CN111801770A - Photocurable composition for imprint containing polymer - Google Patents

Abstract

An object of the present invention is to provide a novel photocurable composition for imprint containing a polymer. The solution is a photocurable composition for imprint, which contains the following (a) component, the following (b) component, the following (c) component, the following (d) component, and the following (e) component . (a): Surface-modified silica particles having a primary particle diameter of 1 nm to 100 nm, (b): Alicyclic (meth)acrylic acid having at least one (meth)acryloyloxy group in one molecule Ester monomer, (c): urethane (meth)acrylate compound or epoxy (meth)acrylate compound, (d): having a repeating structural unit represented by the following formula (1) and the following The polymer of the repeating structural unit represented by the formula (2), (e): a photoradical initiator (in the formula, R ¹ and R ² each independently represent a methyl group or a hydrogen atom, and A ¹ represents a carbon number of 1 to 1 The alkyl group of 8, A ² represents a single bond or an alkylene group having 1 to 4 carbon atoms, X represents a polymerizable group having one or more (meth)acryloyloxy groups, and Z ¹ represents a divalent group group.)

Description

Photocurable composition for imprint containing polymer

technical field

The present invention relates to a surface-modified silica particle comprising an alicyclic (meth)acrylate monomer, a urethane (meth)acrylate compound or an epoxy (meth)acrylate compound, having free A photocurable composition for imprinting of a polymer based on a polymerizable group and a photoradical initiator. More specifically, since it is excellent in optical properties (transparency, high refractive index, high Abbe number), the anti-reflection layer (AR layer) is formed on the upper layer of the cured product and the molded body, and the anti-reflection layer is thermally treated. A photocurable composition which does not generate cracks and further does not generate cracks in the cured product even after washing with an organic solvent or development.

Background technique

Resin lenses are used in electronic devices such as cellular phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical properties according to the purpose of the electronic devices. In addition, depending on the form of use, high durability such as heat resistance and weather resistance, and high productivity that can be molded with good yield are required. As a material for resin lenses that satisfies such requirements, thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacrylic resins are used, for example.

In addition, a high-resolution camera module uses a plurality of lenses, but mainly uses a lens with a low wavelength dispersion, that is, a high Abbe number, and requires an optical material for forming the lens. Furthermore, in the manufacture of resin lenses, in order to improve the yield and production efficiency, and to further suppress the optical axis shift during lens lamination, research has been actively conducted from the injection molding of thermoplastic resins to the use of curing properties that are liquid at room temperature. The transformation of wafer-level molding by resin extrusion molding. Wafer-level molding is generally a hybrid lens method in which a lens is formed on a support such as a glass substrate from the viewpoint of productivity.

As a photocurable resin capable of wafer-level molding, a radically curable resin composition has been conventionally used from the viewpoints of high transparency, thermal yellowing resistance, and releasability from a mold (Patent Document 1). In addition, it is known that a cured product having a high Abbe number can be obtained by containing oxide particles surface-modified, such as silica particles surface-modified with a silane compound, zirconia particles surface-modified with a dispersant, or the like. Curable composition (for example, Patent Document 2 and Patent Document 3).

prior art literature

Patent Literature

Patent Document 1: Japanese Patent No. 5281710 (International Publication No. 2011/105473)

Patent Document 2: Japanese Patent Laid-Open No. 2014-234458

Patent Document 3: International Publication No. 2016/104039

SUMMARY OF THE INVENTION

The problem to be solved by the invention

When the molded body is a lens, an antireflection layer made of an inorganic substance such as silicon oxide or titanium oxide is formed on the upper layer. Therefore, there is a problem that cracks are generated in the anti-reflection layer due to the heat treatment of the lens covered with the anti-reflection layer. In addition, about the curable composition containing the oxide particles that have been surface-modified as described above, a development step in which 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 is washed with an organic solvent Among them, there is a problem that the above-mentioned wafer-shaped molded body is significantly eroded by the organic solvent, and cracks are generated in the wafer-shaped molded body.

A molded body that has a high Abbe number (eg, 53 or more) and high transparency and can be used as a lens for a high-resolution camera module can be obtained. Cracks have occurred, and further, in the development process of cleaning the uncured portion such as the outer peripheral portion of the wafer-shaped molded body with an organic solvent, there is still no curable resin material that does not cause cracks in the wafer-shaped molded body, and development of such a material is desired. . The present invention has been made in view of such circumstances, and an object of the present invention is to provide a photocurable composition capable of forming a molded body exhibiting a high Abbe number, a high refractive index, high transparency, and thermal yellowing resistance, and which can A high crack-resistant molded body having an antireflection layer on the molded body is formed so that cracks are not generated by subjecting the molded body to heat treatment, and no cracks are generated even when exposed to a development process.

means of solving problems

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that the surface-modified silica particles and the polymer having a radically polymerizable group are each blended in a predetermined ratio in a photocurable composition. , so that the molded body obtained from the photocurable composition has a high refractive index n _D (1.50 or more) and a high Abbe number ν _D (53 or more), exhibits a high transmittance of 90% or more at a wavelength of 410 nm, and is The antireflection layer of the upper layer of the molded body was heat-treated at 175° C. without cracks and wrinkles, and further, cracks were not generated in the development process using an organic solvent, and the present invention was completed.

That is, the first aspect of the present invention is a photocurable composition for imprint comprising the following (a) component, the following (b) component, the following (c) component, the following (d) component and the following The component (e), wherein the component (a) is 10 to 40 parts by mass relative to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d) parts by mass, the component (b) is 10 to 50 parts by mass, the component (c) is 10 to 50 parts by mass, the component (d) is 1 to 10 parts by mass, and the (e) A component is 0.1 mass part - 5 mass parts.

(a) Component: Surface-modified silica particles having a primary particle diameter of 1 nm to 100 nm

(b) Component: Alicyclic (meth)acrylate monomer having at least one (meth)acryloyloxy group in 1 molecule (The compound as the (c) component is not included.)

(c) Component: urethane (meth)acrylate compound or epoxy (meth)acrylate compound (but does not include the polymer as the (d) component.)

(d) Component: a polymer having a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2)

(e) Component: photoradical initiator

(in the formula, R ¹ and R ² each independently represent a methyl group or a hydrogen atom, A ¹ represents an alkyl group having 1 to 8 carbon atoms, A ² represents a single bond or an alkylene group having 1 to 4 carbon atoms, X represents a polymerizable group having one or more (meth)acryloyloxy groups, and Z ¹ represents a divalent group represented by the following formula (a1), formula (a2), formula (a3) or formula (a4) group.)

