Composition

Abstract

This composition contains metal oxide particles (A), a monomer (B), and a photopolymerization initiator (C), and either does not contain a solvent (F) or contains a solvent (F) in the range of 150 parts by mass or less per 100 parts by mass for the total of the metal oxide particles (A) and the monomer (B). The monomer (B) contains at least one selection from the group consisting of possibly substituted naphthylmethyl (meth)acrylates (B1), monomers (B2) represented by formula (2), and esters (B3) between a bishydroxyarylfluorene or oxyalkylene adduct thereof and (meth)acrylic acid.

Description

composition

[0001] In a first aspect, the present invention relates to a technique for curing a composition using energy such as active energy rays, and preferably relates to a composition useful for producing a molded article having a nano-level surface micro-relief structure controlled by curing a resin monomer with active energy rays. In a second aspect, the present invention relates to a curable composition, and more specifically, to a composition capable of giving a cured product having excellent adhesion to a glass substrate.

[0002] An example of a controlled nano-level surface micro-relief structure is a moth-eye structure for anti-reflection, and such a surface structure can be produced by nanoimprinting technology. One known nanoimprinting technique involves forming a thin film of ultraviolet-curable resin on a transparent substrate, pressing a mold onto the thin film to form a shape, while irradiating the resin with active energy rays to cure the resin, and then removing the mold (photo-nanoimprinting technology). This method is promising from the standpoints of fine processing and short processing time. Patent Document 1, for example, discloses a composition containing a copolymer of 2-vinyloxyethoxyethyl acrylate (VEEA) and 2,3-dihydroxyfuran as a curable resin applicable to such photo-nanoimprinting technology. This copolymer is known to be promising in that it can suppress warping of the film during curing and has excellent scratch resistance.

[0003] Patent Document 2 discloses a resin composition containing a resin (A) having a radical reactive group and an acid group in a side chain. Patent Document 3 discloses a film-forming composition for photoimprinting, which contains (A) a photopolymerizable monomer having a hydrophilic group, (B) inorganic nanoparticles, and (C) a photopolymerization initiator, has an organic solvent content of 20% by mass or less, contains as component (A) a monomer having a viscosity of 500 cP or less in an amount of 30% by mass or more relative to the total amount of component (A) and component (B), and has a refractive index of 1.56 or more after curing.

[0004] JP 2012-227190 A JP 2008-238416 A JP 2013-191800 A

[0005] In recent years, diffractive optical elements (DOEs) have attracted attention as molded articles with nano-level surface micro-relief structures. Diffractive optical elements are optical elements that utilize the diffraction phenomenon of light and are capable of controlling laser beams to output various light patterns. Such diffractive optical elements are being considered for use in 3D sensors and as input diffractive elements (in-coupling gratings) and output diffractive elements (out-coupling gratings) in AR / VR glasses. Diffractive optical elements (DOEs) require advanced surface shape control at the nano-level. However, when a thin resin film is formed and then molded, the resin film generally contains a solvent for film-forming purposes. When the film is dried, molded, and hardened, the evaporation of the solvent easily causes shrinkage and deformation, making it difficult to achieve the designed shape. Therefore, it is necessary to reduce the amount of solvent as much as possible. Furthermore, for such optical elements, a high refractive index is desirable to achieve the desired properties in a thin film. Therefore, adding high-refractive index metal oxide particles to a photocurable resin and performing photo-nanoimprinting is considered. However, it has been found that increasing the amount of metal oxide particles added reduces the fluidity of the composition and the strength of the resin matrix, making it difficult to impart a shape to the resin using a molding die and causing damage to the material surface during demolding, resulting in poor nanoimprintability. In particular, achieving excellent nanoimprintability (shaping in a molding die and preventing damage to the material surface during demolding) has not been achieved in the past, given the extremely unfavorable conditions for nanoimprinting, such as a low solvent content and the inclusion of metal oxide particles. The present invention in its first aspect has been made in light of the above-mentioned circumstances, and its objective is to provide a composition capable of forming a desired surface micro-texture even when photo-nanoimprinting a resin material containing metal oxide particles and a low solvent content. A preferred objective of the present invention is to provide a composition capable of forming a micro-texture with a pitch of approximately 1 μm, and a more preferred objective is to provide a composition capable of forming a micro-texture with a pitch of approximately 0.5 μm.

[0006] Furthermore, conventional photosensitive compositions for imprinting, such as those described in Patent Documents 2 and 3, have a problem in that they have low adhesion between the resin material and the glass substrate, and when a mold is released from the resin material during the formation of a finer pattern, part of the resin material peels off from the substrate, causing damage to the pattern film and preventing good transfer of the fine pattern.

[0007] The present invention in a second aspect has been made in view of the above-mentioned current situation, and aims to provide a composition capable of giving a cured product having excellent adhesion to a glass substrate. Here, excellent adhesion preferably includes being capable of forming a fine uneven shape with a pitch of about 0.5 μm.

[0008] That is, the present invention is characterized by the following configuration: [1] A composition comprising metal oxide particles (A), a monomer (B), and a photopolymerization initiator (C), wherein the composition does not contain a solvent (F) or contains the solvent (F) in an amount of 150 parts by mass or less per 100 parts by mass of the total of the metal oxide particles (A) and the monomer (B), and the monomer (B) comprises a naphthylmethyl (meth)acrylate (B1) which may have a substituent, a monomer (B2) represented by the following formula (2), (In the formula, R ２１ is a hydrogen atom, a methyl group, or —CH ２ OCH ２ CH=CH ２ L represents an alkylene group having 1 to 10 carbon atoms, -CH ２ CH ２ O- or -CH ２ CHCH ３ represents O-, and a is an integer of 0 to 3. ２２ and R ２３are the same or different and represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. b and c are the same or different and represent an integer of 0 to 4. When b is 2 or more, multiple R ２２ may be the same or different and may be bonded to each other to form a ring structure. ２３ may be the same or different and may be bonded to each other to form a ring structure.) and at least one selected from the group consisting of (B3) esters of bishydroxyarylfluorene or an oxyalkylene adduct thereof with (meth)acrylic acid. [2] The composition according to [1], wherein the monomer (B) further contains (B4) an α,β-unsaturated carboxylic acid compound having a boiling point of 170 to 500°C. [3] The composition according to [1] or [2], wherein the naphthylmethyl (meth)acrylate (B1) optionally having a substituent is a compound represented by the following formula (1): (wherein n1 represents an integer of 0 to 7. R １ is a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH=CH ２ Represents R ２ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. When n1 is 2 or more, multiple R ２ may be different from each other or may be bonded to each other. ２may be combined to form a ring fused with the naphthalene ring of formula (1).) [4] The composition according to any one of [1] to [3], wherein the ester (B3) of the bishydroxyarylfluorene or its oxyalkylene adduct with (meth)acrylic acid is a compound represented by the following formula (3): (In the formula, n2 and n3 each independently represent an integer of 0 to 5, n4 and n5 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 0 to 7. Ar １ , Ar ２ R each independently represents an aromatic ring. ３ represents a hydrogen atom or a methyl group. ４ , R ５ R each independently represents a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. ６ represents a hydrogen atom or a (meth)acryloyl group. ７ ~R １０ are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, or an aromatic ring. ７ When n3 is 2 or more, a plurality of R ８ When n4 is 2 or more, a plurality of R ９ When n5 is 2 or more, a plurality of R １０ may be different from each other.) [5] A composition comprising metal oxide particles (A), a monomer (B), and a photopolymerization initiator (C), wherein the monomer (B) contains a compound represented by formula (1) and / or a compound represented by formula (2), and an α,β-unsaturated carboxylic acid compound (B4) having a boiling point of 170 to 500°C. (wherein n1 represents an integer of 0 to 7. R １ is a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH=CH ２ Represents R ２represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. When n1 is 2 or more, multiple R ２ may be different from each other or may be bonded to each other. ２ may be combined to form a ring fused with the naphthalene ring of formula (1). (In the formula, R ２１ is a hydrogen atom, a methyl group, or —CH ２ OCH ２ CH=CH ２ L represents an alkylene group having 1 to 10 carbon atoms, -CH ２ CH ２ O- or -CH ２ CHCH ３ represents O-, and a is an integer of 0 to 3. ２２ and R ２３ are the same or different and represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. b and c are the same or different and represent an integer of 0 to 4. When b is 2 or more, multiple R ２２ may be the same or different and may be bonded to each other to form a ring structure. ２３may be the same or different and may be bonded to each other to form a ring structure.) [6] The composition according to any one of [1] to [5], wherein the metal oxide particles (A) contain oxide particles of at least one element selected from the group consisting of Ti, Al, Zr, In, Zn, Sn, La, Y, Ce, Mg, Ba, Ca, and Sb. [7] The composition according to any one of [1] to [6], wherein the metal oxide particles (A) are zirconium oxide and / or titanium oxide. [8] The composition according to any one of [1] to [7], wherein the metal oxide particles (A) have an average primary particle diameter of 1 to 50 nm. [9] The composition according to any one of [1] to [8], wherein the metal oxide particles (A) are particles surface-treated with a surface treatment agent containing a phosphate ester.

[10] The composition according to any one of [1] to [9], wherein the metal oxide particles (A) are particles surface-treated with a surface treatment agent containing a phosphate ester compound represented by the following formula (3X): (In formula (3X), R ３１ are the same or different and represent a linear or branched alkyl group having 1 to 10 carbon atoms. ３２are the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 10. a is an integer of 1 to 3.)

[11] The composition according to any one of [1] to

[10] , which contains 10 to 900 parts by mass of monomer (B) relative to 100 parts by mass of metal oxide particles (A).

[12] The composition according to any one of [1] to

[11] , which contains 0 to 5% by mass of a (meth)acrylic acid ester containing an epoxy group as monomer (B) relative to 100% by mass of monomer (B).

[13] The composition according to any one of [1] to

[12] , which does not contain a monomer having two or more (meth)acryloyl groups as monomer (B), or which contains such a monomer in an amount of 10% by mass or less relative to 100% by mass of monomer (B).

[14] The composition according to any one of [1] to

[13] , wherein the photopolymerization initiator (C) comprises at least one selected from the group consisting of an acetophenone-based initiator (C1), an alkylaminobenzoate-based initiator (C2), an oxime-based initiator (C3), a thioxanthone-based initiator (C6), an α-aminoketone-based initiator (C7), and an acylphosphine oxide-based initiator (C8).

[15] The composition according to any one of [1] to

[14] , further comprising a dispersant (D).

[16] The composition according to

[15] , wherein the dispersant (D) is one selected from the group consisting of an organic phosphorus compound or a salt thereof (D1) and an organic sulfur compound or a salt thereof (D2).

[17] The composition according to any one of [1] to

[16] , further comprising a leveling agent (E).

[18] The composition according to

[17] , wherein the leveling agent (E) is a silicone-based surfactant.

[19] The composition according to any one of [1] to

[18] , wherein a cured product of the composition has a glass transition temperature (Tg) of 22° C. or higher.

[20] The composition according to any one of [1] to

[19] , which is for use in photoimprinting.

[0009] According to the composition of the present invention in the first aspect, the amount of solvent is reduced and the composition contains metal oxide particles, yet it is possible to form a desired fine surface irregularity by photonanoimprinting. Preferably, a fine irregularity with a pitch of about 1 μm can be formed, and more preferably, a fine irregularity with a pitch of about 0.5 μm can be formed. According to the composition (photosensitive composition) of the present invention in the second aspect, it is possible to obtain a cured product having excellent adhesion to glass substrates. Therefore, this photosensitive composition can be suitably used for forming a patterned film using an imprinting method.

[0010] The composition of the present invention is a curable composition that can be cured by energy such as active energy rays, and may hereinafter be simply referred to as a curable composition (and a cured product of the curable composition may hereinafter be simply referred to as a cured product). The curable composition is preferably a photosensitive composition and contains metal oxide particles (A), a monomer (B), and a photopolymerization initiator (C). The inclusion of the metal oxide particles (A) can increase the refractive index of the cured product. Such a composition (active energy ray-curable resin composition) is useful in applications requiring a high refractive index, such as diffractive optical elements (DOEs).

[0011] (1) Metal Oxide Particles (A) Examples of the metal oxide particles (A) include oxide particles of metals belonging to Group IIA of the periodic table (e.g., Mg, Ca, Ba), metals belonging to Group IIIB of the periodic table (e.g., Y, La, Ce), metals belonging to Group IVB of the periodic table (e.g., Ti, Zr), metals belonging to Groups VB to IIB of the periodic table (e.g., Zn), metals belonging to Group IIIA of the periodic table (e.g., Al, In), metals belonging to Group IVA of the periodic table (e.g., Sn), and metals belonging to Group VA of the periodic table (e.g., Sb). The metal oxide particles (A) are not only useful for increasing the refractive index but also contribute to improving nanoimprintability when the amount of solvent (F) used is small. In particular, from the perspective of increasing the refractive index, particles of at least one oxide selected from the group consisting of Ce, Ti, Zr, Zn, Al, and Sn are preferred, and Ti oxide particles (i.e., titanium oxide (TiO ２ ) particles), Zr oxide particles (i.e., zirconium oxide (ZrO ２The metal oxide may be an oxide of a single metal, a solid solution of two or more oxides, or a composite oxide.

[0012] Examples of single metal oxides include magnesium oxide (MgO, etc.), calcium oxide (CaO, etc.), barium oxide (BaO, etc.), yttrium oxide (Y ２ O ３ etc.), lanthanum oxide (La ２ O ３ etc.), cerium oxide (CeO ２ etc.), titanium oxide (TiO ２ etc.), zirconium oxide (ZrO ２ etc.), zinc oxide (ZnO etc.), aluminum oxide (Al ２ O ３ etc.), indium oxide (In ２ O ３ etc.), tin oxide (SnO ２ etc.), antimony oxide (Sb ２ O ３ etc.)

