WO2020003863A1 - Photocurable composition for imprinting - Google Patents

Abstract

[Problem] To provide a novel photocurable composition for imprinting. [Solution] A photocurable composition for imprinting which comprises component (a), component (b), component (c), and component (d), wherein component (a) is contained in an amount of 10 to 40 parts by mass, component (b) is contained in an amount of 10 to 50 parts by mass, component (c) is contained in an amount of 1 to 10 parts by mass, and component (d) is contained in an amount of 0.1 to 5 parts by mass relative to a total of 100 parts by mass of a compound having an ethylenically unsaturated group contained in the composition. (a) Silica particles that have a primary particle size of 1 to 100 nm, and are surface-modified with functional groups having ethylenically unsaturated groups. (b) A mono-functional (meth)acrylate compound having an ethylenically unsaturated group. (c) Polyrotaxane having an ethylenically unsaturated group. (d) A photo-radical initiator.

Description

Photocurable composition for imprint

The present invention relates to a silica particle surface-modified with a functional group having an ethylenically unsaturated group, a monofunctional (meth) acrylate compound having an ethylenically unsaturated group, a polyrotaxane having an ethylenically unsaturated group, and a photoradical initiator. And a photocurable composition for imprints comprising: In detail, the optical characteristics (high refractive index, high Abbe number, low birefringence) are excellent, and after forming an anti-reflection layer (AR layer) on a cured product and a molded product, the anti-reflection layer is subjected to heat treatment. The present invention relates to a photocurable composition which does not generate cracks and does not generate cracks in a cured product even after washing or development with an organic solvent.

BACKGROUND ART Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic devices. In addition, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with a high yield are required in accordance with the usage mode. As a material for a resin lens satisfying such requirements, for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, and a methacrylic resin has been used.

A high-resolution camera module uses a plurality of lenses. However, a lens having low wavelength dispersion, that is, a lens having a high Abbe number is mainly used, and an optical material for forming the lens is required. In addition, in order to improve the yield and production efficiency in the production of resin lenses, and to suppress the optical axis deviation when laminating the lenses, injection molding of thermoplastic resin to pressing molding using liquid curable resin at room temperature The shift to wafer-level molding due to the above has been actively studied. In the wafer level molding, from the viewpoint of productivity, a hybrid lens system in which a lens is formed on a support such as a glass substrate is generally used.

Conventionally, a radical curable resin composition has been used as a photocurable resin capable of being formed at a wafer level from the viewpoints of high transparency, heat-resistant yellow discoloration and mold release properties (Patent Document 1). ). When the molded product is a lens, an antireflection layer made of an inorganic substance such as silicon oxide or titanium oxide is formed on the lens. Therefore, there is a problem that cracks occur in the antireflection layer when the lens covered with the antireflection layer is heat-treated.

In addition, a curable composition capable of obtaining a cured product having a high Abbe number by containing surface-modified oxide particles such as silica particles surface-modified with a silane compound and zirconium oxide particles surface-modified with a dispersant. Things are known (for example, Patent Document 2 and Patent Document 3). The curable composition containing such oxide particles is used in a developing step of cleaning an uncured portion such as an outer peripheral portion of a wafer-shaped molded body on which a plurality of lens patterns are formed after imprinting with an organic solvent. However, there is a problem that erosion of the wafer-shaped molded body becomes remarkable, and cracks occur in the wafer-shaped molded body.

Furthermore, in a cured product molded from a general radical-curable resin composition, stress due to curing shrinkage accumulates in the cured product, causing birefringence. If a cured product having a high birefringence is used as a lens for a high pixel camera module, the resulting image will be distorted. Therefore, a low birefringence material is required as a curable resin composition for a lens.

On the other hand, it has a cyclic molecule having an opening, a linear molecule, and a blocking group (stopper), and the opening of the cyclic molecule is attached to both ends of a pseudo-polyrotaxane that is skewingly included by the linear molecule. A polyrotaxane in which a blocking group is disposed and the cyclic molecule has a (meth) acryl group is known (for example, Patent Document 4). The linear molecule penetrates the opening of the cyclic molecule, and the blocking group is provided so that the cyclic molecule does not separate from the linear molecule. In addition, “inclusion” means taking in another molecule into the space of the opening of the cyclic molecule, and “pseudopolyrotaxane” means polyrotaxane having no blocking group. The photocurable composition containing the polyrotaxane can produce a photocured product having high strength, high elastic modulus, and excellent toughness.

Patent No. 5281710 (WO 2011/105473) JP 2014-234458 A International Publication No. 2016/104039 International Publication No. WO 2016/072356

A molded article having a high Abbe number (for example, 53 or more) and low birefringence and usable as a lens for a high-resolution camera module is obtained, and the antireflection layer formed on the molded article is subjected to a subsequent heat treatment. In the developing step of cleaning an uncured portion such as an outer peripheral portion of the wafer-shaped molded body with an organic solvent, no crack is generated in the wafer-shaped molded body. Instead, its development was desired. The present invention has been made in view of such circumstances, and it is possible to form a molded article having a high Abbe number, a high refractive index, and low birefringence, and to reflect the upper layer by heat-treating the molded article. It is an object of the present invention to provide a photocurable composition capable of forming a molded article having high crack resistance, in which no crack is generated in the prevention layer and no crack is generated even when exposed to a developing step.

