TW202307036A - Photocurable composition for film formation - Google Patents

Abstract

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

Description

Photocurable composition for thin film formation

The present invention relates to silicon oxide particles containing a monofunctional or polyfunctional (meth)acrylate having one or more (meth)acryloxy groups in one molecule, a photoradical initiator, and a surface modified by a specific silane coupling agent And a photocurable composition of a polyrotaxane having a (meth)acryloxy group. The low viscosity of the photocurable composition of the present invention enables thin film coating such as spin coating, and the cured product and molded article obtained from the photocurable composition can be patterned by imprinting , and has high transparency, and has a refractive index of n ₅₅₀ =1.50 close to glass.

The imprinting method is a technique in which a mold (commonly known as a stamper or template) engraved with a concave-convex mold with a size of tens of nm to hundreds of nm is pressed against the resin material to cause mechanical deformation, and the fine pattern of the model is precisely transferred. . If the mold is manufactured at one time, it is easy to repeat the molding of the microstructure of the nanometer size, so it is more economical than the conventional pattern forming technology using lithography and etching.

The imprint method is roughly classified into two types according to the method. One is called a thermal imprint method using a thermoplastic resin as shown in Patent Document 1, and the other is called a photoimprint method using a photocurable resin as shown in Patent Document 2. In particular, the photoimprint method can shorten the manufacturing time because it uses an uncured material for pressing, and because it does not require high-pressure and high-temperature heating, it can also be used for components with weak heat resistance. Therefore, the yield is good, so the photoimprint method is widely used in the creation of optical materials.

In order to improve the imprinting yield by the photoimprinting method, generally a low-viscosity curable composition is coated on the substrate. Thereby, the curable composition can be fully filled in the mold. As a method of coating the curable composition for imprint on the substrate, known methods such as spin coating method, dip coating method, inkjet method and the like as shown in Patent Documents 3 and 4 are exemplified.

Examples of inventions using these methods include curable imprint compositions that have low viscosity and less volatilization of components on the substrate when applied, as shown in Patent Document 5.

On the other hand, as a method of improving the heat resistance, adhesiveness, optical properties, etc. of the cured product, the technique of compounding inorganic fine particles such as silicon oxide particles and zirconium oxide particles with an organic resin is well known. In the example shown in Patent Document 6, it is reported that by formulating a specific amount of a specific polyfunctional polymerizable monomer, silicon oxide particles surface-modified with a specific silane coupling agent, and a polyfunctional thiol in each curable composition, the improvement can be achieved. The transmittance of cured products and molded products obtained from curable compositions. [Prior Art Literature] [Patent Document]

[Patent Document 1] Specification of US Patent No. 5772905 [Patent Document 2] Specification of US Patent No. 6334960 [Patent Document 3] Japanese Patent No. 5348433 [Patent Document 4] Japanese Patent No. 5671377 [Patent Document 5] Japanese Unexamined Patent Publication No. 2014-170949 [Patent Document 6] International Publication No. 2020/129902

[Problem to be solved by the invention]

In Patent Document 5, when evaluating low volatility, since the remaining rate of a single polymerizable monomer is evaluated, the degree of low volatility of a curable composition containing two or more polymerizable monomers is unclear. Furthermore, the curable composition described in Patent Document 6 has a very high viscosity, and when it is applied to a substrate by a method such as a spin coating method, there is a problem that the uniformity of the film surface is significantly lowered. There has been no particle-added resin composition that has high transparency that can be used as an optical material, and can be coated with a uniform film by spin coating, etc., and its development is desired. The present invention was made in view of the above circumstances, and an object of the present invention is to provide a curable composition capable of solving the above-mentioned problems. [Means to solve the problem]

As a result of active examination by the present inventors in order to solve the above-mentioned problems, it was found that by blending a specific amount of a specific monofunctional or polyfunctional (meth)acrylate into the photocurable composition, the photocurable composition can be made A composition that can be used for thin film coating such as spin coating. Furthermore, the inventors of the present invention have found that a pattern can be formed by imprinting on a cured product and a molded product obtained from this photocurable composition.

(式中，X ¹表示氫原子或(甲基)丙烯醯氧基，R ¹及R ²分別獨立表示氫原子或碳原子數1或2之烷基，m表示1至14之整數，n表示0至2之整數) (d)：具有(甲基)丙烯醯氧基之聚輪烷。 That is, the first aspect of the present invention is a photocurable composition comprising the following (a) component to (d) component, relative to the total of 100 parts by mass of the (a) component to (d) component, The content of the (a) component is 80 to 99 parts by mass, the viscosity of the photocurable composition at 25.0°C is 1 mPa‧s to 50 mPa‧s, (a): one or more (a) in one molecule group) at least 2 kinds of monofunctional or polyfunctional (meth)acrylates of acryloxy group (except for the following (d) component), (b): photoradical initiator, (c): through the following Silicon oxide particles with a primary particle size of 1 nm to 100 nm surface-modified by at least one silane coupling agent represented by the above formula (1),

(In the formula, ^X1 represents a hydrogen atom or a (meth)acryloyloxy group, ^R1 and ^R2 independently represent a hydrogen atom or an alkyl group with 1 or 2 carbon atoms, m represents an integer from 1 to 14, and n represents an integer of 0 to 2) (d): a polyrotaxane having a (meth)acryloxy group.

(式中，R ³表示單鍵、碳原子數1至6之直鏈狀伸烷基或碳原子數3至6之分支鏈狀伸烷基，X ²表示單鍵、酯鍵或醚鍵，Q ¹表示包含至少1個雜原子或不含雜原子之碳原子數2至12之有機基或雜原子，p表示2至6之整數)。 上述雜原子表示氮、氧、硫等之碳及氫以外之原子。 The photocurable composition of the present invention may further contain the following (e) component, (e): a multifunctional thiol represented by the following formula (2)

(wherein, R ³ represents a single bond, a straight chain alkylene group with 1 to 6 carbon atoms or a branched chain alkylene group with 3 to 6 carbon atoms, X ² represents a single bond, an ester bond or an ether bond, Q ¹ represents an organic group or a heteroatom having at least one heteroatom or no heteroatom and having 2 to 12 carbon atoms, and p represents an integer of 2 to 6). The aforementioned heteroatoms represent atoms other than carbon and hydrogen such as nitrogen, oxygen, and sulfur.

The photocurable composition of this invention may contain following (f) component and/or following (g) component further. (f): Phenolic antioxidant (g): Thioether-based antioxidant

(式中，R ⁴表示氫原子或甲基，Q ²表示碳原子數4至10之直鏈狀或分支鏈狀之伸烷基)。 Said (a) component is selected from the group which consists of following (a1) component, following (a2) component, and following (a3) component, for example. (a1): Monofunctional (meth)acrylate (a2): Difunctional urethane (meth)acrylate (a3): Bifunctional (meth)acrylate represented by the following formula (3)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Q ² represents a linear or branched chain alkylene group having 4 to 10 carbon atoms).

The aforementioned component (c) is, for example, silicon oxide particles surface-modified with a silane coupling agent in which X ¹ of the aforementioned formula (1) is a (meth)acryloxyl group.

The second aspect of the present invention is a cured product, which is a cured product of the aforementioned photocurable composition having a film thickness of 1.0 μm to 10.0 μm.

The third aspect of the present invention is a method of manufacturing a molded body, which includes the step of embossing the aforementioned photocurable composition.

The fourth aspect of the present invention is a method of manufacturing a molded body, which is a method of manufacturing a molded body of a photocurable composition, and includes the following steps: a step of supplying the aforementioned photocurable composition on a substrate; An imprinting step in which the photocurable composition is brought into contact with a mold having a reverse pattern of the intended molded body shape; after the imprint step, the photocurable composition is exposed through the mold to form photocurable The photohardening step of the part; and the demoulding step of separating the photohardened part from the mold.

The aforementioned step of supplying the photocurable composition is a step of coating the photocurable composition by a spin coating method, a slit scan method or an inkjet method.

After the photohardening step, before, during or after the demoulding step, further includes the step of heating the photohardening part.

The aforementioned forming system is, for example, an optical film for flat panel displays. [Invention effect]

The photocurable composition of the present invention contains the aforementioned (a) component to the aforementioned (d) component as essential components, optionally includes the aforementioned (e) component, and further optionally includes the aforementioned (f) component and/or the aforementioned (g) component. By the existence of the aforementioned component (a) and the aforementioned component (b), when the aforementioned photocurable composition is exposed to light, a three-dimensional crosslinked body can be formed to obtain a cured product. In addition, it was found that component (a) lowered the viscosity of the composition to enable thin film coating such as spin coating, and at the same time, it was possible to form a pattern by imprinting.

