Method for manufacturing patterned film, patterned film, and polymerizable composition

Abstract

The present invention provides a method for manufacturing a patterned film having a high refractive index, wherein the method can satisfactorily transfer a high-definition pattern shape possessed by a mold and form a highly reliable patterned film which shows a small change in the pattern shape even after heating. The present invention relates to a method for manufacturing the patterned film, wherein the manufacturing method includes a step for pressing a polymerizable composition containing a polymerizable monomer represented by general formula (1), by using a mold. (In the formula (1), R1 represents an organic group having 1-30 carbon atoms and having an aromatic group. R2 represents -O-, -S-, or -NH-. R3 represents a hydrogen atom or a methyl group. X1, Y1 and Z1 are the same or different, and each represents -CR4R5- or an oxygen atom. R4 and R5 are the same or different, and represent a hydrogen atom or a methyl group. At least one of X1, Y1, and Z1 is an oxygen atom. n represents an integer of 1 or larger).　

Description

Method for manufacturing a patterned film, patterned film, and polymerizable composition

[0001] This invention relates to a method for manufacturing a patterned film, a patterned film, and a polymerizable composition. More specifically, it relates to a method for manufacturing a patterned film, a patterned film, and a polymerizable composition useful for manufacturing optical materials, semiconductor devices, and the like.

[0002] The imprint method is a technique that transfers fine patterns onto a material by directly pressing a mold with a fine, textured pattern onto a resin or other material. Because the imprint method allows for the easy creation of fine patterns, it is expected to have applications in various fields, including semiconductor devices. In particular, nanoimprint technology, which forms nano-order level fine patterns, is attracting attention.

[0003] For example, Patent Document 1 discloses a resin composition for nanoimprinting that includes a resin (A) having a radical-reactive group and an acid group in its side chain. Patent Document 2 also discloses a film-forming composition for photoimprinting that contains (A) a photopolymerizable monomer having a hydrophilic group, (B) inorganic nanoparticles, and (C) a photopolymerization initiator, with an organic solvent content of 20% by mass or less, and containing 30% by mass or more of the monomer having a viscosity of 500 cP or less as component (A) relative to the total amount of component (A) and component (B), and having a refractive index of 1.56 or more after curing.

[0004] Japanese Patent Publication No. 2008-238416 Japanese Patent Publication No. 2013-191800

[0005] As mentioned above, although various methods for forming patterned films using nanoimprint lithography have been disclosed, there is a need for technologies that can reliably transfer and mold the highly detailed pattern shape of a mold, and for technologies that can form a highly reliable pattern shape without change in the pattern shape when the patterned film formed by transfer is heated. Furthermore, for applications in fields such as optics, there is also a need for technologies that can reliably form patterned films with a high refractive index.

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing a pattern film that has a high refractive index, can favorably transfer and mold a high-definition pattern shape possessed by a mold, and further can manufacture a highly reliable pattern film with little change in the pattern shape even when heated.

[0007] As a result of various studies on the method for manufacturing a pattern film, the present inventor has found that in the nanoimprint method for manufacturing a pattern film by pressing using a mold, by using a polymerizable composition containing a specific polymerizable monomer, a pattern film having a high refractive index, a high-definition pattern shape, and little change in the pattern shape even when heated can be efficiently manufactured, and thus the present invention has been completed.

[0008] The present invention includes the following method for manufacturing a pattern film. [1] A method for manufacturing a pattern film, the manufacturing method including a step of pressing a polymerizable composition containing a polymerizable monomer represented by the following general formula (1) using a mold.

[0009]

[0010] (In formula (1), R ４ , ４ , ５ , <00003​​​​​​​​​​​​​​​​​​​​​​​​At least one of them is an oxygen atom. n represents an integer of 1 or more.) [2] The method for producing a patterned film according to [1], wherein the refractive index of the patterned film at a wavelength of 589 nm is 1.55 or more. [3] The method for producing a patterned film according to [1] or [2], wherein the polymerizable composition further comprises inorganic particles and at least one dispersant selected from the group consisting of sulfur-based dispersants, phosphoric acid-based dispersants, carboxylic acid-based dispersants, and silane-based dispersants, and the sulfur-based dispersant comprises a polymer having a constituent unit (U1) represented by the following general formula (2).