A first aspect of the present invention is a photocurable composition for imprints comprising the following component (a), the following component (b), the following component (c), and the following component (d). The component (a) is 10 to 40 parts by mass, the component (b) is 10 to 50 parts by mass, and the component (c) is 100 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group contained therein. A photocurable composition for imprints, comprising 1 to 10 parts by mass of a component and 0.1 to 5 parts by mass of the component (d).
(A): Silica particles having a primary particle diameter of 1 nm to 100 nm and surface-modified with a functional group having an ethylenically unsaturated group (b): Monofunctional (meth) acrylate compound having an ethylenically unsaturated group (c) : Polyrotaxane having an ethylenically unsaturated group (d): Photo-radical initiator

The photocurable composition for imprints of the present invention further comprises 5 parts by mass to 50 parts by mass of the following component (e) based on 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition. And / or may contain the following component (f).
(E): a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group and containing no aromatic ring (provided that the component (c) is a polyrotaxane and the component (f) is a urethane (meth) acrylate compound or epoxy (meth) ) Excluding acrylate compounds.)
(F): a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound having an ethylenically unsaturated group (excluding the polyrotaxane of the component (c))

The photocurable composition for imprints of the present invention further comprises 0.05 to 3 parts by mass of the following component (g) based on 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. And / or 0.1 to 3 parts by mass of the following component (h) with respect to 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition.
(G): phenolic antioxidant (h): sulfide antioxidant

The silica particles surface-modified with the functional group having an ethylenically unsaturated group of the component (a) are, for example, silica particles surface-modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group. Particles. The divalent linking group is, for example, an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms.

The polyfunctional (meth) acrylate compound containing no aromatic ring of the component (e) may be composed of two or more compounds. In that case, at least one of the two or more compounds has an alicyclic hydrocarbon group.

The imprint photocurable composition has a refractive index n _D at a wavelength of 589nm of the cured product is not less 1.49 or more and is the Abbe number [nu _D of the cured product is 53 or more. The refractive index _{n D,} the Abbe number [nu _D but is preferably as high values both, for example, the refractive index _{n D} is 1.49 or more 1.55 or less, the Abbe number [nu _D be in the range of 53 or more and 60 or less Good.

A second aspect of the present invention is a cured product of the photocurable composition for imprints.

A third aspect of the present invention is a method for producing a resin lens, comprising a step of imprint molding the photocurable composition for imprint.

A fourth aspect of the present invention is a method for producing a molded article of the photocurable composition for imprints, wherein the photocurable composition for imprints is a space between a support and a mold that are in contact with each other, or A method for producing a molded article, comprising a step of filling a space inside a dividable mold and a step of exposing the photocurable composition for imprints filled in the space to photocuring. The mold is also called a mold.

In the method for producing a molded article of the present invention, after the step of photocuring, the step of taking out the obtained photocured product and releasing the mold, and the photocured product, before the step of releasing the mold, halfway or The method may further include a step of heating later.

After the releasing step and before the heating step, the method may further include a developing step using an organic solvent.

In the method for producing a molded article of the present invention, the molded article is, for example, a lens for a camera module.

The photocurable composition for imprints of the present invention contains the components (a) to (d), and optionally, the component (e) and / or the component (f), and the component (g). And / or component (h). Therefore, a cured product and a molded article obtained from the photocurable composition exhibit desirable optical properties for an optical device, for example, a lens for a high-resolution camera module, that is, a high Abbe number, a high refractive index, and a low birefringence. Further, in the cured product and the molded product obtained from the photocurable composition of the present invention, the cured antireflection layer on the cured product and the molded product does not crack or wrinkle by heat treatment at 175 ° C. No crack is generated in the developing step using an organic solvent.

Each component of the photocurable composition for imprints of the present invention will be described in more detail. In the present invention, an ethylenically unsaturated group is a group having a double bond between two carbon atoms, for example, a (CH ₂ CH) — group and a [CH ₂ ＣC (CH ₃ )] — group Is mentioned. The compound having an ethylenically unsaturated group contained in the photocurable composition for imprints of the present invention is a component (a) to a component (c), and the composition is the component (e) and the component (f). When at least one of these components is contained, these components also apply.

[Component (a): silica particles surface-modified with a functional group having an ethylenically unsaturated group]
The silica particles surface-modified with a functional group having an ethylenically unsaturated group, which can be used as the component (a) of the photocurable composition for imprints of the present invention, have a primary particle diameter of 1 nm to 100 nm. Here, the primary particles are particles constituting a powder, and the particles obtained by aggregating the primary particles are referred to as secondary particles. The primary particle diameter is determined by the gas adsorption method (BET method), the specific surface area (surface area per unit mass) S of the silica particles surface-modified with the functional group having an ethylenically unsaturated group, It can be calculated from the relational expression that holds between the density ρ of the silica particles and the primary particle diameter D: D = 6 / (ρS). The primary particle diameter calculated from the relational expression is an average particle diameter and is a diameter of the primary particles. The silica particles surface-modified with a functional group having an ethylenically unsaturated group are surface-modified with, for example, a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group. When using the silica particles surface-modified with the functional group having an ethylenically unsaturated group, the surface-modified silica particles may be used as they are, and the surface-modified silica particles may be used as an organic solvent as a dispersion medium. A colloidal state (sol in which colloidal particles are dispersed in a dispersion medium) which has been dispersed in a solvent in advance may be used. When a sol containing the surface-modified silica particles is used, a sol having a solid content in the range of 10% by mass to 60% by mass can be used.

Examples of the sol containing silica particles surface-modified with a functional group having an ethylenically unsaturated group include, for example, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM- AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L (manufactured by Nissan Chemical Industry Co., Ltd.), and ELCOM (registered trademark) V-8802, V-8804 (manufactured by Nikki Shokubai Kasei Co., Ltd.) Manufactured).

The content of the component (a) of the photocurable composition for imprints of the present invention is from 10 parts by mass to 40 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition. Parts, preferably 15 parts by mass to 35 parts by mass. If the content of the component (a) is less than 10 parts by mass, cracks in the cured product obtained from the photocurable composition for imprints and the antireflection layer formed on the molded product may not be suppressed. When the amount is more than 40 parts by mass, haze is generated in the cured product and the molded article, and the transmittance may be reduced.