Furthermore, by using the silicon oxide particles surface-modified by a silane coupling agent represented by the aforementioned formula (1) as the aforementioned (c) component, that is, a silane coupling agent having a hydrocarbon group having 1 to 14 carbon atoms, and As a result of improving the affinity and adhesion between the surface of the silicon oxide particles and the organic resin, the dispersibility of the silicon oxide particles can be improved, and the transparency of the cured product and molded product can be improved.

The photocurable composition of the present invention has a viscosity at 25.0°C of 1 mPa‧s to 70 mPa‧s, preferably 1 mPa‧s to 50 mPa‧s, more preferably 1 mPa‧s to 45 mPa‧s. Each component of the photocurable composition of this invention is demonstrated in detail. Also, in the present invention, the (meth)acryloxy group means a methacryloxy group represented by "CH ₂ =C(CH ₃ )-C(=O)O-" or a methacryloxy group represented by "CH ₂ =CH Acryloxy group represented by -C(=O)O-".

[Component (a): Monofunctional or polyfunctional (meth)acrylates having at least two types of (meth)acryloxy groups in one molecule] In this specification, among monofunctional or polyfunctional (meth)acrylates having one or more (meth)acryloxy groups in one molecule that can be used as component (a) of the photocurable composition of the present invention, The monofunctional (meth)acrylate is referred to as component (a1), and the compound having at least one urethane bond represented by "-NH-C(=O)O-" [difunctional aminomethyl Ester (meth)acrylate] is called (a2) component, and the bifunctional (meth)acrylate represented by said formula (3) is called (a3) component. When the photocurable composition of the present invention contains the component (a2), the cured product and molded article obtained from the photocurable composition have excellent adhesion to the substrate. When the photocurable composition of the present invention contains the component (a3), the cured product and the molded article obtained from the photocurable composition have excellent flexibility, and are compatible with the polycyclic resin having a (meth)acryloxy group described later. Excellent compatibility with alkanes. The component (a) of the photocurable composition of the present invention excludes the component (d) described later.

[(a1) Component: Monofunctional (meth)acrylate] Examples of the component (a1) include 2-acryloxyethyl phthalate, 2-acryloxy 2-hydroxyethyl phthalate, 2-acrylhexahydrophthalate Oxyethyl ester, 2-acryloxypropyl phthalate, 2-ethyl-2-butylpropylene glycol acrylate, 2-ethylhexyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl carbitol, 2-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-methoxy (meth)acrylate Ethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimer acrylate, benzyl (meth)acrylate, 1-naphthyl (meth)acrylate , 2-naphthyl (meth)acrylate, butanediol mono(meth)acrylate, butoxyethyl (meth)acrylate, butyl (meth)acrylate, crystal wax (meth)acrylate, Ethylene oxide modification (hereinafter referred to as "EO modification") cresol (meth)acrylate, dipropylene glycol (meth)acrylate, ethoxylated phenyl (meth)acrylate, ethyl (meth)acrylate , Isoamyl (meth)acrylate, Isobutyl (meth)acrylate, Isooctyl (meth)acrylate, Cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, (Meth) Dicyclopentyl acrylate, Dicyclopentyloxyethyl (meth)acrylate, Isomyristyl (meth)acrylate, Lauryl (meth)acrylate, Methoxydipropylene glycol (meth)acrylate, Methoxydipropylene glycol (meth)acrylate, Oxytripropylene Glycol (Meth) Acrylate, Methoxy Polyethylene Glycol (Meth) Acrylate, Methoxy Triethylene Glycol (Meth) Acrylate, Methyl (Meth) Acrylate, Neopentyl Diacrylate Alcohol Benzoate (Meth)acrylate, Nonylphenoxy Polyethylene Glycol (Meth)acrylate, Nonylphenylphenoxy Polypropylene Glycol (Meth)acrylate, Octyl (Meth)acrylate ester, p-cumylphenoxyethylene glycol (meth)acrylate, epichlorohydrin modified phenoxyacrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (methyl ) acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, stearyl (meth)acrylate, EO modified succinic acid (meth)acrylate, tertiary butyl (meth)acrylate, (meth) ) Tribromophenyl acrylate, EO modified (meth)tribromophenyl acrylate, tridecyl (meth)acrylate.

[(a2) Component: Difunctional (meth)acrylate] Examples of the aforementioned (a2) components include U-2PPA, U-200PA, U-160TM, U-290TM, UA-4200, UA-4400, UA-122P, and UA-W2A (above, Shin-Nakamura Chemical Co., Ltd.) ), AH-600, UF-8001G (above, manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL (registered trademark) 210, 230, 270, 280/15IB, 284, 4491, 4683, Same as 4858, same 8307, same 8402, same 8411, same 8413, same 8804, same 8807, same 9270, same 246/20HEMA, same 1271, same 286, same 4859, same 8409, same 8809, same 8810, same 8811, KRM (registered trademark) 7735, Tong 8961, Tong 8191 (above, manufactured by DAICEL ALLNEX Co., Ltd.), M-1100, M-1200 (above, manufactured by Toagosei Co., Ltd.), UV-2000B, UV-3000B, UV -3200B, UV-3300B, UV-3310B, UV-3500BA, UV-3520EA, UV-3700B, UV-6640B, and UV-6630B (the above are manufactured by Mitsubishi Chemical Co., Ltd.).

The said (a2) component can be used individually by 1 type or in combination of 2 or more types.

[Component (a3): Bifunctional (meth)acrylate represented by the aforementioned formula (3)] As the aforementioned (a3) component, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, ) acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate , 1,8-nonanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2,4,4-trimethyl-1,6-hexanediol di( Meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate ester, 1,9-decanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

Commercially available products can also be used as the aforementioned (a3) component, and specific examples include VISCOAT #195, VISCOAT #230, VISCOAT #260 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), BD, NPG, A-NPG, HD- N, A-HD-N, NOD-N, A-NOD-N, A-IND, DOD-N, A-DOD-N (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-121M, FA- 124M, FA-125M, FA-129AS (above, manufactured by Showa Denko Materials Co., Ltd.), LIGHT ESTER 1.4BG, LIGHT ESTER NP, LIGHT ESTER 1.6HX, LIGHT ESTER 1.9ND, LIGHT ACRYLATE 1.6HX-A, LIGHT ACRYLATE 1.9 ND-A, LIGHT ACRYLATE NP-A, LIGHT ACRYLATE MPD-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), HDDA (above, manufactured by DAICEL ALLNEX Co., Ltd.), HDDA, L-C9A and ND-DA ( Above, Daiichi Industrial Pharmaceutical Co., Ltd.).

The said (a3) component can be used individually by 1 type or in combination of 2 or more types.

Examples of difunctional (meth)acrylates that do not correspond to any of the above-mentioned (a2) component and the above-mentioned (a3) component among the above-mentioned polyfunctional (meth)acrylates include, for example, cyclohexanediol di(methyl) ) acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, diethylene glycol di( Meth)acrylate, Triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate , dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene polypropylene glycol di(meth)acrylate, polytetramethylene glycol Di(meth)acrylate, propylene oxide modified (hereinafter referred to as "PO modified") neopentyl glycol di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO Modified bisphenol A di(meth)acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate and hydroxypivalate neopentyl glycol di(meth)acrylate.

Commercially available products can also be used as difunctional (meth)acrylates that do not correspond to any of the above-mentioned (a2) component and the above-mentioned (a3) component. Chemical Industry Co., Ltd.), DCP, A-DCP, A-DOG, 2G, 3G, 4G, 9G, 14G, 23G, A-200, A-400, A-600, A-1000, APG-100, APG-200, APG-400, APG-700, 3PG, 9PG, A-1206PE, A-0612PE, A-0412PE, A-1000PER, A-3000PER, A-PTMG-65, ABE-300, A-BPE- 4. A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-222A, FA-220M, FA-240M, FA-240A, FA-P240A, FA-P270A, FA-023M, FA-PTG9M, FA-PTG9A, FA-320M, FA-321M, FA-3218M, FA-321A, FA-324A (Above, Showa Denko Materials ( Share) system), LIGHT ESTER 2EG, same 3EG, same 4EG, same 9EG, same 14EG, same BP-2EMK, LIGHT ACRYLATE (registered trademark) DCP-A, same 3EG-A, same 4EG-A, same 9EG-A , Same as 14EG-A, Same as PTMGA-250, Same as BP-4EAL, Same as BP-4PA, Same as HPP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.), DPGDA, TPGDA, IRR 214-K, EBECRYL ( Registered trademark) 11, Tong 130, Tong 145, Tong 150 (above, DAICEL ALLNEX (stock) system), PE-200, PE-300, PE-400, PE-600, PEM-1000, BPEM-4, BPE- 4. BPEM-10, BPE-10, BPE-20, HBPE-4, HBPEM-10 and HPN (manufactured by Daiichi Pharmaceutical Co., Ltd.).