The photocurable composition for imprint of the present invention may further contain 1 to 15 parts by mass relative to 100 parts by mass of the sum of the above-mentioned (a) component, the above-mentioned (b) component, the above-mentioned (c) component and the above-mentioned (d) component. The following (f) component of a mass part.

(f) Component: a polyfunctional thiol compound represented by the following formula (3)

(In the formula, A ³ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, and Z ² represents a single bond, an ester bond "-C(=O)O-" or an ether bond "-O-", Q represents an organic group containing 2 to 12 carbon atoms or a hetero atom containing at least one heteroatom or no heteroatom, and r represents an integer of 2 to 6.)

Here, a hetero atom means an atom other than a carbon atom and a hydrogen atom, for example, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned.

The photocurable composition for imprint of the present invention may further contain 0.05 parts by mass to 100 parts by mass of the sum of the above-mentioned (a) component, the above-mentioned (b) component, the above-mentioned (c) component and the above-mentioned (d) component. 3 parts by mass of the following (g) component; and/or 0.1 to 3 parts by mass relative to 100 parts by mass of the sum of the above-mentioned (a) component, the above-mentioned (b) component, the above-mentioned (c) component and the above-mentioned (d) component The following (h) component in parts by mass.

(g) Component: Phenolic antioxidant

(h) Component: thioether-based antioxidant

Surface-modified silica particles having a primary particle diameter of 1 nm to 100 nm as the component (a) are surface-modified, for example, with (meth)acryloyloxy groups bonded to silicon atoms via a divalent linking group. Modified silica 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 urethane (meth)acrylate compound or the epoxy (meth)acrylate compound as the component (c) is a compound having, for example, two or three (meth)acryloyloxy groups in one molecule.

The polymer as the component (d) may further have a repeating structural unit represented by the following formula (4).

(In the formula, R ³ represents a methyl group or a hydrogen atom, Z ³ represents a single bond or an ethyleneoxy group, and A ⁴ represents an alicyclic hydrocarbon group having 5 to 13 carbon atoms.)

When the above-mentioned Z ³ represents an ethyleneoxy group (-CH ₂ CH ₂ O- group), the O atom of the ethyleneoxy group is bonded to A ⁴ which represents the above-mentioned alicyclic hydrocarbon group.

The above-mentioned alicyclic hydrocarbon group having 5 to 13 carbon atoms is, for example, cyclopentyl, cyclohexyl, isobornyl, tricyclo[5.2.1.02,6]dec-8-yl, tricyclodecenyl, or may have carbon An adamantyl group in which an alkyl group having 1 to 3 atoms is a substituent.

The polymerizable group having one or more (meth)acryloyloxy groups is, for example, the following formula (X0), formula (X1), formula (X2), formula (X3), formula (X4), formula (X5) or a group represented by the formula (X6), or a group obtained by substituting a part or all of the acryloyloxy groups contained in these groups with methacryloyloxy groups.

The cured product of the photocurable composition for imprint of the present invention has a refractive index n _D at a wavelength of 589 nm of 1.50 or more, and the cured product has an Abbe number ν _D of 53 or more. Both the refractive index n _D and the Abbe number ν _D are preferably as high as possible. For example, the refractive index n _D may be in the range of 1.50 or more and 1.55 or less, and the Abbe number ν _D may be 53 or more and 60. The following range is sufficient.

A second aspect of the present invention is a cured product of the above-mentioned photocurable composition for imprint.

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

A fourth aspect of the present invention is a method for producing a molded body, which is a method for producing a molded body of a photocurable composition for imprint, comprising the step of filling each other with the photocurable composition for imprint A step of filling the space between the contacting support and the casting mold, or the inner space of the detachable casting mold; and a photocuring step of exposing and photocuring the photocurable composition for imprint filled in the space. The above-mentioned casting mold is also called a model.

The method for producing a molded body of the present invention may further include steps of: after the above-mentioned photocuring step, a mold release step of taking out the obtained photocured product; and the photocured product before and during the mold release step Or a heating step of heating after that. After the mold release step and before the heating step, a development step of washing the uncured portion with an organic solvent may be further included. The photocured material after the above-mentioned development step may be exposed to light again and photocured.

In the manufacturing method of the molded object of this invention, this molded object is, for example, the lens for camera modules.

effect of invention

The photocurable composition for imprint of the present invention contains the above-mentioned (a) component to the above-mentioned (e) component, further optionally the above-mentioned (f) component, and the above-mentioned (g) component and/or the above-mentioned (h) component, Therefore, cured products and molded bodies obtained from the photocurable composition exhibit optical properties desired as lenses for optical devices such as high-resolution camera modules, ie, high Abbe number, high refractive index, high transparency, and resistance to Thermal yellowing. In addition, with regard to the cured product and the molded body obtained from the photocurable composition of the present invention, the antireflection layer on the upper layer of the cured product and the molded body did not generate cracks or wrinkles by heat treatment at 175° C. No cracks were generated in the development process of the solvent.

Detailed ways

[Component (a): Surface-modified silica particles]

The primary particle diameter of the surface-modified silica particle that can be used as the component (a) of the photocurable composition for imprint of the present invention is 1 nm to 100 nm. Here, the primary particles are particles constituting the powder, and the particles obtained by aggregating the primary particles are referred to as secondary particles. The above-mentioned primary particle size can be determined by the specific surface area (surface area per unit mass) S of the above-mentioned surface-modified silica particles measured by a gas adsorption method (BET method), and the surface-modified silica particles. The relational expression established between the density ρ and the primary particle diameter D: D=6/(ρS) was calculated. The primary particle diameter calculated from this relational expression is the average particle diameter, which is the diameter of the primary particle. In addition, the above-mentioned surface-modified silica particles are surface-modified with, for example, a (meth)acryloyloxy group bonded to a silicon atom via a divalent linking group. When the above-mentioned surface-modified silica particles are used, the surface-modified silica particles may be used as they are, or the surface-modified silica particles may be pre-dispersed in an organic dispersion medium. A substance in a colloidal state obtained by a solvent (a sol in which colloidal particles are dispersed in a dispersion medium). When a sol containing the surface-modified silica particles is used, a sol having a solid content concentration in the range of 10% by mass to 60% by mass can be used.