The silica particles surface-modified with a functional group having an ethylenically unsaturated group of the component (a) can be used alone or in combination of two or more.

[Component (b): monofunctional (meth) acrylate compound having an ethylenically unsaturated group]
The monofunctional (meth) acrylate compound having an ethylenically unsaturated group, which can be used as the component (b) of the photocurable composition for imprints of the present invention, has a (meth) acryloyloxy group in one molecule of the compound. It is a compound having one. Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (Meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) a Acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, tricyclo [5.2.1.0 (2,6)] decanyl (meth) acrylate, tricyclo [5.2.1.0 (2,6)] decanyloxyethyl (meth) acrylate. Among them, it is preferable to use an alicyclic (meth) acrylate compound having an alicyclic structure from the viewpoint of the refractive index.

As the monofunctional (meth) acrylate compound having an ethylenically unsaturated group, commercially available products may be used. For example, Biscoat # 155, IBXA, ADMA (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A- IB, IB, AS, S, S-1800A, A-1800M (all manufactured by Shin-Nakamura Chemical Co., Ltd.), and FANCRILL (registered trademark) FA-511AS, FA-512AS, FA- 513AS, FA-512M, FA-512MT, and FA-513M (all manufactured by Hitachi Chemical Co., Ltd.).

The content of the component (b) of the photocurable composition for imprints of the present invention is from 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition. Parts, preferably 20 to 45 parts by weight. If the content of the component (b) is less than 10 parts by mass, the effect of reducing the birefringence of the cured product and the molded product obtained from the photocurable composition for imprints may be insufficient. If the amount is more than the mass part, the crosslinked density of the cured product and the molded product may be reduced, and the shape of the cured product and the molded product may be deformed during the heat treatment.

The monofunctional (meth) acrylate compound having an ethylenically unsaturated group of the component (b) can be used alone or in combination of two or more.

[Component (c): polyrotaxane having an ethylenically unsaturated group]
The polyrotaxane having an ethylenically unsaturated group, which can be used as the component (c) of the photocurable composition for imprints of the present invention, is a pseudopolyrotaxane in which the opening of a cyclic molecule is skewingly included by a linear molecule. A blocking group is arranged at both ends of the polymer so that the cyclic molecule is not removed, and the cyclic molecule has an ethylenically unsaturated group. The cyclic molecule, the linear molecule, and the blocking group, which are components of the polyrotaxane having an ethylenically unsaturated group, will be described.

<C-1. Cyclic molecule>
The cyclic molecule of the polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it is cyclic, has an opening, and is included in a skewered manner by a linear molecule. The constituent element of the polyrotaxane having an ethylenically unsaturated group is preferably a cyclic molecule, and the ethylenically unsaturated group may be directly bound to the cyclic molecule or bound via a spacer. Examples of the spacer include, but are not particularly limited to, an alkylene group, an alkylene oxide group, a hydroxyalkylene group, a carbamoyl group, an acrylate chain, a polyalkylene ether chain, and a polyalkylene carbonate chain. As the cyclic molecule, for example, it is preferable to select from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

<C-2. Linear molecule>
The linear molecule of the polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it can be included in a skewered manner at the opening of the cyclic molecule to be used. For example, examples of the linear molecule include compounds (polymers) exemplified in Patent Document 4, and among them, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, A polymer selected from the group consisting of polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether is preferred, and polyethylene glycol is particularly preferred.

The linear molecule has a weight average molecular weight of 1,000 or more, preferably 3,000 to 100,000, more preferably 6,000 to 50,000. In the polyrotaxane having an ethylenically unsaturated group as the component (c), the combination of (cyclic molecule, linear molecule) is preferably (α-cyclodextrin-derived or polyethylene glycol-derived).

<C-3. Blocking group>
The blocking group of the polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it is a group disposed at both ends of the pseudopolyrotaxane and acts so as to prevent the used cyclic molecule from being eliminated. For example, examples of the blocking group include blocking groups exemplified in Patent Document 4, among which dinitrophenyl groups, cyclodextrins, adamantyl groups, trityl groups, fluoresceins, silsesquioxanes, And a blocking group selected from the group consisting of pyrenes, and more preferably adamantyl groups or cyclodextrins. The blocking group is bonded to the linear molecule through, for example, a —NH—C (＝ O) — group.

A commercially available product may be used as the polyrotaxane having an ethylenically unsaturated group. (Manufactured by Co., Ltd.).

The content of the component (c) of the photocurable composition for imprints of the present invention is from 1 part by mass to 10 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition. Parts, preferably 3 to 7 parts by mass. When the content of the component (c) is less than 1 part by mass, the effect of suppressing the occurrence of cracks in the cured product in the developing step using an organic solvent may be insufficient, and the amount is more than 10 parts by mass. Then, the change in shape of the cured product and the molded product during heating may increase due to the low elastic modulus.

The polyrotaxane having an ethylenically unsaturated group as the component (c) can be used alone or in combination of two or more.

[Component (d): Photoradical initiator]
Examples of the photoradical initiator usable as the component (d) of the photocurable composition for imprints of the present invention include alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, and benzoylbenzoate. , Oxime esters, tetramethylthiuram monosulfides, and thioxanthones, and a photo-cleavable photo-radical polymerization initiator is particularly preferable. Commercially available photo-radical initiators such as IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, and CG 24 -61, TPO, 1116, 1173 (all manufactured by BASF Japan K.K.) and ESACURE KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, and KIP75 (all manufactured by Lamberti) Can be adopted.

The content of the component (d) of the photocurable composition for imprints of the present invention is from 0.1 part by mass to 5 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition. Parts, preferably 0.5 to 3 parts by mass. When the content of the component (d) is less than 0.1 part by mass, the strength of a cured product and a molded product obtained from the photocurable composition for imprints may be reduced, and when the content is more than 5 parts by mass. There is a possibility that the heat-resistant yellowing of the cured product and the molded article may be deteriorated.