The difunctional (meth)acrylate which does not correspond to any one of said (a2) component and said (a3) component can be used individually by 1 type, or can use it in combination of 2 or more types.

Examples of trifunctional or higher functional (meth)acrylates in the aforementioned polyfunctional (meth)acrylates include U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA-53H, UA -33H, UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-306T, UA-3061, UA-510H (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL (registered Trademark) 220, same 8800, same 294/25HD, same 4220, same 4513, same 4738, same 4740, same 4820, same 8311, same 9260, same 8701, same 4265, same 4587, same 4666, same 4680, same 8210 , Same 8405, Same 1290, Same 5129, Same 8301R, Same 4501, Same 2221, Same 8465, Same 1258, Same 4101, Same 4201, Same 8209, Same 1291, Same 8602, Same 225, KRM (registered trademark) 8667, Same as 8296, same 8528, same 8200, same 8200AE, same 8530, same 8904, same 8531BA, same 8452 (the above are made by DAICEL ALLNEX), UV-2750B, UV-7000B, UV-7510B, UV-1700B, Aminomethyl for UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, and UV-7650B (the above are manufactured by Mitsubishi Chemical Co., Ltd.) Ester (meth)acrylate.

Other examples of (meth)acrylic acid esters having more than three functions include VISCOAT #295, same #300, and same #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300-1CL, and A-GLY -9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, TMPT, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550 . TMP-A, same as PE-3A, same as PE-4A, same as DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), PETIA, PETRA, TMPTA, OTA480, EBECRYL (registered trademark) 160S, same 40, same EBECRYL (registered trademark) 140, Tong 1142, PETA, DPHA (made by DAICEL ALLNEX Co., Ltd. above), TMPTM, TMPT, TMP-2P, TMP-3P, TMP-3, PET-3, PETA-4, TEICA, MF -001, MF-101 (manufactured by the above Daiichi Pharmaceutical Co., Ltd.), M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-350, M-360, M-400, M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-460 and M-471 (the above Dongyahecheng (shares) )system).

The said trifunctional or more functional (meth)acrylate can be used individually by 1 type, or can use it in combination of 2 or more types.

The content of component (a) of the photocurable composition of the present invention is based on 100 mass of the sum of component (a), component (b), component (c) and component (d) contained in the photocurable composition Parts are 80 to 99 parts by mass, preferably 83.5 to 98 parts by mass, more preferably 87 to 97 parts by mass. When the said (a) component is less than 80 mass parts, there exists a possibility that the spin coating of the said composition may become impossible. Furthermore, the cured product and molded article obtained from the aforementioned photocurable composition cannot form an organic resin matrix with sufficient crosslink density, and the cured product and molded article may become brittle due to the low crosslink density.

When the aforementioned component (a) contains a component selected from the group consisting of component (a1), component (a2) and component (a3), its content is relative to the component (a) contained in the photocurable composition of the present invention , (b) component, (c) component and (d) component sum 100 mass parts, satisfy all following formula (4) to following formula (6), or following formula (4), following formula (5 ) and the relationship represented by the following formula (7), preferably satisfying all the following formulas (4') to (6'), or the following formula (4'), the following formula (5') and the following formula ( 7') the relationship represented, better satisfy all the following formulas (4") to (6"), or the following formula (4"), the following formula (5 ") and the following formula (7") Relation. Here, let the content of the aforementioned (a1) component be X parts by mass, the content of the aforementioned (a2) component be Y parts by mass, and the content of the aforementioned (a3) component be Z parts by mass. Formula (4): 80 parts by mass≦(X+Y+Z)≦99 parts by mass Formula (5): 0 parts by mass≦Y≦30 parts by mass Formula (6): 80 parts by mass≦(X+Y)≦99 parts by mass Formula (7): 86 parts by mass≦(Y+Z) Formula (4'): 83.5 parts by mass≦(X+Y+Z)≦98 parts by mass Formula (5'): 0 parts by mass≦Y≦20 parts by mass Formula (6'): 83.5 parts by mass≦(X+Y)≦98 parts by mass Formula (7'): 87 parts by mass≦(Y+Z) Formula (4"): 87 parts by mass≦(X+Y+Z)≦97 parts by mass Formula (5"): 0 parts by mass≦Y≦10 parts by mass Formula (6"): 87 parts by mass≦(X+Y)≦97 parts by mass Formula (7"): 88 parts by mass≦(Y+Z)

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

[(b) Component: Photoradical Initiator] Examples of photoradical initiators that can be used as component (b) of the photocurable composition of the present invention include benzophenones, benzophenones, biphenylyls, anthraquinones, acyl Phosphine oxides, benzoyl benzoates, oxime esters, and thioxanthones are especially preferred as intramolecular cleavage photoradical polymerization initiators. Commercially available products can be used as the aforementioned photoradical initiator, for example, OMNIRAD (registered trademark) 127, TO 184, TO 369, TO 369E, TO 379EG, TO 500, TO 651, TO 819, TO 784, TO 907, same as 1173, same as 2959, same as TPO H (above, manufactured by IGM Resins), IRGACURE (registered trademark) OXE01, same as OXE02, same as OXE03, same as OXE04, CGI1700, same as CGI1750, same as CGI1850, same as CG24-61 (above , Japan BASF (stock) system), ESACURE KIP150, same KIP65LT, same KIP100F, same KT37, same KT55, same KTO46 and same KIP75 (above, made by Lamberti Company).

The content of component (b) in the photocurable composition of the present invention is 0.1 mass parts relative to 100 parts by mass of the sum of component (a), component (c) and component (d) contained in the photocurable composition 5 parts by mass, preferably 0.5 parts by mass to 3 parts by mass. If the content of the aforementioned component (b) is less than 0.1 parts by mass, the strength of the cured product and molded body obtained from the aforementioned photocurable composition may decrease. If the content of the aforementioned component (b) is more than 5 parts by mass, the heat resistance of the cured product and molded product may deteriorate.

The said (b) component can be used individually by 1 type, or can use it in combination of 2 or more types.

[Component (c): silicon oxide particles with a primary particle size of 1 nm to 100 nm surface-modified by at least one silane coupling agent represented by the aforementioned formula (1)] The characteristic of the silane coupling agent represented by the aforementioned formula (1) that modifies the surface of the silicon oxide particles of (c) component of the photocurable composition of the present invention is that m in the formula (1) is an integer of 1 to 14, and also That is, a straight-chain hydrocarbon group with 1 to 14 carbon atoms in the molecule. Specifically, an alkoxysilane compound in which a straight-chain alkyl group with 1 to 14 carbon atoms is bonded to a silicon atom, or a (meth)acryloxy group via a straight-chain alkylene compound with 1 to 14 carbon atoms An alkoxysilane compound in which the group is bonded to a silicon atom. In the case of a silane coupling agent in which m in the aforementioned formula (1) is 15 or more, the crystallinity of the linear hydrocarbon group becomes remarkable, and the silicon oxide particles surface-modified with the silane coupling agent may aggregate.

Examples of silane coupling agents represented by the aforementioned formula (1) include methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, and n-pentyltrimethoxysilane. Nylsilane, n-hexyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane Silane, n-butyltriethoxysilane, n-pentyltriethoxysilane, n-hexyltriethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, dimethyldi Methoxysilane, Diethyldimethoxysilane, 3-(Meth)acryloxypropylmethyldimethoxysilane, Dimethyldiethoxysilane, Diethyldiethoxy Silane, 3-(meth)acryloxypropylmethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, 3-(meth)acryloxypropyl Dimethylmethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-octylmethyldimethoxysilane, n-octylethyldimethoxysilane, n-octyl Methyldiethoxysilane, n-octylethyldiethoxysilane, n-octyldimethylmethoxysilane, n-octyldiethylmethoxysilane, n-octyldimethylethoxy Silane, n-octyldiethylethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane , n-tetradecyltrimethoxysilane, n-tetradecyltriethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 8-(meth)acryloxyoctyl Triethoxysilane, 8-(meth)acryloxyoctylmethyldimethoxysilane, 8-(meth)acryloxyoctylethyldimethoxysilane, 8-( Meth)acryloxyoctylmethyldiethoxysilane, 8-(meth)acryloxyoctylethyldiethoxysilane, 8-(meth)acryloxyoctyldiethoxysilane Methylmethoxysilane, 8-(meth)acryloxyoctyldiethylmethoxysilane, 8-(meth)acryloxyoctyldimethylethoxysilane, 8-( Meth)acryloxyoctyldiethylethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, 10-(meth)acryloxydecyltriethoxy Silane, 12-(meth)acryloxydodecyltrimethoxysilane, 12-(meth)acryloxydodecyltriethoxysilane, 14-(meth)acryloxy 14-(meth)acryloxytetradecyltrimethoxysilane and 14-(meth)acryloxytetradecyltriethoxysilane.

