阅读说明：本技术 压印用光固化性组合物 (Photocurable composition for imprinting ) 是由 长泽伟大 首藤圭介 加藤拓 铃木朋哉 今井翔太 于 2018-12-21 设计创作，主要内容包括：本发明的课题是提供能够形成光学特性优异、压印后的支持体的翘曲量远小于以往的高弹性模量的固化物(成型体),并且通过热处理而在该固化物的上层的防反射层不易产生裂缝的光固化性组合物。解决手段是包含下述(a)成分、下述(b)成分、下述(c)成分、下述(d)成分和下述(e)成分的压印用光固化性组合物。(a)：1分子中具有至少1个(甲基)丙烯酰氧基的脂环式(甲基)丙烯酸酯化合物(但是,(b)成分的化合物除外。)(b)：氨基甲酸酯(甲基)丙烯酸酯化合物或环氧(甲基)丙烯酸酯化合物(c)：一次粒径为1nm～100nm的进行了表面修饰的二氧化硅粒子(d)：下述式(1)所示的多官能硫醇化合物(e)：光自由基引发剂(式中,R<Sup>1</Sup>表示单键或碳原子数1～6的直链状或支链状的亚烷基,X表示单键、酯键或醚键,A<Sup>1</Sup>表示包含至少1个杂原子或不包含杂原子的碳原子数2～12的有机基、或杂原子,r<Sup>1</Sup>表示2～6的整数。)<Image he="256" wi="700" file="DDA0002587017130000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention addresses the problem of providing a photocurable composition that can form a cured product (molded product) having excellent optical properties and a support after imprinting that has a much smaller warpage than conventional high-elastic modulus, and that is less likely to crack an antireflective layer that is an upper layer of the cured product upon heat treatment. The solution is a photocurable composition for imprinting, which comprises the following component (a), the following component (b), the following component (c), the following component (d) and the following component (e). (a) The method comprises the following steps 1 alicyclic (meth) acrylate compound having at least 1 (meth) acryloyloxy group in the molecule (except for the compound of the component (b)) (b): urethane (meth) acrylate compound or epoxy (meth) acrylate compound (c): surface-modified silica particles having a primary particle diameter of 1 to 100nm (d): a polyfunctional thiol compound (e) represented by the following formula (1): photo radical initiator (in the formula, R) 1 Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond, an ester bond or an ether bond, A 1 Represents an organic group having 2 to 12 carbon atoms containing at least 1 hetero atom or no hetero atom, or a hetero atom 1 Represents an integer of 2 to 6. ))

1. A photocurable composition for imprinting, comprising 10 to 50 parts by mass of a component (a), 20 to 55 parts by mass of a component (b), 10 to 35 parts by mass of a component (c), 1 to 15 parts by mass of a component (d), and 0.1 to 5 parts by mass of a component (e) per 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d),

(a) the method comprises the following steps 1 an alicyclic (meth) acrylate compound having at least 1 (meth) acryloyloxy group in the molecule thereof, except for the compound of the component (b),

(b) the method comprises the following steps Urethane (meth) acrylate compounds or epoxy (meth) acrylate compounds,

(c) the method comprises the following steps Surface-modified silica particles having a primary particle diameter of 1 to 100nm,

(d) the method comprises the following steps A polyfunctional thiol compound represented by the following formula (1),

(e) the method comprises the following steps A photo-radical initiator, which is a compound of formula (I),

in the formula, R¹Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond, an ester bond or an ether bond, A¹Represents an organic group having 2 to 12 carbon atoms containing at least 1 hetero atom or no hetero atom, or a hetero atom¹Represents an integer of 2 to 6.

2. The photocurable composition for imprinting according to claim 1, wherein the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (b) has 2 or 3 (meth) acryloyloxy groups in 1 molecule of the compound.

3. The photocurable composition for imprints of claim 1 or 2, wherein the component (c) is a silica particle surface-modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group.