As the sol containing the surface-modified silica particles, for example, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK can be used -AC-2140Z, MIBK-SD-L (above, manufactured by Nissan Chemical Co., Ltd.), and ELCOM (registered trademark) V-8802, ELCOM V-8804 (above, manufactured by Nissan Chemical Co., Ltd.).

The content of the component (a) in the photocurable composition for imprint of the present invention is based on the content of the component (a), the component (b) described later, the component (c) described later, and the component (d) described later. and 100 parts by mass are 10 parts by mass to 40 parts by mass, 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 antireflection layer formed on the upper layer of the cured product and molded body obtained from the photocurable composition for imprint may not be suppressed. When the content of the component (a) exceeds 40 parts by mass, haze may occur in the cured product and the molded body, and the transmittance may decrease.

The surface-modified silica particles as the component (a) may be used alone or in combination of two or more.

[Component (b): Alicyclic (meth)acrylate monomer]

The alicyclic (meth)acrylate monomer that can be used as the component (b) of the photocurable composition for imprint of the present invention has at least one, for example, one or two (methyl) in one molecule of the monomer. group) acryloyloxy group, and one alicyclic hydrocarbon, and does not include the monomer compound which is the compound of (c) component mentioned later. Examples of the alicyclic (meth)acrylate monomer include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and 3,3,5-trimethyl (meth)acrylate. Cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, menthyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, (meth)acrylate 1-adamantyl acrylate, 2-adamantyl (meth)acrylate, 2-methyladamantan-2-yl (meth)acrylate, 2-ethyladamantane-2 (meth)acrylate - ester, tricyclo[5.2.1.0(2,6)]decyl (meth)acrylate, tricyclo[5.2.1.0(2,6)]decyloxyethyl (meth)acrylate, 1 ,4-cyclohexanedimethanol di(meth)acrylate, tricyclo[5.2.1.0(2,6)]decanedimethanol di(meth)acrylate, and 1,3-adamantanediol di(meth)acrylate (Meth)acrylate.

As the above-mentioned alicyclic (meth)acrylate monomer, commercially available products can be used, and examples thereof include ビスコート#155, IBXA, ADMA (the above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and NK エステルA-IB. , NK ESTER IB, NK ESTER A-DCP, NK ESTER DCP (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and FA-511AS (registered trademark), FA-512AS, FA-513AS, FA-512M, FA-512MT, FA-513M (above, manufactured by Hitachi Chemical Co., Ltd.).

The content of the component (b) in the photocurable composition for imprint of the present invention is 100 with respect to the sum of the component (a), the component (b), the component (c) described later, and the component (d) described later. The mass part is 10 parts by mass to 50 parts by mass, preferably 20 parts by mass to 45 parts by mass. If the content of the component (b) is less than 10 parts by mass, the refractive index of the cured product and molded body obtained from the photocurable composition for imprint may be reduced to less than 1.50. If the content of the component (b) is more than 50 parts by mass, the amount of warpage of the support on which the cured product and the molded body are formed may increase.

The alicyclic (meth)acrylate monomer which is the said (b) component can be used individually by 1 type or in combination of 2 or more types.

[Component (c): urethane (meth)acrylate compound or epoxy (meth)acrylate compound]

The urethane (meth)acrylate compound that can be used as the component (c) of the photocurable composition for imprint of the present invention has at least two (meth)acryloyloxy groups and at least two (meth)acryloyloxy groups in one molecule. A urethane structure represented by "-NH-C(=O)O-", and the compound which is a polymer of the component (d) described later is not included. Examples of the urethane (meth)acrylate compound include EBECRYL (registered trademark) 230, EBECRYL 270, EBECRYL 280/15IB, EBECRYL 284, EBECRYL 4491, EBECRYL 4683, EBECRYL 4858, EBECRYL 8307, EBECRYL 8402 、EBECRYL 8411、EBECRYL 8804、EBECRYL 8807、EBECRYL 9270、EBECRYL 8800、EBECRYL294/25HD、EBECRYL 4100、EBECRYL 4220、EBECRYL 4513、EBECRYL 4738、EBECRYL4740、EBECRYL 4820、EBECRYL 8311、EBECRYL 8465、EBECRYL 9260、EBECRYL 8701、KRM7735 , KRM8667, KRM 8296 (above, manufactured by ダイセル オルネクス Co., Ltd.), UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500B, UV -3520EA, UV-3700B, UV-6640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE (above, manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G (above, manufactured by Kyoeisha Chemical Co., Ltd.), M-1100, M-1200 (above, manufactured by Toagosei Co., Ltd.), and NK Origo U-2PPA, NK Origo U-6LPA , NKオリゴU-200PA, U-200PA, NKオリゴU-160TM, NKオリゴU-290TM, NKオリゴUA-4200, NKオリゴUA-4400, NKオリゴUA-122P, NKオリゴUA-7100, NKオリゴUA -W2A (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

The epoxy (meth)acrylate compound that can be used as the component (c) of the photocurable composition for imprint of the present invention is a compound having at least two epoxy rings in one molecule and (meth)acrylic acid reacted The obtained ester does not include the compound which is the polymer of (d) component mentioned later. As the epoxy (meth)acrylate compound, for example, EBECRYL (registered trademark) 645, EBECRYL 648, EBECRYL 860, EBECRYL 3500, EBECRYL 3608, EBECRYL 3702, and EBECRYL 3708 (above, ダイセルオルネクス Co., Ltd.) can be mentioned. made), DA-911M, DA-920, DA-931, DA-314, DA-212 (above, manufactured by Nagetsu Co., Ltd.), HPEA-100 (manufactured by ケーエスエム Co., Ltd.), and UNITED (registered) Trademarks) V-5500, Unitec V-5502, Unitec V-5508 (above, manufactured by DIC Co., Ltd.).

As the urethane (meth)acrylate compound or epoxy (meth)acrylate compound of the component (c), it is preferable to use the compound having two or three (meth)acryloyloxy groups in one molecule. compound of.

The content of the component (c) in the photocurable composition for imprint of the present invention is based on 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d) described later. , (c) component is 10 mass parts - 50 mass parts, Preferably it is 30 mass parts - 50 mass parts. If the content of the component (c) is less than 10 parts by mass, the cured product and the molded body obtained from the photocurable composition for imprint become brittle, and the crack resistance of the cured product and the molded body at the time of heating may become brittle. reduce. If the content of the component (b) is more than 50 parts by mass, there is a possibility that the change in shape of the cured product and the molded product during heating may increase due to a decrease in crosslinking density.