As the silane coupling agent represented by the aforementioned formula (1), commercially available products can be used, and specific examples are KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-13, KBE-13, KBM -22, KBE-22, KBM-3033, KBM-3033, KBM-3063, KBE-3063, KBM-5803, KBM-3103C, and KBE-3083 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The silane coupling agents represented by the aforementioned formula (1) may be used alone or in combination of two or more.

Also, the silane coupling agent represented by the aforementioned formula (1) and other silane coupling agents not represented by the formula (1) may be used in combination. As the other silane coupling agents, for example, isopropyltrimethoxysilane, isobutyl Cyclopentyltrimethoxysilane, Cyclopentyltrimethoxysilane, Cyclohexyltrimethoxysilane, Isooctyltrimethoxysilane, Vinyltrimethoxysilane, Allyltrimethoxysilane, Phenyltrimethoxysilane , p-tolyltrimethoxysilane, p-styryltrimethoxysilane, benzyltrimethoxysilane, 1-naphthyltrimethoxysilane, trimethoxy[3-(anilino)propyl]silane , [3-(N,N-dimethylamino)propyl]trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 8-(2-aminoethylamino ) octyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, tris[3-(trimethoxysilane )propyl]isocyanurate, isopropyltriethoxysilane, isobutyltriethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, isooctyltriethoxysilane Oxysilane, Vinyltriethoxysilane, Allyltriethoxysilane, Phenyltriethoxysilane, p-Tolyltriethoxysilane, p-Styryltriethoxysilane, Benzyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, tris[3-(triethyl Trialkoxysilanes such as oxysilyl)propyl]isocyanurate, diisobutyldimethoxysilane, cyclopentylmethyldimethoxysilane, dicyclopentyldimethoxy silane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, di-p-tolyldimethylsilane Oxysilane, 3-Aminopropylmethyldimethoxysilane, 3-Mercaptopropylmethyldimethoxysilane, Diisobutyldiethoxysilane, Cyclopentylmethyldiethoxysilane Silane, Dicyclopentyldiethoxysilane, Cyclohexylmethyldiethoxysilane, Vinylmethyldiethoxysilane, Phenylmethyldiethoxysilane, Diphenyldiethoxysilane , Two-p-tolyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3- Dialkoxysilanes such as mercaptopropylmethyldiethoxysilane, vinyldimethylmethoxysilane, phenyldimethylmethoxysilane, diphenylmethylmethoxysilane, three Monoalkoxysilanes such as phenylmethoxysilane and polyfunctional silane coupling agents.

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

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

When the silane coupling agent represented by the aforementioned formula (1) is used to modify the surface of silicon oxide particles with other silane coupling agents not represented by the aforementioned formula (1), the amount of these silane coupling agents used in the silicon oxide particle Per 1g, satisfy all the relationships represented by the following formula (8) and the following formula (9), preferably satisfy all the relationships represented by the following formula (8') and the following formula (9'), more preferably satisfy all of the relationships represented by the following formula (9') The relationship represented by the following formula (8") and the following formula (9"). Here, let the usage-amount of the silane coupling agent represented by said formula (1) be y millimole, and let the usage-amount of the other silane coupling agent not represented by said formula (1) be z millimole. Formula (8): 0.1 millimolar≦(y+z)≦2 millimolar Formula (9): 0.1 millimolar≦y Formula (8'): 0.2 millimolar≦(y+z)≦1.5 millimolar Formula (9'): 0.2 millimolar≦y Formula (8"): 0.3 millimolar≦(y+z)≦1 millimolar Formula (9"): 0.3 millimolar≦y

When the amount of the silane coupling agent represented by the aforementioned formula (1) is less than 0.1 millimoles, the affinity and adhesion between the surface of the silicon oxide particles and the organic resin become insufficient, and the photocurable properties of the present invention may be reduced. There is a risk that the transmittance of the cured product and molded product obtained from the composition will decrease. If the total amount of the silane coupling agent represented by the aforementioned formula (1) and other silane coupling agents not represented by the aforementioned formula (1) is more than 2 millimoles, the silane coupling agent becomes excessive relative to the silicon oxide particles , the silane coupling agent that is not consumed in the surface modification of the silicon oxide particles is remarkably produced, which may deteriorate the storage stability and mechanical properties of the aforementioned cured product and molded product.

The silicon oxide particles of the component (c) of the photocurable composition of the present invention have a primary particle size of 1 nm to 100 nm. Here, the so-called primary particles are the particles constituting the powder, and the aggregated particles of the primary particles are called secondary particles. The aforementioned primary particle size can be obtained from the relationship between the specific surface area (surface area per unit mass) S of the aforementioned silicon oxide particles measured by the gas adsorption method (BET method), the density ρ of the silicon oxide particles, and the primary particle size D Formula: D=6/(ρS) and calculated. The primary particle diameter calculated from the aforementioned relational formula is the average particle diameter, and is the diameter of the primary particle. When the primary particle diameter is less than 1 nm, the silicon oxide particles are likely to aggregate, and the storage stability may deteriorate. When the primary particle size exceeds 100 nm, there is a possibility that the transparency of the cured product and the molded product may be impaired.

The silicon oxide particles of the aforementioned component (c) can be those obtained by reacting non-surface-modified silicon oxide particles with the aforementioned silane coupling agent by various known methods. As the aforementioned surface-modified silicon oxide particles, for example, one in which the silicon oxide particles are dispersed in an organic solvent (organic silicon oxide sol) is preferably used.

Commercially available products can be used as the organic silica sol, for example, CHO-ST-M, DMAC-ST, DMAC-ST-ZL, EAC-ST, EG-ST, EG-ST-ZL, EG-ST-XL30 , IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, methanol silica sol, MA-ST-M, MA-ST-L, MA-ST-ZL, MA-ST- UP, MEK-ST, MEK-ST-40, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-ST-L, NMP-ST, NPC-ST-30, PMA-ST, PGM-ST, PGM-ST, PGM-ST-UP, and TOL-ST (manufactured by Nissan Chemical Co., Ltd.).

As the aforementioned organosilica sol, those obtained by substituting commercially available water-dispersed silica sols with organic solvents by known methods such as vacuum distillation or ultrafiltration, or those obtained by dispersing commercially available powdered silica particles in organic solvents can also be used.

The silicon oxide solid content concentration in the aforementioned organosilica sol is not particularly limited, but is generally preferably 60% by mass or less.

The content of component (c) in the photocurable composition of the present invention is based on 100 parts by mass of the sum of component (a), component (b), component (c) and component (d) contained in the photocurable composition , is 0.5 to 13 parts by mass, preferably 1 to 11.5 parts by mass, more preferably 1.5 to 10 parts by mass. If the content of the aforementioned component (c) is less than 0.5 parts by mass, the adhesiveness and heat resistance of the cured product and molded body obtained from the aforementioned photocurable composition may deteriorate. When content of the said (c) component exceeds 13 mass parts, fogging may generate|occur|produce in the said hardened|cured material and a molded object, and there exists a possibility that transmittance may fall.

The said (c) component can be used individually by 1 type, or can use it in combination of 2 or more types. For example, a plurality of silicon oxide particles with different primary particle diameters can be combined, and a plurality of silicon oxide particles with different types or amounts of silane coupling agents used for surface modification can also be combined.

[(d) component: polyrotaxane having (meth)acryloxy group] The polyrotaxane having a (meth)acryloxy group, which can be used as the component (d) of the photocurable composition of the present invention, is a pseudo-polyrotaxane that is included in the opening of a cyclic molecule in a chain-fired shape of a linear molecule. Blocking groups are arranged at both ends of the polyrotaxane so that the aforementioned cyclic molecule having a (meth)acryloyloxy group is not detached. The cyclic molecules, linear molecules and blocking groups which are the constituent elements of the aforementioned polyrotaxanes will be described.

＜d-1. Cyclic molecule＞ The cyclic molecule of the aforementioned polyrotaxane is not particularly limited as long as it is cyclic and has an opening, and is included in a chain of linear molecules. The aforementioned (meth)acryloxy group may be directly bonded to the aforementioned cyclic molecule, or may be bonded via a spacer. The aforementioned spacer is not particularly limited, but is exemplified by those selected from, for example, alkylene groups, (poly)alkylene glycols, hydroxyalkylene groups, urethane bonds [-NH-C(=O)O-], 1 or a combination of 2 or more of the group of ester bond [-C(=O)O-] and carbonate bond [-O-C(=O)O-]. The aforementioned cyclic molecule is preferably, for example, selected from the group consisting of α-cyclodextrin, β-cyclodextyl and γ-cyclodextrin.