[0011]

[0012] (In formula (2), X ２ (wherein represents a divalent aromatic hydrocarbon group which may have substituents.) [4] A polymerizable composition comprising a polymerizable monomer represented by the following general formula (1), a sulfur-based dispersant containing a polymer having a constituent unit (U1) represented by the following general formula (2), and inorganic particles.

[0013]

[0014] (In formula (1), R １ R represents an organic group having 1 to 30 carbon atoms and containing an aromatic group. ２ R represents -O-, -S-, or -NH-. ３ X represents a hydrogen atom or a methyl group. １ , Y １ and Z １ They are the same or different, -CR ４ R ５ - or represents an oxygen atom. R ４ and R ５ X represents a hydrogen atom or a methyl group, either identical or distinct. １ , Y １ and Z １ At least one of them is an oxygen atom. (n represents an integer greater than or equal to 1.)

[0015]

[0016] (In formula (2), X ２(wherein represents a divalent aromatic hydrocarbon group which may have substituents.) [5] A patterned film which is a cured product of a polymerizable composition comprising a polymerizable monomer represented by the following general formula (1), and having a pattern.

[0017]

[0018] (In formula (1), R １ R represents an organic group having 1 to 30 carbon atoms and containing an aromatic group. ２ R represents -O-, -S-, or -NH-. ３ X represents a hydrogen atom or a methyl group. １ , Y １ and Z １ They are the same or different, -CR ４ R ５ - or represents an oxygen atom. R ４ and R ５ X represents a hydrogen atom or a methyl group, either identical or distinct. １ , Y １ and Z １ At least one of them is an oxygen atom. n represents an integer of 1 or more.) [6] The pattern film according to [5], wherein the pattern film is a film in which a pattern shape is formed by pressing the polymerizable composition using a mold having a pattern shape and then curing it. [7] The pattern film according to [5] or [6], wherein the refractive index at a wavelength of 589 nm is 1.55 or more.

[0019] The method for manufacturing patterned films of the present invention can produce patterned films with a high refractive index, a highly detailed pattern shape, and minimal change in the pattern shape even when heated, making them highly reliable. Therefore, they can be suitably used in the manufacture of optical materials, semiconductor devices, and the like.

[0020] Preferred embodiments of the present invention will be described below in detail, but the present invention is not limited to the following descriptions and can be modified and applied as appropriate without changing the gist of the invention. Furthermore, embodiments combining two or more of the individual preferred embodiments of the present invention described below also fall under the category of preferred embodiments of the present invention. In this specification, "(meth)acrylate" means "acrylate" or "methacrylate," "(meth)acrylic" means "acrylic" or "methacrylic," and "(meth)acryloyl" means "acryloyl" or "methacryloyl."

[0021] 1. Method for Manufacturing Patterned Films The present invention relates to a method for manufacturing patterned films, characterized in that the manufacturing method includes a step of pressing a polymerizable composition containing a polymerizable monomer represented by the above general formula (1) using a mold. By pressing a polymerizable composition containing a specific polymerizable monomer using a mold, it is possible to manufacture a patterned film having a high refractive index, a highly detailed pattern shape, and a highly reliable pattern shape that does not change much even when heated.

[0022] The method for manufacturing patterned films of the present invention can produce patterned films with a high refractive index, a highly detailed pattern shape, and minimal change in the pattern shape even when heated, resulting in a highly reliable patterned film. This is due to the following reasons: In the present invention, the polymerizable monomer used to form the patterned film has an aromatic group in its structure, which increases its refractive index. Furthermore, the presence of a chain containing an unsaturated polymerizable group introduced at the α-position of the acryloyl group improves its curability, resulting in good moldability of the patterned film. Moreover, its good thermal stability means that the pattern shape changes minimally even when heated, resulting in excellent reliability.