[0013] Examples of solid solutions of two or more oxides include indium tin oxide (ITO) and antimony tin oxide (ATO). Examples of composite oxides include barium titanate (BaTiO ３ etc.), perovskite (CaTiO ３ etc.), spinel (MgAl ２ O ４ etc.)

[0014] The metal oxide particles (A) are preferably nano-sized fine particles. Nano-sized particles refer to particles having a maximum primary particle diameter of less than 1 μm, preferably less than 500 nm, and more preferably less than 100 nm. The average primary particle diameter of the metal oxide particles (A) may be, for example, approximately 1 to 100 nm, but is preferably 1 to 50 nm, more preferably 3 to 30 nm, and even more preferably 5 to 20 nm. Having an average primary particle diameter of the metal oxide particles (A) within the above range facilitates enhanced transparency of the cured product. The average primary particle diameter can be determined by magnifying and observing the metal oxide particles (A) with a transmission electron microscope (TEM), field-emission transmission electron microscope (FE-TEM), field-emission scanning electron microscope (FE-SEM), or the like, randomly selecting 100 particles, measuring their longitudinal lengths, and calculating the arithmetic mean. For example, the average primary particle diameter of the metal oxide particles (A) can be measured by observation with an ultra-high resolution field-emission scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) or the like. For example, coated zirconium oxide particles are observed at a magnification of 150,000 times, and the length of each of 100 randomly selected particles in the major axis direction is measured, and the average value thereof can be taken as the average primary particle diameter.

[0015] The shape of the metal oxide particles is not particularly limited and may be any of amorphous, granular, plate-like, columnar, needle-like, etc., but granular is preferred, and among granular, spherical is preferred. The granular shape means a uniform shape with an aspect ratio of 1.5 or less. Regarding the shape of the metal oxide particles, when the aspect ratio is the value obtained by dividing the longest diameter by the shortest diameter within the particle, the aspect ratio is preferably 1.4 or less, more preferably 1.35 or less, and even more preferably 1.3 or less.

[0016] The metal oxide particles (A) may be crystalline or amorphous, but are preferably crystalline in view of a high refractive index.

[0017] The crystallinity of the metal oxide particles (A) is preferably 50% or more, more preferably 55% or more, and even more preferably 60% or more, in terms of a high refractive index. The crystallinity can be determined by X-ray diffraction.

[0018] When the metal oxide particles (A) are crystalline, the crystallite diameter of the metal oxide particles (A) is, for example, 1 to 20 nm, preferably 1 to 15 nm, and more preferably 1 to 10 nm. The smaller the crystallite diameter, the more the light transmittance of the cured product can be improved. The crystallite diameter can be determined by X-ray diffraction.

[0019] The crystal structure of the metal oxide particles (A) can be identified by X-ray diffraction, and is preferably cubic, tetragonal, monoclinic, or the like, and multiple crystal structures may be present. It is difficult to distinguish between cubic and tetragonal crystals of the metal oxide particles (A) in X-ray diffraction measurement, and even if cubic crystals are present, their proportion is counted as the proportion of tetragonal crystals. From the viewpoint of improving the refractive index, it is preferable that 50% or more of the entire crystal structure is tetragonal and / or cubic. Furthermore, the total ratio of tetragonal and cubic crystals to monoclinic crystals ((tetragonal + cubic) / monoclinic crystal) is, for example, 1.0 to 5, preferably 1.1 to 5. For example, the crystal structure of the metal oxide particles (A) can be identified by the reference intensity ratio method (RIP method) using calculation software (PDXL, Rigaku Corporation) based on values ​​calculated using an X-ray diffractometer (RINT-TTRIII, Rigaku Corporation). In this case, peak assignments can also be identified by following the specifications of the calculation software.

[0020] The amount of the metal oxide particles (A) is, for example, 10 to 80% by mass, preferably 30 to 70% by mass, and more preferably 40 to 60% by mass, based on 100% by mass of the curable composition. The amount of the metal oxide particles (A) is preferably 10 to 90% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 90% by mass, based on 100% by mass of the total solids content of the curable composition. The higher the proportion of the metal oxide particles (A), the easier it is to increase the refractive index of the cured product. On the other hand, the lower the proportion of the metal oxide particles (A), the more improved the nanoimprintability (e.g., ease of shaping using a molding die, suppression of damage to the material surface during demolding, etc.). In this specification, the solids content (total solids content) of the curable composition refers to the remaining content after drying and curing the composition, and refers to, for example, the total amount of components other than the solvent (F) in the curable composition.

[0021] The refractive index of the metal oxide particles (A) is preferably 1.6 or more. The refractive index of the metal oxide particles (A) may be 3.0 or less, more preferably 1.8 to 2.9. The refractive index may also be greater than 1.8. When the refractive index exceeds 1.8, there is a significant tendency for adhesion to decrease. However, according to the second aspect, adhesion can be improved not only when the refractive index is 1.8 or less, but also when the refractive index exceeds 1.8.

[0022] (2) Monomer (B) Monomer (B) has a functional group containing a polymerizable unsaturated bond such as a vinyl group or a (meth)acryloyl group, and monomer (B) may have a substituent, for example, an allyloxymethyl group may be present as a substituent at the α-position of the (meth)acryloyl group. In the first embodiment, monomer (B) preferably contains at least one selected from the group consisting of naphthylmethyl (meth)acrylates (B1) (hereinafter simply referred to as "naphthylmethyl (meth)acrylates (B1)") which may have a substituent, esters (B2) of (meth)acrylic acid and biphenyl group-containing alcohols which may have a substituent (hereinafter sometimes referred to as "biphenyl group-containing (meth)acrylates (B2)"), and esters (B3) of bishydroxyarylfluorene or its oxyalkylene adduct and (meth)acrylic acid (hereinafter sometimes referred to as "fluorene group-containing (meth)acrylates (B3)"). The substituent includes an allyloxymethyl group bonded to the α-position of the (meth)acryloyl group. When the curable composition contains metal oxide particles (A) and the content of solvent (F) is reduced, the nanoimprintability is likely to decrease. However, by using a specific monomer (B), it is possible to ensure or improve the nanoimprintability even when the curable composition contains metal oxide particles (A) and the content of solvent (F) is low (including when no solvent (F) is present). In the first aspect, the monomer (B) may contain an α,β-unsaturated carboxylic acid (including a high-boiling point unsaturated carboxylic acid compound (B4) described later).

[0023] In a second embodiment, the monomer (B) includes at least one selected from naphthylmethyl (meth)acrylates (B1) and biphenyl group-containing (meth)acrylates (B2), and further includes an α,β-unsaturated carboxylic acid (B4) having a boiling point of 170 to 500°C (hereinafter, sometimes referred to as "high-boiling-point unsaturated carboxylic acid (B4)"). By including the monomer (B) in this combination, adhesion can be improved. In the second embodiment, the composition may also include a fluorene group-containing (meth)acrylate (B3) and an α,β-unsaturated carboxylic acid having a boiling point of less than 170°C (hereinafter, sometimes referred to as "low-boiling-point unsaturated carboxylic acid").

[0024] The amount of monomer (B) can be appropriately set depending on the type of monomer, and may be, for example, 10 to 900 parts by mass, preferably 15 to 500 parts by mass, more preferably 20 to 120 parts by mass, even more preferably 30 to 100 parts by mass, and particularly preferably 40 to 80 parts by mass, relative to 100 parts by mass of metal oxide particles (A). The greater the amount of monomer (B), the better the nanoimprintability. Furthermore, the smaller the amount of monomer (B), the easier it is to increase the refractive index of the cured product.

[0025] (2.1) Naphthylmethyl (meth)acrylates (B1) Naphthylmethyl (meth)acrylates are esters formed from a monool having a naphthylmethanol structure and (meth)acrylic acid. The (meth)acrylic acid may have an allyloxymethyl group at the α-position. As long as the monool has a naphthylmethanol structure, it may have various hydrocarbon groups or substituents. The naphthylmethanol structure refers to a structure in which a naphthalene ring is bonded to the methyl group of methanol, and in this specification, the term "naphthalene ring" is used to include rings having a naphthalene skeleton, such as an acenaphthylene ring, phenalene ring, phenanthrene ring, anthracene ring, and pyrene ring.

[0026] The naphthylmethyl (meth)acrylate (B1) is preferably a compound represented by the following formula (1).

[0027] (wherein n1 represents an integer of 0 to 7. R １ is a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH=CH ２ Represents R ２ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. When n1 is 2 or more, multiple R ２ may be different from each other or may be bonded to each other. ２ may be combined to form a ring fused with the naphthalene ring of formula (1).

[0028] R １ is a hydrogen atom or a methyl group, ２ OCH ２ CH=CH ２ In this case, the adhesion is high.

[0029] n1 is R bonded to the naphthalene ring ２ represents the number of groups, and is preferably 0 to 6, more preferably 0 to 4, and even more preferably 0 to 3. The smaller n is, the lower the viscosity becomes. ２ Examples of the linear alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, and the like. Of these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and the like are preferred, a methyl group, an ethyl group, an n-propyl group, and the like are more preferred, and a methyl group, an ethyl group, and the like are most preferred.

[0030] R ２The branched alkyl group represented by the formula (I) is preferably a branched alkyl group having 3 to 8 carbon atoms, such as an i-propyl group, an i-butyl group, a t-butyl group, a methylbutyl group, an ethylpropyl group, or a dimethylpropyl group, and more preferably a branched alkyl group having 3 to 5 carbon atoms.

[0031] R ２ Examples of the linear alkenyl group represented by the formula (I) include a vinyl group, an allyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.

[0032] R ２ Examples of the branched alkenyl group represented by the formula (I) include a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, and a 2-methyl-2-propenyl group.

[0033] R ２ Examples of the cycloalkyl group represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Of these, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group are preferred, and a cyclopentyl group and a cyclohexyl group are more preferred.

[0034] R ２ Examples of the linear alkoxy group represented by the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, an n-heptoxy group, an n-octoxy group, an n-nonoxy group, and an n-decoxy group. Of these, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, and an n-hexoxy group are preferred, a methoxy group, an ethoxy group, and an n-propoxy group are more preferred, and a methoxy group, an ethoxy group, and an n-propoxy group are most preferred.

[0035] R ２ The branched alkoxy group represented by the formula (I) is preferably a branched alkoxy group having 3 to 8 carbon atoms, such as an i-propoxy group, an i-butoxy group, a t-butoxy group, a methylbutoxy group, an ethylpropoxy group, or a dimethylpropoxy group, and more preferably a branched alkoxy group having 3 to 5 carbon atoms.

[0036] R ２ Examples of the cyclic alkoxy group represented by the formula (I) include a cyclopropoxy group, a cyclobutoxy group, a cyclopentoxy group, a cyclohexoxy group, a cycloheptoxy group, a cyclooctoxy group, a cyclononoxy group, and a cyclodecoxy group. A cyclobutoxy group, a cyclopentoxy group, a cyclohexoxy group, and a cycloheptoxy group are preferred, and a cyclopentoxy group and a cyclohexoxy group are more preferred.

[0037] R ２ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom and a bromine atom being preferred, and a bromine atom being more preferred.

[0038] R ２ Examples of the aromatic ring represented by the formula (I) include an aromatic hydrocarbon ring and an aromatic heterocycle. The aromatic ring may be a monocycle or a polycycle. Examples of polycycles include two or more monocycles or monocycles fused or bonded with an aliphatic ring. An example of a monocyclic aromatic hydrocarbon ring is a benzene ring. Examples of polycyclic aromatic hydrocarbon rings include fused rings such as a naphthalene ring, an anthracene ring, a phenalene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a triphenylene ring, a fluorene ring, and a fluorene ring, and bonded rings such as a biphenyl ring, a terphenyl ring, and a binaphthalene ring. Examples of the aromatic hydrocarbon ring are preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0039] The aromatic heterocycle is an aromatic ring containing at least one oxygen atom, sulfur atom or nitrogen atom.

[0040] Examples of monocyclic aromatic heterocycles include a furan ring, a pyran ring, a thiophene ring, a thiopyran ring, a pyrrole ring, a pyridine ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an oxazole ring, an isoxazole ring, a furazan ring, a thiazole ring, and an isothiazole ring.

[0041] Examples of polycyclic fused aromatic rings include a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, an indole ring, an isoindole ring, a carbazole ring, a quinoline ring, a phenanthridine ring, a benzimidazole ring, a purine ring, and a phenothiazine ring.

[0042] Examples of the polycyclic linked aromatic ring include a bipyridine ring, a bithiophene ring, a phenylpyridine ring, a phenylthiophene ring, and a diphenylthiophene ring.

[0043] The number of carbon atoms in the aromatic ring is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 12, in terms of low viscosity.

[0044] R ２ Examples of the divalent group forming a ring structure include the linear alkyl group having 1 to 10 carbon atoms, the branched alkyl group having 3 to 10 carbon atoms, the linear alkenyl group having 2 to 10 carbon atoms, the branched alkenyl group having 3 to 10 carbon atoms, the cycloalkyl group having 3 to 10 carbon atoms, the linear alkoxy group having 1 to 10 carbon atoms, the branched alkoxy group having 3 to 10 carbon atoms, the cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, or a divalent group having a structure in which one hydrogen atom has been removed from an aromatic ring, and these divalent groups can be bonded to each other to form a ring structure.

[0045] Multiple R ２ When a ring fused with the naphthalene ring of formula (1) is formed by combining the above, the fused ring formed is a fused ring of a naphthalene ring with an aromatic ring or an aliphatic ring, and preferably a fused ring of a naphthalene ring with an aromatic ring. Examples of the fused ring of a naphthalene ring with an aromatic ring include an anthracene ring, an acenaphthylene ring, a phenalene ring, a phenanthrene ring, a pyrene ring, an acephenanthrylene ring, and a triphenylene ring. Among these, an anthracene ring, an acenaphthylene ring, a phenalene ring, and a phenanthrene ring are preferred in terms of low viscosity, and an acenaphthylene ring, a phenalene ring, and a phenanthrene ring are more preferred. The number of carbon atoms in the fused ring is preferably 10 to 25, more preferably 10 to 20, and even more preferably 10 to 15.