The photo radical initiator of the component (d) can be used alone or in combination of two or more.

[Component (e): polyfunctional (meth) acrylate compound having an ethylenically unsaturated group and not containing an aromatic ring]
The polyfunctional (meth) acrylate compound containing no aromatic ring which can be used as the component (e) of the photocurable composition for imprints of the present invention has at least two (meth) acryloyloxy groups in one molecule of the compound. And a compound containing no aromatic ring, except for the polyrotaxane of the component (c) and the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (f) described later. Here, the aromatic ring is a carbocyclic or heterocyclic ring satisfying the Huckel rule, for example, benzene, naphthalene, azulene, anthracene, tetracene, pentacene, phenanthrene, pyrene, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, pyridine. , Pyridazine, pyrimidine, pyrazine and triazine. Therefore, not including an aromatic ring means not including a carbon ring or a hetero ring satisfying the Huckel rule. Examples of the polyfunctional (meth) acrylate compound containing no aromatic ring include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin tri (meth) acrylate. ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, polyglycerin monoethylene oxide poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethanol di (meth) Acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , 1,9-nonanediol di (meth) acrylate, and tris (2-acryloyloxyethyl) isocyanurate.

As the polyfunctional (meth) acrylate compound containing no aromatic ring, a commercially available product may be used. For example, NK ester # A-200, A-400, A-600, A-1000, A-9300, A-9300-1CL, 1G, 2G, 3G, 4G, 9G, 14G, 23G, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, ATM-4E, ATM-35E, A-DPH, A-TMPT, A-DCP, A-HD-N, A-NOD- N, AD-TMP, A-DOG, TMPT, DCP, NPG, HD-N, NOD-N, D-TMP (all manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD ( (Registered trademark) DPHA, NPGDA, ET30, the DPEA-12, the PEG400DA, the RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), M-210, M-350 (Toagosei Co., Ltd.) and the like.

When the photocurable composition for imprints of the present invention contains the component (e), the content is 5 parts by mass with respect to 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. Parts to 50 parts by mass, preferably 5 parts to 30 parts by mass. When the content of the component (e) is less than 5 parts by mass, the crosslinked density of the cured product and the molded product obtained from the photocurable composition for imprints decreases, and the shape of the cured product and the molded product during heat treatment is reduced. When the amount is more than 50 parts by mass, the effect of reducing the birefringence of the cured product and the molded article may be insufficient.

The polyfunctional (meth) acrylate compound containing no aromatic ring of the component (e) can be used alone or in combination of two or more.

[Component (f): urethane (meth) acrylate compound or epoxy (meth) acrylate compound having an ethylenically unsaturated group]
The urethane (meth) acrylate compound that can be used as the component (f) of the photocurable composition for imprints of the present invention has at least two (meth) acryloyloxy groups and “—NH—C (= O) A compound having at least two urethane structures represented by O- ". Examples of the urethane (meth) acrylate compound include, for example, EBECRYL (registered trademark) 230, 270, 280 / 15IB, 284, 4491, 4683, 4858, 8307, 8402, 8411, 8804, 8807, 9270, 8800, 294 / 25HD, 4100, 4220, 4513, 4738, 4740, 4820, 8311, 8465, 9260, 8701, KRM7735, 8667, 8296 (all manufactured by Daicel Ornex), UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500B, UV-3520EA, UV -3700B, UV-6640B, V-6630B, UV-7000B, UV-7510B, UV-7461TE (all made by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G (all made by Kyoeisha) M-1100, M-1200 (all manufactured by Toagosei Co., Ltd.), NK Oligo U-2PPA, U-6LPA, U-200PA, U-200PA, U-160TM UA-4200, UA-4400, UA-122P, UA-7100, and UA-W2A (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

The epoxy (meth) acrylate compound usable as the component (f) of the photocurable composition for imprints of the present invention is obtained by reacting a compound having at least two epoxy rings in one molecule with (meth) acrylic acid. Ester. Examples of the epoxy (meth) acrylate compound include EBECRYL (registered trademark) 645, 648, 860, 3500, 3608, 3702, and 3708 (all manufactured by Daicel Ornex Co., Ltd.), DA-911M , DA-920, DA-931, DA-314, DA-212 (both manufactured by Nagase ChemteX Corporation), HPEA-100 (manufactured by KSEM Corporation), and Unidick (registered trademark) V-5500, V-5502 and V-5508 (both manufactured by DIC Corporation).

As the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (f), a compound having two or three (meth) acryloyloxy groups in one molecule of the compound is preferably used.

When the photocurable composition for imprints of the present invention contains the component (f), the content is 5 parts by mass relative to 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. Parts to 50 parts by mass, preferably 5 parts to 30 parts by mass. When the content of the component (f) is less than 5 parts by mass, the cured product and the molded product obtained from the photocurable composition for imprints become brittle, so that the cured product and the molded product have high resistance during heating. Cracking properties may be reduced, and if it is more than 50 parts by mass, a change in shape of the cured product and the molded product during heating may be increased due to a decrease in crosslinking density.

The urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (f) can be used alone or in combination of two or more.

[(G) component: phenolic antioxidant]
Examples of the phenolic antioxidant that can be used as the component (g) of the photocurable composition for imprints of the present invention include, for example, IRGANOX (registered trademark) 245, 1010, 1035, 1076, and 1135 (both described above). BASF Japan, Ltd.), SUMILIZER (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R (all manufactured by Sumitomo Chemical Co., Ltd.), and ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 (all manufactured by ADEKA Corporation).