[0023] The method for producing the patterned film described above includes a step of pressing a polymerizable composition containing the polymerizable monomer represented by the general formula (1) using a mold. In this specification, the step of pressing using a mold is also referred to as the "pressing step." The polymerizable composition used in the present invention will be described later.

[0024] The method for producing the patterned film described above may include a step of pressing a composition made from the polymerizable composition using a mold, but it is preferable to include a step of applying the polymerizable composition to a substrate to form a coating film (precursor film), a step of pressing a mold onto the coating film obtained in the coating film formation step, and a step of peeling the mold off the patterned film obtained in the pressing step.

[0025] The method for applying the polymerizable composition in the above coating film formation process is not particularly limited, and conventionally known methods can be used. Among these, spin coating, bar coating, squeegee coating, inkjet coating, spray method, roll coating method, and rotary coating method are preferred. The coating thickness is not particularly limited and can be appropriately selected depending on the intended use of the patterned film. The coating thickness is preferably 0.01 to 1000 μm, more preferably 0.01 to 100 μm, and even more preferably 0.08 to 10 μm.

[0026] In the above coating film formation process, the viscosity of the polymerizable composition when applying it is not particularly limited, but it is preferable that the viscosity at 25°C is 1 to 10,000 cps. Within this viscosity range, it becomes easier to apply and easier to control the coating film thickness. The viscosity is more preferably 2 to 2,000 cps, and even more preferably 3 to 200 cps.

[0027] In the above coating film formation process, it is preferable to heat and / or irradiate the applied film (coating film) with active energy rays. When heating is performed, the solvent contained in the coating film can be evaporated and removed. Furthermore, by heating or by irradiating with active energy rays, the reaction of polymerizable monomers and other components contained in the coating film can be promoted and curing can be advanced. This makes it possible to efficiently obtain a cured film (pattern film) on which the mold pattern shape described later has been transferred. In addition, if the polymerizable composition contains a solvent, heating can evaporate and remove some or all of the solvent, and the viscosity of the precursor film subjected to the pressing process can be adjusted to a preferred range described later.

[0028] In the above coating film formation process, when heating is performed, the heating temperature is not particularly limited, but is preferably 30 to 300°C, and more preferably 50 to 200°C. The heating time is also not particularly limited, but is preferably 0.001 to 5 hours, and more preferably 0.01 to 1 hour.

[0029] In the method using the above-described active energy beam, ultraviolet light or electron beams are preferred as the active energy beam, with ultraviolet light being more preferred. When ultraviolet irradiation is performed, there are no particular restrictions on the ultraviolet irradiation dose (cumulative exposure), but it is 0.001 to 100 J / cm². ２ It is preferable to irradiate within the range of 0.01 to 50 J / cm², and more preferably within the range of 0.01 to 50 J / cm². ２ More preferably 0.05 to 10 J / cm² ２ As a light source, various mercury lamps, LEDs, etc., can be used, but ultra-high pressure mercury lamps, metal halide lamps, and LEDs are preferred.

[0030] In the above coating film formation process, the viscosity of the formed coating film (precursor film subjected to the pressing process) is not particularly limited, but it is preferable that the viscosity at 25°C be 100 to 10,000 cps. Within this viscosity range, the transferability at low pressure is superior. More preferably, it is 100 to 6,000 cps, and even more preferably 100 to 3,500 cps. Furthermore, it is preferable to control the composition of the polymerizable composition used for coating so that the solid content viscosity of the polymerizable composition, described later, is equal to the preferred viscosity of the precursor film.

[0031] In the above coating film formation step, the formed coating film (precursor film subjected to the pressing step) may contain a solvent. The solvent content in the precursor film is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.1 to 3% by mass, based on 100% by mass of the solid content of the precursor film.

[0032] The viscosity of the precursor film and the solvent content in the precursor film are preferably the viscosity and solvent content of the precursor film immediately before it is pressed in the pressing process. In some cases, the viscosity and solvent content of the precursor film after the coating film formation process may be adjusted before the pressing process is carried out.