4. The photocurable composition for imprints of any one of claims 1 to 3, further comprising:

0.05 to 3 parts by mass of the following component (f) and/or based on 100 parts by mass of the sum of the components (a), (b), (c) and (d)

0.1 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),

(f) the method comprises the following steps A phenolic antioxidant, which is a phenolic antioxidant,

(g) the method comprises the following steps A thioether-based antioxidant.

5. The photocurable composition for imprints of any one of claims 1 to4, further comprising: a polymer having a repeating structural unit represented by the following formula (2) and a repeating structural unit represented by the following formula (3) in an amount of 1 to 10 parts by mass based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d), wherein the component (b) does not contain a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound,

in the formula, R²And R³Each independently represents a methyl group or a hydrogen atom, R⁴Represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents a single bond or an alkylene group having 1 to4 carbon atoms, Q 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),

6. the photocurable composition for imprints according to claim 5, the polymer further having a repeating structural unit represented by the following formula (4),

in the formula, R⁶Represents a methyl group or a hydrogen atom, Z²Represents a single bond or an ethyleneoxy group, A²An alicyclic hydrocarbon group having 5 to 13 carbon atoms.

7. The photocurable composition for imprinting according to any one of claims 1 to 6, wherein a cured product of the photocurable composition for imprinting has a refractive index n at a wavelength of 589nm_DHas an Abbe number of 1.50 or more, and the cured product hasNumber v_DIs 53 or more.

8. The photocurable composition for imprinting according to any one of claims 1 to 7, wherein a cured product of the photocurable composition for imprinting has a dynamic elastic modulus at a frequency of 1Hz and a temperature of 30 ℃ of 1000MPa to 4000 MPa.

9. A cured product of the photocurable composition for imprinting according to claim 7 or 8.

10. 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 8 to imprint molding.

11. A method for producing a molded article of a photocurable composition for imprinting, comprising the steps of: a step of filling the space between the support and the mold to be bonded or the internal space of the dividable mold with the photocurable composition for imprinting according to any one of claims 1 to 8; and a step of exposing the photocurable composition for imprinting filled in the space to light to cure the composition.

12. The method for producing a molded article according to claim 11, comprising the steps of: a step of taking out the obtained photo-cured product and releasing the photo-cured product after the step of photo-curing; and a step of heating the photo-cured product before, during or after the step of releasing the photo-cured product from the mold.

13. The method for producing a molded article according to claim 11 or 12, wherein the molded article is a lens for a camera module.

Technical Field

The present invention relates to a photocurable composition for imprinting, which contains an alicyclic (meth) acrylate compound, a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, surface-modified silica particles, a polyfunctional thiol compound, and a photo-radical initiator. More specifically, the present invention relates to a photocurable composition which is excellent in optical characteristics (transparency, high refractive index, and high abbe number), has a much smaller amount of warpage of a support after imprinting than a conventional cured product and a conventional molded product, has a high dynamic elastic modulus of the cured product and the molded product, and is free from cracking even after an antireflection layer (AR layer) is formed on the upper layer of the cured product and the molded product and is heat-treated.

Background

Resin lenses are used in electronic devices such as mobile phones, digital cameras, and vehicle-mounted cameras, and are required to have excellent optical characteristics 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 enabling molding in good yield are required. As a material for a resin lens that satisfies such a demand, for example, thermoplastic transparent resins such as polycarbonate resin, cycloolefin polymer, and methacrylic resin are used.

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

As a photocurable resin capable of being molded at a wafer level, a radical curable resin composition has been conventionally used from the viewpoint of high transparency, resistance to thermal yellowing, and mold releasability from a mold (patent document 1). Further, a curable composition is known which contains silica particles surface-modified with a silane compound, zirconia particles surface-modified with a dispersant, or other surface-modified oxide particles to obtain a cured product having a high abbe number (for example, patent documents 2 and 3).