When the photocurable composition for imprints of the present invention contains the component (g), the content is preferably 0.05 parts by mass to 3 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group. Parts, preferably 0.1 to 1 part by mass.

The phenolic antioxidant of the component (g) can be used alone or in combination of two or more.

[(H) component: sulfide antioxidant]
Examples of the sulfide-based antioxidant usable as the component (h) of the photocurable composition for imprints of the present invention include, for example, ADK STAB (registered trademark) AO-412S and AO-503 (all manufactured by ADEKA Corporation) ), IRGANOX (registered trademark) PS802 and PS800 (all manufactured by BASF), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).

When the photocurable composition for imprints of the present invention contains the component (h), the content is 0.1 parts by mass with respect to 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. It is from 3 parts by mass to 3 parts by mass, preferably from 0.1 part by mass to 1 part by mass.

The sulfide-based antioxidant of the component (h) can be used alone or in combination of two or more.

<Other additives>
Further, the photocurable composition for imprints of the present invention may contain a chain transfer agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology, if necessary, as long as the effects of the present invention are not impaired. It may contain a regulator, an adhesion auxiliary agent such as a silane coupling agent, a pigment, a dye, an antifoaming agent, and the like.

<Method for preparing photocurable composition for imprint>
The method for preparing the photocurable composition for imprints of the present invention is not particularly limited. As the preparation method, for example, the component (a), the component (b), the component (c) and the component (d), and if desired, the component (e) and / or the component (f), the component (g) and / or ( h) A method of mixing the components at a predetermined ratio to obtain a uniform solution.

Further, the photocurable composition for imprints of the present invention prepared in a solution is preferably used after being filtered using a filter having a pore size of 0.1 μm to 5 μm.

<Cured product>
The photocurable composition for imprints of the present invention can be exposed (photocured) to obtain a cured product, and the present invention is also directed to the cured product. Light rays to be exposed include, for example, ultraviolet rays, electron beams and X-rays. As a light source used for ultraviolet irradiation, for example, a solar ray, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. After exposure, post-baking may be performed to stabilize the physical properties of the cured product. The post-baking method is not particularly limited, but is usually performed using a hot plate, an oven or the like at 50 ° C. to 260 ° C. for 1 minute to 24 hours.

Cured product obtained by photocuring the imprint photocurable composition of the present invention has an Abbe number [nu _D is 53 or more and high refractive index n _D at a wavelength of 589 nm (D line) 1. 49 or more. Therefore, the photocurable composition for imprints of the present invention can be suitably used for forming a resin lens.

<Molded body>
The photocurable composition for imprints of the present invention can easily produce various molded articles in parallel with the formation of a cured product, for example, by using an imprint molding method. As a method for producing a molded article, for example, a step of filling the photocurable composition for imprinting of the present invention into a space between a contacting support and a mold, or a space inside a dividable mold, Exposing the photocurable composition for imprinting filled in and photocuring, removing the photocured product obtained by the photocuring process and releasing the mold, and the photocured product, A method including a heating step before, during, or after the releasing step is exemplified. At that time, after the step of removing and releasing the photocured product obtained by the photocuring step, the method may further include a developing step of washing and removing an uncured portion with an organic solvent before the heating step. Good. The method for producing the uncured portion is not particularly limited, but a portion that is not exposed, that is, an uncured portion can be produced by exposing only a predetermined position by mask exposure, projection exposure, or the like. Further, if necessary, the photocured product after the development step may be exposed again to be photocured.

The step of light curing by exposure can be performed by applying the conditions for obtaining the above-mentioned cured product. Further, the condition of the step of heating the photocured product is not particularly limited, but is usually appropriately selected from the range of 50 ° C. to 260 ° C. for 1 minute to 24 hours. The heating means is not particularly limited, and includes, for example, a hot plate and an oven. The molded article manufactured by such a method can be suitably used as a lens for a camera module.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. In the following Examples and Comparative Examples, devices and conditions used for sample preparation and physical property analysis are as follows.

(1) Stirring defoamer Equipment: Rotating / revolving mixer manufactured by Shinky Corporation Nawataro Naritaro (registered trademark) ARE-310
(2) UV exposure equipment: Batch type UV-LED irradiation equipment (wavelength 365 nm) manufactured by CCS Corporation
(3) Refractive index n _D , Abbe number ν _D
Equipment: Multiwavelength refractometer Abbemat MW manufactured by Anton Paar
Measurement temperature: 23 ° C
(4) Birefringence measuring device: WPA-100 manufactured by Photonic Lattice Co., Ltd.
Conditions: wavelength = 543 nm, temperature = room temperature (5) Digital microscope (evaluation of crack resistance in a developing process using an organic solvent)
Apparatus: KH-7700, MXG-2500REZ manufactured by Hi-Rox Co., Ltd.
Conditions: Reflection (dark field), Low-Range, 100 times (6) Anti-reflection layer deposition apparatus: Shinko Seiki Co., Ltd. SRV4300 series method: RF sputtering / magnetron method Condition: Target material = SiO ₂ , target・ Vertical distance between substrates = 100 mm,
Temperature = room temperature, sputtering time = 29 minutes (7) Optical microscope (observation of antireflection film)
Equipment: VHX-1000, VH-Z1000R manufactured by KEYENCE CORPORATION
Conditions: Reflection (bright field), objective 500 times (8) Lens molding Equipment: Nanoimprinter for 6 inches manufactured by Meisho Kiko Co., Ltd. Light source: High-pressure mercury lamp, i-line bandpass filter HB0365 (manufactured by Asahi Spectroscopy) Molding condition: Pressing pressure 100N, 20mW / cm ² × 300 seconds (9) Lens height measuring device: Non-contact surface texture measuring device PF-60 manufactured by Mitaka Optical Co., Ltd.