[0033] The substrate to which the above polymerizable composition is applied is not particularly limited, but examples of preferred substrates include light-transmitting substrates such as glass plates, quartz plates, organic resin films, organic resin molded products, and films, sheets, or plates having a transparent inorganic oxide layer on their surface; light-receiving substrates such as Si semiconductor substrates and compound semiconductor substrates such as InGaAs; and light-emitting substrates such as LEDs, organic ELs, and laser diodes (semiconductor lasers).

[0034] The material of the mold surface used in the above pressing process is not particularly limited, but examples include silicone resins, fluororesins, epoxy resins, acrylic resins, polyurethane resins, phenolic resins, melamine resins, polyester resins, propylene resins, vinyl chloride resins, polystyrene, cycloolefin polymers, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, quartz, and glass. In particular, silicone resins, fluororesins, epoxy resins, acrylic resins, polyurethane resins, polyester resins, propylene resins, and cycloolefin polymers are preferred in terms of good release properties when releasing the mold from the cured film, and more preferably silicone resins, fluororesins, epoxy resins, acrylic resins, polyurethane resins, and cycloolefin polymers.

[0035] The shape of the pattern on the mold surface described above is not particularly limited, but examples include line and space shapes, pillar shapes, hole shapes, honeycomb shapes, slanted shapes, moth-eye shapes, multi-step shapes, blazed shapes, conical shapes, rectangular prism shapes, rectangular pyramidal shapes, triangular prism shapes, triangular pyramidal shapes, polygonal prism shapes, polygonal pyramidal shapes, and lattice shapes. Preferably, the pattern shape is a line and space shape, pillar shape, hole shape, honeycomb shape, slanted shape, moth-eye shape, multi-step shape, or blazed shape.

[0036] When the shape of the above pattern is line and space, the line width is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm. The space width is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0037] The width of the upper surface of the protrusion on the mold surface is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0038] The height of the protrusions on the mold surface is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0039] The width of the bottom surface of the recess on the mold surface is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0040] The depth of the grooves in the recesses of the mold surface is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0041] In the pressing process described above, the pressure used to press the mold onto the coating obtained in the coating formation process is not particularly limited, but is preferably 0.1 to 5 MPa, more preferably 0.2 to 2 MPa, and even more preferably 0.3 to 1 MPa.

[0042] In the pressing process described above, it is preferable to cure the coating film obtained in the coating film formation process while pressing the mold onto it. The curing method is not particularly limited, but heating and / or irradiation with active energy rays is preferred. More preferably, the curing method is irradiation with active energy rays, and even more preferably, ultraviolet irradiation. The amount of ultraviolet irradiation (cumulative exposure) is not particularly limited, but is 0.001 to 100 J / cm². ２ It is preferable to irradiate within the range of 0.01 to 50 J / cm², and more preferably within that range. ２More preferably 0.05 to 10 J / cm² ２ The heating conditions are not particularly limited, but the heating temperature is preferably 30 to 300°C, more preferably 40 to 200°C, and even more preferably 50 to 150°C. The heating time is preferably 0.001 to 5 hours, more preferably 0.01 to 2 hours, and even more preferably 0.01 to 1 hour.

[0043] More specifically, in the above pressing process, it is preferable to fill the mold with the precursor film (resin) obtained in the coating film formation process in a light-shielded environment without exposure. When filling the mold with the precursor film, the mold may be heated before filling, but it is preferable to do so at room temperature. In the above pressing process, after filling the mold with the precursor film at room temperature and under light-shielded conditions, it is preferable to maintain the press pressure for a predetermined time. After maintaining the press pressure for a predetermined time at room temperature and under light-shielded conditions, it is preferable to further cure by irradiating with light while maintaining the press pressure. In the present invention, a form in which the above pressing process includes a step of filling the mold with the precursor film (filling step) and a step of curing (solidifying and molding) (curing step) is one of the preferred embodiments. In the above filling step, it is preferable to maintain the press pressure at room temperature and under light-shielded conditions. In the above curing step, light irradiation may be performed while maintaining the press pressure, or light irradiation may be performed in a state where the pressure has been released and the pressure has been reduced (for example, at normal pressure).