[0046] R２ As the alkyl group, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a branched alkoxy group having 3 to 6 carbon atoms, a hydroxy group, a halogen atom, etc. are preferred, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a halogen atom, etc. are more preferred, and the linear alkyl group, branched alkyl group, linear alkoxy group, branched alkoxy group, halogen atom, etc. are preferably those exemplified above.

[0047] Preferred compounds represented by formula (1) include (1-naphthyl)methyl methacrylate, (2-naphthyl)methyl methacrylate, (1-naphthyl)methyl acrylate, (2-naphthyl)methyl acrylate, 5,8-dibromo-(2-naphthyl)methyl methacrylate, 6-methoxy-(2-naphthyl)methyl methacrylate, 6-methyl-(2-naphthyl)methyl methacrylate, 4-bromo-(1-naphthyl)methyl methacrylate, 4,7-dibromo-6-methyl-(1-naphthyl)methyl acrylate, iodinated 1-naphthyl methyl acrylate, and iodinated 1-naphthyl methyl methacrylate. Of these, 1-naphthylmethyl(meth)acrylate is preferred, and 1-naphthylmethylacrylate is more preferred, due to its low viscosity.

[0048] The content of the (meth)acrylates (B1) is preferably 0 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0049] (2.2) Biphenyl Group-Containing (Meth)acrylates (B2) Biphenyl group-containing (meth)acrylates are esters formed from (meth)acrylic acid and biphenyl group-containing alcohols. The (meth)acrylic acid may have an allyloxymethyl group at the α-position. The biphenyl group-containing alcohols may have various hydrocarbon groups or substituents, as long as they have a biphenyl group and a hydroxyl group. The hydroxyl group may be directly bonded to the biphenyl group, but is preferably bonded to the biphenyl group via another group (particularly a hydrocarbon group).

[0050] The biphenyl group-containing (meth)acrylate (B2) is preferably a compound represented by the following formula (2). (In the formula, R ２１ is a hydrogen atom, a methyl group, or —CH ２ OCH ２ CH=CH ２ L represents an alkylene group having 1 to 10 carbon atoms, -CH ２ CH ２ O- or -CH ２ CHCH ３ represents O-, and a is an integer of 0 to 3. ２２ and R ２３ are the same or different and represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. b and c are the same or different and represent an integer of 0 to 4. When b is 2 or more, multiple R ２２ may be the same or different and may be bonded to each other to form a ring structure. ２３ may be the same or different and may be bonded to each other to form a ring structure.

[0051] R ２１ is superior in adhesion, and -CH ２ OCH ２ CH=CH ２ is preferred.

[0052] The alkylene group represented by L preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom. L is preferably —CH ２ CH ２ O- or -CH ２ CHCH ３ It is preferably O-.

[0053] a is preferably 1 to 3, and more preferably 1 or 2. When a is 2 or more, the multiple Ls may be the same or different. When a is 2 or more, it is preferable that the alkyl groups are not consecutive.

[0054] R ２２ , R ２３ The linear alkyl group having 1 to 10 carbon atoms, the branched alkyl group having 3 to 10 carbon atoms, the linear alkenyl group having 2 to 10 carbon atoms, the branched alkenyl group having 3 to 10 carbon atoms, the cycloalkyl group having 3 to 10 carbon atoms, the linear alkoxy group having 1 to 10 carbon atoms, the branched alkoxy group having 3 to 10 carbon atoms, the cyclic alkoxy group having 3 to 10 carbon atoms, the halogen atom, the aromatic ring, and the divalent group forming a ring structure are the same as those represented by the above R ２ Among them, the groups represented by R ２２ and R ２３ are the same or different and are preferably a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, or an aromatic ring, more preferably a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, or an aromatic ring, and even more preferably a halogen atom or an aromatic ring.

[0055] R ２２ a ring structure formed by bonding together, or R ２３ Examples of the ring structure formed by bonding are a fused ring of a benzene ring and an aromatic ring or an aliphatic ring, and a fused ring of a benzene ring and an aromatic ring is preferred. Examples of such a fused ring include a naphthalene ring and a phenanthrene ring, and a naphthalene ring is preferred.

[0056] b is preferably 0 to 3, more preferably 0 to 2. c is preferably 0 to 3, more preferably 0 to 2.

[0057] Examples of the compound represented by formula (2) include p-biphenylethoxy(meth)acrylate, m-biphenylethoxy(meth)acrylate, o-biphenylethoxy(meth)acrylate, p-biphenyl(meth)acrylate, m-biphenyl(meth)acrylate, o-biphenyl(meth)acrylate, p-biphenylmethyl(meth)acrylate, m-biphenylmethyl(meth)acrylate, o-biphenylmethyl(meth)acrylate, p-biphenylethyl(meth)acrylate, m-biphenylethyl(meth)acrylate, o-biphenylethyl(meth)acrylate, p-biphenylpropiooxy Examples of the alkyl acrylate include methyl (meth)acrylate, m-biphenylpropiooxy (meth)acrylate, o-biphenylpropiooxy (meth)acrylate, o-biphenylethoxyallyloxymethyl acrylate, p-biphenylethoxyallyloxymethyl acrylate, m-biphenylethoxyallyloxymethyl acrylate, o-biphenylethoxyallyloxymethyl acrylate, o-biphenylethoxyallyloxymethyl acrylate, p-biphenylmethylallyloxymethyl acrylate, m-biphenylmethylallyloxymethyl acrylate, and o-biphenylmethylallyloxymethyl acrylate.Among these, p-biphenylethoxy(meth)acrylate, m-biphenylethoxy(meth)acrylate, o-biphenylethoxy(meth)acrylate, p-biphenylpropioxy(meth)acrylate, m-biphenylpropioxy(meth)acrylate, o-biphenylpropioxy(meth)acrylate, o-biphenylethoxyallyloxymethylacrylate, p-biphenylethoxyallyloxymethylacrylate, m-biphenylethoxyallyloxymethylacrylate, o-biphenylethoxyallyloxymethylacrylate, o-biphenylethoxyallyloxymethylacrylate, p-biphenylmethylallyloxymethylacrylate, m-biphenylmethylallyloxymethylacrylate, p-biphenyl ethoxy (meth)acrylate, m-biphenyl ethoxy (meth)acrylate, o-biphenyl ethoxy (meth)acrylate, o-biphenyl ethoxy allyloxy methyl acrylate, p-biphenyl ethoxy allyloxy methyl acrylate, m-biphenyl ethoxy allyloxy methyl acrylate, o-biphenyl ethoxy allyloxy methyl acrylate, o-biphenyl ethoxy allyloxy methyl acrylate, p-biphenyl methyl allyloxy methyl acrylate, m-biphenyl methyl allyloxy methyl acrylate, and o-biphenyl methyl allyloxy methyl acrylate are more preferred.

[0058] The mass ratio of the naphthylmethyl (meth)acrylates (B1) to the biphenyl group-containing (meth)acrylates (B2) can be designed to be in the range of 0 / 100 to 100 / 0. The monomer (B) preferably contains at least one of the naphthylmethyl (meth)acrylates (B1) and the biphenyl group-containing (meth)acrylates (B2).

[0059] The content of the biphenyl group-containing (meth)acrylates (B2) is preferably 0 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass%, relative to 100 mass% of the total solid content of the curable composition. In the first aspect, the total amount of the (meth)acrylates (B1) and the biphenyl group-containing (meth)acrylates (B2) is preferably 0 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0060] In the second embodiment, the total amount of the (meth)acrylates (B1) and the biphenyl group-containing (meth)acrylates (B2) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, relative to 100% by mass of the total solid content of the curable composition. It may also be 5 to 60% by mass, or 20 to 40% by mass.

[0061] (2.3) Fluorene Group-Containing (Meth)acrylates (B3) The fluorene group-containing (meth)acrylates (B3) are compounds obtained by esterifying a compound having two hydroxyaryl groups at the 9-position of fluorene with one or two (meth)acrylic acids, and also include compounds obtained by adding an oxyalkylene unit to the hydroxy group of the hydroxyaryl group and then esterifying the resulting compound with (meth)acrylic acid.

[0062] The fluorene group-containing (meth)acrylate (B3) is preferably a compound represented by the following formula (3). (In the formula, n2 and n3 each independently represent an integer of 0 to 5, n4 and n5 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 0 to 7. Ar １ , Ar ２ R each independently represents an aromatic ring. ３ represents a hydrogen atom or a methyl group. ４ , R ５ R each independently represents a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. ６represents a hydrogen atom or a (meth)acryloyl group. ７ ~R １０ are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, or an aromatic ring. ７ When n3 is 2 or more, a plurality of R ８ When n4 is 2 or more, a plurality of R ９ When n is 5 or more, a plurality of R １０ may be different from each other.)

[0063] n2 to n5 are Ar １ , Ar ２ or R bonded to the fluorene ring ７ ~R １０ n2 and n3 are each independently preferably 0 to 4, more preferably 0 to 3. n4 and n5 are each independently preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. m1 and m2 represent the number of moles of oxyalkylene units added, and are each independently preferably 0 to 6, more preferably 1 to 3.

[0064] Ar １ , Ar ２ The aromatic ring represented by R ２ The examples of the aromatic rings are the same as those of the aromatic rings represented by R ４ , R ５ The linear alkylene group represented by the formula (I) corresponds to the alkylene of the oxyalkylene adduct, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decylene group. Of these, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group are preferred, an ethylene group, an n-propylene group, and an n-butylene group are more preferred, and an ethylene group is particularly preferred.

[0065] R ４ , R ５ The branched alkylene group represented by the formula (I) also corresponds to the alkylene of the oxyalkylene adduct, and examples thereof include a propane-1,2-diyl group, an n-butane-1,2-diyl group, an n-butane-1,3-diyl group, and a 1,4-n-butanediyl group, with a propane-1,2-diyl group being preferred.

[0066] R ７ ~R １０ The linear alkyl group, the branched alkyl group, the cycloalkyl group, the linear alkoxy group, the branched alkoxy group, the cyclic alkoxy group, the halogen atom, or the aromatic ring each represents R ２ Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cycloalkyl group, a linear alkoxy group, a branched alkoxy group, a cyclic alkoxy group, a halogen atom, or a group similar to the aromatic ring, each of which represents the following formula (I), and the preferred ranges are also similar.

[0067] R ７ ~R １０ As the alkyl group, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a branched alkoxy group having 3 to 6 carbon atoms, a hydroxy group, a halogen atom, etc. are preferred, and a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms, a branched alkoxy group having 3 to 5 carbon atoms, a hydroxy group, a halogen atom, etc. are more preferred, and the linear alkyl group, branched alkyl group, linear alkoxy group, branched alkoxy group, halogen atom, etc. are preferably those exemplified above. １ , Ar ２is a benzene ring, and examples where n2 and n3 are 0 (hereinafter referred to as first examples) include mono(meth)acrylic acid esters of bis(hydroxyphenyl)fluorene, di(meth)acrylic acid esters of bis(hydroxyphenyl)fluorene, esters of a compound in which one oxyethylene has been added to each hydroxy group of bis(hydroxyphenyl)fluorene and one (meth)acrylic acid, esters of a compound in which one oxyethylene has been added to each hydroxy group of bis(hydroxyphenyl)fluorene and two (meth)acrylic acids, esters of a compound in which two oxyethylenes have been added to each hydroxy group of bis(hydroxyphenyl)fluorene and one (meth)acrylic acid, esters of a compound in which two oxyethylenes have been added to each hydroxy group of bis(hydroxyphenyl)fluorene and two (meth)acrylic acids, an ester of a compound having three oxyethylene groups added to each of the hydroxy groups of bis(hydroxyphenyl)fluorene and one (meth)acrylic acid, an ester of a compound having three oxyethylene groups added to each of the hydroxy groups of bis(hydroxyphenyl)fluorene and two (meth)acrylic acids, an ester of a compound having four oxyethylene groups added to each of the hydroxy groups of bis(hydroxyphenyl)fluorene and one (meth)acrylic acid, an ester of a compound having four oxyethylene groups added to each of the hydroxy groups of bis(hydroxyphenyl)fluorene and two (meth)acrylic acids, an ester of a compound having one oxypropylene added to each of the hydroxy groups of bis(hydroxyphenyl)fluorene and one (meth)acrylic acid, an ester of a compound having one oxypropylene added to each of the hydroxy groups of bis(hydroxyphenyl)fluorene and two (meth)acrylic acids, an ester of a compound in which two oxypropylene groups are added to each hydroxy group of bis(hydroxyphenyl)fluorene with one (meth)acrylic acid; an ester of a compound in which two oxypropylene groups are added to each hydroxy group of bis(hydroxyphenyl)fluorene with two (meth)acrylic acids;Examples include an ester of a compound in which three oxypropylene groups have been added to each hydroxy group of bis(hydroxyphenyl)fluorene with one (meth)acrylic acid, an ester of a compound in which three oxypropylene groups have been added to each hydroxy group of bis(hydroxyphenyl)fluorene with two (meth)acrylic acids, an ester of a compound in which four oxypropylene groups have been added to each hydroxy group of bis(hydroxyphenyl)fluorene with one (meth)acrylic acid, and an ester of a compound in which four oxypropylene groups have been added to each hydroxy group of bis(hydroxyphenyl)fluorene with two (meth)acrylic acids.