Disclosure of Invention

Problems to be solved by the invention

In recent years, with market demand for thinning of camera modules, the thickness of a support used in the hybrid lens system is reduced. Therefore, if the radical curable resin composition described in patent document 1 is used, a problem arises that the support having the molded body such as a lens is easily warped after the mounting process involving the heat treatment. In order to solve the above problem, a measure to reduce the elastic modulus of the photocurable resin used is taken. However, when the elastic modulus of the molded body is low, there is a problem that scratches are introduced into the surface of the molded body in the dicing step of dicing the molded body on the support and the transportation step of the diced sheet material, thereby lowering the yield. Further, when the molded article is a lens, an antireflection layer made of an inorganic substance such as silicon oxide or titanium oxide is formed on the molded article. Therefore, there is a problem that cracks are generated in the antireflection layer by heat-treating a lens formed on a support having a small warpage and covered with the antireflection layer. In addition, if the elastic modulus of a cured product formed using the curable compositions described in patent documents 2 and 3 is increased, the warpage amount of a substrate increases, and it is difficult to achieve both a high elastic modulus and a low warpage amount.

There has been no curable resin material which has a high abbe number (for example, 53 or more) and high transparency, has a small amount of warpage of a support such as a glass substrate in a hybrid lens system, exhibits a high elastic modulus, and can be used as a lens for a high-resolution camera module, and further is free from cracks in an antireflection layer formed on an upper layer of the molded body by a subsequent heat treatment, and development thereof has been desired. The present invention has been made in view of the above circumstances, and an object thereof is to provide a photocurable composition which can form a molded article exhibiting a high abbe number, a high refractive index, high transparency and thermal yellowing resistance, is suitable for producing the molded article in a hybrid lens system because the amount of warpage of a support is smaller than that of conventional molded articles, and has a high elastic modulus, and which does not cause cracking in an antireflection layer on the upper layer of the molded article by heat treatment.

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, they have found that a molded article obtained from a photocurable composition by blending surface-modified silica particles and a polyfunctional thiol compound having 2 or more thiol groups in 1 molecule in a predetermined ratio in the photocurable composition has a high refractive index n_D(1.50 or more) and a high Abbe number v_D(53 or more) exhibits a high transmittance of 90% or more at a wavelength of 410nm, has a small amount of warpage of the support (0 μm or more and less than 3.0 μm), has a high dynamic elastic modulus at 30 ℃ of the molded article (1000MPa or more and 4000MPa or less), and does not cause any crack or wrinkle in the upper anti-reflection layer of the molded article by heat treatment at 175 ℃.

That is, a first aspect of the present invention is a photocurable composition for imprinting, comprising 10 to 50 parts by mass of a component (a), 20 to 55 parts by mass of a component (b), 10 to 35 parts by mass of a component (c), 1 to 15 parts by mass of a component (d), and 0.1 to 5 parts by mass of a component (e), 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 method comprises the following steps 1 alicyclic (meth) acrylate compound having at least 1 (meth) acryloyloxy group in the molecule (except for the compound of the component (b))

(b) The method comprises the following steps Urethane (meth) acrylate compound or epoxy (meth) acrylate compound

(c) The method comprises the following steps Surface-modified silica particles having a primary particle diameter of 1 to 100nm

(d) The method comprises the following steps A polyfunctional thiol compound represented by the following formula (1)

(e) The method comprises the following steps Photo-radical initiator

(in the formula, R¹Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond, an ester bond "-C (═ O) O-" or an ether bond "-O-", A¹Represents an organic group having 2 to 12 carbon atoms containing at least 1 hetero atom or no hetero atom, or a hetero atom¹Represents an integer of 2 to 6. )

Here, the hetero atom means an atom other than a carbon atom and a hydrogen atom, and examples thereof include a nitrogen atom, an oxygen atom and a sulfur atom.

The alicyclic (meth) acrylate compound of the component (a) has, for example, 1 or 2 (meth) acryloyloxy groups in the molecule of the compound 1.

The urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (b) has, for example, 2 or 3 (meth) acryloyloxy groups in the molecule of the compound 1.

The surface-modified silica particles having a primary particle diameter of 1nm to 100nm as component (c) are, for example, silica particles surface-modified by (meth) acryloyloxy groups bonded to silicon atoms via a divalent linking group. 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 photocurable composition for imprinting of the present invention may further comprise: 0.05 to 3 parts by mass of the following component (f) 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 (g) per 100 parts by mass of the sum of the components (a), (b), (c) and (d).