[0044] The method for manufacturing the pattern film described above preferably includes a step of further curing the pattern film obtained after peeling the mold off the pattern film obtained in the pressing step. The curing method preferably involves heating and / or irradiation with active energy rays, and more preferably heating. The heating temperature is not particularly limited, but is preferably 50 to 250°C, and more preferably 80 to 200°C. The heating time is not particularly limited, but is preferably 5 to 240 minutes, and more preferably 15 to 120 minutes.

[0045] Next, the polymerizable composition used in the method for producing the patterned film described above will be explained.

[0046] [Polymerizable Composition] <Polymerizable Monomer> The polymerizable composition used in the above method for producing the patterned film includes a polymerizable monomer represented by the above general formula (1). In the above general formula (1), R １ R represents an organic group having 1 to 30 carbon atoms and containing an aromatic group. １ The organic group having the aromatic group represented by is an n-valent organic group, and is preferably a 1- to 3-valent organic group.

[0047] The above R １ The organic group having the aromatic group represented by may be an aromatic group, or a group consisting of an aromatic group and another structure. Examples of groups consisting of an aromatic group and another structure include an aromatic group and -O-, -NH-, -S-, -SO-, -SO ２ -, -SO ３ -, -S-S-, -S-SO ２ -, -SO ２ Examples of groups include those consisting of NH-, -Se-, -Te-, aliphatic hydrocarbon chains, or combinations thereof. １ The organic groups represented are aromatic groups and -O-, -NH-, -S-, -SO-, -SO ２ -, -SO ３ -, -S-S-, -S-SO ２ -, -SO ２ In the case of a group consisting of NH-, -Se-, -Te-, an aliphatic hydrocarbon chain, or a combination thereof, the organic group may contain two or more aromatic groups or two or more aliphatic hydrocarbon chains, etc. １ Among the organic groups having aromatic groups represented by , groups consisting of an aromatic group and -O-, -NH-, -S-, -SO-, an aliphatic hydrocarbon chain, or a combination thereof are preferred, as they have a high refractive index and tend to result in a lower viscosity of polymerizable compositions. Groups consisting of an aromatic group and -O-, an aliphatic hydrocarbon chain, or a combination thereof are more preferred.

[0048] Examples of the aromatic group mentioned above include aromatic hydrocarbon groups and aromatic heterocyclic groups. The aromatic group may be monocyclic or polycyclic. Examples of polycyclic aromatic groups include groups having two or more monocyclic rings (e.g., benzene rings), or groups in which a monocyclic ring and an aliphatic ring are fused or bonded. From the viewpoint of refractive index, aromatic hydrocarbon groups are preferred.

[0049] Examples of the aliphatic rings mentioned above include cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclopentene rings, cyclohexene rings, norbornane rings, norbornene rings, adamantane rings, isobornyl rings, and tricyclodecane rings.

[0050] Examples of the aromatic hydrocarbon groups mentioned above include monocyclic rings such as benzene rings, fused rings such as naphthalene rings, anthracene rings, phenanthrene rings, triphenylene rings, pyrene rings, perylene rings, fluorene rings, and fluorantene rings, and groups formed by removing n hydrogen atoms from bonded rings such as biphenyl rings, terphenyl rings, and binaphthalene rings. Among these, groups formed by removing n hydrogen atoms from monocyclic rings such as benzene rings, fused rings such as naphthalene rings, anthracene rings, phenanthrene rings, fluorene rings, and fluorantene rings, biphenyl rings, and binaphthalene rings are preferred because they have a high refractive index and tend to result in a lower viscosity of polymerizable compositions. Groups formed by removing n hydrogen atoms from monocyclic rings such as benzene rings, naphthalene rings, phenanthrene rings, fluorene rings, and biphenyl rings are even more preferred.