＜d-2. Linear molecule＞ The linear molecule of the aforementioned polyrotaxane is not particularly limited as long as the opening of the cyclic molecule used is included in a skewer shape. As the linear molecule, preferably selected from polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene , polyvinyl alcohol and polyvinyl methyl ether, particularly preferably polyethylene glycol.

The aforementioned linear molecules have a weight average molecular weight of not less than 1,000, preferably 3,000-100,000, more preferably 6,000-50,000. Among the aforementioned polyrotaxanes, a preferred combination of (cyclic molecule, linear molecule) is (derived from α-cyclodextrin, derived from polyethylene glycol).

＜d-3. Blockade base＞ The aforementioned blocking group of the polyrotaxane is not particularly limited as long as it is a group arranged at both ends of the pseudopolyrotaxane and acts so as not to detach the cyclic molecule used. As the aforementioned blocking group, for example, those selected from dinitrophenyls, cyclodextrins, adamantyls, triphenylmethyls, fluoresceins, silsesquioxanes and pyrenes are preferred. The group of blocking groups is more preferably adamantyls or cyclodextrins. This blocking group can be bonded to the aforementioned linear molecule via, for example, [-NH-C(=O)-].

Commercially available products can be used as the aforementioned polyrotaxane, and specific examples thereof are CELM (registered trademark) superpolymer SA1305P, TO SA1303P, TO SA1305P-10, TO SA2403P, TO SA2405P-10, TO SA3403P, TO SM1303P, TO SM2403P and TO SM3403P [The above is made by ASM (stock) (formerly ADVANCED SOFTMATERIALS (stock))].

When the photocurable composition of the present invention contains component (d), its content is 100% relative to the sum of component (a), component (b), component (c) and component (d) contained in the photocurable composition. The mass parts are 0.5 to 7 mass parts, preferably 1 to 5 mass parts. By blending the above-mentioned component (d), toughness can be imparted to the cured product and molded product obtained from the above-mentioned photocurable composition, and the mechanical properties and thermal shock resistance can be improved.

The said (d) component can be used individually by 1 type, or can use it in combination of 2 or more types.

[(e) component: multifunctional thiol represented by the aforementioned formula (2)] The polyfunctional thiol represented by the aforementioned formula (2) that can be used as the component (e) of the photocurable composition of the present invention is, for example, 1,2-ethaneedithiol, 1,3-propaneedithiol , bis(2-mercaptoethyl) ether, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)ethyl]isocyanurate, tetraethylenedi Alcohol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(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), trimethylolethane tris(3-mercaptobutyrate), and pentaerythritol tris(3-mercaptopropyl) ether.

Commercially available products can be used as the multifunctional thiol compound represented by the aforementioned formula (2), for example, CURRENTSMT (registered trademark) PE1, Tong NR1, Tong BD1, TPMB, TEMB (manufactured by Showa Denko Co., Ltd.), TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, and PEPT (manufactured by SC Organic Chemical Co., Ltd.).

The content of component (e) in the photocurable composition of the present invention is based on 100 parts by mass of the sum of component (a), component (b), component (c) and component (d) contained in the photocurable composition , is 0 to 4 parts by mass, preferably 0.2 to 3 parts by mass. By mixing the aforementioned component (e), polymerization inhibition due to oxygen is reduced during photocuring of the aforementioned photocurable composition, and the radical reaction efficiency can be improved. Moreover, the transmittance of cured products and molded products obtained from the aforementioned photocurable composition can be improved. When the content of the component (e) is more than 4 parts by mass, when the cured product and the molded product are exposed to a high temperature/high humidity environment, cloudiness or the like may be generated, thereby deteriorating reliability.

The said (e) component can be used individually by 1 type, or can use it in combination of 2 or more types.

[(f) component: phenolic antioxidant] Phenolic antioxidants that can be used as component (f) of the photocurable composition of the present invention include, for example, IRGANOX (registered trademark) 245, TO 1010, TO 1035, TO 1076, TO 1135 (the above are Japanese BASF (stock) )), SUMILIZER (registered trademark) GA-80, same GP, same MDP-S, same BBM-S, same WX-R (the above are manufactured by Sumitomo Chemical Co., Ltd.), ADEKASTAB (registered trademark) AO-20, Same as AO-30, same as AO-40, same as AO-50, same as AO-60, same as AO-80 and same as AO-330 (the above are made by ADEKA).

When the photocurable composition of the present invention contains component (f), its content is 100% relative to the sum of component (a), component (b), component (c) and component (d) contained in the photocurable composition. The parts by mass are 0.05 parts by mass to 3 parts by mass, preferably 0.1 parts by mass to 1 part by mass.

The said (f) component can be used individually by 1 type, or can use it in combination of 2 or more types.

[(g) ingredient: sulfide-based antioxidant] The thioether-based antioxidant that can be used as the component (g) of the photocurable composition of the present invention includes, for example, ADEKASTAB (registered trademark) AO-412S, Tong AO-503 (the above are manufactured by ADEKA Co., Ltd.), IRGANOX (registered trademark) PS802, the same PS800 (the above are made by BASF Co., Ltd. of Japan) and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).

When the photocurable composition of the present invention contains component (g), its content is 100% relative to the sum of component (a), component (b), component (c) and component (d) contained in the photocurable composition. The mass part is 0.2 mass part to 1 mass part, preferably 0.5 mass part to 0.7 mass part.

The said (g) component can be used individually by 1 type, or can use it in combination of 2 or more types.

＜Other additives＞ Furthermore, the photocurable composition of the present invention may contain chain transfer agents, ultraviolet absorbers, light stabilizers, leveling agents, rheology modifiers, silane coupling agents, etc. as necessary, as long as the effects of the present invention are not impaired. Additives for auxiliary agents, pigments, dyes, defoamers, etc.

＜Preparation method of photocurable composition＞ The preparation method of the photocurable composition of this invention is not specifically limited. As a preparation method, for example, components (a), (b), (c), and (d) and, if necessary, (e), (f) and/or (g) are mixed in specific proportions Mix to make a homogeneous solution.

Also, the photocurable composition of the present invention prepared as a solution is preferably used after being filtered through a filter having a pore diameter of 0.1 μm to 10 μm.

＜hardened material＞ The photocurable composition of the present invention is exposed (photocured) to obtain a cured product, and the present invention is also intended to be such a cured product. The light to be exposed is not particularly limited as long as the above-mentioned cured product can be obtained, but examples thereof include ultraviolet rays, electron beams, and X-rays. As a light source for ultraviolet irradiation, for example, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used. In addition, post-baking may be performed to stabilize the physical properties of the cured product after exposure. The post-baking method is not particularly limited, but is usually carried out at 50°C to 260°C for 1 minute to 24 hours using a hot plate, an oven, or the like.

The cured product obtained by photocuring the photocurable composition of the present invention has a high transmittance of 90% or more at a wavelength of 410 nm. Therefore, the photocurable composition of the present invention can be preferably used as an optical film for flat panel displays.

＜Molded body＞ The photocurable composition of the present invention can easily produce various molded objects (patterns) in parallel with the formation of a cured product by using, for example, an imprint method. The following describes the detailed process for the production of the molded body.

＜Coating procedure＞ The manufacturing method of the molded article of the present invention is a step of supplying (preferably applying, more preferably coating) the photocurable composition of the present invention on a substrate to form a coating layer (pattern forming layer). As the coating method for supplying the photocurable composition of the present invention on the substrate by coating, there are generally known coating methods such as spin coating, dip coating, and air knife coating. coating method, curtain flow coating method, wire bar coating method, gravure coating method, extrusion coating method and other coating methods; slit scanning method; inkjet method, etc.

Also, the thickness of the coating layer made of the photocurable composition of the present invention varies depending on the application, but may be about 0.05 μm to 10 μm. Furthermore, the photocurable composition of the present invention can also be applied by multiple coating. Moreover, other organic layers, such as a planarization layer, etc. can also be formed between a base material and the coating layer which consists of the photocurable composition of this invention, for example. Thereby, since the coating layer is not in direct contact with the substrate, it is possible to prevent dust from adhering to the substrate or damage to the substrate. In addition, the molded article (pattern) formed of the photocurable composition of the present invention has excellent adhesion to the organic layer even when an organic layer is provided on the substrate.

In the method of manufacturing a molded body using the photocurable composition of the present invention, among the aforementioned coating methods, the coating method in which the surface area per constant volume of the composition (specific surface area) is significantly increased during coating can more significantly express the present invention. The effect of the invention is therefore better. As a preferable coating method, a spin coating method, a slit scanning method, and an inkjet method are mentioned. In the method for producing the molded article of the present invention, the method of supplying the photocurable composition on the substrate is more preferably a spin coating method or an inkjet method.