[0068] As the compound represented by formula (2), Ar １ , Ar ２ is a benzene ring, n2 and n3 are 1 or 2, and R ７ , R ８ is a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a hydroxyl group, the bis(hydroxyphenyl)fluorene moiety in Example 1 is bis(4-hydroxy-3-methylphenyl)fluorene, bis(3-hydroxy-2-methylphenyl)fluorene, bis(4-hydroxy-3,5-dimethylphenyl)fluorene, bis(4-hydroxy-2,6-dimethylphenyl)fluorene, bis(4-hydroxy-3,5-di-t-butylphenyl)fluorene, bis(3,4-dihydroxyphenyl)fluorene (biscatecholfluorene (BCAF)), bis(2,4-dihydroxyphenylfluorene), bis(2,5-dihydroxyphenylfluorene), bis(3,4-dihydroxy-6-methylfluorene), Examples of the fluorene include bis(3,4,5-trihydroxyphenyl)fluorene, bis(2,4,6-trihydroxyphenylfluorene), and compounds in which the fluorene is replaced by bis(2,3,4-trihydroxyphenylfluorene), bis(2,3,5-trihydroxyphenylfluorene).

[0069] When the total mass of the naphthylmethyl (meth)acrylates (B1) and the biphenyl group-containing (meth)acrylate (B2) is (BX), the mass ratio (BX / B3) of (BX) to the fluorene group-containing (meth)acrylate (B3) can be appropriately designed in the range of 0 / 100 to 100 / 0, preferably 20 / 80 to 95 / 5, more preferably 50 / 50 to 90 / 10, even more preferably 60 / 40 to 90 / 10, and particularly preferably 75 / 25 to 90 / 10, and may be 80 / 20 or less. Adjusting the mass ratio (BX / B3) may sometimes make it possible to adjust the change in ink viscosity over time. In particular, when the biphenyl group-containing (meth)acrylate (B2) is not contained, the mass ratio (B1 / B3) of the naphthylmethyl (meth)acrylate (B1) to the fluorene group-containing (meth)acrylate (B3) can be appropriately designed in the range of 0 / 100 to 100 / 0, preferably 20 / 80 to 95 / 5, more preferably 50 / 50 to 90 / 10, and even more preferably 60 / 40 to 80 / 20. It is also preferable to contain naphthylmethyl (meth)acrylates (B1) and / or biphenyl group-containing (meth)acrylates (B2) as essential monomers. In this case, the amount of the fluorene group-containing (meth)acrylates (B2) is, for example, 0 to 300 parts by mass, preferably 0 to 120 parts by mass, more preferably 0 to 80 parts by mass, or alternatively 10 to 80 parts by mass, or alternatively 20 to 80 parts by mass, per 100 parts by mass of the naphthylmethyl (meth)acrylates (B1) and / or the biphenyl group-containing (meth)acrylates (B2) in total.

[0070] The total amount of the naphthylmethyl (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), and the fluorene group-containing (meth)acrylates (B3) is, for example, 10 to 100 parts by mass, preferably 60 to 95 parts by mass, more preferably 70 to 95 parts by mass, and particularly preferably 80 to 90 parts by mass, per 100 parts by mass of the monomer (B).

[0071] The content of the fluorene group-containing (meth)acrylates (B3) is preferably 0 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 1 to 10 mass%, relative to 100 mass% of the total solid content of the curable composition. In the first aspect, the total amount of the (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), and the fluorene group-containing (meth)acrylates (B3) is preferably 10 to 60 mass%, more preferably 15 to 50 mass%, and even more preferably 20 to 40 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0072] (2.4) α,β-Unsaturated Carboxylic Acid Compound (High-Boiling Point Unsaturated Carboxylic Acid Compound (B4)) Monomer (B) may contain an α,β-unsaturated carboxylic acid compound. The α,β-unsaturated carboxylic acid compound may be a compound with a boiling point of less than 170°C, such as acrylic acid or methacrylic acid (hereinafter, sometimes referred to as a "low-boiling point unsaturated carboxylic acid"), but is preferably a compound (B4) with a boiling point of 170 to 500°C (hereinafter, sometimes referred to as a "high-boiling point unsaturated carboxylic acid (B4)"). The inclusion of a high-boiling point unsaturated carboxylic acid compound (B4) further improves nanoimprintability. The boiling point is a value determined by the equilibrium reflux boiling point method at 1 atmosphere. The boiling point is preferably 170 to 450°C, more preferably 170 to 400°C, and even more preferably 170 to 350°C, in terms of low viscosity.

[0073] Preferred examples of the high-boiling unsaturated carboxylic acid compound (B4) include compounds represented by the following formula (4): (In the formula, R ４１ , R ４２ and R ４３ R may be the same or different and represent a hydrogen atom, a hydrocarbon group which may have a substituent, an alkoxy group, a halogen atom, or a divalent group which forms a ring structure. ４１ , R ４２ and R ４３ may be bonded to each other to form a ring structure.

[0074] In the above formula (4), R４１ , R ４２ and R ４３ Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, an alkenyl group, a cycloalkyl group, and an aromatic ring. Among these, preferred examples of the hydrocarbon group include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aromatic ring. Examples of the substituent that the hydrocarbon group may have include a carboxyl group.

[0075] R ４１ , R ４２ and R ４３ The alkoxy group represented by the formula (I) is preferably a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, or a cyclic alkoxy group having 3 to 10 carbon atoms.

[0076] R ４１ , R ４２ and R ４３ The linear alkyl group, branched alkyl group, linear alkenyl group, branched alkenyl group, cycloalkyl group, linear alkoxy group, branched alkoxy group, cyclic alkoxy group, halogen atom, and divalent group forming a ring structure represented by the formula (1) above include R ２ Among them, the group represented by R ４１ , R ４２ and R ４３ are the same or different and are preferably a hydrogen atom, a linear alkyl group which may have a substituent, a linear alkoxy group, or an aromatic ring, more preferably a hydrogen atom, a linear alkyl group which may have a substituent, or an aromatic ring, still more preferably a hydrogen atom, a linear alkyl group, or an aromatic ring, and particularly preferably a hydrogen atom or an aromatic ring.

[0077] R ４１ , R ４２ and R ４３ and the ring structure formed by bonding with each other is preferably a non-aromatic saturated or unsaturated aliphatic hydrocarbon ring. ４１ and R４２ The ring formed by bonding R is preferably a cyclohexene ring having about 5 to 10 carbon atoms, such as a cyclopentene ring, a cyclohexene ring, or a cycloheptene ring. ４２ and R ４３ The ring formed by these is preferably a cyclohexane ring having about 5 to 10 carbon atoms forming the ring, such as a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring.

[0078] A preferred embodiment is R ４１ is a hydrogen atom, and R ４２ and R ４３ is a hydrogen atom, and the other is the above-mentioned linear alkyl group, branched alkyl group, cycloalkyl group, linear alkoxy group, branched alkoxy group, cyclic alkoxy group, halogen atom, or aromatic ring. In a more preferred embodiment, R ４１ is a hydrogen atom, and R ４２ and R ４３ is a hydrogen atom, and the other is the above-mentioned linear alkyl group having 1 to 10 carbon atoms or an aromatic ring. The above-mentioned aromatic ring is preferably a benzene ring, a naphthalene ring, or a biphenyl ring, and more preferably a benzene ring.

[0079] In a preferred embodiment, R ４１ is a linear or branched alkyl group having a carboxy group, and R ４２ and R ４３ is a hydrogen atom, a linear alkyl group, a branched alkyl group, a cycloalkyl group, a linear alkoxy group, a branched alkoxy group, a cyclic alkoxy group, a halogen atom, or an aromatic ring, particularly R ４１ is a linear or branched alkyl group having a carboxy group, and R ４２ and R ４３ is a hydrogen atom.

[0080] Specific examples of the high-boiling unsaturated carboxylic acid compound (B4) include crotonic acid, cinnamic acid, benzoic acid, itaconic acid, tiglic acid, isocrotonic acid, angelic acid, etc. Among these, crotonic acid, cinnamic acid, benzoic acid, and itaconic acid are preferred because of their high polarity, crotonic acid and cinnamic acid are more preferred, and cinnamic acid is even more preferred.

[0081] The low-boiling unsaturated carboxylic acid compound and the high-boiling unsaturated carboxylic acid compound (B4) may each be used alone or in combination of two or more. The content of the α,β-unsaturated carboxylic acid compound in the curable composition of the first aspect is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass, based on 100% by mass of the total solid content of the curable composition. The content of the high-boiling unsaturated carboxylic acid compound (B4) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass, based on 100% by mass of the total solid content of the curable composition.

[0082] The content of the high-boiling unsaturated carboxylic acid (B4) in the curable composition of the second aspect is preferably 1 to 20 mass%, more preferably 1 to 15 mass%, and even more preferably 1 to 10 mass%, relative to 100 mass% of the total solid content of the curable composition. The content of the low-boiling unsaturated carboxylic acid (B) in the curable composition of the second aspect is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 5 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0083] The amount of the α,β-unsaturated carboxylic acid compound relative to 100% by mass of the monomer (B) is, for example, 0 to 40% by mass, preferably 1 to 30% by mass, more preferably 5 to 25% by mass. The amount of the high-boiling unsaturated carboxylic acid compound (B4) relative to 100% by mass of the monomer (B) is, for example, 0 to 40% by mass, preferably 1 to 30% by mass, more preferably 5 to 25% by mass.

[0084] In 100% by mass of the monomer (B), the total amount of the naphthylmethyl (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), the fluorene group-containing (meth)acrylates (B3), and the α,β-unsaturated carboxylic acid compound is, for example, 50 to 100% by mass, preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

[0085] Monomer (B) may contain a monomer (B5) other than naphthylmethyl (meth)acrylates (B1), biphenyl group-containing (meth)acrylates (B2), fluorene group-containing (meth)acrylates (B3), and α,β-unsaturated carboxylic acid compounds. Examples of other monomers (B5) include (meth)acrylic acid esters; styrene-based monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, and p-chloromethylstyrene; and hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxy-2-hydroxypropyl (meth)acrylate, and 3-phenoxy-2-hydroxypropyl (meth)acrylate. Of these, (meth)acrylic acid esters are preferred.

[0086] Examples of the (meth)acrylic acid ester include monofunctional (meth)acrylic acid esters and crosslinkable (meth)acrylic acid esters, with monofunctional (meth)acrylic acid esters being preferred.Examples of monofunctional (meth)acrylic acid esters include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; 2, (Meth)acrylic acid aryl esters such as 4-dibromo-6-sec-butylphenyl (meth)acrylate, 2,4-dibromo-6-isopropylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, and pentabromophenyl (meth)acrylate; (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate and pentabromobenzyl (meth)acrylate; phenoxyethyl (meth)acrylate, phenoxy-2-methyl ether (meth)acrylic acid esters having an aryloxy unit, such as phenylthioethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate; (meth)acrylic acid esters having an arylthiooxy group, such as acrylate, 1-naphthylthioethyl (meth)acrylate, and 2-naphthylthioethyl (meth)acrylate; alkylene glycol mono(meth)acrylates, such as methoxypolyethylene glycol (meth)acrylate and phenoxypolyethylene glycol (meth)acrylate; and (meth)acrylic acid esters having an epoxy group, such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

[0087] Examples of crosslinkable (meth)acrylic acid esters include monomers having two or more (meth)acryloyl groups, and specific examples thereof include alkylene glycol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and tetramethylene glycol di(meth)acrylate; neopentyl glycol poly(meth)acrylates such as neopentyl glycol di(meth)acrylate and dineopentyl glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; acrylate, ethoxylated (3) trimethylolpropane tri(meth)acrylate, propoxylated (3) trimethylolpropane tri(meth)acrylate, trimethylolpropane poly(meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate; glyceryl poly(meth)acrylates such as glyceryl tri(meth)acrylate, ethoxylated glyceryl tri(meth)acrylate; pentaerythritol poly(meth)acrylates such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; and α-allyloxymethyl acrylic acid alkyl esters such as α-allyloxymethyl methyl acrylate.

[0088] Among the other monomers (B5), it may be preferable not to include (meth)acrylic acid esters containing an epoxy group or monomers having two or more (meth)acryloyl groups. These may react with components other than the monomers in the curable composition. The amount of (meth)acrylic acid esters containing an epoxy group is, for example, 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less, based on 100% by mass of the monomer (B).

[0089] The amount of the monomer having two or more (meth)acryloyl groups is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the monomer (B).

[0090] In the first aspect, the amount of the monomer (B) not belonging to the naphthylmethyl (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), and the fluorene group-containing (meth)acrylates (B3) is preferably 0 to 10 mass%, more preferably 0.1 to 7 mass%, and even more preferably 1 to 5 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0091] In the first aspect, the total amount of the naphthylmethyl (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), and the fluorene group-containing (meth)acrylates (B3) is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, and even more preferably 90 to 100 mass%, relative to 100 mass% of the monomer (B).

[0092] In the second aspect, the amount of the (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), and the monomer (B) not belonging to the high-boiling unsaturated carboxylic acid (B4) is preferably 0 to 10 mass%, more preferably 0.1 to 7 mass%, and even more preferably 1 to 5 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0093] In the second aspect, the total amount of the (meth)acrylates (B1), the biphenyl group-containing (meth)acrylates (B2), and the high-boiling unsaturated carboxylic acid (B4) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, relative to 100% by mass of the monomer (B).

[0094] The curable composition may contain a resin component other than the monomer (B), for example, a binder resin such as an alkali-soluble resin. However, the curable composition usually does not contain any resin component other than the monomer (B). The amount of the resin component other than the monomer (B) is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly 1 part by mass or less, per 100 parts by mass of the curable composition.

[0095] (3) Photopolymerization initiator (C) As the photopolymerization initiator (C), an initiator commonly used in the field of photo-nanoimprinting can be appropriately used, and examples thereof include acetophenone-based initiators (C1), alkylaminobenzoate-based initiators (C2), oxime-based initiators (C3), benzoin-based initiators (C4), benzophenone-based initiators (C5), thioxanthone-based initiators (C6), α-aminoketone-based initiators (C7), acylphosphine oxide-based initiators (C8), etc. The photopolymerization initiator (C) may be one type, or two or more types may be combined.