(f) The method comprises the following steps Phenolic antioxidant

(g) The method comprises the following steps Thioether antioxidant

The photocurable composition for imprinting of the present invention may further comprise: and (b) 1 to 10 parts by mass of a polymer having a repeating structural unit represented by the following formula (2) and a repeating structural unit represented by the following formula (3) per 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d), wherein the component (b) does not contain a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound.

(in the formula, R²And R³Each independently represents a methyl group or a hydrogen atom, R⁴Represents an alkyl group having 1 to 8 carbon atoms, R⁵Represents a single bond or an alkylene group having 1 to4 carbon atoms, Q 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 (a 4). )

The polymerizable group having 1 or 2 or more (meth) acryloyloxy groups is, for example, a group represented by the following formula (Q0), formula (Q1), formula (Q2), formula (Q3), formula (Q4), formula (Q5) or formula (Q6), or a group obtained by replacing a part or all of acryloyloxy groups contained in these groups with methacryloyloxy groups.

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

(in the formula, R⁶Represents a methyl group or a hydrogen atom, Z²Represents a single bond or an ethyleneoxy group, A²An alicyclic hydrocarbon group having 5 to 13 carbon atoms. )

In the above-mentioned Z²Represents an ethyleneoxy group (-CH)₂CH₂O-group), the O atom of the ethyleneoxy group and A which represents the above-mentioned alicyclic hydrocarbon group²And (4) combining.

Examples of the alicyclic hydrocarbon group having 5 to 13 carbon atoms include cyclopentyl, cyclohexyl, isobornyl, tricyclo [5.2.1.0(2,6) ] dec-8-yl, tricyclodecenyl, and adamantyl groups which may have an alkyl group having 1 to 3 carbon atoms as a substituent.

The refractive index n at a wavelength of 589nm of a cured product of the photocurable composition for imprinting of the present invention_DIs 1.50 or more, and the Abbe number v of the cured product_DIs 53 or more. The above refractive index n_DThe Abbe number v_DHigher values of both are preferred, but for example, as long as the refractive index n_DIs 1.50 to 1.55 inclusive, and has an Abbe number v_DThe range of 53 to 60 may be used.

The second aspect of the present invention is a cured product of the photocurable composition for imprinting.

A third aspect of the present invention is a method for manufacturing a resin lens, including the steps of: and a step of subjecting the photocurable composition for imprinting to imprint molding.

A fourth aspect of the present invention is a method for producing a molded article of a photocurable composition for imprinting, the method comprising the steps of: filling the space between the support and the mold to be bonded or the internal space of the dividable mold with the photocurable composition for imprinting; and a step of exposing the photocurable composition for imprinting filled in the space to light to cure the composition. The above-mentioned mold is also referred to as a mold.

The method for producing a molded article of the present invention may further comprise the steps of: a step of taking out the obtained photo-cured product and releasing the photo-cured product after the step of photo-curing; and a step of heating the photo-cured product before, during or after the step of releasing the photo-cured product from the mold.

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

ADVANTAGEOUS EFFECTS OF INVENTION

The photocurable composition for imprinting of the present invention comprises the components (a) to (e) and further optionally comprises the component (f) and/or the component (g) and the polymer, and therefore a cured product and a molded product obtained from the photocurable composition exhibit high abbe number, high refractive index, high transparency and thermal yellowing resistance, which are optical characteristics desired for optical devices such as lenses for high-resolution camera modules. The cured product and the molded body have a small warpage amount (0 μm or more and less than 3.0 μm) of the support, a high dynamic elastic modulus at 30 ℃ of the cured product and the molded body (1000MPa or more and 4000MPa or less), and the anti-reflection layer on the upper layer of the cured product and the molded body is free from cracking or wrinkling by heat treatment at 175 ℃.

Drawings

Fig. 1 is a schematic view showing an evaluation method of the warpage amount of a glass substrate.