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

[(d) Component: Polymer]

The polymer that can be used as the component (d) of the photocurable composition for imprint of the present invention is a copolymer containing a polymerizable group, and has at least the repeating structural unit represented by the above formula (1) and the above formula (2) The repeating structural unit shown may further have the repeating structural unit shown by the above formula (4).

As a repeating structural unit represented by the said formula (1), the repeating structural unit represented by following formula (1-1) - formula (1-6) is mentioned, for example.

As a repeating structural unit represented by the said formula (2), the repeating structural unit represented by following formula (2-1) - formula (2-44) is mentioned, for example.

As a repeating structural unit represented by the said formula (4), the repeating structural unit represented by following formula (4-1) - formula (4-22) is mentioned, for example.

Examples of the polymer of the component (d) include Hiroid (registered trademark) 7975, Hiroid 7975D, Hiroid 7988 (above, manufactured by Hitachi Chemical Co., Ltd.), RP-274S, and RP-310 (above, ケーエスエム (above). Co., Ltd.), アートキュア (registered trademark) RA-3602MI, アートキュアOPA-5000, アートキュアOPA-2511, アートキュア RA-341 (above, Negami Kogyo Co., Ltd.).

The content of the component (d) in the photocurable composition for imprint of the present invention is 1 with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d). Parts by mass to 10 parts by mass, preferably 3 parts by mass to 7 parts by mass. If the content of the component (d) is less than 1 part by mass, the effect of suppressing the occurrence of cracks in the cured product in the development step using a solvent becomes insufficient. If the content of the component (d) is more than 10 parts by mass, the viscosity of the photocurable composition for imprint will be greatly increased, and thus workability will be significantly reduced.

The polymer as the said (d) component can be used individually by 1 type or in combination of 2 or more types.

[Component (e): Photoradical Initiator]

Examples of the photoradical initiator that can be used as the component (e) of the photocurable composition for imprint of the present invention include alkylphenones, benzophenones, and Michler's ketones. , acyl phosphine oxides, benzoyl benzoates, oxime esters, tetramethylthiuram monosulfide and thioxanthones, particularly preferably photolysis-type photoradical polymerization initiators. As the above-mentioned photoradical initiator, commercially available products such as IRGACURE (registered trademark) 184, IRGACURE 369, IRGACURE 651, IRGACURE 500, IRGACURE 819, IRGACURE 907, IRGACURE 784, IRGACURE 2959, IRGACURE CGI1700, IRGACURE CGI1750, IRGACURE CGI1850 can be used , IRGACURE CG24-61, IRGACURE TPO, IRGACURE 1116, IRGACURE 1173 (above, manufactured by BASF Japan Co., Ltd.), and ESACURE KIP150, ESACURE KIP65LT, ESACURE KIP100F, ESACURE KT37, ESACURE KT55, ESACURE KTO46, ESACURE KIP75 (above, Lamberti) system).

The content of the component (e) in the photocurable composition for imprint of the present invention is 0.1 with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d) above. Parts by mass to 5 parts by mass, preferably 0.5 parts by mass to 3 parts by mass. If the content of the component (e) is less than 0.1 part by mass, the strength of the cured product and molded body obtained from the photocurable composition for imprint may be reduced. If the content of the component (e) is more than 5 parts by mass, there is a possibility that the heat-resistant yellowing of the cured product and the molded body may deteriorate.

The photoradical initiator which is the said (e) component can be used individually by 1 type or in combination of 2 or more types.

[Component (f): Polyfunctional thiol compound]

The polyfunctional thiol compound that can be used as the component (f) of the photocurable composition for imprint of the present invention is the polyfunctional thiol compound represented by the above formula (3). As the polyfunctional thiol compound represented by the formula (3), for example, 1,2-ethanedithiol, 1,3-propanedithiol, bis(2-mercaptoethyl)ether, trihydroxyl Methylpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), bis(3-mercaptopropionate) Pentaerythritol hexa(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercapto) Butyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), and Trimethylolethane tris(3-mercaptobutyrate), pentaerythritol tris(3-mercaptopropyl) ether. As the polyfunctional thiol compound represented by the above-mentioned formula (3), commercially available products can be used, for example, KARANZ MT (registered trademark) PE1, KARANZ NR1, KARANZBD1, TPMB, TEMB (the above, manufactured by Showa Denko Co., Ltd.) , and TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (above, manufactured by SC Organic Chemical Co., Ltd.).

When the photocurable composition for imprint of the present invention contains the component (f), the content thereof is based on the sum of the component (a), the component (b), the component (c), and the component (d) above. 100 parts by mass is 1 part by mass to 15 parts by mass, preferably 3 parts by mass to 10 parts by mass. If the content of the component (f) is more than 15 parts by mass, the mechanical properties of the cured product and the molded body obtained from the photocurable composition for imprint are deteriorated, so the cured product and the molded body may deteriorate in the mounting process accompanied by heat treatment. The molded body is deformed.

The polyfunctional thiol compound which is the said (f) component can be used individually by 1 type or in combination of 2 or more types.

[(g) Ingredient: Phenolic antioxidant]

Examples of phenolic antioxidants that can be used as the component (g) of the photocurable composition for imprint of the present invention include IRGANOX (registered trademark) 245, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, and IRGANOX 1135 ( The above, BASF ジャパン Co., Ltd.), SUMILIZER (registered trademark) GA-80, SUMILIZER GP, SUMILIZER MDP-S, SUMILIZER BBM-S, SUMILIZER WX-R (the above, manufactured by Sumitomo Chemical Co., Ltd.), and アデカスタブ ( Registered trademarks) AO-20, Adecus AO-30, Adecus AO-40, Adecus AO-50, Adecus AO-60, Adecus AO-80, Adeka AO-330 (above).

When the photocurable composition for imprint of the present invention contains the component (g), its content is based on the sum of the component (a), the component (b), the component (c), and the component (d) above. 100 parts by mass is 0.05 parts by mass to 3 parts by mass, preferably 0.1 part by mass to 1 part by mass.

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

[(h) Component: thioether-based antioxidant]

As the thioether-based antioxidant that can be used as the component (h) of the photocurable composition for imprint of the present invention, for example, アデカスタブ (registered trademark) AO-412S, アデカスタブ AO-503 (above, Co., Ltd. ) ADEKA), IRGANOX (registered trademark) PS802, IRGANOX PS800 (above, manufactured by BASF Corporation), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).