[0096] Examples of the acetophenone initiator (C1) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer.

[0097] Examples of the alkylaminobenzoate initiator (C2) include ethyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl-4-(dimethylamino)benzoate, poly(ethylene glycol) bisdimethylaminobenzoate, and poly(ethylene glycol) di(β-(4-(acetylphenyl)piperazine))propionate.

[0098] Examples of the oxime initiator (C3) include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (Irgacure OXE01; manufactured by BASF), O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime (Irgacure OXE02; manufactured by BASF), Irgacure OXE03 (manufactured by BASF Japan), and Irgacure OXE04 (manufactured by BASF Japan).

[0099] Examples of the benzoin-based initiator (C4) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0100] Examples of the benzophenone initiator (C5) include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxylcarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride.

[0101] Examples of the thioxanthone initiator (C6) include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride.

[0102] Examples of the α-aminoketone initiator (C7) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.

[0103] Examples of the acylphosphine oxide initiator (C8) include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate.

[0104] These initiators can be used alone or in combination of two or more. Among these initiators, acetophenone-based initiators (C1), alkylaminobenzoate-based initiators (C2), oxime-based initiators (C3), thioxanthone-based initiators (C6), α-aminoketone-based initiators (C7), and acylphosphine oxide-based initiators (C8) are preferred, with acetophenone-based initiators (C1), alkylaminobenzoate-based initiators (C2), thioxanthone-based initiators (C6), α-aminoketone-based initiators (C7), and acylphosphine oxide-based initiators (C8) being more preferred, with acetophenone-based initiators (C1), alkylaminobenzoate-based initiators (C2), and acylphosphine oxide-based initiators (C8) being even more preferred, and acetophenone-based initiators (C1) and alkylaminobenzoate-based initiators (C2) being particularly preferred. The more preferred the initiator, the more effectively the cured product can be suppressed from discoloring and the more improved its transparency.

[0105] The amount of the photopolymerization initiator (C) is, for example, 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the monomer (B).

[0106] The content of the photopolymerization initiator (C) in the curable composition is preferably 0.1 to 10 mass%, more preferably 0.1 to 7 mass%, and even more preferably 0.1 to 5 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0107] The total amount of the metal oxide particles (A), the monomer (B), and the photopolymerization initiator (C) is, for example, 30 to 100 parts by mass, preferably 70 to 100 parts by mass, more preferably 90 to 100 parts by mass, and may be 90 to 95 parts by mass, per 100 parts by mass of the solid content of the curable composition.

[0108] (4) Dispersant (D) The curable composition may contain at least one selected from a dispersant (D) and a leveling agent (E). By containing the dispersant (D), the dispersibility of the metal oxide particles (A) in the monomer (B) can be improved, an increase in viscosity of the curable composition during storage can be suppressed, and storage stability can be improved. Examples of the dispersant (D) include an organic phosphorus compound or a salt thereof (D1), an organic sulfur compound or a salt thereof (D2), and the like, which can be used alone or in appropriate combination.

[0109] The organic phosphorus compound or a salt thereof (D1) includes a compound represented by the following formula (3) or a salt thereof: [In formula (3), R １ａ represents a saturated or unsaturated hydrocarbon group having 1 to 50 carbon atoms, a (meth)acryloyl group, or an aromatic-containing hydrocarbon group having 6 to 100 carbon atoms. a and b each represent an integer of 1 or 2, and the sum of a and b is 3. c represents an integer of 0 or 1. t1 represents an integer of 0 or 1. L １ represents a single bond, a linking group represented by any one of formulas (a1) to (a3), or a linking group formed by combining two or more of the linking groups represented by formulas (a1) to (a3), and when the linking group includes any one of the linking groups represented by formulas (a1) to (a3), the linking group represented by formulas (a1) to (a3) ​​is bonded to the phosphorus atom on the oxygen atom side. (R in formulas (a1) to (a3) ２ａ ~R ４ａ each independently represents a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms; R ２ａ ~R ４ａ may be substituted with an ether group; p1, q1, and r1 each represent an integer of 1 to 200, and the sum of p1, q1, and r1 is 1 to 200.

[0110] Examples of the compound represented by formula (3) include Newcol 1000-FCP (manufactured by Nippon Nyukazai Co., Ltd.), Antox EHD-400 (manufactured by Nippon Nyukazai Co., Ltd.), Phoslex series (manufactured by SC Organic Chemical Co., Ltd.), Light Acrylate P-1A (manufactured by Kyoeisha Chemical Co., Ltd.), Light Acrylate P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), TEGO (registered trademark) Dispers 651, 655, 656 (manufactured by Evonik), DISPERBYK-110, 111, 180 (manufactured by BYK Japan KK), KAYAMERPM-2, KAYAMERPM-21 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0111] As the compound represented by formula (3), the compound represented by the following formula is also preferred.

[0112]

[0113] (In the formula, R ４ａ are the same as above. p11, p12, and p15 each represent an integer of 4 to 20. The total of p11, p12, and p15 is preferably 1 to 50, more preferably 1 to 30. r1 is preferably 1 to 20. r12 has the same meaning as r1.

[0114] Examples of the organic sulfur compound or salt thereof (D2) include a polymer (hereinafter referred to as a sulfur-containing polymer) having a structural unit represented by the following formula (U) and a structural unit represented by the following formula (V), where a portion of the structural unit (U) constitutes the structural unit (V).

[0115] (In the formula, AR １ , A.R. ３each represents a divalent aromatic hydrocarbon group, and AR ２ represents a divalent aromatic hydrocarbon group having a thiol group. These aromatic hydrocarbon groups may have a substituent. １ , S ２ are S, SO, and SO respectively. ２ AR represents at least one selected from the group consisting of １ and A.R. ３ Examples of the divalent aromatic hydrocarbon group represented by the formula (1) include a phenylene group, a naphthylene group, an anthrylene group, a triphenylene group, a biphenylene group, and a phenanthrylene group, and a phenylene group is preferred. ２ As the divalent aromatic hydrocarbon group having a thiol group represented by the formula (I), １ and A.R. ３ Examples of such groups include groups in which one or more (preferably one) thiol groups are bonded to an aromatic hydrocarbon group such as those shown in the following formula: １ , A.R. ２ , A.R. ３ The substituents that the aromatic hydrocarbon group may have include a carboxy group (—COOH), a sulfo group (—SO ３ H), phosphate group (-OPO(OH) ２ ), phosphonic acid group (—PO(OH) ２ ), acid groups such as a phosphinic acid group (—PO(OH)—); a hydroxyl group (—OH); basic functional groups such as an amino group, an ammonium group, an imino group, an amide group, an imide group, and a maleimide group; polymerizable functional groups such as a vinyl group, a (meth)acryloyl group, an allyl group, and a methallyl group; reactive cyclic ether groups such as an epoxy group and an oxetane group; a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an aralkyl group, and among these, alkyl groups, and alkyl groups having 1 to 4 carbon atoms are preferred. １ , A.R. ２ , or AR ３ If any of the following contains an acid group as a substituent, the organosulfur compound can form a salt.

[0116] In the sulfur-containing polymer of the present invention, the content of the structural unit (U) is preferably 1 to 100 mol %, more preferably 30 mol % or more, even more preferably 50 mol % or more, and still more preferably 80 mol % or more, relative to the total content of all structural units in the polymer (100 mol %).

[0117] The content of the structural unit (V) in the sulfur-containing polymer of the present invention is not particularly limited. The content of the structural unit (V) relative to 100 mol% of the structural unit (U) contained in the sulfur-containing polymer of the present invention is preferably 1 to 100 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 20 mol%. The content of the structural unit (V) refers to the proportion of the structural unit (U) constituting the structural unit (V) relative to the total amount of the structural unit (U) contained in the sulfur-containing polymer of the present invention, and the content of the structural unit (V) refers to the ratio of the S constituting the structural unit (U). １ S constituting the structural unit (V) relative to 100 mol % ２ It is also the content of

[0118] In the sulfur-containing polymer of the present invention, the content of sulfide groups (-S-) is preferably 50 to 100 mol %, more preferably 80 to 100 mol %, and even more preferably 95 to 100 mol %, relative to 100 mol % of the content of the structural unit (U) in the polymer. In each preferred case, the remainder is a sulfoxide (-S(O)-) and sulfone group (-S(O) ２ The content of the structural unit (U) in the polymer refers to the total content of sulfide groups (-S-), sulfoxide groups (-S(O)-), and sulfone groups (-S(O)-) in the structural unit (U) of the polymer. ２ -) total content (i.e., S 1 The same applies hereinafter. From the viewpoint of improving processability, the sulfur-containing polymer of the present invention is preferably formed by adding sulfoxide (—S(O)—) and sulfone groups (—S(O) ２The total content of sulfoxide (-S(O)-) groups is preferably 50 to 100 mol %, more preferably 80 to 100 mol %, and even more preferably 95 to 100 mol %, relative to 100 mol % of the content of structural units (U) in the polymer. The remainder in each preferred case is the content of sulfide groups (-S-) in the polymer. From the viewpoint of increasing the dissolution rate and increasing the refractive index, the content of sulfoxide (-S(O)-) groups in the sulfur-containing polymer of the present invention is preferably 20 to 80 mol %, more preferably 30 to 70 mol %, and even more preferably 40 to 60 mol %, relative to 100 mol % of the content of structural units (U) in the polymer. The remainder in each preferred case is the content of sulfide groups (-S-) and sulfone groups (-S(O)-) in the polymer. ２ -) is the total content.

[0119] The amount of thiol groups is, for example, 1 to 400 mol %, preferably 5 to 100 mol %, more preferably 10 to 70 mol %, and even more preferably 15 to 50 mol %, based on 100 mol % of aromatic hydrocarbon groups.

[0120] The weight-average molecular weight (Mw) of the sulfur-containing polymer of the present invention is preferably 500 to 10,000,000. When the weight-average molecular weight is in the above range, the polymer can be suitably used as an optical material. From the viewpoint of improving mechanical properties, the weight-average molecular weight is more preferably 1,000 or more, more preferably 1,100 or more, and even more preferably 1,500 or more. On the other hand, from the viewpoint of improving the dispersibility of inorganic particles, the weight-average molecular weight is more preferably 1,000,000 or less, even more preferably 100,000 or less, and even more preferably 10,000 or less.

[0121] Examples of salts that form salts of organic phosphorus compounds, organic sulfur compounds, etc. include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as calcium salts; and quaternary ammonium salts.

[0122] The total amount of the organic phosphorus compound or a salt thereof (D1) and the organic sulfur compound or a salt thereof (D2) is, for example, 50 to 100 parts by mass, preferably 70 to 100 parts by mass, more preferably 90 to 100 parts by mass, and may be 90 to 95 parts by mass, per 100 parts by mass of the dispersant (D).

[0123] The content of the dispersant (D) is, for example, 0 to 30 parts by mass, preferably 0 to 20 parts by mass, more preferably 0 to 15 parts by mass, and may be 1 to 10 parts by mass, relative to 100 parts by mass of the metal oxide particles (A).

[0124] The dispersant (D) may be used as a surface treatment agent for the metal oxide particles (A). The surface treatment can further improve the dispersibility of the metal oxide particles in the curable composition.

[0125] The dispersant (D) used as the surface treatment agent is preferably a phosphate ester, since this improves the dispersibility of the metal oxide particles. That is, the metal oxide particles (A) are preferably particles that have been surface-treated with a surface treatment agent containing a phosphate ester.

[0126] The phosphate ester is preferably a compound represented by the formula (3), and particularly preferably a phosphate ester compound represented by the following formula (3X).

[0127]

[0128] (In formula (3X), R ３１ are the same or different and represent a linear or branched alkyl group having 1 to 10 carbon atoms. ３２ are the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms; n is an integer of 1 to 10; and a is an integer of 1 to 3.

[0129] In the above formula (3X), R ３１Examples of the linear or branched alkyl group having 1 to 10 carbon atoms and represented by the formula (I) include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups, and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpropyl, isopentyl, neopentyl, and 3-methylpentyl groups. ３１ The alkyl group represented by the formula (I) is preferably a linear alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, or an n-hexyl group, and even more preferably a methyl group, an ethyl group, or an n-propyl group.

[0130] In the above formula (3X), R ３２ Examples of the linear or branched alkylene group having 2 to 4 carbon atoms represented by the formula: ２ H ４ -, -C ３ H ６ -, -C ４ H ８ -, a linear alkylene group of -CH(CH ３ ) -, -CH(C ２ H ５ ) -, -CH(C ３ H ６ ) -, -CH(CH ３ ) ２ -, -CH(CH ３ ) CH ２ -, -CH(C ２ H ５ ) CH ２ -, -C(CH ３ ) ２ CH ２ -, -CH ２ CH (CH ３ ) -, -CH ２ CH(C ２ H ５ ) -, -CH ２ C(CH ３ ) ２ Among them, the branched alkylene group -C is preferred because of its high flexibility. ２ H ４ -, -C ３ H ６ -, -C４ H ８ - is preferred.

[0131] In the above formula (3X), n is an integer of 1 to 10, preferably 1 to 8, and more preferably 1 to 4, in terms of good compatibility with metal oxide particles.

[0132] In the above formula (3X), a is an integer of 1 to 3, and is preferably 1 to 2 in terms of good compatibility with the metal oxide particles.

[0133] The method for surface treating the metal oxide particles (A) with the dispersant (D) or the surface treatment agent containing the phosphate ester is not particularly limited, and may be a known method, such as mixing the metal oxide particles (A) and the surface treatment agent in a solvent, if necessary with heating, and then removing the solvent to obtain coated particles.