Detailed Description

[ (a) ingredient: alicyclic (meth) acrylate Compound)

The alicyclic (meth) acrylate compound that can be used as component (a) of the photocurable composition for imprinting of the present invention has at least 1 (meth) acryloyloxy group and 1 alicyclic hydrocarbon group in the molecule of compound 1, with the exception of the compounds of component (b) described later. Examples of the alicyclic (meth) acrylate compound include compounds selected from cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, tricyclo [5.2.1.0(2,6) ] decyl (meth) acrylate, tricyclo [5.2.1.0(2,6) ] decyloxyethyl (meth) acrylate, and mixtures thereof, Alicyclic (meth) acrylate monomers among 1, 4-cyclohexanedimethanol di (meth) acrylate, tricyclo [5.2.1.0(2,6) ] decanedimethanol di (meth) acrylate, and 1, 3-adamantanediol di (meth) acrylate.

As the alicyclic (meth) acrylate compound, commercially available products can be used, and examples thereof include ビスコート #155, IBXA, ADMA (see above, manufactured by Osaka organic chemical industry Co., Ltd.), NK エステル A-IB, NK エステル IB, NK エステル A-DCP, NK エステル DCP (see above, manufactured by Newzhongmura chemical industry Co., Ltd.), and ファンクリル (registered trademark) FA-511AS, ファンクリル FA-512AS, ファンクリル FA-513AS, ファンクリル FA-512M, ファンクリル FA-512MT and ファンクリル FA-513M (see above, manufactured by Hitachi chemical Co., Ltd.).

The content of the component (a) in the photocurable composition for imprinting of the present invention is 10 to 50 parts by mass, preferably 20 to 40 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b) described later, the component (c) described later, and the component (d) described later. If the content of the component (a) is less than 10 parts by mass, the refractive index of a cured product obtained from the above photocurable composition for imprint may decrease to less than 1.50. If the content of the component (a) is more than 50 parts by mass, the amount of warpage of the support on which the cured product and the molded article obtained from the above-mentioned photocurable composition for imprinting are formed may increase.

The alicyclic (meth) acrylate compound of the component (a) may be used alone in 1 kind or in combination with 2 or more kinds.

[ (b) component: urethane (meth) acrylate compound or epoxy (meth) acrylate compound ]

The urethane (meth) acrylate compound that can be used as the component (b) of the photocurable composition for imprinting according to the present invention is a compound having a urethane structure represented by at least 2 (meth) acryloyloxy groups and at least 2 ″ -NH-C (═ O) O ″ "in 1 molecule. Examples of the urethane (meth) acrylate compound include EBECRYL (registered trademark) 230, EBECRYL270, EBECRYL280/15IB, EBECRYL284, EBECRYL4491, EBECRYL4683, EBECRYL4858, EBECRYL8307, EBECRYL8402, EBECRYL8411, EBECRYL4, EBECRYL8807, EBECRYL9270, EBECRYL8800, EBECRYL294/25HD, EBECRYL4100, EBECRYL4220, EBECRYL4513, EBECRYL4738, EBECRYL4740, EBECRYL4820, EBECRYL294/25HD, EBECRYL8465, EBECRYL9260, EBECRYL8701, KRM7735, KRM8667, KRM8296 (see above, KRM 6363 ダイセル, E464 (see above), EBECRYL 6335-60, EBECRYL 4635, EBECRYL 4680, EBECRYL 354635-4760, JP-7-E-36567, JP-3-7-W-366368, JP-3-b-80-3-b-80-3-2-3-2-150-2, UA-510H, UF-8001G (manufactured by Kyowa Kagaku Co., Ltd.), M-1100, M-1200 (manufactured by Toyo Seisaku Co., Ltd.), NK オリゴ U-2PPA, NK オリゴ U-6LPA, NK オリゴ 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, and NK オリゴ UA-W2A (manufactured by Kyowa chemical industry Co., Ltd.).