The suppliers of the compounds used in each of the Production Examples, Examples and Comparative Examples are as follows.
A-DCP: manufactured by Shin-Nakamura Chemical Co., Ltd. Product name: NK Ester A-DCP
MEK-AC-2140Z: Nissan Chemical Industry Co., Ltd. Product name: Organosilica sol MEK-AC-2140Z
FA-513AS: manufactured by Hitachi Chemical Co., Ltd. Product name: Fancryl (registered trademark) FA-513AS
FA-512AS: manufactured by Hitachi Chemical Co., Ltd. Product name: Fancryl (registered trademark) FA-512AS
SA1303P: Advanced Soft Materials Co., Ltd. Product name: Celum (registered trademark) Superpolymer SA1303P
IBA: Osaka Organic Chemical Industry Co., Ltd. Product name: IBXA
UA-4200: manufactured by Shin-Nakamura Chemical Co., Ltd. Product name: NK Oligo UA-4200
I184: trade name: Irgacure (registered trademark) 184 manufactured by BASF
I245: Product name: Irganox (registered trademark) 245 manufactured by BASF
AO-503: manufactured by ADEKA Corporation Trade name: ADK STAB (registered trademark) AO-503

[Production Example 1]
In a 500 mL eggplant flask, (e) 200 g of A-DCP as the polyfunctional (meth) acrylate compound containing no aromatic ring was weighed and dissolved in 200 g of methyl ethyl ketone (hereinafter abbreviated as MEK in the present specification). . Then, (a) MEK-AC-2140Z (silica particles having a primary particle diameter of 10 nm to 15 nm and surface-modified with (meth) acryloyloxy group) as the silica particles surface-modified with the functional group having an ethylenically unsaturated group. (MEK dispersion having a solid content of 45% by mass) was added and stirred to homogenize. Thereafter, MEK was distilled off using an evaporator under the conditions of 50 ° C. and a reduced pressure of 133.3 Pa or less, and an A-DCP dispersion of silica particles surface-modified with the functional group having an ethylenically unsaturated group (the said A surface-modified silica particle content of 50% by mass) was obtained.

[Production Example 2]
100 g of FA-513AS (b) as a monofunctional (meth) acrylate compound was weighed and dissolved in 100 g of MEK in a 500 mL eggplant flask. Then, (a) MEK-AC-2140Z (silica particles having a primary particle diameter of 10 nm to 15 nm and surface-modified with (meth) acryloyloxy group) as the silica particles surface-modified with the functional group having an ethylenically unsaturated group. , A solid dispersion (MEK dispersion having a solid content of 45% by mass) was added and stirred to homogenize. Thereafter, MEK was distilled off using an evaporator under the conditions of 50 ° C. and a degree of vacuum of 133.3 Pa or less, and the FA-513AS dispersion of silica particles surface-modified with the functional group having an ethylenically unsaturated group was prepared. A surface-modified silica particle content of 50% by mass) was obtained.

[Production Example 3]
50.0 g of UA-4200 (f) urethane (meth) acrylate compound was weighed and dissolved in 50.0 g of MEK in a 500 mL eggplant flask. Then, (a) MEK-AC-2140Z (silica particles having a primary particle diameter of 10 nm to 15 nm and surface-modified with (meth) acryloyloxy group) as the silica particles surface-modified with the functional group having an ethylenically unsaturated group. 111 g of a MEK dispersion having a solid content of 45% by mass), followed by stirring to homogenize. Thereafter, MEK was distilled off using an evaporator under the conditions of 60 ° C. and a reduced pressure of 133.3 Pa or less, and a UA-4200 dispersion of silica particles surface-modified with the functional group having an ethylenically unsaturated group (the UA-4200 dispersion liquid) was used. A surface-modified silica particle content of 50% by mass) was obtained.

[Production Example 4]
In a 500 mL eggplant-shaped flask, (e) 20.0 g of A-DCP as the polyfunctional (meth) acrylate compound having an ethylenically unsaturated group and containing no aromatic ring was weighed. Thereafter, (c) 40.0 g of SA1303P (a polyrotaxane having an acrylic group on a side chain of a cyclic molecule composed of cyclodextrin, MEK dispersion having a solid content of 50% by mass) was added as the polyrotaxane having an ethylenically unsaturated group, Stir to homogenize. Thereafter, using an evaporator, MEK was distilled off under conditions of 50 ° C. and a degree of reduced pressure of 133.3 Pa or less, and an A-DCP solution of the polyrotaxane having an ethylenically unsaturated group (containing the polyrotaxane having the ethylenically unsaturated group) was removed. 50% by mass).

[Example 1]
(A) The solid content of the A-DCP dispersion obtained in Production Example 1 as silica particles surface-modified with a functional group having an ethylenically unsaturated group, and the FA-513AS dispersion obtained in Production Example 2. Solid content, (b) FA-513AS as a monofunctional (meth) acrylate compound having an ethylenically unsaturated group, and (c) a polyrotaxane having an ethylenically unsaturated group as the polyrotaxane obtained in Production Example 4. Solid content, (d) I184 as a photoradical initiator, (e) A-DCP as an aromatic ring-free polyfunctional (meth) acrylate compound having an ethylenically unsaturated group, and (f) ethylenically unsaturated group. UA-4200 as a urethane (meth) acrylate compound, (g) I245 as a phenolic antioxidant, and (h) AO- as a sulfide antioxidant 03 were compounded in a ratio according to each following Table 1. The ratio of A-DCP shown in Table 1 below is the A-DCP component contained in the A-DCP dispersion and the A-DCP solution, and the ratio of FA-513AS is FA contained in the FA-513AS dispersion. -513AS. Thereafter, the composition was shaken at 50 ° C. for 16 hours, and the mixture was stirred and defoamed for 10 minutes using the stirring defoaming machine to prepare a photocurable composition 1 for imprint. In Table 1, “parts” represents “parts by mass”.