When the photocurable composition for imprint of the present invention contains the component (h), the content thereof is based on the sum of the component (a), the component (b), the component (c), and the component (d) above. 100 parts by mass is 0.1 part by mass to 3 parts by mass, preferably 0.1 part by mass to 1 part by mass.

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

<Preparation method of photocurable composition for imprint>

The preparation method of the photocurable composition for imprint of this invention is not specifically limited. As a preparation method, for example, (a) component, (b) component, (c) component, (d) component and (e) component, and if necessary (f) component, (g) component and/or Or (h) a method of mixing the components in a predetermined ratio to prepare a homogeneous solution.

In addition, the photocurable composition for imprint of the present invention prepared as a solution is preferably used after filtering using a filter or the like having a pore diameter of 0.1 μm to 5 μm.

<Cured product>

The photocurable composition for imprint of the present invention can be exposed to light (photocured) to obtain a cured product, and this cured product is also targeted in the present invention. As light rays for exposure, for example, ultraviolet rays, electron rays, and X rays are mentioned. As the light source used for ultraviolet irradiation, for example, solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used. Furthermore, after exposure, in order to stabilize the physical properties of the cured product, post-baking may be performed. Although it does not specifically limit as the method of post-baking, Usually, it uses a hotplate, an oven, etc., and it performs in the range of 50 degreeC - 260 degreeC, and 1 minute - 24 hours.

The cured product obtained by photocuring the photocurable composition for imprint of the present invention is a cured product having an Abbe number ν _D of 53 or more, and a refractive index n _D at a wavelength of 589 nm (D line) of 1.50 or more, In addition, no yellowing caused by heating was observed. Therefore, the photocurable composition for imprint of the present invention can be suitably used for forming a resin lens.

＜Molded body＞

By using the photocurable composition for imprint of the present invention, for example, by using an imprint molding method, various molded articles can be easily produced simultaneously with the formation of a cured product. As a method of producing a molded body, for example, a method including a step of filling the space between the support and the mold in contact with the photocurable composition for imprint of the present invention, or a separable mold can be mentioned. The filling process of the inner space of the ; the photocuring process of exposing the photocurable composition for imprint filled in the space to light and curing it; the mold release process of taking out the photocured product obtained by the photocuring process; A heating step of heating the photocured material before, during, or after the mold release step. In this case, after the mold release step of taking out the photocured product obtained by the photocuring step, a development step of washing/removing the uncured portion with an organic solvent may be further included before the heating step. Although there is no restriction|limiting in particular as a method of producing the said uncured part, It is possible to produce an unexposed part, ie, an uncured part, by exposing only predetermined positions by mask exposure, projection exposure, or the like. Furthermore, as needed, the photocured material after the said image development process may be exposed again and photocured may be performed.

The photocuring process of the said exposure and photocuring can be implemented by applying the conditions for obtaining the said hardened|cured material. Furthermore, it does not specifically limit as conditions of the heating process which heats the said photocured material, Usually, it selects suitably from the range of 50 degreeC - 260 degreeC and 1 minute - 24 hours. Moreover, it does not specifically limit as a heating method, For example, a hot plate and an oven are mentioned. The molded body manufactured by such a method can be used suitably as a lens for camera modules.

Example

Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, in the following Examples and Comparative Examples, the apparatuses and conditions used for the preparation of the samples and the analysis of the physical properties are as follows.

(1) Gel permeation chromatography (GPC)

Equipment: GPC system manufactured by Shimadzu Corporation

Column: Showa Denko Co., Ltd. Shodex (registered trademark) GPC KF-804L, GPC KF-803L

Column temperature: 40℃

Solvent: Tetrahydrofuran

Standard sample: polystyrene

(2) Stirring and defoaming machine

Device: Rotation/revolution mixer あわとり Rentaro (registered trademark) ARE-310 manufactured by Shinki Co., Ltd.

(3) UV exposure

Apparatus: Intermittent UV irradiation apparatus (high-pressure mercury lamp 2kW x 1 lamp) manufactured by Aigurafex Co., Ltd.

(4) Transmittance

Device: UV-Vis-NIR Spectrophotometer V-670 manufactured by Nippon Spectrophotometer Co., Ltd.

Reference: Air

(5) Refractive index n _D , Abbe number ν _D

Device: Abbemat MW, a multi-wavelength refractometer manufactured by ANTONPARU

Measurement temperature: 23℃

(6) Optical microscope (evaluation of crack resistance in the development process using an organic solvent)

Device: MX61A, DP72, BX-UCB manufactured by Orinpas Co., Ltd.

Conditions: Reflection (bright field), objective 5x

(7) Film formation of antireflection layer

Device: RF Sputtering Device SRS-700T/LL manufactured by Sanyu Electronics Co., Ltd.

Method: RF sputtering / magnetron method

Conditions: target = silicon, RF power = 250W,

Vertical distance between target/substrate = 100mm, offset = 100mm,

Ar flow = 45sccm, O flow = _2sccm ,

Temperature = room temperature, sputtering time = 15 minutes

(8) Optical microscope (observation of anti-reflection film)

Device: VHX-1000, VH-Z1000R, manufactured by KENSU Co., Ltd.

Conditions: Reflection (bright field), objective 500x

(9) Lens molding

Device: 6-inch compatible nanoprinter manufactured by Myungchang Machinery Co., Ltd.

Light source: high pressure mercury lamp, exposed through i-ray bandpass filter HB0365 (manufactured by Asahi Corporation)

Molding conditions: Pressing pressure 100N, 20mW/ ^cm2 × 300 seconds

(10) Measurement of lens height

Device: Non-contact surface property measuring device PF-60 manufactured by Mitaka Koki Co., Ltd.

The supply sources of the compounds used in the production examples, examples, and comparative examples are as follows.

