (a), 1.80 g of the UA-4200 dispersion obtained in Production Example 1 (0.99 g in terms of MOTMS-modified silica particles) as the component (c), and 0.76 g of the V#260 dispersion obtained in Production Example 2 (0.38 g in terms of polyrotaxane) as the component (d) were used, and the solutions were mixed together in the same manner as in Example 8, and then 0.20 g of PEPT was added as the component (e).

[0127] Comparative Example 7 A photocurable composition 19 was prepared in the same manner as in Example 1, except that 1.1 g of UA-4200, 2.6 g of V#230, and 0.20 g of APG-100 were used as the component (a), 0.73 g of the UA-4200 dispersion obtained in Production Example 1 (0.40 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.39 g of the V#260 dispersion obtained in Production Example 2 (0.20 g in terms of polyrotaxane) was used as the component (d).

[0128] Comparative Example 8 A photocurable composition 20 was prepared in the same manner as in Example 1, except that 1.7 g of UA-4200, 2.7 g of V#230, and 0.10 g of APG-100 were used as the component (a), 0.36 g of the UA-4200 dispersion obtained in Production Example 1 (0.20 g in terms of MOTMS-modified silica particles) was used as the component (c), and 0.20 g of the V#260 dispersion obtained in Production Example 2 (0.10 g in terms of polyrotaxane) was used as the component (d).

[0129] Comparative Example 9 Photocurable composition 21 was prepared in the same manner as in Example 8, except that 1.3 g of UA-4200 and 2.7 g of V#260 were used as the component (a), the UA-4200 dispersion obtained in Production Example 1 was not added as the component (c), and 0.79 g (0.40 g in terms of polyrotaxane) of the V#260 dispersion obtained in Production Example 2 was used as the component (d). After mixing the solutions, 0.20 g of PEPT was added as the component (e).

[0130] The components of photocurable compositions 1 to 21 prepared in Examples 1 to 12 and Comparative Examples 1 to 9 are shown in Tables 1 and 2 below. In Tables 1 and 2 below, "parts" represents "parts by mass." In Tables 1 and 2 below, the parts by mass of component (c) represent only the surface-modified silica particle component in the UA-4200 dispersion obtained in Production Example 1, and the parts by mass of component (d) represent only the polyrotaxane component in the V#260 dispersion obtained in Production Example 2.

[0131]

[0132] [Viscosity Measurement] 1 mL of each photocurable composition prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was collected using a disposable syringe and injected into a viscometer cup. The cone rotor of the viscometer was then rotated at rotation speeds of 10 rpm, 1.0 rpm, and 0.5 rpm, and the viscosity of the photocurable composition after 2 minutes was measured using the E-type viscometer. The results are shown in Table 3 below.

[0133] [Film Thickness Measurement] Each of the photocurable compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was cast onto a 4-inch silicon wafer cut into quarters and spin-coated at 1,000 rpm for 30 seconds. The film thickness of the coating layer of the photocurable composition obtained on the silicon wafer was measured using the film thickness meter. In addition, film formability immediately after spin coating was also observed visually. If film thickness measurement was impossible, it was indicated by "-". If the surface of the coating layer was uniform and film formability was good, it was indicated by "○". If interference unevenness or liquid unevenness was observed in part of the coating layer, it was indicated by "△". If the coating layer did not spread (stretch) and significant liquid unevenness was observed in the coating layer, it was indicated by "X". The results are shown in Table 3 below.

[0134]

[0135] The photocurable compositions prepared in Examples 1 to 12 had viscosities at 25.0°C of more than 1 mPa·s and less than 50 mPa·s. All of the photocurable compositions were spin-coatable, and had good film-forming properties, allowing film thickness measurements. The lower the viscosity of the photocurable composition, the better the film-forming properties.

[0136] The photocurable compositions prepared in Comparative Examples 1 to 9 had viscosities at 25.0°C higher than 50 mPa·s. Although all of the photocurable compositions could be spin-coated, film-formability was poor, and it was impossible to measure the film thickness of the photocurable compositions prepared in Comparative Examples 1, 4, and 5. For photocurable compositions with a viscosity of more than 100 mPa·s at 25.0°C, the coating layer did not spread evenly, further worsening the film-formability. For photocurable compositions with a viscosity of more than 250 mPa·s at 25.0°C, the coating layer did not spread, further worsening the film-formability, and it was impossible to measure the film thickness.

[0137] [Transmittance Measurement] The photocurable composition prepared in Example 11 was sandwiched between a glass substrate that had been primer-treated by applying a solution of Shin-Etsu Chemical Co., Ltd.'s adhesion promoter (trade name: KBM-5803) diluted to 10% by mass with propylene glycol monomethyl ether acetate and drying it, and a glass substrate that had been release-treated by applying Novec (registered trademark) 1720 (3M Japan Ltd.) and drying it. The photocurable composition sandwiched between the primer-treated glass substrate and the release-treated glass substrate was then pressed with 100 N using the hybrid nanoimprinter and exposed to UV light at 6 J. After exposure, the resulting cured product was heated on a hot plate at 100°C for 10 minutes and then peeled off from the release-treated glass substrate to produce a 5 μm-thick cured product. The transmittance of the cured product at a wavelength of 410 nm was measured using the spectrophotometer. The results are shown in Table 4 below.