The epoxy (meth) acrylate compound that can be used as the component (b) of the photocurable composition for imprinting of the present invention is an ester obtained by reacting a compound having at least 2 epoxy rings in 1 molecule with (meth) acrylic acid. Examples of the epoxy (meth) acrylate compound include EBECRYL (registered trademark) 645, EBECRYL648, EBECRYL860, EBECRYL3500, EBECRYL3608, EBECRYL3702, EBECRYL3708 (manufactured by ダイセル, オルネクス, supra), DA-911M, DA-920, DA-931, DA-314, DA-212 (manufactured by ナガセケムテックス, supra), HPEA-100 (manufactured by ケーエスエム, infra), and ユニディック (registered trademark) V-5500, ユニディック V-5502, ユニディック V-5508 (manufactured by DIC (co., Ltd.).

As the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (b), a compound having 2 or 3 (meth) acryloyloxy groups in the molecule of the compound 1 is preferably used. A support having a cured product and a molded body formed from a photocurable composition for imprinting containing a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound having 6 or more (meth) acryloyloxy groups in 1 molecule may have an excessively large amount of warpage.

The content of the component (b) in the photocurable composition for imprinting of the present invention is 20 to 55 parts by mass, or 30 to 50 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) described later, and the component (d) described later. If the content of the component (b) is less than 20 parts by mass, the amount of warpage of the support on which the cured product and the molded article obtained from the above-mentioned photocurable composition for imprinting are formed may increase. If the content of the component (b) is more than 55 parts by mass, the elastic modulus of a cured product or a molded article obtained from the photocurable composition for imprinting may be lowered.

The urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (b) may be used alone in 1 kind or in combination of 2 or more kinds.

[ (c) ingredient: surface-modified silica particles

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

Examples of the sol containing the surface-modified silica particles include MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L (manufactured by Nissan Chemicals Co., Ltd.), ELCOM (registered trademark) V-8802, and ELCOMV-8804 (manufactured by Nissan catalytic Chemicals Co., Ltd.).

The content of the component (c) in the photocurable composition for imprints of the present invention is 10 to 35 parts by mass, preferably 15 to 35 parts by mass, 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. If the content of the component (c) is less than 10 parts by mass, cracks in the antireflection layer formed on the cured product obtained from the photocurable composition for imprinting and the upper layer of the molded body may not be suppressed. If the content of the component (c) is more than 35 parts by mass, haze may be generated in a cured product or a molded article obtained from the above-mentioned photocurable composition for imprinting, and the transmittance may be lowered.

The surface-modified silica particles of the component (c) may be used alone in 1 kind or in combination of 2 or more kinds.

[ (d) ingredient: polyfunctional thiol Compound ]

The polyfunctional thiol compound that can be used as the component (d) of the photocurable composition for imprints of the present invention is a polyfunctional thiol compound represented by the above formula (1). Examples of the polyfunctional thiol compound represented by the formula (1) include 1, 2-ethanedithiol, 1, 3-propanedithiol, bis (2-mercaptoethyl) ether, trimethylolpropane tris (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -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 formula (1), commercially available products such as カレンズ MT (registered trademark) PE1, カレンズ NR1, カレンズ BD1, TPMB, TEMB (manufactured by SHOWA DENKO K.K.), TMMP, TEMP, PEMP, EGMP-4, DPMP, TMMP II-20P, and PEMP II-20P, PEPT (manufactured by SC ORGANIC CHEMICAL CO., LTD.) can be used.

The content of the component (d) in the photocurable composition for imprints of the present invention is 1 to 15 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d). If the content of the component (d) is less than 1 part by mass, the amount of warpage of the support on which the cured product and the molded article obtained from the above-mentioned photocurable composition for imprinting are formed may become large. If the content of the component (d) 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, and thus the cured product and the molded body may be deformed in a mounting process accompanied by heat treatment.

The polyfunctional thiol compound of the component (d) may be used alone in 1 kind or in combination of 2 or more kinds.