Also, the aforementioned base material is, for example, a semiconductor substrate of silicon coated with a silicon oxide film, a semiconductor substrate of silicon coated with a silicon nitride film or a silicon oxide nitride film, a silicon nitride substrate, a quartz substrate, a glass substrate ( Including non-alkali glass, low-alkali glass, crystallized glass), glass substrate with ITO film formed.

＜Imprinting procedure＞ The manufacturing method of the molded article of the present invention includes a step of pressing a mold against the surface of the coating layer in order to transfer the pattern to the coating layer (pattern forming layer). Thereby, the fine patterns previously formed on the pressing surface of the mold can be transferred to the coating layer. The material of the foregoing mold is not limited as long as it is a material through which light such as ultraviolet light used in the photocuring step described later is permeable, but examples include (meth)acrylic resins such as polymethyl methacrylate, cycloolefin polymers ( COP) resin, quartz, borosilicate glass and calcium fluoride. When the material of the aforementioned mold is resin, it can be any one of non-photosensitive resin and photosensitive resin. As the photosensitive resin, for example, the imprint replica mold material disclosed in International Publication No. 2019/031359 is exemplified. And the aforementioned mold may also have a light-shielding film, and the material of the light-shielding film is not limited as long as it is impermeable to light such as ultraviolet light used in the photohardening step described later, but examples are aluminum, chromium, nickel, cobalt, titanium, Tantalum, Tungsten and Molybdenum.

The above-mentioned mold is desirably used after applying a mold release agent and drying it for a mold release process in the mold release process described later. The above-mentioned release agent can be obtained as a commercial product, for example, Novec (registered trademark) 1700, Tong 1710, Tong 1720 (the above are manufactured by Japan 3M Co., Ltd.), FLUORO SURF (registered trademark) FG-5084, Tong FG- 5093 (the above are made by FLUORO TECHNOLOGY (stock)), DURA SURF (registered trademark) DP-500, same as DP-200, same as DS-5400, same as DH-100, same as DH-405TH, same as DH-610, same as DS- 5800, the same as DS-5935 (the above are made by HARVES (stock)), POLYFLON (registered trademark) PTFE TC-7105GN, the same as PTFE TC-7109BK, the same as PTFE TC-7113LB, the same as PTFE TC-7400CR, the same as PTFE TC-7405GN, Same as PTFE TC-7408GY, same as PTFE TC-7409BK, same as PTFE TC-7609M1, same as PTFE TC-7808GY, same as PTFE TC-7809BK, same as PTFE TC-7139BD, OPTOOL (registered trademark) DAC-HP, same as DSX-E, OPTOACE (registered trademark) WP-140, DIEFREE (registered trademark) GW-4000, same as GW-4010, same as GW-4500, same as GW-4510, same as GW-8000, same as GW-8500, same as MS-175, same as GF -700, same as GF-750, same as MS-600, same as GA-3000, same as GA-9700, same as GA-9750 (the above are manufactured by DAIKIN Industry Co., Ltd.), MAGAFAC (registered trademark) F-553, same as F- 555, same as F-558, same as F-561 (the above are manufactured by DIC), SFE-DP02H, SNF-DP20H, SFE-B002H, SNF-B200A, SCV-X008, SFEX008, SNF-X800, SR-4000A , S-680, S-685, MR F-6441-AL, MR F-6711-AL, MR F-6758-AL, MR F-6811-AL and MR EF-6521-AL (the above are AGC SEMICHEMICAL (stock )system). Examples of the release agent include, for example, the release agent for a mold disclosed in International Publication No. 2019/031312 in addition to the above-mentioned commercially available products.

＜Photohardening step＞ The method for producing a molded article of the present invention includes, after the imprinting step, a photocuring step of exposing the photocurable composition through the mold to form a photocurable portion. The light to be exposed is not particularly limited as long as it can form the photohardened portion, but examples thereof include ultraviolet rays, electron beams, and X-rays. As a light source for ultraviolet irradiation, for example, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used. The film thickness of the photohardening part is usually 1 μm to 10 μm, preferably 1.5 μm to 8 μm, more preferably 2 μm to 6 μm. When the aforementioned mold is made of a material that is permeable to ultraviolet light and the like and has a light-shielding film that does not transmit the ultraviolet light or the like, it is used as a mask in this step.

＜Heating step＞ In the method for producing a molded article of the present invention, it is preferable to include a heating step after the aforementioned photocuring step and before the later-described demolding step. By including the heating step, the effects of the present invention are more remarkably exhibited. The heating temperature is preferably from 30°C to 150°C, more preferably from 40°C to 120°C, and more preferably from 50°C to 110°C. The heating time is preferably from 10 seconds to 5 minutes, more preferably from 20 seconds to 3 minutes, and more preferably from 30 seconds to 2 minutes.

＜Demolition procedure＞ The manufacturing method of the molded article of this invention has the demoulding process which separates the said photohardening part from the said mold. The mold release method is not particularly limited as long as it can completely separate from the mold without damaging or deforming the photocured portion. The above mold can be easily separated from the mold by applying the release agent to the mold and drying it. After the aforementioned light hardening step, before, during or after this demoulding step, there may be a step of heating the aforementioned light hardening part. In this case, the heating condition of the photo hardening part can be from, for example, 50°C to 260°C for 1 minute The range from 24 hours to 24 hours is properly selected. Moreover, it does not specifically limit as a heating means, For example, a hot plate and an oven are mentioned.

＜Anti-reflection film formation process＞ The manufacturing method of the molded article of the present invention further includes the step of forming an anti-reflection film on the surface of the photohardened portion after the aforementioned demolding step. The anti-reflection film is formed on the surface of the photo-cured product in order to suppress the reflection of light incident on the photo-cured product and increase the transmittance. Examples of methods for forming the aforementioned antireflection film include vacuum evaporation, sputtering, CVD, atomization, spin coating, dip coating, and spray coating. Furthermore, examples of the aforementioned antireflection film include inorganic films such as magnesium fluoride and silicon dioxide, and organic films such as organopolysiloxane.

The molded body (pattern) produced by these methods can be preferably used in interlayer insulating films of semiconductor elements, gate insulating films, spacers, protective films, polarizers of liquid crystal display elements, optical components, and the like. [Example]

The following examples are given to describe the present invention more specifically, but the present invention is not limited to the following examples. In addition, in the following examples and comparative examples, the equipment and conditions used for preparation of samples and analysis of physical properties are as follows.

(1) stirring defoaming Device: AWATORY Rentaro (registered trademark) ARE-310, rotation and revolution mixer made by THINKY Co., Ltd. (2) Viscosity determination Device: E-type viscometer TVE-22L manufactured by Toki Sangyo Co., Ltd. (3) Film thickness measurement Apparatus: Film thickness measuring device F-20 (n=1.50) manufactured by Filmerics Co., Ltd. (4) UV exposure and embossing Device: Mingchang Machinery Co., Ltd. thermal UV hardening type corresponding hybrid nanoprinter NM-0801HB (wavelength 365nm) (5) Measurement of transmittance Device: UV-visible-near-infrared spectrophotometer V-670 manufactured by Nippon Spectroscopic Co., Ltd. Reference material: air (6) Refractive index measurement Device: Metricon Co., Ltd. Metricon coupler MODEL2010/M (7) Embossability evaluation Device: Field emission scanning electron microscope S-4800 manufactured by Hitachi High-Tech Co., Ltd.

The supply sources of the compounds used in the respective production examples, examples, and comparative examples are as follows. APG-100: Manufactured by Shin Nakamura Chemical Co., Ltd. Product name: NK ESTER APG-100 UA-4200: Manufactured by Shin Nakamura Chemical Co., Ltd. Product name: NK OLIGO UA-4200 V#150: Made by Osaka Organic Chemical Industry Co., Ltd. Product name: VISCOAT #150 V#160: Made by Osaka Organic Chemical Industry Co., Ltd. Product name: VISCOAT #160 V#190: Made by Osaka Organic Chemical Industry Co., Ltd. Product name: VISCOAT #190 V#230: Made by Osaka Organic Chemical Co., Ltd. Product name: VISCOAT #230 V#260: Made by Osaka Organic Chemical Co., Ltd. Product name: VISCOAT #260 I184: IGM Resins product name OMNIRAD (registered trademark) 184 MOTMS: Shin-Etsu Chemical Co., Ltd. Product name: KBM-5803 Silica sol i: Nissan Chemical Co., Ltd. product name: MA-ST-M PEPT: manufactured by SC Organic Chemical Co., Ltd. Trade name: PEPT SA1305P: ASM (stock) (formerly made by ADVANCED SOFTMATERIALS (stock)) Trade name: CELM (registered trademark) super polymer SA1305P I245: Japan BASF Co., Ltd. product name: IRGANOX (registered trademark) 245

V#150, V#160, and V#190 are monofunctional (meth)acrylates having one (meth)acryloxy group in one molecule that can be used as the component (a1).