[0134] When the metal oxide particles are coated with the dispersant (D) or the surface treatment agent containing the phosphate ester, the amount of the phosphate ester is preferably 5 to 30 mass %, more preferably 10 to 30 mass %, and even more preferably 13 to 30 mass %, relative to 100 mass % of the coated metal oxide particles.

[0135] (5) Leveling Agent (E) The curable composition preferably contains a leveling agent (E). The inclusion of the leveling agent (E) can reduce the surface energy of the cured product, improving the releasability of the cured product from the mold during demolding and improving nanoimprintability. In particular, the combined use of naphthylmethyl (meth)acrylates (B1) and / or the specific esters (B2) with the leveling agent (E) can significantly improve nanoimprintability. As the leveling agent (E), various surfactants such as silicone surfactants, fluorine-based surfactants, and polyalkylene oxide surfactants can be used. The leveling agent (E) may be one type or two or more types. Furthermore, the silicone surfactants, fluorine-based surfactants, polyalkylene oxide surfactants, etc. may each be one type or two or more types. As the leveling agent (E), silicone surfactants, fluorine-based surfactants, etc. are preferred, with silicone surfactants being particularly preferred. The inclusion of a silicone surfactant improves the smoothness of the coating film.

[0136] Examples of silicone surfactants include compounds having a repeating unit containing a siloxane bond in the main chain, such as Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow-Toray Industries, Inc.); TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials, Inc.); KP341, and KF600. BYK-1, KF6002 (all manufactured by Shin-Etsu Silicones Co., Ltd.); BYK-333, BYK-301, BYK-331, BYK-345, BYK-307, BYK-378, BYK-310, BYK-313, BYK-323, BYK-306, BYK-377, BYK-330, BYK-342, BYK-370, BYK-302, BYK-300, BYK-UV3505, BYK-UV3575, BYK-UV3510, BYK-UV3500, BYK-UV3570 (all manufactured by BYK Japan KK) are preferably used. As the fluorine-based surfactant, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (all manufactured by Dainippon Ink and Chemicals, Inc.), NBX-15, and FTX-218 (manufactured by Neos Corporation) are preferably used.

[0137] The content of the silicone surfactant in the curable composition is preferably 0.01 to 2 mass%, more preferably 0.01 to 1 mass%, and even more preferably 0.01 to 0.5 mass%, relative to 100 mass% of the total solid content of the curable composition.

[0138] (6) Solvent (F) In this specification, the term "solvent" refers to a solvent that is in a liquid state at room temperature and normal pressure (e.g., 25°C, 1 atm) and does not have the characteristics of the monomer (B), and preferably has a boiling point. The curable composition of the first embodiment does not contain a solvent (F), or contains the solvent (F) in an amount of 150 parts by mass or less per 100 parts by mass of the metal oxide particles (A) and the monomer (B). By reducing the use of the solvent (F), shrinkage and deformation during molding can be suppressed. In the first embodiment, the solvent (F) is preferably contained in a large amount within an acceptable range for shrinkage and deformation during molding. The greater the amount of solvent (F), the greater the fluidity of the curable composition, making it easier for the composition to penetrate into narrow portions of a molding die. The amount of solvent (F) is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, even more preferably 10 to 70 parts by mass, and particularly preferably 20 to 50 parts by mass per 100 parts by mass of the metal oxide particles (A) and the monomer (B).

[0139] In the second embodiment, the amount of the solvent (F) is not particularly limited and may be set within a range of, for example, 0 to 500 parts by mass, more preferably 0 to 300 parts by mass, and even more preferably 0 to 150 parts by mass, relative to 100 parts by mass of the total of the metal oxide particles (A) and the monomer (B), and may be 0 to 100 parts by mass, particularly 0 to 70 parts by mass.

[0140] Examples of the solvent (F) include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 1-methoxy-2-propanol, and ethylene glycol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and propyl acetate; ethers such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether; modified ethers such as propylene glycol monomethyl ether acetate (particularly ether-modified and / or ester-modified alkylene glycols); hydrocarbons such as benzene, toluene, xylene, ethylbenzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and mineral spirits; halogenated hydrocarbons such as dichloromethane and chloroform; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; water; and oils such as mineral oil, vegetable oil, wax oil, and silicone oil. These may be used alone or in combination of two or more. From the viewpoint of ease of handling, a solvent having a boiling point at normal pressure (1013 hPa) of approximately 40° C. or more and 250° C. or less is suitable. The solvent (F) may be a solvent contained in the dispersion of metal oxide particles (A), or may be a solvent added from outside the dispersion when preparing the curable composition, or may be both.

[0141] In addition to the above-mentioned components, the curable composition may contain other components as necessary. Examples of such other components include heat resistance improvers; development aids; silane-based, aluminum-based, titanium-based, and other coupling agents; fillers; colorants; adhesion improvers; release agents; plasticizers; thermosetting resins such as epoxy resins, phenolic resins, and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyhydric phenol compounds; cationically polymerizable compounds; acid generators; photosensitizers; and the like. These may be used alone or in combination of two or more. These other components may be appropriately selected from known compounds and used, and the amount used may also be appropriately determined.

[0142] The curable composition has a glass transition temperature (Tg) of, for example, 22 to 100°C, preferably 25 to 90°C, more preferably 30 to 85°C, and may be 40 to 80°C when cured (particularly when cured of the monomer (B)). The higher the glass transition temperature, the more suppressed is the destruction of the material surface when released from the mold after nanoimprint molding, and the better the nanoimprintability. The glass transition temperature of the curable composition is preferably 20 to 350°C, more preferably 25 to 250°C, and even more preferably 30 to 150°C, in order to further improve adhesion to the glass substrate, improve mold releasability, and further enhance imprintability. The glass transition temperature can be measured using a dynamic viscoelasticity measuring device and can be determined by the method described in the examples below.

[0143] The refractive index of the curable composition or a cured product thereof is, for example, 1.60 to 2.00, preferably 1.65 to 1.90, more preferably 1.70 to 1.85, and may be 1.70 to 1.80. The higher the refractive index, the thinner the diffractive optical element (DOE) obtained from the composition can be. The curable composition or a cured product thereof is preferably colorless. The yellowness index (YI) of the curable composition or a cured product thereof is, for example, 0.0 to 1.0%, preferably 0.0 to 0.9%, and more preferably 0.0 to 0.8%. The curable composition or a cured product thereof is preferably transparent. The total light transmittance of the curable composition or a cured product thereof is, for example, 75 to 100%, preferably 80 to 95%, more preferably 81 to 92%, and may be 82 to 90%. The curable composition preferably has excellent storage stability. The increase in viscosity (cone-plate viscometer, standard rotor, measurement temperature 25°C) of the curable composition after leaving it at a temperature of 40°C for 7 days relative to the viscosity before leaving it is, for example, 0 to 5 mPa s, preferably 0 to 3 mPa s, and more preferably 0 to 1 mPa s.

[0144] The method for preparing the curable composition is not particularly limited, and any known method may be used. For example, the curable composition can be prepared by mixing the above-mentioned components using a known mixer, disperser, kneader, or the like, such as an extruder, a blender, a mixer, or a kneader.

[0145] <Curing Method> The method for curing the curable composition to obtain a cured product is not particularly limited, and examples thereof include heating, irradiation with active energy rays, and a combination of these. The heating temperature is usually preferably 50 to 300°C, more preferably 50 to 280°C, and even more preferably 60 to 250°C. Heating may be performed at a constant temperature, or may be performed by a method in which the temperature is continuously increased at a predetermined temperature increase rate and the temperature is maintained at the predetermined temperature, or may be performed by a method in which the temperature increase and the temperature maintenance are repeated two or more times.

[0146] The active energy rays may be those commonly used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle rays such as electron beams, neutron beams, and proton beams. Of these, ultraviolet rays are preferred.

[0147] When the cured product of the curable composition is a cured film, the thickness thereof is not particularly limited and may be appropriately selected depending on the purpose and application. However, in terms of improving adhesion to the substrate, the thickness is preferably 0.01 to 100 μm, more preferably 0.05 to 50 μm, and even more preferably 0.1 to 10 μm.

[0148] <Applications> The curable composition of the present invention may be capable of forming a desired fine surface irregularity, and may be capable of providing a cured product having excellent curability and excellent adhesion to a substrate (particularly a glass substrate). Therefore, the composition can be suitably used in applications requiring these excellent properties. Furthermore, the curable composition of the present invention can provide a cured product having excellent transparency. Therefore, the composition can be used in applications requiring transparency in addition to the above properties. Examples of such applications include resist applications, optical applications, coating applications, and adhesive applications. The curable composition is preferably a photosensitive composition for imprints (particularly a photosensitive composition for photo-nanoimprints). When the curable composition is used as a photosensitive composition for imprints, it exhibits excellent adhesion to a substrate and releasability from a mold, and can favorably form a transparent, finely patterned film.

[0149] (7) Nanoimprinting (including photo-nanoimprinting) The curable composition can be molded by nanoimprinting to produce a molded article having a fine uneven surface. Nanoimprinting is a technique in which the curable composition is applied to a substrate, dried as needed, and then pressed against a mold to form (nanoimprint) the coating film. The curable composition is cured by applying energy such as by irradiation with active energy rays, and then the mold is removed. The substrate can be made of silicon, various metal materials, glass, quartz, ceramic, plastic (organic resin film, organic resin molded product), or the like. It is preferable that either the substrate or the mold be made of a transparent material. When the mold is opaque, a transparent substrate is preferably used. The curable composition of the second aspect has excellent adhesion to substrates formed from these materials, and particularly excellent adhesion to glass substrates.

[0150] For the coating, known coating methods can be used, such as dip coating, spin coating, inkjet coating, slit scanning, bar coating, spraying, roll coating, etc. The curable composition of the present invention is excellent in coatability because it is composed of the predetermined monomers (B1), (B2), (B3), etc.

[0151] The mold is made of a material that satisfies a predetermined level of strength and processing accuracy. For example, silicon wafers, various metal materials, glass, quartz, ceramics, plastics, etc. can be used as appropriate. Specific examples include Si, SiC, SiN, polycrystalline Si, Ni, Cr, Cu, and materials containing one or more of these, with quartz being particularly preferred from the viewpoint of enhancing transparency. The material of the mold surface is not particularly limited, and examples include silicone-based resins, fluorine-based resins, epoxy-based resins, acrylic-based resins, polyurethane-based resins, phenolic resins, melamine-based resins, polyester resins, propylene resins, vinyl chloride resins, polystyrene, cycloolefin polymers, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, quartz, glass, etc. The curable composition of the first aspect of the present invention is composed of a predetermined monomer, has good fluidity, and low surface energy, so the material flows well on the mold surface and has excellent micromachining properties. The mold surface may be subjected to a release treatment. The release treatment can further reduce adhesion with the resin, improving fine processing and the resistance to resin peeling during release. Silicone-based release agents, fluorine-based release agents, etc. can be used for the release treatment.

[0152] The shape of the pattern on the mold surface is not particularly limited, but examples thereof include a line and space shape, a pillar shape, a hole shape, a honeycomb shape, a slanted shape, a moth-eye shape, a cone shape, a square prism shape, a square pyramid shape, a triangular prism shape, a triangular pyramid shape, a polygonal prism shape, a polygonal pyramid shape, and a lattice shape.

[0153] In the pressing step, the pressure with which the mold is pressed against the coating film obtained in the coating film forming step is not particularly limited, but is preferably 0.01 to 10 MPa, more preferably 0.05 to 5 MPa, and even more preferably 0.1 to 1 MPa.

[0154] In the pressing step, it is preferable to cure the coating film obtained in the coating film forming step while pressing the mold against the coating film. The curing method is not particularly limited, but it is preferable to perform an energy imparting treatment such as heating and / or active energy ray irradiation. Among these, it is more preferable to perform photoimprinting by active energy ray irradiation.

[0155] Examples of active energy rays used to cure the curable composition include light or radiation with wavelengths in the near ultraviolet, far ultraviolet, visible, infrared, etc. Examples of ultraviolet light sources include ultraviolet fluorescent lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, and sun lamps. Examples of radiation include microwaves and EUV (Extreme Ultra Violet).

[0156] The amount of ultraviolet light irradiation (cumulative exposure amount) is not particularly limited, but is preferably 0.05 to 30 J / cm ２ It is preferable to irradiate so that the radiation dose is in the range of 0.1 to 20 J / cm. ２ , more preferably 1 to 10 J / cm ２ is.

[0157] After the curing, the mold is released from the formed pattern film. After the mold is released, the resulting pattern film may be further cured. The curing method is preferably heating and / or active energy ray irradiation, more preferably heating. The heating temperature is not particularly limited, but may be 50 to 300°C, preferably 80 to 200°C, for 5 to 60 minutes, preferably 10 to 30 minutes.

[0158] The patterned film thus obtained has excellent adhesion to the substrate. It also has excellent mold releasability and transparency. By using the curable composition of the present invention, a transparent, finely patterned film can be successfully produced, which has good curability, excellent adhesion to the substrate, and good mold releasability.

[0159] (8) Diffractive Optical Element (DOE) The nanoimprinted molded article obtained as described above has a controlled nano-level (less than 1 μm) fine uneven structure on the surface and a high refractive index, and therefore can be suitably used as a diffractive optical element (DOE). Specifically, it can be used as an element for controlling a laser beam to output light of various patterns (for example, an element for a 3D sensor), an input diffractive element (in-coupling grating) or an output diffractive element (out-coupling grating) in AR / VR glasses, etc.

[0160] This application claims the benefit of priority based on Japanese Patent Application No. 2024-2807, filed on January 11, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-2807, filed on January 11, 2024, are incorporated herein by reference. This application claims the benefit of priority based on Japanese Patent Application No. 2024-164052, filed on September 20, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-164052, filed on September 20, 2024, are incorporated herein by reference. This application claims the benefit of priority based on Japanese Patent Application No. 2024-199378, filed on November 15, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-199378, filed on November 15, 2024, are incorporated herein by reference.