A-DCP: Shin-Nakamura Chemical Industry Co., Ltd. product name: NK エステル A-DCP

MEK-AC-2140Z: Nissan Chemical Co., Ltd. Brand name: オルガノシリカゾルMEK-AC-2140Z

AOI: Showa Denko Co., Ltd. product name: Karenza AOI (registered trademark)

BEI: Showa Denko Co., Ltd. Brand name: Karenza BEI (registered trademark)

FA-513AS: Hitachi Chemical Co., Ltd. trade name: Fagan (registered trademark) FA-513AS

UA-4200: Shin-Nakamura Chemical Industry Co., Ltd. product name: NK オリゴUA-4200

DA-212: ナガセケムテックス Co., Ltd. product name: デナコールアクレートDA-212

NR1: Showa Denko Co., Ltd. product name: KARANZ (registered trademark) MT NR1

I184: BASF ジャパン Co., Ltd. product name: Irgacure (registered trademark) 184

I245: BASF ジャパン Co., Ltd. Brand name: Irganox (registered trademark) 245

AO-503: manufactured by ADEKA Co., Ltd. Trade name: Adekas タブ (registered trademark) AO-503

[Production Example 1]

In a 500 mL eggplant-shaped flask, 120 g of A-DCP, which is (b) the alicyclic (meth)acrylate monomer, was weighed, and the measurement was carried out with 120 g of methyl ethyl ketone (hereinafter, abbreviated as MEK in this specification). dissolved. Next, as (a) the above-mentioned surface-modified silica particles, MEK-AC-2140Z (silica particles with a primary particle diameter of 10 nm to 15 nm, surface-modified with a (meth)acryloyloxy group) were added. Solid content 46 mass % MEK dispersion liquid) 260.3g, it stirred and homogenized. Then, MEK was distilled off under the conditions of 50° C. and a reduced pressure of 133.3 Pa or less using an evaporator to obtain the A-DCP dispersion liquid of the above-mentioned surface-modified silica particles (the surface-modified silica particles). Silica particle content 50% by mass).

[Manufacturing example 2]

In a 500 mL eggplant-shaped flask, 112.5 g of A-DCP as the (b) alicyclic (meth)acrylate monomer was weighed, and 112.5 g of methyl ethyl ketone (hereinafter, abbreviated as MEK in this specification) was used. g was dissolved. Next, as (a) the above-mentioned surface-modified silica particles, MEK-AC-2140Z (silica particles with a primary particle diameter of 10 nm to 15 nm, surface-modified with a (meth)acryloyloxy group) were added. Solid content 46 mass % MEK dispersion liquid) 305g, it stirred and homogenized. Then, MEK was distilled off under the conditions of 50° C. and a reduced pressure of 133.3 Pa or less using an evaporator to obtain the A-DCP dispersion liquid of the above-mentioned surface-modified silica particles (the surface-modified silica particles). Silica particle content 55 mass %).

[Production Example 3]

45.2 g of propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA in this specification) was placed in a 4-neck flask with a dropping funnel, and 50.0 g of methyl methacrylate was added to the dropping funnel. g, a solution obtained by dissolving 29.7 g of isobornyl acrylate, 9.28 g of 2-hydroxyethyl methacrylate, and 5.86 g of 2,2'-azobisisobutyronitrile in 176.2 g of PGMEA. After the atmosphere in the 4-neck flask was replaced with nitrogen, the temperature in the 4-neck flask was raised to 80° C., and the solution in the dropping funnel was added dropwise to the 4-neck flask over 3 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and after stirring at 110°C for 1 hour, the temperature in the 4-necked flask was lowered to 60°C. To the obtained reaction solution, 0.266 g of p-methoxyphenol, 0.451 g of dibutyltin dilaurate, and 15.1 g of AOI were added, and the mixture was stirred at 60° C. for 3 hours. The reaction solution was returned to room temperature, and reprecipitated/dried using methanol cooled to 10° C. to obtain 53.0 g of a polymer 1 having a repeating structural unit represented by the following formula (A). The weight average molecular weight Mw of the obtained polymer 1 measured in terms of polystyrene by GPC was 12,900.

[Production Example 4]

26.5 g of PGMEA was added to a 4-neck flask with a dropping funnel, and 45.0 g of methyl methacrylate, 6.50 g of 2-hydroxyethyl methacrylate, and 2,2'- A solution obtained by dissolving 4.10 g of azobisisobutyronitrile in 103.3 g of PGMEA. After the atmosphere in the 4-neck flask was replaced with nitrogen, the temperature in the 4-neck flask was raised to 80° C., and the solution in the dropping funnel was added dropwise to the 4-neck flask over 3 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and after stirring at 110°C for 1 hour, the temperature in the 4-necked flask was lowered to 60°C. To the obtained reaction solution, 0.186 g of p-methoxyphenol, 0.315 g of dibutyltin dilaurate, and 10.6 g of AOI were added, and the mixture was stirred at 60° C. for 3 hours. The reaction solution was returned to room temperature, reprecipitated/dried using methanol cooled to 10°C, and 27.7 g of a polymer 2 having a structural unit represented by the following formula (B) was obtained. The weight average molecular weight Mw of the obtained polymer 2 measured in terms of polystyrene by GPC was 10,200.

[Manufacturing example 5]

33.1 g of PGMEA was placed in a 4-neck flask with a dropping funnel, and 25.0 g of methyl methacrylate, 20.8 g of isobornyl acrylate, and 19.5 g of 2-hydroxyethyl methacrylate were added to the dropping funnel. g, and a solution obtained by dissolving 4.10 g of 2,2'-azobisisobutyronitrile in 128.9 g of PGMEA. After the atmosphere in the 4-neck flask was replaced with nitrogen, the temperature in the 4-neck flask was raised to 80° C., and the solution in the dropping funnel was added dropwise to the 4-neck flask over 3 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and after stirring at 110°C for 1 hour, the temperature in the 4-necked flask was lowered to 60°C. To the obtained reaction solution, 0.558 g of p-methoxyphenol, 0.946 g of dibutyltin dilaurate, and 53.8 g of BEI were added, and the mixture was stirred at 60° C. for 3 hours. The reaction solution was returned to room temperature, and was reprecipitated/dried using methanol cooled to 10° C. to obtain 4.36 g of a polymer 3 having a structural unit represented by the following formula (C). The weight average molecular weight Mw of the obtained polymer 3 measured in terms of polystyrene by GPC was 17,000.

[Example 1]

The solid content of the above-mentioned A-DCP dispersion obtained in Production Example 1 as (a) the above-mentioned surface-modified silica particles, and (b) the above-mentioned alicyclic (meth)acrylate monomer A-DCP, UA-4200 as (c) urethane (meth)acrylate compound, Polymer 1 obtained in the above-mentioned Production Example 3 as (d) above-mentioned polymer, (e) as photo-free I184 as the base initiator, I245 as the (g) phenolic antioxidant, and AO-503 as the (h) thioether-based antioxidant were blended in the ratios shown in Table 1 below, respectively. In addition, the ratio of A-DCP shown in following Table 1 contains the A-DCP component contained in the said A-DCP dispersion liquid. Then, the complex was shaken at 50°C for 3 hours and mixed, then NR1 as the (f) polyfunctional thiol compound was added, and the mixture was stirred and mixed for 30 minutes using the above stirring defoamer. Furthermore, the photocurable composition 1 for imprints was prepared by performing stirring and defoaming for 10 minutes using this apparatus. In addition, in following Table 1, "part" means "mass part".