APG-100, UA-4200, V#230, and V#260 are polyfunctional (meth)acrylates having two or more (meth)acryloxy groups in one molecule that can be used as the aforementioned component (a). These are all difunctional (meth)acrylates with 2 (meth)acryloxy groups in one molecule, and among them, UA-4200 is the difunctional urethane of the aforementioned component (a2) (Meth)acrylates, V#230 and V#260 are difunctional (meth)acrylates represented by the aforementioned formula (3) of the aforementioned (a3) component.

I184 is a photofree radical initiator that can be used as the aforementioned (b) component.

The aforementioned MOTMS is a silane coupling agent represented by the aforementioned formula (1) that modifies the surface of the silicon oxide particles of the aforementioned (c) component.

Silica sol i (methanol-dispersed silica sol, primary particle diameter 20nm to 25nm, silica particle concentration 40% by mass) is the raw material of silicon oxide particles of the aforementioned (c) component, which contains primary particle diameter 1nm to 100nm without surface Organic silicon oxide sol of modified silicon oxide particles.

SA1305P (the cyclic molecule is cyclodextrin, the straight-chain molecule is a polyethylene glycol chain, and the blocking group is made of adamantyl group, and the side chain spacer of the cyclic molecule has acryloxyl group) Ethyl acetate dispersion of alkane, solid content concentration 50% by mass) is a polyrotaxane having a (meth)acryloxy group that can be used as the aforementioned component (d).

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

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

[manufacturing example 1] In a 100mL pear-shaped flask, weigh 50g of silica sol i and 5g of MOTMS (0.8 millimole per 1g of silica particles), and carry out the hydrolysis and condensation reaction in an oil bath at 65°C for a total of 6 hours. Next, in a 200mL pear-shaped flask, weigh 40g of the methanol dispersion of MOTMS-modified silicon oxide particles (solid content concentration: 45% by mass), and 15g of UA-4200. Methanol was distilled off at a pressure of 133.3 Pa or less to obtain a UA-4200 dispersion of MOTMS-modified silicon oxide particles (the concentration of the MOTMS-modified silicon oxide particles was 55% by mass).

[Manufacturing example 2] In a 100mL pear-shaped flask, weigh 20g of V#260 and 40g of SA1305P, stir and homogenize, then use a rotary evaporator to distill off ethyl acetate at 50°C and a reduced pressure of 133.3Pa or less to obtain the polyrotaxane V#260 dispersion liquid (this polyrotaxane concentration is 50% by mass).

In the preparation of the photocurable composition of the Examples and Comparative Examples described later, when mixing the surface-modified silicon oxide particles of the aforementioned (c) component, it was formulated as the UA-4200 dispersion obtained in the aforementioned Production Example 1. For the polyrotaxane of the aforementioned (d) component, it is formulated as the V# 260 dispersion liquid obtained in the aforementioned Production Example 2.

[Example 1] Prepare 0.7 g of UA-4200 and 3.6 g of V#260 as the aforementioned (a) component, 0.05 g of the aforementioned I184 as the aforementioned (b) component, and 0.45 g of the UA-4200 dispersion obtained in Production Example 1 as the aforementioned (c) component g (0.25 g in terms of MOTMS-modified silica particles), 0.25 g (0.13 g in terms of polyrotaxane) of the V#260 dispersion obtained in Production Example 2 of the above-mentioned (d) component, shake at 25.0°C for 15 hours After mixing, stirring and defoaming was performed for 10 minutes using the aforementioned stirring and defoaming machine to prepare photocurable composition 1 .

[Example 2] In addition to using 0.1 g of UA-4200 and 4.2 g of V#260 as the aforementioned (a) component, 0.55 g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned (c) component (0.30 g in terms of MOTMS-modified silica particles) ), except that 0.15 g (0.075 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, a photocurable composition 2 was prepared in the same procedure as in Example 1.

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

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

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

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

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

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

[Example 9] In addition to using 0.05 g of UA-4200 and 3.6 g of V#260 as the aforementioned component (a), 0.90 g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned component (c) (0.50 g in terms of MOTMS-modified silica particles) ), except that 0.38 g (0.19 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, the procedure was the same as that of Example 8, and after mixing the solution, add as the aforementioned (e) A photocurable composition 9 was prepared in the same procedure as in Example 8 except that 0.10 g of PEPT was used as a component.

[Example 10] In addition to using 0.02g of UA-4200 and 4.4g of V#260 as the aforementioned component (a), 0.36g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned component (c) (0.20g in terms of MOTMS-modified silica particles) ), except that 0.15 g (0.075 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, the procedure was the same as in Example 8. After mixing the solution, add as the aforementioned (e) A photocurable composition 10 was prepared in the same procedure as in Example 8 except for 0.04 g of PEPT as a component.

[Example 11] In addition to using 0.01g of UA-4200 and 4.7g of V#260 as the aforementioned component (a), 0.17g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned component (c) (0.094g in terms of MOTMS-modified silica particles) ), except that 0.07 g (0.035 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, the procedure was the same as in Example 8. After mixing the solution, add as the aforementioned (e) A photocurable composition 8 was prepared in the same procedure as in Example 10 except for 0.02 g of PEPT as a component.

[Example 12] In addition to using 0.02 g of UA-4200 and 4.4 g of V#150 as the aforementioned (a) component, 0.36 g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned (c) component (0.20 g in terms of MOTMS-modified silica particles) ), except that 0.15 g (0.075 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, the procedure was the same as in Example 8. After mixing the solution, add as the aforementioned (e) A photocurable composition 12 was prepared in the same procedure as in Example 8 except for 0.04 g of PEPT as a component.

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

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

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

[Comparative example 4] In addition to using 1.1 g of UA-4200 and 2.8 g of V#230 as the aforementioned (a) component, 0.73 g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned (c) component (0.40 g in terms of MOTMS-modified silica particles) ), except that 0.39 g (0.20 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the above-mentioned (d) component, a photocurable composition 16 was prepared in the same procedure as in Example 1.

[Comparative Example 5] In addition to using 0.09g of UA-4200 and 2.1g of V#260 as the aforementioned component (a), 1.80g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned component (c) (0.99g in terms of MOTMS-modified silica particles) ), except that 0.76 g (0.38 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, the procedure was the same as that of Example 8, and after mixing the solution, add as the aforementioned (e) A photocurable composition 17 was prepared in the same procedure as in Example 8 except for 0.20 g of PEPT as a component.

[Comparative Example 6] In addition to using 0.09g of UA-4200 and 2.1g of V#150 as the aforementioned component (a), 1.80g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned component (c) (0.99g in terms of MOTMS-modified silica particles) ), except that 0.76 g (0.38 g in terms of polyrotaxane conversion) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, the procedure was the same as that of Example 8, and after mixing the solution, add as the aforementioned (e) A photocurable composition 18 was prepared in the same procedure as in Example 8 except that 0.20 g of PEPT was used as a component.

[Comparative Example 7] In addition to using 1.1g of UA-4200, 2.6g of V#230, and 0.20g of APG-100 as the aforementioned (a) component, 0.73g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned (c) component (modified and oxidized with MOTMS 0.40 g in terms of silicon particles), except that 0.39 g (0.20 g in terms of polyrotaxane) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, and the photocurability was adjusted in the same procedure as in Example 1. Composition 19.

[Comparative Example 8] In addition to using 1.7g of UA-4200, 2.7g of V#230, and 0.10g of APG-100 as the aforementioned (a) component, 0.36g of the UA-4200 dispersion obtained in Production Example 1 was used as the aforementioned (c) component (modified and oxidized with MOTMS 0.20 g in terms of silicon particles), except that 0.20 g (0.10 g in terms of polyrotaxane) of the V#260 dispersion obtained in Production Example 2 was used as the aforementioned (d) component, and the photocurability was adjusted in the same procedure as in Example 1. Composition 20.

[Comparative Example 9] In addition to using 1.3g of UA-4200 and 2.7g of V#260 as the above-mentioned component (a), the UA-4200 dispersion obtained in the production example 1 as the above-mentioned component (c) was not added, and the production example 2 was used as the above-mentioned component (d) Except for 0.79 g of the obtained V#260 dispersion (0.40 g in terms of polyrotaxane), the procedure was the same as in Example 8. After mixing the solution, 0.20 g of PEPT was added as the aforementioned (e) component. In the same procedure as in Example 8, the photocurable composition 21 was prepared.