[Examples 2 to 5, Comparative Example 1]
In the same procedure as in Example 1, the components (a) to (h) were mixed in the proportions shown in Table 1 below to prepare photocurable compositions 2 to 6 for imprint. However, Comparative Example 1 does not use the components (b) and (c).

[Preparation of cured film]
Each of the photocurable compositions for imprinting prepared in Examples 1 to 5 and Comparative Example 1 was coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) together with a 500 μm thick silicone rubber spacer. Then, it was sandwiched between two glass substrates subjected to release treatment by drying. The sandwiched photocurable composition for imprints was exposed to UV light at 30 mW / cm ² for 200 seconds using the UV-LED irradiation device. After the cured product obtained after the exposure was peeled off from the glass substrate subjected to the release treatment, the cured product was heated on a hot plate at 100 ° C. for 10 minutes to produce a cured film having a diameter of 1 cm and a thickness of 0.5 mm.

[Evaluation of refractive index n _D and Abbe number ν _D ]
The refractive index n _D and Abbe number ν _D at a wavelength of 589 nm of the cured film produced by the above method were measured using the multi-wavelength refractometer. The results are shown in Table 2 below.

[Evaluation of crack resistance of cured film in development process using organic solvent]
An appropriate amount of each photocurable composition for imprints prepared in Examples 1 to 5 and Comparative Example 1 was coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and dried to release. It was dropped on the photomask substrate (opening 1 cm square). Thereafter, the photocurable composition for imprinting on the photomask substrate subjected to the release treatment was sandwiched by a 4-inch glass wafer (0.7 mm thickness) via a silicone rubber spacer having a thickness of 500 μm. The 4-inch glass wafer is prepared by diluting an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. to 30% by mass with propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA in the present specification). The solution thus obtained was applied and dried to perform a close contact treatment. The sandwiched photocurable composition was exposed to UV light at 115 mW / cm ² for 2.2 seconds using the UV-LED irradiation device. After the cured product obtained after the exposure is peeled from the photomask substrate subjected to the release treatment, the cured product is immersed (developed) in stirred PGMEA, and further rinsed with PGMEA to remove an unexposed portion. A 1-cm square, 0.5-mm-thick cured film was formed on the 4-inch glass wafer subjected to the adhesion treatment. The obtained cured film was observed on the side surface of the cured film with a digital microscope manufactured by Hi-Lox Co., Ltd., and the case where cracks were confirmed was evaluated as x, and the case where cracks were not observed was evaluated as ○. The results are shown in Table 2 below.

[Measurement of birefringence of cured film]
0.030 g of each of the photocurable compositions for imprints prepared in Examples 1 to 5 and Comparative Example 1 was applied by applying NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and drying. It was weighed on a glass substrate that had been subjected to a mold treatment. Thereafter, the photocurable composition for imprinting on a glass substrate subjected to the release treatment was sandwiched between quartz substrates (4 cm square, 1 mm thickness) via a 500 μm thick silicone rubber spacer. The quartz substrate is obtained by applying a solution prepared by diluting an adhesion auxiliary agent (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. to 30% by mass with PGMEA, followed by drying, followed by adhesion treatment. The sandwiched photocurable composition was exposed to UV light at 30 mW / cm ² for 200 seconds using the UV-LED irradiation device. The cured product obtained after the exposure was peeled from the glass substrate subjected to the release treatment, and then heated on a hot plate at 100 ° C. for 10 minutes. A cured film having a thickness of 5 mm and a mass of 0.030 g was produced. The phase difference in the cured film of the obtained cured film was measured by the phase difference measuring device manufactured by Photonic Lattice Co., Ltd. The phase difference that is the largest in the cured film (however, a portion approximately 1 mm from the outer peripheral portion is excluded from the analysis because a phase difference due to the cross-sectional structure occurs and is excluded from the analysis) is 0.5 mm in thickness of the cured product. And the birefringence of each cured product was calculated. When the birefringence was 2.5 × 10 ⁻⁵ or less, it was judged as ○, and when it was higher than 2.5 × 10 ⁻⁵ , it was judged as ×. The results are shown in Table 2 below.

[Formation of antireflection layer (AR layer) and evaluation of its crack resistance]
0.017 g of each of the photocurable compositions for imprints prepared in Examples 1, 2 and 4 and Comparative Example 1 was coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and dried to release. It was weighed on a glass substrate that had been subjected to a mold treatment. Thereafter, the photocurable composition for imprinting on the glass substrate subjected to the release treatment was sandwiched between quartz substrates (6 cm square, 1 mm thickness) via a 300 μm thick silicone rubber spacer. The quartz substrate is obtained by applying a solution prepared by diluting an adhesion auxiliary agent (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. to 30% by mass with PGMEA, followed by drying, followed by adhesion treatment. The sandwiched photocurable composition was exposed to UV light at 30 mW / cm ² for 200 seconds using the UV-LED irradiation device. After the cured product obtained after the exposure was peeled off from the glass substrate subjected to the release treatment, it was heated on a hot plate at 100 ° C. for 10 minutes, so that a diameter of 1 cm, a thickness of 0.3 mm, and a mass were formed on the quartz substrate. A 0.017 g cured film was produced.

On the cured film formed on the quartz substrate, a silicon oxide layer having a thickness of 200 nm was formed as an antireflection layer using the RF sputtering apparatus under the above-described film forming conditions. After observing the presence of cracks by observing the antireflection layer on the cured film by using the optical microscope manufactured by KEYENCE CORPORATION, the quartz substrate is heated on a hot plate at 175 ° C. for 2 minutes and 30 seconds to provide heat resistance. A sex test was performed. Also for the quartz substrate after the heat resistance test, the presence or absence of cracks in the antireflection layer on the cured film was observed using the optical microscope manufactured by Keyence Corporation, and the crack resistance of the antireflection layer was determined. The case where cracks were visible in the antireflection layer on the cured film was evaluated as x, and the case where neither cracks nor wrinkles were observed in the antireflection layer on the cured film was evaluated as ○. The results are shown in Table 2 below.