[0161] The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to the following examples, and it is of course possible to carry out the invention by making appropriate modifications within the scope of the above and below-described aims, and all such modifications are included in the technical scope of the present invention.

[0162] The following were used in the examples and comparative examples. (1) Metal oxide particles (A) ZP-153: Zirconia dispersion (manufactured by Nippon Shokubai Co., Ltd., Zircostar (registered trademark) "ZP-153") Dispersion liquid: methyl ethyl ketone (MEK), particle content: 70% by mass, dispersion refractive index: 1.53, particle refractive index: 1.8, particle size: 11 nm (dynamic light scattering method), average primary particle size: 11 nm, main crystal system: tetragonal ZP-489: Zirconia dispersion (manufactured by Nippon Shokubai Co., Ltd., Zircostar (registered trademark) "ZP-489") Dispersion medium: propylene glycol monomethyl ether acetate (PEGMEA), particle content: 70% by mass, dispersion refractive index: 1.57, particle refractive index: 1.86, average primary particle size: 18 nm, main crystal system: tetragonal

[0163] (2) Monomer (B) (2.1) Naphthyl (meth)acrylates (B1) NMT-A: 1-naphthyl methyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light Acrylate NMT-A"

[0164] (2.2) Biphenyl group-containing (meth)acrylates (B2) HRD-01: o-biphenylethoxyacrylate (manufactured by Nisshoku Techno Fine Chemical Co., Ltd.)

[0165] AOMA-BP: Allyloxymethylacrylic acid p-methylenebiphenyl ester (manufactured by Nippon Shokubai Co., Ltd.)

[0166] (2.3) Fluorene group-containing (meth)acrylate (B3) EA-0200: product name "OGSOL EA0200" manufactured by Osaka Gas Chemicals Co., Ltd.

[0167] (2.4) α,β-unsaturated carboxylic acid compound: methacrylic acid (boiling point 161°C) High-boiling point unsaturated carboxylic acid compound (B4): crotonic acid (boiling point 180°C), cinnamic acid (boiling point 300°C), itaconic acid (boiling point 268°C)

[0168] (2.5) Other Monomers (B5) POBA: m-phenoxybenzyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light Acrylate POB-A")

[0169] (3) Photopolymerization initiator (C) (3.1) Acetophenone-based initiator (C1) Omnirad 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by IGM Resins B.V., former trade name "Irgacure 1173") (3.2) Alkylaminobenzoate-based initiator (C2) Omnipol ASA: Poly(ethylene glycol) bisdimethylaminobenzoate (manufactured by IGM Resins B.V.) (3.3) Oxime-based initiator (C3) OXE02: O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime (manufactured by BASF) (3.4) Acylphosphine oxide-based initiator (C8) Omnirad TPO-L: ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate (manufactured by IGM Resins B.V.)

[0170] (4) Dispersant (D) (4.1) Organic phosphorus compound (D1) BYK111: Phosphate-based dispersant (manufactured by BYK-Chemie) (4.2) Organic sulfur compound (D2): Organic sulfur dispersant (OSD) synthesized as follows: (4.21) Synthesis of bis(4-methylphenyl) disulfide In a 500 mL three-necked flask, water (98 mL), p-toluenethiol (4-methylbenzenethiol) (18.2 g, 0.147 mol), tetrabutylammonium iodide (54.3 mg, 0.147 mol) was added, and then 30% hydrogen peroxide solution (15.2 mL, 0.147 mol) was added dropwise at 1 mL / min and stirred at 60 ° C. for 2 hours. After cooling to room temperature, the supernatant (aqueous layer) was removed, and then an aqueous sodium thiosulfate solution was added, followed by stirring at room temperature for 2 hours, and the supernatant (aqueous layer) was removed. The reaction solid was filtered, washed with pure water and then with methanol, and dried under vacuum to recover bis(4-methylphenyl)disulfide in a yield of 98%.

[0171] (4.22) Synthesis of organosulfur polymer (Po1a) In a 3.0 L three-neck flask, diphenyl disulfide (218.33 g, 1.00 mol), the bis(4-methylphenyl) disulfide obtained above (49.21 g, 0.20 mol), iron(III) chloride (9.73 g, 60.00 mmol), (+)-CSA ((+)-10-camphorsulfonic acid) (2.79 g, 12.00 mmol), Na ２ S2O8 (sodium peroxodisulfate) (2.57 g, 12.00 mmol) was added. Next, the three-neck flask was heated to 160°C while nitrogen flow (20 mL / min) was performed for 10 minutes, and then the flow was switched to air bubbling (150 mL / min), and the mixture was stirred for 40 hours to carry out oxidative polymerization, thereby producing a polymer having a polyphenylene sulfide skeleton in which a portion of the sulfide structure was oxidized.

[0172] After polymerization was complete, air bubbling was stopped, and 240 mL of N-methylpyrrolidone was added and stirred for 10 minutes. The reaction mixture was then cooled to room temperature, and THF (2.2 L) was added as a solvent. After stirring for 10 minutes, 192 mL of pure water was added and stirred for 5 minutes. Next, while the recovery flask was cooled on an ice bath, trichloroisocyanuric acid (122.11 g, 0.66 mol) was added, and after stirring for 2 hours, zinc powder (31.53 g, 0.48 mol) was added and stirred at room temperature for 14 hours. After the reaction was complete, methanol (12 L) was added to the reaction mixture to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum dried at room temperature to obtain a white polymer (Po1a) powder. The yield was 92%. GPC analysis revealed Mw = 2,400 and Mn = 1,150. XPS confirmed that the ratio of sulfide groups to sulfoxide groups to sulfone groups was 45:55:0 mol %. IR revealed a peak at 2570 cm －１ A peak derived from mercapto was observed around this point, confirming that the terminal structure was -SH. From Mn = 1,150, it was confirmed that the proportion of terminal aromatic rings (structural units) was 9.5 mol % relative to 100 mol % of all aromatic rings (all structural units).

[0173] [GPC conditions] GPC measurement of the organosulfur polymer (Po1a) was carried out as follows. Apparatus 1: SHIMADZU, CBM-20A Apparatus 2: Agilent Technologies 1260Infinity Detector: Differential refractive index detector (RI) (SHIMADZU, SPD-20MA), and ultraviolet-visible-infrared spectrophotometer (SHIMADZU, SPD-20MA) Column: TOSOH, TSKgel Super HM-N Column temperature: 40°C Flow rate: 0.3 ml / min Calibration curve: Polystyrene Standards Eluent: Tetrahydrofuran [XPS conditions] XPS measurement of the organosulfur polymer (Po1a) was carried out as follows. A polymer solution was prepared by dissolving the organosulfur polymer (Po1a) in an organic solvent (chloroform) to a concentration of 10 wt %. 0.25 ml of the prepared polymer solution was spin-coated (*1) onto a silicon wafer to form a film, which was used as a sample. A JEOL photoelectron spectrometer (JPS-9010TR, XPS device, light source: Mg, X-ray output: 400 W) was used to measure the peak intensity derived from the 2p orbital of sulfur atoms and the peak intensity derived from the 1s orbital of oxygen atoms, and the O / S ratio was calculated by calculating their integral ratio. If necessary, the peak intensity derived from the 1s orbital of carbon atoms was also measured, and the O / S ratio was calculated taking these results into consideration. The measurement method, bond energy position, etc. were based on the Handbook of X-ray Photoelectron Spectroscopy (JEOL, March 1991). １For samples in which the sulfide and sulfoxide peaks could be separated by H-NMR measurement, the O / S ratio was calculated by calculating the integral ratio of each. Bond energy was measured as follows: A polymer solution was prepared by dissolving an organosulfur polymer (Po1a) in an organic solvent (chloroform) to a concentration of 10% by weight. 0.25 ml of the prepared polymer solution was spin-coated*1 onto a silicon wafer to form a film. Using this film as a sample, the bond energy was measured from the peak position of the 2p3 / 2 orbital of the sulfur atom using a JEOL photoelectron spectrometer (JPS-9010TR, XPS device). *1: The spin coating was performed using a Mikasa "Spin Coater 1H-D7." Each composition was dropped onto the surface of a substrate (glass slide, silicon wafer, etc.) placed on the spin coater, and the substrate was rotated at 1,000 rpm for 20 seconds.

[0174] [IR Measurement] IR measurement of the organosulfur polymer (Po1a) was carried out as follows. Apparatus: JASCO Fourier transform infrared spectrophotometer (FT / IR-6100). Sample preparation: Approximately 2 mg of sample was diluted with approximately 300 mg of dry potassium bromide (KBr). The mixture was ground with a mortar and pestle and molded.

[0175] (4.23) Synthesis of Organic Sulfur Dispersant (OSD) (Further Introduction of Thiol Groups) 200.0 g of the above white polymer (Po1a) was added to a 2.0 L three-neck flask, and 1.1 L of sulfolane was added as a solvent. Next, the three-neck flask was heated to 130 °C while nitrogen flow (0.5 L / min) was performed for 10 minutes, and then allowed to cool to room temperature. After cooling, the three-neck flask was immersed in a water-cooled bath, and 98.3 g of chlorosulfuric acid was gradually added dropwise while nitrogen flow (0.25 L / min) was performed. After completion of the addition, the mixture was stirred at room temperature for 2 hours. 16.6 g of zinc was added again while cooling the three-neck flask in a water-cooled bath, and the mixture was stirred for 14 hours. After completion of the reaction, the resulting reaction solution was added dropwise to 5.5 L of methanol to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum dried at room temperature to obtain an organic sulfur dispersant (OSD) powder. The yield was 90%. GPC revealed Mw = 2370 and Mn = 1150. IR revealed a peak at 2570 cm －１ A peak derived from mercapto was observed near the peak, confirming the presence of 27.7 mol% of thiol (-SH) groups relative to all aromatic rings. The thiol group content increased by 18.2 mol% compared to the thiol group content (9.5 mol%) of polymer (Po1a). The measurements of the organic sulfur dispersant (OSD) were performed in the same manner as the measurements of the above-mentioned organic sulfur polymer (Po1a).

[0176] Leveling agent (surfactant) (E) BYK307: Polyether-modified polydimethylsiloxane (manufactured by BYK-Chemie)

[0177] Examples 1 to 16 and Comparative Examples 1 and 2 The above-mentioned components were mixed in the proportions (by mass) shown in Tables 1 to 3. The properties of the resulting compositions were evaluated as follows. [Viscosity] The viscosity of the resulting compositions at 25°C was measured using a cone-plate type rotational viscometer (E-type viscometer) (TVE22LT, manufactured by Toki Sangyo Co., Ltd.). The viscosity was compared immediately after preparation and after storage at 40°C for 7 days. A standard rotor (name: 1°34' x R24) was used for the cone-plate. [Nanoimprintability (pitch 1 μm)] The resulting composition was dropped onto a glass substrate (8 cm x 8 cm) on a spin coater using a pipette, and spin-coated for 20 seconds at 1000 rpm. The coating film on the glass substrate thus prepared was placed on a hot plate preheated to 50°C and held for 1 minute to remove the solvent. The coating film on the glass substrate was then allowed to cool to room temperature. A mold having parallel convex portions with a rectangular cross section, each 1 μm high and 1 μm wide, was then pressed onto the coating film using a roller. The mold had a height of 1 μm, a width of 1 μm, and a rectangular cross section, and was spaced 1 μm apart within an area of ​​1 cm × 1 cm. The mold was then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) under a nitrogen atmosphere. ２ ) for 90 seconds. Thereafter, the mold was peeled off and the substrate was left to stand on a hot plate heated to 150°C for 10 minutes, yielding a transfer pattern in which stripe-shaped convex portions corresponding to the concave portions of the mold were formed. The same procedure was repeated to prepare 20 transfer patterns, and for each transfer pattern, the transfer pattern (multiple stripe-shaped convex portions) was cut perpendicular to the stripes using a glass cutter. The cross-sectional shape of the pattern was observed using an FE-SEM (manufactured by JEOL Ltd.: JSM7600F) at a magnification of 10,000 times (field of view 12 μm × 9 μm), and the presence or absence of defects in each pattern was confirmed. Here, defects refer to insufficient height of the cured film convex portions due to insufficient filling of the composition, chipping or bending of the cured film convex portions when the mold was peeled off, etc. If one or more stripes had such defects, the pattern was evaluated as a defective pattern. The proportion of defective patterns among all 20 patterns was calculated and evaluated based on the following criteria. ○: No defects (no defects in all 20 patterns) △: Less than 30% defects (less than 6 patterns out of all 20 patterns have defects) ×: More than 30% defects (6 or more patterns out of all 20 patterns have defects)

[0178] [Nanoimprintability (Pitch: 0.5 μm)] The resulting composition was dropped onto a glass substrate on a spin coater using a pipette, and spin-coated at 1,500 rpm for 20 seconds. The resulting coating film on the glass substrate was placed on a hot plate preheated to 50°C and held there for 1 minute to remove the solvent. Replica mold A was pressed onto the coating film on the glass substrate, which had been allowed to cool to room temperature, using a roller. The coating film was then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength: 365 nm, illuminance: 80 mW / cm) under a nitrogen atmosphere. ２ ) was performed for 90 seconds. Thereafter, the mold was peeled off and the resulting mixture was allowed to stand on a hot plate heated to 150°C for 10 minutes. The glass substrate on which the cured film having the transferred pattern was formed was observed with an FE-SEM (JSM7600F, manufactured by JEOL Ltd.), and the presence or absence of defects in the transferred pattern on the glass substrate was visually observed and evaluated based on the following criteria: ○: No defects △: Less than 30% defects ×: 30% or more defects Furthermore, compositions that were evaluated as having imprintability of "○" with replica mold A were subjected to a similar evaluation of imprintability using replica mold B. The presence or absence of defects in the transferred pattern with replica mold B was observed, and those with no defects were evaluated as having imprintability of "◎". Replica molds A and B were prepared by the following methods.