[0051] The number of carbon atoms in the above aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 25, and even more preferably 6 to 15, in that it allows for a higher refractive index, lower viscosity, and better transfer of the pattern shape.

[0052] Examples of the above aromatic heterocyclic groups include groups formed by removing n hydrogen atoms from a thiophene ring, furan ring, pyrrole ring, thiopyran ring, thiazole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, isoindole ring, indole ring, indazole ring, purine ring, isoquinoline ring, quinoline ring, carbazole ring, acridine ring, benzofuran ring, dibenzofuran ring, naphthofuran ring, dinaphthofuran ring, benzothiophene ring, dibenzothiophene ring, naphthothiophene ring, dinaphthothiophene ring, etc. In particular, groups formed by removing n hydrogen atoms from a thiophene ring, thiazole ring, triazole ring, thiadiazole ring, pyrimidine ring, pyridazine ring, triazine ring, carbazole ring, benzothiophene ring, dibenzothiophene ring, naphthothiophene ring, or dinaphthothiophene ring are more preferred because they tend to have a higher refractive index and a lower viscosity in the polymerizable composition.

[0053] The number of carbon atoms in the above aromatic heterocyclic group is preferably 2 to 30, more preferably 3 to 25, and even more preferably 3 to 20, in that it results in a higher refractive index and a lower viscosity of the polymerizable composition.

[0054] The above aromatic group may have substituents, and examples of such substituents include hydrocarbon groups (e.g., alkyl groups), hydroxyl groups, alkoxy groups, carboxyl groups, nitrogen-containing groups (e.g., amino groups, imino groups, nitro groups, nitroso groups), substituents containing halogen atoms (e.g., halogeno groups), and substituents containing sulfur atoms (e.g., thiol groups, thioether groups, sulfoxide groups, sulfone groups). Among these, substituents containing halogen atoms and substituents containing sulfur atoms are preferred.

[0055] Examples of the aliphatic hydrocarbon chain include divalent saturated or unsaturated aliphatic hydrocarbon groups, and preferably saturated aliphatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon chain is preferably 1 to 8, and more preferably 1 to 3.

[0056] Examples of divalent saturated aliphatic hydrocarbon groups include divalent groups formed by removing one hydrogen atom from linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups, or from branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, and t-butyl groups.

[0057] Examples of divalent unsaturated aliphatic hydrocarbon groups include divalent groups formed by removing one hydrogen atom from alkenyl groups such as vinyl group (ethenyl group), 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-hexenyl group, and pentenyl group.

[0058] The above R １ The number of carbon atoms in the organic group having the aromatic group represented by (the total number of carbon atoms in the organic group, including the number of carbon atoms in the aromatic group) is 1 to 30, preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8, in that the refractive index is higher and the viscosity of the polymerizable composition tends to be lower. In another preferred embodiment, the number of carbon atoms in the above organic group is preferably 3 to 20, more preferably 4 to 12, and even more preferably 6 to 8.

[0059] In the above general formula (1), R ２ -O-, -S-, or -NH- represent -O-, with -O- being preferred.

[0060] In the above general formula (1), R ３ R represents a hydrogen atom or a methyl group. In terms of excellent curability, ３ It is preferable that it be a hydrogen atom.

[0061] In the above general formula (1), X １ , Y １ and Z １ They are the same or different, -CR ４ R ５ - or represents an oxygen atom. R ４ and R ５ X represents a hydrogen atom or a methyl group, either identical or distinct. １ , Y １ and Z １ At least one of them is an oxygen atom.