[Example 2 to Example 8, Comparative Example 1 to Comparative Example 3]

The photocurable compositions 2 to 11 for imprint were prepared by mixing the components (a) to (h) in the ratios shown in Table 1 below in the same procedure as in Example 1. However, Example 4 does not use (f) component, Comparative Example 1 does not use (a) component, (d) component and (f) component, Comparative Example 2 does not use (a) component and (f) component, Comparative Example 3 Components (d) and (f) are not used.

[Table 1]

[Production of cured film]

The photocurable compositions for imprint prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were coated with NOVEC (registered trademark) 1720 ( The two glass substrates which carried out the mold release process by drying and drying were sandwiched. The sandwiched photocurable composition for imprint was subjected to UV exposure at 20 mW/cm ² for 300 seconds through an i-ray bandpass filter (manufactured by Asahi Corporation) using the above-mentioned UV irradiation apparatus. After exposure, the obtained hardened|cured material was peeled from the said glass substrate which performed the mold release process, and it heated with the hotplate of 100 degreeC for 10 minutes, and produced the cured film of diameter 3cm and thickness 0.5mm.

[Evaluation of transmittance and thermal yellowing]

The transmittance|permeability of the wavelength 410nm of the cured film produced by the said method was measured using the said ultraviolet-visible-near-infrared spectrophotometer. The results are shown in Table 2 below. Furthermore, the above-mentioned cured film was placed on a silicon wafer, and the heat resistance test was performed by heating on a hot plate heated to 175° C. for 2 minutes and 30 seconds via the silicon wafer. The transmittance at a wavelength of 410 nm of the cured film after the heat resistance test was measured using the above-mentioned ultraviolet-visible-near-infrared spectrophotometer, and heat-resistant yellowing was evaluated from the transmittance change before and after heating. The results are combined and shown in Table 2 below.

[Refractive index n _D / Abbe number ν _D evaluation]

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

[Evaluation of crack resistance in development process using organic solvent]

Each of the photocurable compositions for imprint prepared in Examples 1 to 8 and Comparative Examples 1 to 3 was added dropwise to NOVEC (registered trademark) 1720 (manufactured by Suri-Emjibon Co., Ltd.) On the photomask board|substrate (opening part 1 cm square) which dried and performed the mold release process. Then, the adhesive agent (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. was diluted with PGMEA to a solution of 5% by mass by coating through a 500-μm-thick silicone rubber spacer, and dried. A 4-inch glass wafer (0.7 mm thick) with a bonding process was sandwiched. The sandwiched photocurable composition was subjected to UV exposure at 62 mW/cm ² for 5 seconds through an i-ray bandpass filter (manufactured by Asahi Corporation) using the above-mentioned UV irradiation apparatus. After exposure, the obtained cured product was peeled from the glass substrate subjected to the mold release treatment described above, immersed (developed) in a stirred PGMEA, rinsed with PGMEA to remove the unexposed portion, and adhered as described above. A cured film of 1 cm square and 0.5 mm thickness was produced on the treated 4-inch glass wafer. The side surface of the cured film obtained was observed with the optical microscope made by the above-mentioned Olinpas Co., Ltd., and the case where cracks were observed was judged as ×, and the case where no cracks were observed was judged as ○. The results are combined and shown in Table 2 below.

[Film formation and crack resistance evaluation of antireflection layer]

0.020 g of each of the photocurable compositions for imprint prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were weighed and weighed in NOVEC (registered trademark) 1720 (manufactured by Sri エムジャパン Co., Ltd.) by coating. ) and dried on the glass substrate subjected to mold release treatment. Then, the adhesive agent (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. was diluted with PGMEA to 5 mass % by coating through a 300 μm-thick silicone rubber spacer, and dried. The adhesion-treated quartz substrate (6 cm square, 1 mm thick) was sandwiched with the photocurable composition for imprint on the glass substrate. The sandwiched photocurable composition was subjected to UV exposure at 20 mW/cm ² for 300 seconds through an i-ray bandpass filter (manufactured by Asahi Corporation) using the above-mentioned UV irradiation apparatus. After exposing, the obtained cured product was peeled from the said glass substrate, and it heated with the hotplate of 100 degreeC for 10 minutes, and produced the cured film of diameter 1cm, thickness 0.3mm, and mass 0.020g on the said quartz substrate.

On the above-mentioned 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 above-mentioned RF sputtering apparatus under the above-mentioned film-forming conditions. After observing the antireflection layer on the cured film using the optical microscope manufactured by the above-mentioned Co., Ltd. to confirm the presence or absence of cracks, the quartz substrate was heated with a hot plate at 175° C. for 2 minutes and 30 seconds to conduct a heat resistance test. After the heat resistance test, the presence or absence of cracks in the antireflection layer on the cured film was also observed using an optical microscope manufactured by the above-mentioned Co., Ltd., and the crack resistance of the antireflection layer was determined. The case where cracks were observed in the antireflection layer on the above cured film was judged as x, and the case where neither crack nor wrinkle in the antireflection layer on the cured film was observed was judged as ○. The respective results are combined and shown in Table 2 below.

[Table 2]

Table 2

The antireflection layer formed on the cured films prepared from the photocurable compositions for imprint of Comparative Example 1 not containing (a) component and (d) component and Comparative Example 2 not containing (a) component became in the Results of cracks after heat resistance test. Furthermore, the cured film prepared from the photocurable composition for imprint of Comparative Example 3 which contains (a) component but does not contain (d) component is after the development step of washing the uncured part using an organic solvent, and then the The sidewalls of the cured film develop cracks as a result. According to the above results, the cured film obtained from the photocurable composition for imprint of the present invention exhibits high Abbe number, high refractive index, high transparency, and thermal yellowing resistance, and exhibits antireflection with the upper layer of the cured film The layer was heat-treated at 175° C. without cracks or wrinkles, and the cured film did not crack even when exposed to an organic solvent, which is a characteristic desired as a lens for a high-resolution camera module.