[0179] Preparation of replica mold A (polydimethylsiloxane) Cosmoshine A4360 (polyester film, thickness 188 μm) (manufactured by Toyobo Co., Ltd.) was spin-coated (2000 rpm, 10 seconds) with a solution of a 1:1 mixture of KER-4690-A and KER-4690-B (silicone-based resin) manufactured by Shin-Etsu Chemical Co., Ltd. Mold DTM-7-1 (L&S with a depth of 1 μm and a pitch of 0.5 μm) manufactured by Kyodo International Co., Ltd. After lamination, UV-LED irradiation (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) was performed. ２ ) and exposure (4 J / cm ２ ) was carried out, and after leaving it at room temperature for 24 hours, mold DTM-7-1 was released to obtain replica mold A.

[0180] Preparation of replica mold B (epoxy resin) Cosmoshine A4360 (polyester film, thickness 188 μm) (manufactured by Toyobo Co., Ltd.) was spin-coated (2000 rpm, 10 seconds) with OEX-028-X433T (epoxy resin) manufactured by Autech Co., Ltd. This coating film was heated on a hot plate at 85°C for 5 minutes, and then laminated with mold DTM-7-1 (L&S with a depth of 1 μm and a pitch of 0.5 μm) manufactured by Kyodo International Co., Ltd. After lamination, UV-LED irradiation (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) was performed. ２ After leaving it at room temperature for 5 minutes, mold DTM-7-1 was released to obtain replica mold B.

[0181] [Yellowness Index (YI)] The obtained composition was dropped onto a glass substrate on a spin coater using a pipette, and spin-coated at 1000 rpm for 20 seconds. The prepared coating film on the glass substrate was placed on a hot plate preheated to 50°C and held for 1 minute to remove the solvent. The coating film (thickness 2 μm) on the glass substrate was allowed to cool to room temperature, and then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) under a nitrogen atmosphere. ２ ) was performed for 90 seconds. Thereafter, the substrate was left to stand on a hot plate heated to 150°C for 10 minutes. The glass substrate on which the 2 μm-thick coating film was formed was measured for transmittance using a Cary 60 UV-vis (1 / 3) (manufactured by Agilent Technologies) to determine the YI value.

[0182] [Glass transition temperature (Tg)] A Kapton film was placed on a glass substrate, and a 0.5 mm thick silicone sheet with inner dimensions of 2 cm × 6 cm was placed on top of that. 0.6 g of the obtained composition was placed in a silicone frame and uniformly distributed within the frame. The composition was placed on a hot plate preheated to 50°C and held for 5 minutes to remove the solvent. The coating film (0.3 mm thick) on the glass substrate was allowed to cool to room temperature and then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) under a nitrogen atmosphere. ２) for 90 seconds. Thereafter, the sample was left to stand on a hot plate heated to 150°C for 10 minutes. The cured film was peeled off from the Kapton film, and a sample was cut into a size of 5 mm x 6 cm. The viscoelasticity of the sample was measured at temperatures from -50°C to 185°C using a dynamic viscoelasticity measuring device RSA-G2 (manufactured by TA Instruments), and Tg was determined.

[0183] [Refractive Index] The obtained composition was dropped onto a glass substrate on a spin coater using a pipette, and spin-coated at 1000 rpm for 20 seconds. The prepared coating film on the glass substrate was placed on a hot plate preheated to 50°C and held for 1 minute to remove the solvent. The coating film (thickness 2 μm) on the glass substrate was allowed to cool to room temperature, and then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) under a nitrogen atmosphere. ２ ) was performed for 90 seconds. Then, the glass substrate was left to stand on a hot plate heated to 150°C for 10 minutes. The coated glass substrate was measured using a Filmetrics F-20 device (manufactured by Filmetrics), and the refractive index was determined by fitting.

[0184] [Total Light Transmittance (%)] The obtained composition was dropped onto a glass substrate on a spin coater using a pipette, and spin-coated at 1000 rpm for 20 seconds. The prepared coating film on the glass substrate was placed on a hot plate preheated to 50°C and held for 1 minute to remove the solvent. The coating film (thickness 2 μm) on the glass substrate was allowed to cool to room temperature, and then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm) under a nitrogen atmosphere. ２ ) was performed for 90 seconds. Then, the substrate was left to stand on a hot plate heated to 150°C for 10 minutes. The transmittance of the coated glass substrate was measured using a Cary 60 UV-vis (1 / 3) transmittance meter (Agilent Technologies).

[0185] [HAZE] The obtained photosensitive composition was dropped onto a glass substrate mounted on a spin coater using a pipette, and spin-coated at 1000 rpm for 20 seconds to produce a coating film. The prepared coating film on the glass substrate was placed on a hot plate preheated to 50°C and held for 1 minute to remove the solvent. The coating film on the glass substrate was then allowed to cool to room temperature and then irradiated with UV-LED (area-type irradiator manufactured by CCS Corporation) (wavelength 365 nm, illuminance 80 mW / cm2) for 90 seconds under a nitrogen atmosphere. The substrate was then placed on a hot plate heated to 150°C for 10 minutes to form a 2 μm-thick coating film on the glass substrate. The haze of the coated glass substrate was measured using a NDH-7000 haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0186] The results are shown in Tables 1 to 3.

[0187] Because Examples 1 to 16 are compositions containing specific monomers, they exhibit excellent nanoimprintability (pitch 1 μm) even when they contain metal oxide particles (A) and use a small amount of solvent (F). As can be seen from the poor nanoimprintability in Comparative Example 2 when metal oxide particles are not included, metal oxide particles (A) are not only useful for increasing the refractive index, but also contribute to improving nanoimprintability when a small amount of solvent (F) is used. In particular, the incorporation of a leveling agent further improves nanoimprintability (Examples 1 to 3, 5 to 16). Note that the use of a leveling agent alone does not improve nanoimprintability (Comparative Example 1); only the combined use of a specific monomer and leveling agent achieves further improvement. Furthermore, compared to when the initiator was OXE02 (Examples 5 and 12), the yellowness index (YI) could be reduced in examples where the initiator was changed to something other than OXE02 (Examples 1 to 4, 6 to 11, 13 to 16). In the examples (Examples 8 to 14) in which a high-boiling unsaturated carboxylic acid compound was used in combination as a monomer, good nanoimprinting properties (pitch 0.5 μm) were also achieved.

[0188] Examples 1A to 6A, Comparative Examples 1A to 4A Photosensitive compositions were prepared by mixing the components to obtain the formulations (solid content amounts) shown in Table 4. The resulting photosensitive compositions were evaluated for nanoimprintability (pitch 0.5 μm), YI value (2 μm), glass transition temperature (Tg), and haze using the methods described above. The results are shown in Table 4.

[0189] Table 1 shows that the photosensitive compositions of Examples 1A to 6A, which contain metal oxide particles (A), a monomer represented by the above formula (1) and / or a monomer represented by the above formula (2) (B), an α,β-unsaturated carboxylic acid compound (C) having a boiling point of 170 to 500°C, and a photopolymerization initiator (D), exhibit excellent adhesion to glass substrates and good nanoimprintability (pitch of 0.5 μm). The photosensitive compositions of the examples also exhibit high transparency. Note that the Tg of Comparative Example 4A could not be measured because the sample was brittle and broke before the temperature reached Tg.

[0190] The composition of the present invention can be used in imprinting techniques such as photo-nanoimprinting.

Claims

1. A composition containing metal oxide particles (A), a monomer (B), and a photopolymerization initiator (C), containing no solvent (F) or containing the solvent (F) in an amount of 150 parts by mass or less with respect to 100 parts by mass in total of the metal oxide particles (A) and the monomer (B), wherein the monomer (B) is at least one selected from the group consisting of naphthylmethyl (meth) acrylates (B1) which may have a substituent, a monomer (B2) represented by the following formula (2), (In the formula, R ２１ represents a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH = CH ２ . L represents an alkylene group having 1 to 10 carbon atoms, -CH ２ CH ２ O- or -CH ２ CHCH ３ O-. a is an integer of 0 to 3. R ２２ and R ２３ are the same or different and each represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. b and c are the same or different and each is an integer of 0 to 4. When b is 2 or more, the plurality of R ２２ may be the same or different and may be bonded to each other to form a ring structure. When c is 2 or more, the plurality of R ２３ may be the same or different and may be bonded to each other to form a ring structure.), and esters (B3) of bishydroxyarylfluorene or an oxyalkylene adduct thereof and (meth) acrylic acid.

2. The composition according to claim 1, wherein the monomer (B) further contains an α,β-unsaturated carboxylic acid compound (B4) having a boiling point of 170 to 500°C.

3. The composition according to claim 1, wherein the naphthylmethyl (meth) acrylates (B1) which may have the above substituents are compounds represented by the following formula (1). (In the formula, n1 represents an integer of 0 to 7. R １ represents a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH=CH ２ . R ２ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. When n1 is 2 or more, a plurality of R ２ may be different from each other or may be bonded to each other. Further, when n1 is 2 or more, a plurality of R ２ may combine to form a ring that is fused to the naphthalene ring of formula (1).) 4. The composition according to claim 1, wherein the esters (B3) of the bis-hydroxyarylfluorene or its oxyalkylene adduct and (meth)acrylic acid are compounds represented by the following formula (3). (In the formula, n2 and n3 each independently represent an integer of 0 to 5, and n4 and n5 each independently represent an integer of 0 to 4. m1 and m2 each independently represent an integer of 0 to 7. Ar １ , Ar ２ each independently represent an aromatic ring. R ３ represents a hydrogen atom or a methyl group. R ４ , R ５ each independently represent a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. R ６ represents a hydrogen atom or a (meth)acryloyl group. R ７ to R １０ each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, or an aromatic ring. When n2 is 2 or more, the plurality of Rs ７ may be different from each other. When n3 is 2 or more, the plurality of Rs ８ may be different from each other. When n4 is 2 or more, the plurality of Rs ９ may be different from each other. When n5 is 2 or more, the plurality of Rs １０ may be different from each other.) 5. A composition containing metal oxide particles (A), a monomer (B), and a photopolymerization initiator (C), wherein the monomer (B) contains a compound represented by formula (1) and / or a compound represented by formula (2), and an α,β-unsaturated carboxylic acid compound (B4) having a boiling point of 170 to 500 °C. (In the formula, n1 represents an integer of 0 to 7. R １ represents a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH=CH ２ . R ２ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a hydroxy group, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. When n1 is 2 or more, a plurality of R ２ may be different from each other or may be bonded to each other. When n1 is 2 or more, a plurality of R ２ may combine to form a ring that condenses with the naphthalene ring of formula (1).) (In the formula, R ２１ represents a hydrogen atom, a methyl group, or -CH ２ OCH ２ CH=CH ２ . L represents an alkylene group having 1 to 10 carbon atoms, -CH ２ CH ２ O- or -CH ２ CHCH ３ O-. a is an integer of 0 to 3. R ２２ and R ２３ is, the same or different, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, an aromatic ring, or a divalent group forming a ring structure. b and c are, the same or different, integers from 0 to 4. When b is 2 or more, a plurality of R ２２ may be the same or different and may be bonded to each other to form a ring structure. When c is 2 or more, a plurality of R ２３ may be the same or different and may be bonded to each other to form a ring structure.) 6. The composition according to claim 1 or 5, wherein the metal oxide particles (A) contain oxide particles of at least one element selected from the group consisting of Ti, Al, Zr, In, Zn, Sn, La, Y, Ce, Mg, Ba, Ca, and Sb.

7. The composition according to claim 1 or 5, wherein the metal oxide particles (A) are zirconium oxide and / or titanium oxide.

8. The composition according to claim 1 or 5, wherein the metal oxide particles (A) have an average primary particle diameter of 1 to 50 nm.

9. The composition according to claim 1 or 5, wherein the metal oxide particles (A) are particles surface-treated with a surface treatment agent containing a phosphate ester.

10. The composition according to claim 1 or 5, wherein the metal oxide particles (A) are particles surface-treated with a surface treatment agent containing a phosphate ester compound represented by the following formula (3X). (In the formula (3X), R ３１ represents, identically or differently, a linear or branched alkyl group having 1 to 10 carbon atoms. R ３２ represents, identically or differently, a linear or branched alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 10. a is an integer of 1 to 3.) 11. The composition according to claim 1 or 5, which contains 10 to 900 parts by mass of the monomer (B) with respect to 100 parts by mass of the metal oxide particles (A).

12. The composition according to claim 1 or 5, wherein the (meth)acrylate ester containing an epoxy group as the monomer (B) is 0 to 5% by mass in 100% by mass of the monomer (B).

13. The composition according to claim 1 or 5, which does not contain a monomer having two or more (meth)acryloyl groups as the monomer (B), or contains it in a range of 10% by mass or less in 100% by mass of the monomer (B).

14. The composition according to claim 1 or 5, wherein the photopolymerization initiator (C) contains at least one selected from the group consisting of an acetophenone-based initiator (C1), an alkylaminobenzoate-based initiator (C2), an oxime-based initiator (C3), a thioxanthone-based initiator (C6), an α-aminoketone-based initiator (C7), and an acylphosphine oxide-based initiator (C8).

15. The composition according to claim 1 or 5, which further contains a dispersant (D).

16. The composition according to claim 15, wherein the dispersant (D) is one selected from the group consisting of an organic phosphorus compound or its salt (D1) and an organic sulfur compound or its salt (D2).

17. The composition according to claim 1 or 5, which further contains a leveling agent (E).

18. The composition according to claim 17, wherein the leveling agent (E) is a silicone-based surfactant.

19. The composition according to claim 1 or 5, wherein the glass transition temperature (Tg) of the cured product obtained by curing the composition is 22°C or higher.

20. The composition according to claim 1 or 5, which is for optical imprinting.

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