[ (e) ingredient: photo radical initiator

Examples of the photo-radical initiator that can be used as the component (e) of the photocurable composition for imprint of the present invention include alkylbenzophenones, benzophenones, Michler's (Michler) ketones, acylphosphine oxides, benzoylbenzoates, oxime esters, tetramethylthiuram monosulfide, and thioxanthones, and particularly preferred is a photo-cleavage type photo-radical polymerization initiator. As the photo radical initiator, commercially available products such as IRGACURE (registered trademark) 184, IRGACURE369, IRGACURE651, IRGACURE500, IRGACURE819, IRGACURE907, IRGACURE784, IRGACURE2959, IRGACURE CGI1700, IRGACURE CGI1750, IRGACURE CGI1850, IRGACUREC 24-61, IRGACURE TPO, IRGACURE 1116, IRGACURE 1173 (see above, manufactured by BASF ジャパン Co., Ltd.), and ESACURE KIP150, ESACURE KIP65LT, ESACURE KIP100F, ESACURE 37, ESURE 55, ESURE KTO46, ESACURE KIP75 (see above, manufactured by Lamberti Co., Ltd.) can be used.

The content of the component (e) in the photocurable composition for imprints of the present invention is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d). If the content of the component (e) is less than 0.1 part by mass, the strength of a cured product and a molded article obtained from the above-mentioned photocurable composition for imprinting may be reduced. If the content of the component (e) is more than 5 parts by mass, the heat yellowing resistance of a cured product and a molded article obtained from the photocurable composition for imprinting may be deteriorated.

The photo radical initiator of the component (e) may be used alone in 1 kind or in combination of 2 or more kinds.

[ (f) component: phenol-based antioxidant

Examples of the phenolic antioxidant that can be used as the component (f) of the photocurable composition for imprinting according to the present invention include IRGANOX 245, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 (see above, manufactured by BASF ジャパン Co., Ltd.), SUMILIZER (see registered trademarks) GA-80, SUMILIZER GP, SUMILIZER MDP-S, SUMILIZER BBM-S, SUMILIZER WX-R (see above, manufactured by Sumitochem Co., Ltd.), and アデカスタブ (see registered trademarks) AO-20, アデカスタブ AO-30, アデカスタブ AO-40, アデカスタブ AO-50, アデカスタブ AO-60, アデカスタブ AO-80, アデカスタブ -330 (see above, manufactured by ADEKA Co., Ltd.).

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

The phenolic antioxidant of the component (f) may be used alone in 1 kind or in combination of 2 or more kinds.

[ (g) ingredient: thioether-based antioxidant

Examples of the thioether-based antioxidant that can be used as the component (g) of the photocurable composition for imprint of the present invention include アデカスタブ (registered trademark) AO-412S, アデカスタブ AO-503 (available from ADEKA corporation), IRGANOX (registered trademark) PS802, IRGANOX PS800 (available from BASF ジャパン corporation), and SUMILIZER (registered trademark) TP-D (available from sumitomo chemical corporation).

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

The thioether antioxidant of the component (g) may be used singly or in combination of 1 or more.

[ other ingredients ]

The photocurable composition for imprints of the present invention may contain, as other components, components other than the above-mentioned components (a) to (g). Examples of the other component include a polyfunctional (meth) acrylate compound having a polymerizable group, a copolymer having a polymerizable group, and a polyrotaxane having a polymerizable group. Examples of the polyfunctional (meth) acrylate compound having a polymerizable group include NK エステル AD-TMP, NK エステル D-TMP, NK エステル A-TMPT, NK エステル TMPT, NK エステル A-TMMT, NK エステル A-GLY-3E, NK エステル A-GLY-9E, NK エステル A-DPH, NK エステル A-9300 (manufactured by Ninghamu chemical industry Co., Ltd.), KAYARAD PET-30 and KAYARAD GPO-303 (manufactured by Nippon Kagaku Co., Ltd.). Examples of the copolymer containing a polymerizable group include a polymer having a repeating structural unit represented by the above formula (2), a repeating structural unit represented by the above formula (3), and optionally a repeating structural unit represented by the above formula (4).