[0062] In terms of the excellent curability of the polymerizable monomer represented by the general formula (1) above, X １ , Y １ and Z １ Among them, one is an oxygen atom, and the other two are the same or different and are -CR ４ R ５ -, or X １ and Z １ are oxygen atoms, and Y １ is -CR ４ R ５ - is preferable. More preferably, among X​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Specific examples of polymerizable monomers represented by the above general formula (1) include, for example, α-(allyloxymethyl)acrylate phenyl, α-(allyloxymethyl)acrylate methylphenyl, α-(allyloxymethyl)acrylate dimethylphenyl, α-(allyloxymethyl)acrylate trimethylphenyl, α-(allyloxymethyl)acrylate 4-tert-butylphenyl, α-(allyloxymethyl)acrylate benzyl, α-(allyloxymethyl)acrylate 1-naphthylmethyl, α-(allyloxymethyl)acrylate 3- Phenoxybenzyl, α-(allyloxymethyl)acrylate 2-(2-biphenylyloxy)ethyl, α-(allyloxymethyl)acrylate 4-phenylbenzyl, α-(allyloxymethyl)acrylate 9-fluorenylmethyl, α-(allyloxymethyl)acrylate diphenylethyl, α-(allyloxymethyl)acrylate cinnamyl, α-(allyloxymethyl)acrylate naphthyl, α-(allyloxymethyl)acrylate anthracenyl, α-(allyloxymethyl)acrylate orthophenylphenyl, α-(allyloxymethyl)acrylate Monovalent allyloxymethyl acrylic acid esters such as 2-(1-naphthyloxy)ethyl acrylate, 2-(2-naphthyloxy)ethyl α-(allyloxymethyl)acrylate, 8-quinolinyl α-(allyloxymethyl)acrylate, 2-(9H-carbazole-9-yl)ethyl α-(allyloxymethyl)acrylate, and 2-(2-naphthylthio)ethyl α-(allyloxymethyl)acrylate; benzenedimethanol di(α-(allyloxymethyl))acrylate, 1,4-bis(2-hydroxyethoxy)- Divalent allyloxymethyl acrylic acid esters such as naphthalenedi(α-(allyloxymethyl))acrylate, xylylene glycol di(α-(allyloxymethyl))acrylate, hydroquinone di(α-(allyloxymethyl))acrylate, bisphenol A di(α-(allyloxymethyl))acrylate, bisphenol F di(α-(allyloxymethyl))acrylate, bisphenol S di(α-(allyloxymethyl))acrylate, and bisphenol F orange (α-(allyloxymethyl)) acrylate;Examples include trivalent allyloxymethyl acrylic acid esters such as tris(2-hydroxyethyl)tri(α-(allyloxymethyl))acrylate isocyanurate. Among these, monovalent and divalent allyloxymethyl acrylic acid esters are preferred due to their high refractive index and appropriate viscosity, with 1-naphthylmethyl α-(allyloxymethyl)acrylic acid, 3-phenoxybenzyl α-(allyloxymethyl)acrylic acid, 2-(2-biphenylyloxy)ethyl α-(allyloxymethyl)acrylic acid, 4-phenylbenzyl α-(allyloxymethyl)acrylic acid, naphthyl α-(allyloxymethyl)acrylate, orthophenylphenyl α-(allyloxymethyl)acrylic acid, bisphenol A di(α-(allyloxymethyl))acrylate, bisphenol F di(α-(allyloxymethyl))acrylate, and bisphenol F orange(α-(allyloxymethyl))acrylate being more preferred.

[0065] The content of the polymerizable monomer is preferably 5 to 100% by mass, more preferably 5 to 90% by mass, even more preferably 10 to 60% by mass, and particularly preferably 15 to 40% by mass, based on 100% by mass of the total solid content of the polymerizable composition. The total solid content of the polymerizable composition refers to the total amount of components contained in the polymerizable composition excluding the solvent and polymerization initiator. Furthermore, if the polymerizable composition contains a solvent, the content of the polymerizable monomer is preferably 1 to 40% by mass, more preferably 2 to 25% by mass, and even more preferably 3 to 20% by mass, based on 100% by mass of the polymerizable composition.