The components of photocurable composition 1 to photocurable composition 21 prepared in Examples 1 to 12 and Comparative Examples 1 to 9 are shown in Table 1 and Table 2 below. In addition, in the following Table 1 and Table 2, "parts" means "parts by mass". Also, in the following Tables 1 and 2, the parts by mass of component (c) only represent the surface-modified silicon oxide particle components in the UA-4200 dispersion obtained in Production Example 1, and the parts by mass of component (d) only represent The polyrotaxane component in the V#260 dispersion obtained in Production Example 2 above.

[Viscosity determination] Take 1 mL of the photocurable composition prepared in Examples 1 to 12 and Comparative Examples 1 to 9 with a disposable syringe, and pour it into the cup of the viscometer. Subsequently, the conical rotor of the viscometer was rotated at a rotation speed of 10 rpm, 1.0 rpm, and 0.5 rpm, and the viscosity of the photocurable composition was measured using the aforementioned E-type viscometer after 2 minutes. The results are shown in Table 3 below.

[Film thickness measurement] The photocurable compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 were casted on a 4-inch silicon wafer cut into 1/4, and spin-coated at 1000 rpm for 30 seconds. The film thickness of the coating layer of the photocurable composition obtained on the aforementioned silicon wafer was measured using the aforementioned film thickness measuring device. In addition, film formability was visually observed immediately after spin coating. When the film thickness cannot be measured, it is indicated by "-", when the surface of the coating layer is uniform and the film forming property is good, it is indicated by "○", and when interference unevenness or liquid unevenness is observed in a part of the coating layer, it is indicated by "Δ " indicates that the coating layer cannot be expanded (not stretched) and large liquid unevenness is observed on the coating layer, and "×" is indicated, and the results are shown in Table 3 below.

The viscosity of the photocurable composition prepared in Examples 1 to 12 at 25.0° C. is higher than 1 mPa‧s and lower than 50 mPa‧s. All of the photocurable compositions can be spin-coated, have good film-forming properties, and can be used for film thickness measurement. The lower the viscosity of the photocurable composition, the better the film-forming property.

The viscosity of the photocurable compositions prepared in Comparative Examples 1 to 9 at 25.0° C. is higher than 50 mPa‧s. Although all the photocurable compositions can be spin-coated, they have poor film-forming properties, and the photocurable compositions prepared in Comparative Example 1, Comparative Example 4, and Comparative Example 5 cannot be measured for film thickness. For photocurable compositions with a viscosity exceeding 100mPa‧s at 25.0°C, the coating layer cannot spread uniformly, and the film-forming property deteriorates. For photocurable compositions with a viscosity exceeding 250mPa‧s at 25.0°C, the coating layer cannot be expanded, the film forming property is further deteriorated, and the film thickness cannot be measured.

[Transmittance measurement] The photocurable composition prepared in Example 11 was sandwiched between two glass substrates. A glass substrate subjected to primer treatment by diluting a solution of methyl ether acetate to 10% by mass and drying, and a glass substrate subjected to mold release treatment by coating and drying Novec (registered trademark) 1720 (manufactured by Japan 3M Co., Ltd.) substrate. Subsequently, the photocurable composition sandwiched between the primer-treated glass substrate and the release-treated glass substrate was pressed at 100N using the aforementioned hybrid nanoimprinter, and exposed at 6J. After exposure, the obtained cured product was heated on a hot plate at 100° C. for 10 minutes, and then peeled off from the aforementioned glass substrate subjected to mold release treatment to produce a 50 μm thick cured product. The transmittance at a wavelength of 410 nm of the aforementioned cured product was measured using the aforementioned spectrophotometer. The results are shown in Table 4 below.

[Measurement of Refractive Index] The refractive index of the cured product produced in the same procedure as the transmittance measurement was measured using the aforementioned refractive index measuring device. The results are shown in Table 4 below.

[Imprint confirmation] The photocurable composition prepared in Example 11 was sandwiched between a glass substrate and a silicon mold. The glass substrate was coated with an adhesive auxiliary agent (trade name: KBM-5803) manufactured by Shin-Etsu Chemical Co., Ltd. A glass substrate that was primed with a solution diluted to 10% by mass with propylene glycol monomethyl ether acetate and dried, and the silicon mold was coated with Novec (registered trademark) 1720 (manufactured by Japan 3M Co., Ltd.) And dry silicon mold for demoulding treatment. Subsequently, the photocurable composition sandwiched between the primer-treated glass substrate and the release-treated silicon mold was pressed at 100N using the aforementioned hybrid nanoimprinter, and UV exposure was performed at 6J. After exposure, the resulting hardened product was heated on a heating plate at 100°C for 10 minutes, and then peeled off from the aforementioned silicon mold that had been subjected to mold release treatment, and a molded body (pattern) was produced on the aforementioned primer-treated glass substrate. As a result of observation using the above-mentioned field emission scanning electron microscope, the molded body produced showed the embossability of forming a desired pattern. The results are shown in FIG. 1 , and are indicated by “◯” in Table 4.

From the above, the photocurable composition comprising the aforementioned (a) component to the aforementioned (d) component of the present invention can be spin-coated, and the surface of the coating layer has uniformity. Embossability was confirmed and high transmittance was shown.

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

Claims (10)

A photocurable composition comprising the following components (a) to (d), wherein the content of the component (a) is 80 parts by mass relative to the total of 100 parts by mass of the components (a) to (d) to 99 parts by mass, the viscosity of the photocurable composition at 25.0°C is from 1mPa‧s to 50mPa‧s, (a): at least two kinds of (meth)acryloxy groups having one or more (meth)acryloyloxy groups in one molecule Monofunctional or polyfunctional (meth)acrylate (except the following component (d)), (b): photoradical initiator, (c): at least one silane represented by the following formula (1) Coupling agent surface-modified silicon oxide particles with a primary particle size of 1nm to 100nm,

(In the formula, ^X1 represents a hydrogen atom or a (meth)acryloyloxy group, ^R1 and ^R2 independently represent a hydrogen atom or an alkyl group with 1 or 2 carbon atoms, m represents an integer from 1 to 14, and n represents an integer of 0 to 2) (d): a polyrotaxane having a (meth)acryloxy group. The photocurable composition according to Claim 1, further comprising at least one component selected from the group consisting of the following (e) component, (f) component, and the following (g) component, (e): the following Multifunctional thiol represented by formula (2) (f): phenolic antioxidant (g): thioether antioxidant

(wherein, R ³ represents a single bond, a straight chain alkylene group with 1 to 6 carbon atoms or a branched chain alkylene group with 3 to 6 carbon atoms, X ² represents a single bond, an ester bond or an ether bond, Q ¹ represents an organic group or a heteroatom having at least one heteroatom or no heteroatom and having 2 to 12 carbon atoms, and p represents an integer of 2 to 6). The photocurable composition according to Claim 1 or 2, wherein the aforementioned (a) component is selected from the group consisting of the following (a1) component, the following (a2) component, and the following (a3) component, (a1) : Monofunctional (meth)acrylate (a2): Difunctional urethane (meth)acrylate (a3): Difunctional (meth)acrylate represented by the following formula (3)

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Q ² represents a linear or branched chain alkylene group with 4 to 10 carbon atoms). The photocurable composition according to any one of Claims 1 to 3, wherein the aforementioned (c) component is surface-modified by a silane coupling agent in which X in the aforementioned formula ( ¹ ) represents a (meth)acryloxyl group Silicon oxide particles. A hardened product of the photocurable composition according to any one of claims 1 to 4, the film thickness of which is 1.0 μm to 10.0 μm. A method of manufacturing a molded body, comprising the step of embossing the photocurable composition according to any one of Claims 1 to 4. A method for manufacturing a molded body, which is a method for manufacturing a molded body of a photocurable composition, and includes the following steps: a step of supplying the photocurable composition according to any one of claims 1 to 4 on a substrate ; An imprinting step in which the photocurable composition is brought into contact with a mold having a reversed pattern of the intended molded body shape; after the imprinting step, exposing the photocurable composition through the mold to form a photohardening step of the photohardening part; and a demoulding step of separating the photohardening part from the mold. The method of manufacturing a molded body as claimed in Claim 7, wherein the step of supplying the photocurable composition is to apply the photocurable composition by a spin coating method, a slit scan method or an inkjet method step. The method of manufacturing a molded article according to claim 7 or 8, further comprising the step of heating the photohardening part after the photohardening step, before, during or after the demolding step. The method for manufacturing a molded article according to any one of claims 6 to 9, wherein the molded system is an optical film for flat panel displays.

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