The cured film prepared from the photocurable composition for imprints of Comparative Example 1, which does not contain the component (b) and the component (c), has a crack on the side surface of the cured film after the development step using an organic solvent. At the same time, the birefringence of the cured product was also high. From the above results, the cured film obtained from the photocurable composition for imprints of the present invention exhibited a high Abbe number, a high refractive index, and a low birefringence, and the antireflection layer as the upper layer of the cured film was 175. No cracks or wrinkles were generated by the heat treatment at ° C, and no cracks were generated in the cured film even when exposed to an organic solvent, indicating that the lens has desirable characteristics as a lens for a high-resolution camera module.

[Production of lens]
Each of the photocurable compositions for imprinting prepared in Examples 1, 2 and 4 was used as a nickel mold (a lens mold having a diameter of 2 mm × 300 μm and a total of 15 lenses of 3 rows × 5 rows). Using a nanoimprinter and a nanoimprinter, a lens was formed on a quartz substrate as a support in accordance with the above-described method for manufacturing a formed body. The mold used was previously subjected to a release treatment with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Ltd.). Further, the glass substrate used was subjected to close contact treatment by applying a solution prepared by diluting an adhesion auxiliary agent (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. to 30% by mass with PGMEA, followed by drying. After removing the cured product from the mold, the cured product was heated on a hot plate at 100 ° C. for 10 minutes to produce a convex lens on the glass substrate subjected to the close contact treatment.

With respect to the convex lens obtained on the glass substrate, the lens height (thickness) before and after the heating test is measured by the non-contact surface texture measuring device, and the rate of change is expressed by the following formula “[(lens height before heating−heating) Height after heating / lens height before heating] × 100 ″, and dimensional stability due to heating was evaluated. Further, the presence or absence of cracks in the convex lens after the heating test was observed with a microscope attached to the non-contact surface texture measuring device. Note that the heating test is a test in which a convex lens obtained on a glass substrate is heated on a hot plate at 175 ° C. for 2 minutes and 30 seconds, and then allowed to cool to room temperature (about 23 ° C.). The results are shown in Table 3 below.

As shown in Table 3, the convex lens obtained from the photocurable composition for imprints of the present invention showed a small change in the lens height even after a heat history of 175 ° C. for 2 minutes and 30 seconds (rate of change of 0.1 mm). (Less than 30%), resulting in high dimensional stability.

Claims (12)

A photocurable composition for imprints comprising the following component (a), the following component (b), the following component (c), and the following component (d), wherein the ethylenically unsaturated group contained in the composition is The component (a) is 10 parts by mass to 40 parts by mass, the component (b) is 10 parts by mass to 50 parts by mass, and the component (c) is 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the total compound. Parts of the photocurable composition for imprints, wherein the component (d) is 0.1 to 5 parts by mass.
(A): Silica particles having a primary particle diameter of 1 nm to 100 nm and surface-modified with a functional group having an ethylenically unsaturated group (b): Monofunctional (meth) acrylate compound having an ethylenically unsaturated group (c) : Polyrotaxane having an ethylenically unsaturated group (d): Photo-radical initiator The composition further contains 5 to 50 parts by mass of the following component (e) and / or the following component (f) based on 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. 2. The photocurable composition for imprint according to 1.
(E): a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group and containing no aromatic ring (provided that the component (c) is a polyrotaxane and the component (f) is a urethane (meth) acrylate compound or epoxy (meth) ) Excluding acrylate compounds.)
(F): a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound having an ethylenically unsaturated group (excluding the polyrotaxane of the component (c)) Furthermore, 0.05 to 3 parts by mass of the following component (g) and / or the ethylenically unsaturated compound contained in the composition may be 0.05 to 3 parts by mass based on 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. The photocurable composition for imprints according to claim 1 or 2, comprising 0.1 to 3 parts by mass of the following component (h) based on 100 parts by mass of the total of the compound having a saturated group.
(G): phenolic antioxidant (h): sulfide antioxidant 4. The silica particle according to claim 1, wherein the component (a) is a silica particle surface-modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group. 5. A photocurable composition for imprints. The polyfunctional (meth) acrylate compound containing no aromatic ring of the component (e) is composed of two or more compounds, and at least one of the two or more compounds has an alicyclic hydrocarbon group. The photocurable composition for imprints according to claim 2. 4. The photocurable composition for imprints, wherein the cured product has a refractive index n _{D at} a wavelength of 589 nm of 1.49 or more, and the cured product has an Abbe number ν _D of 53 or more. Item 6. The photocurable composition for imprints according to any one of items 5. A cured product of the photocurable composition for imprints according to claim 6. A method for producing a resin lens, comprising a step of imprint-molding the photocurable composition for imprint according to any one of claims 1 to 6. A method for producing a molded article of the photocurable composition for imprints, wherein the photocurable composition for imprints according to any one of claims 1 to 6, wherein the support and the mold are in contact with each other. Filling the space between the molds or the space inside the dividable mold, and exposing the photocurable composition for imprints filled in the space to photocuring, comprising the steps of: . After the photocuring step, the step of taking out the obtained photocured product and releasing the mold, and further comprising a step of heating the photocured product before, during or after the releasing step, Item 10. The method for producing a molded article according to Item 9. The method for producing a molded article according to claim 10, further comprising a development step using an organic solvent after the releasing step and before the heating step. The method for manufacturing a molded article according to any one of claims 9 to 11, wherein the molded article is a lens for a camera module.