Examples of the repeating structural unit represented by the above formula (2) include repeating structural units represented by the following formulae (2-1) to (2-6).

Examples of the repeating structural unit represented by the above formula (3) include repeating structural units represented by the following formulae (3-1) to (3-44).

Examples of the repeating structural unit represented by the above formula (4) include repeating structural units represented by the following formulae (4-1) to (4-22).

Examples of the copolymer containing a polymerizable group include ヒタロイド (registered trademark) 7975, ヒタロイド 7975D, ヒタロイド 7988 (manufactured by Hitachi chemical Co., Ltd.), RP-274S, RP-310 (manufactured by ケーエスエム 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, and アートキュア RA-341 (manufactured by Industrial Co., Ltd.).

The polyrotaxane having a polymerizable group is a pseudopolyrotaxane in which both ends of the polyrotaxane are included in a string form by a linear molecule such as polyethylene glycol at an opening of a cyclic molecule such as cyclodextrin, and a blocking group such as an adamantyl group is arranged so that the cyclic molecule does not detach. The polymerizable group and the cyclic molecule are bonded via a spacer or directly bonded. Examples of the polyrotaxane having a polymerizable group include セルム (registered trademark) superpolymers SA1303P, セルム superpolymers SA2403P, セルム superpolymers SA3403P, セルム superpolymers SM1303P, セルム superpolymers SM2403P, and セルム superpolymer 3403P (see above, manufactured by アドバンスト and ソフトマテリアルズ corporation).

When the photocurable composition for imprints of the present invention contains the other component(s), the content thereof is 1 to 10 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). When the other component is a copolymer containing a polymerizable group, if the content is more than 10 parts by mass, the viscosity of the photocurable composition for imprinting is greatly increased, and thus the workability is significantly reduced.

The other components can be used alone in 1 or a combination of 2 or more.

< method for producing photocurable composition for imprinting >

The method for preparing the photocurable composition for imprinting of the present invention is not particularly limited. The preparation method includes, for example, a method of mixing the component (a), the component (b), the component (c), the component (d), the component (e), and, if necessary, the component (f) and/or the component (g) and the other components at a predetermined ratio to prepare a uniform solution.

The photocurable composition for imprinting of the present invention prepared into a solution is preferably used after being filtered using a filter having a pore size of 0.1 to 5 μm or the like.

< cured product >

The photocurable composition for imprint of the present invention can be exposed to light (photocured) to obtain a cured product, and the cured product of the present invention is also an object. Examples of the light for exposure include ultraviolet rays, electron beams, and X-rays. 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. After exposure, post-baking may be performed to stabilize the physical properties of the cured product. The post-baking is not particularly limited, and is usually carried out at 50 to 260 ℃ for 1 minute to 24 hours using a hot plate, an oven or the like.

Abbe number v of cured product obtained by photocuring the photocurable composition for imprint of the present invention_DRefractive index n at a wavelength of 589nm (D line) of 53 or more_DIs 1.50 or more, and further, it is alsoNo yellowing due to heating was observed. Therefore, the photocurable composition for imprints of the present invention can be suitably used for forming resin lenses.

< shaped body >

The photocurable composition for imprinting of the present invention can be used, for example, in an imprint molding method, to easily produce various molded articles simultaneously with the formation of a cured product. Examples of a method for producing a molded article include a method comprising the following steps: filling the space between the support and the mold to be bonded or the internal space of the dividable mold with the photocurable composition for imprinting of the present invention; a step of exposing the photocurable composition for imprinting filled in the space to light to cure the composition; a step of taking out and releasing the photo-cured product obtained in the step of photo-curing; and a step of heating the photo-cured product before, during or after the step of releasing the mold.

The step of photocuring by exposure may be performed under conditions for obtaining the cured product. Further, the conditions for the step of heating the photo-cured product are not particularly limited, but are generally appropriately selected from the range of 50 ℃ to 260 ℃ and 1 minute to 24 hours. The heating means is not particularly limited, and examples thereof include a hot plate and an oven. The molded article produced by such a method can be suitably used as a lens for a camera module.