[production of lens]

The photocurable composition for imprint 1 prepared in Example 1, the photocurable composition for imprint 4 prepared in Example 4, and the photocurable composition 8 for imprint prepared in Example 8 were used, respectively. A nickel casting mold (15 lens molds with a diameter of 2 mm × 300 μm depth were arranged in a total of 3 vertical rows × 5 horizontal rows) and a nanoprinter were formed on a glass substrate as a support according to the above-mentioned manufacturing method of the molded body. lens shape. In addition, the mold used was previously subjected to mold release treatment with NOVEC (registered trademark) 1720 (manufactured by SURI エムジャパン Co., Ltd.). In addition, the glass substrate used was previously adhering treatment by coating and drying an adhesive adjuvant (product name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. diluted with PGMEA into a solution of 5 mass %. After removing the hardened|cured material from the said casting_mold|template, this hardened|cured material was heated with the hotplate of 100 degreeC for 10 minutes, and the convex lens was produced on the said glass substrate which performed the adhesion process.

Regarding the convex lens obtained on the above-mentioned glass substrate, the lens height (thickness) before and after the heating test was measured with the above-mentioned non-contact surface property measuring device, and the following formula "[(lens height before heating - lens height after heating)/before heating The lens height] × 100" was calculated to calculate the change rate, and the dimensional stability based on heating was evaluated. In addition, the presence or absence of cracks in the convex lenses after the heating test was observed with a microscope attached to the above-mentioned non-contact surface property measuring device. In addition, the heating test is a test in which the convex lens obtained on the glass substrate was heated with a 175 degreeC hotplate for 2 minutes and 30 seconds, and it was left to cool to room temperature (about 23 degreeC). The results are shown in Table 3 below.

[table 3]

table 3

As shown in Table 3, the convex lens obtained from the photocurable composition for imprint of the present invention obtained a small change in lens height (change rate of 0.20% or less) even after a thermal history of 175° C. for 2 minutes and 30 seconds. This results in high dimensional stability.

Claims (15)

1. A photocurable composition for imprinting, comprising a component (a) 10 to 40 parts by mass, a component (b) 10 to 50 parts by mass, a component (c) 10 to 50 parts by mass, a component (d) 1 to 10 parts by mass, and a component (e) 0.1 to 5 parts by mass, with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d),

(a) the components: surface-modified silica particles having a primary particle diameter of 1 to 100nm,

(b) the components: 1 an alicyclic (meth) acrylate monomer having at least 1 (meth) acryloyloxy group in the molecule, excluding a compound as the component (c),

(c) the components: a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, excluding a polymer as the component (d),

(d) the components: a polymer having a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2),

(e) the components: a photo-radical initiator, which is a compound of formula (I),

in the formula, R¹And R²Each independently represents a methyl group or a hydrogen atom, A¹Represents an alkyl group having 1 to 8 carbon atoms, A²Represents a single bond or an alkylene group having 1 to4 carbon atoms, X represents a polymerizable group having 1 or 2 or more (meth) acryloyloxy groups, Z¹Represents a divalent group represented by the following formula (a1), formula (a2), formula (a3) or formula (a4)The radical(s) is (are),

2. the photocurable composition for imprints of claim 1, further comprising 1 to 15 parts by mass of the following component (f) per 100 parts by mass of the sum of the components (a), (b), (c) and (d),

(f) the components: a polyfunctional thiol compound represented by the following formula (3),

in the formula, A³Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, Z²Represents a single bond, an ester bond or an ether bond, Q represents an organic group having 2 to 12 carbon atoms and containing at least 1 hetero atom or no hetero atom, or a hetero atom, and r represents an integer of 2 to 6.

3. The photocurable composition for imprints of claim 1 or 2, further comprising: 0.05 to 3 parts by mass of the following component (g) per 100 parts by mass of the sum of the components (a), (b), (c) and (d); and/or 0.1 to 3 parts by mass of the following component (h) per 100 parts by mass of the sum of the components (a), (b), (c) and (d),

(g) the components: a phenolic antioxidant, which is a phenolic antioxidant,

(h) the components: a thioether-based antioxidant.

4. The photocurable composition for imprints of any one of claims 1 to 3, 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. The photocurable composition for imprinting according to any one of claims 1 to4, wherein the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (c) is a compound having 2 or 3 (meth) acryloyloxy groups in 1 molecule.

6. The photocurable composition for imprinting according to any one of claims 1 to 5, wherein the polymer as the component (d) is a polymer further having a repeating structural unit represented by the following formula (4),

in the formula, R³Represents a methyl group or a hydrogen atom, Z³Represents a single bond or an ethyleneoxy group, A⁴An alicyclic hydrocarbon group having 5 to 13 carbon atoms.

7. The photocurable composition for imprints according to claim 6, wherein the alicyclic hydrocarbon group having 5 to 13 carbon atoms is a cyclopentyl group, a cyclohexyl group, an isobornyl group, a tricyclo [5.2.1.02,6] dec-8-yl group, a tricyclodecenyl group, or an adamantyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent.

8. The photocurable composition for imprinting according to any one of claims 1 to 7, wherein the polymerizable group having 1 or 2 or more (meth) acryloyloxy groups is a group represented by formula (X0), formula (X1), formula (X2), formula (X3), formula (X4), formula (X5) or formula (X6), or a group obtained by replacing a part or all of acryloyloxy groups contained in these groups with methacryloyloxy groups,

9. the photocurable composition for imprints of any one of claims 1 to 8,a refractive index n at a wavelength of 589nm of a cured product of the photocurable composition for imprinting_DIs 1.50 or more, and the Abbe number v of the cured product_DIs 53 or more.

10. A cured product of the photocurable composition for imprinting according to claim 9.

11. A method for manufacturing a resin lens, comprising the steps of: a step of subjecting the photocurable composition for imprinting according to any one of claims 1 to 9 to imprint molding.

12. A method for producing a molded article of a photocurable composition for imprinting, comprising the steps of: a filling step of filling the space between the support and the mold in contact with each other or the internal space of the detachable mold with the photocurable composition for imprinting according to any one of claims 1 to 9; and a photocuring step of exposing the photocurable composition for imprinting filled in the space to light to cure the composition.

13. The method for producing a molded article according to claim 12, comprising the steps of: a mold releasing step of taking out the obtained photo-cured product after the photo-curing step; and a heating step of heating the photo-cured product before, during, or after the releasing step.

14. The method for producing a molded article according to claim 13, further comprising the steps of: and a developing step of cleaning the uncured portion with an organic solvent after the mold releasing step and before the heating step.

15. The method for producing a molded article according to any one of claims 12 to 14, wherein the molded article is a lens for a camera module.