[0138] [Measurement of refractive index] The refractive index of each cured product prepared in the same manner as in the transmittance measurement was measured using the refractive index measuring device. The results are shown in Table 4 below.

[0139] [Confirmation of Imprintability] The photocurable composition prepared in Example 11 was sandwiched between a glass substrate that had been primer-treated by applying a solution of Shin-Etsu Chemical Co., Ltd.'s adhesion promoter (trade name: KBM-5803) diluted to 10% by mass with propylene glycol monomethyl ether acetate and drying it, and a silicone mold that had been release-treated by applying Novec (registered trademark) 1720 (manufactured by 3M Japan Ltd.) and drying it. The photocurable composition sandwiched between the primer-treated glass substrate and the release-treated silicone mold was then pressed at 100 N using the hybrid nanoimprinter and exposed to UV light at 6 J. After exposure, the resulting cured product was heated on a hot plate at 100°C for 10 minutes and then peeled from the release-treated silicone mold to produce a molded product (pattern) on the primer-treated glass substrate. When the produced molded product was observed using the field emission scanning electron microscope, it demonstrated imprintability, allowing the formation of the desired pattern. The results are shown in FIG. 1 and are indicated by "○" in Table 4.

[0140]

[0141] From the above, the photocurable composition of the present invention containing the components (a) to (d) can be spin-coated, and the surface of the coating layer is uniform. Furthermore, a molded article produced on a glass substrate using this composition was confirmed to have imprintability and showed high transmittance.

Claims

1. A photocurable composition comprising the following components (a) to (d), wherein the content of component (a) is 80 parts by mass to 99 parts by mass per 100 parts by mass of the sum of components (a) to (d), and the composition has a viscosity at 25.0°C of 1 mPa·s to 50 mPa·s: (a): at least two types of polyfunctional (meth)acrylates having one or more (meth)acryloyloxy groups in one molecule (excluding the component (d) below); (b): Photoradical initiator (c): Silica particles having a primary particle size of 1 nm to 100 nm, the surface of which is modified with at least one silane coupling agent represented by the following formula (1): 【Chemistry 1】 (In the formula, X １ represents a hydrogen atom or a (meth)acryloyloxy group; R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, m represents an integer of 1 to 14, and n represents an integer of 0 to 2. (d): Polyrotaxane having a (meth)acryloyloxy group

2. The photocurable composition according to claim 1, further comprising at least one component selected from the group consisting of the following component (e), component (f), and component (g): (e): A polyfunctional thiol represented by the following formula (2): (f): Phenol-based antioxidant (g): Sulfide-based antioxidant 【Chemistry 2】 (In the formula, R ３ represents a single bond, a linear alkylene group having 1 to 6 carbon atoms, or a branched alkylene group having 3 to 6 carbon atoms; X ２ represents a single bond, an ester bond, or an ether bond. S, Q １ represents an organic group having 2 to 12 carbon atoms, which may contain at least one heteroatom or no heteroatom, or a heteroatom, and p represents an integer of 2 to 6.

3. The photocurable composition according to claim 1 or 2, wherein the component (a) is selected from the group consisting of the following component (a2) and the following component (a3): (a2): Bifunctional urethane (meth)acrylate (a3): a bifunctional (meth)acrylate represented by the following formula (3): 【Chemistry 3】 (In the formula, R ４ represents a hydrogen atom or a methyl group, Q ２ represents a linear or branched alkylene group having 4 to 10 carbon atoms.

4. The component (c) is X in the formula (1). １ The photocurable composition according to claim 1 , wherein the silica particles are surface-modified with a silane coupling agent representing a (meth)acryloyloxy group.

5. 5. A cured product of the photocurable composition according to claim 1, having a film thickness of 1.0 μm to 10.0 μm.

6. A method for producing a molded article, comprising a step of imprint molding the photocurable composition according to claim 1 .

7. 13. A method for producing a molded product from a photocurable composition, the method comprising: a step of supplying the photocurable composition according to claim 1 onto a substrate; an imprinting step of contacting the photocurable composition with a mold having a reverse pattern of a shape of a target molded product; a photocuring step of exposing the photocurable composition through the mold after the imprinting step to form a photocured part; and a demolding step of separating the photocured part from the mold.

8. The method for producing a molded article according to claim 7 , wherein the step of supplying the photocurable composition is a step of applying the photocurable composition by a spin coating method, a slit scanning method or an inkjet method.

9. The method for producing a molded body according to claim 7 or 8, further comprising a step of heating the photocured portion after the photocuring step and before, during or after the demolding step.

10. The method for producing a molded article according to claim 6 , wherein the molded article is an optical film for a flat panel display.

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