[0066] The method for producing the polymerizable monomer is not particularly limited, and known methods include producing it via an α-halomethylacrylate alkyl ester, producing it via a 2,2'-[oxybis(methylene)]bisacrylate alkyl ester, and producing it using a transesterification reaction from a lower ester of α-allyloxymethylacrylic acid such as α-allyloxymethylacrylate methyl ester. In particular, the method for producing the polymerizable monomer preferably includes a step of transesterifying an α-allyloxymethylacrylic acid ester with an alcohol in the presence of a catalyst.

[0067] Examples of preferred α-allyloxymethylacrylic acid lower ester compounds include α-allyloxymethylacrylic acid methyl α-allyloxymethylacrylate, α-allyloxymethylacrylate ethyl α-allyloxymethylacrylate n-propyl α-allyloxymethylacrylate i-propyl α-allyloxymethylacrylate n-butyl α-allyloxymethylacrylate s-butyl α-allyloxymethylacrylate t-butyl α-allyloxymethylacrylate n-amyl α-allyloxymethylacrylate s-amyl α-allyloxymethylacrylate t-amyl α-allyloxymethylacrylate. Among these, α-allyloxymethylacrylic acid ester compounds having an alkyl group with 1 to 3 carbon atoms are more preferred due to the ease of transesterification, and α-allyloxymethylacrylate methyl is even more preferred.

[0068] Examples of the above alcohols include monohydric or polyhydric alcohols containing aromatic groups. Examples of monohydric alcohols containing aromatic groups include alcohols having aromatic hydrocarbon groups or aromatic heterocyclic groups such as phenol, methylphenol, dimethylphenol, trimethylphenol, 4-tert-butylphenol, benzyl alcohol, 1-naphthalenemethanol, 3-phenoxybenzyl alcohol, 2-(2-biphenylyloxy)ethanol, 4-phenylbenzyl alcohol, 9-fluorenylmethanol, diphenylethanol, cinnamyl alcohol, naphthol, antrol, orthophenylphenol, 2-(1-naphthyloxy)ethanol, 2-(2-naphthyloxy)ethanol, 8-quinolinol, 2-(9H-carbazole-9-yl)ethanol, and 2-(2-naphthylthio)ethanol.

[0069] Examples of polyhydric alcohols containing the above aromatic group include benzenedimethanol, 1,4-bis(2-hydroxyethoxy)-naphthalene, xylylene glycol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, bis(hydroxypivalaldehyde)pentaerythritol acetal cyclic acetal, and other dihydric alcohols; and trihydric or higher alcohols such as tris(2-hydroxyethyl) isocyanurate.

[0070] Examples of the catalysts mentioned above include alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonides (e.g., lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal alkoxides (e.g., lithium methoxide, sodium ethoxide, etc.), alkali metal amides (e.g., lithium amide, sodium amide, potassium amide, etc.), titanium alkoxides (e.g., tetraethyl orthotitanate, tetraisopropyl orthotitanate, etc.), and organotin compounds (e.g., dibutyltin oxide). Among these, titanium alkoxides are more preferred because the catalyst can be easily removed by washing with water.

[0071] The amount of catalyst used is not particularly limited, but is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, and even more preferably 1 to 5 mol%, relative to 100 mol% of the alcohol.

[0072] In the above transesterification reaction, it is preferable to use a polymerization inhibitor. The polymerization inhibitor is not particularly limited and includes, for example, benzoquinone, hydroquinones (e.g., hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), phenols (e.g., 2,6-di-t-butyl-4-methylphenol, 6-t-butyl-2,4-xylenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), Irganox 245, Irganox Kus 259, Irganox 565, Irganox 1010, Irganox MD 1024, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1222, Irganox 1330, Irganox 3114 (all manufactured by BASF), Adeka Stub AO-20, Adeka Stub AO-30, Adeka Stub AO-40, Adeka Stub AO-50, Adeka Stub AO- 60, ADEKA stub AO-70, ADEKA stub AO-80, ADEKA stub AO-330 (all manufactured by ADEKA Corporation), RIANOX 245, RIANOX 330, RIANOX 1010, RIANOX 1019, RIANOX 1035, RIANOX 1076, RIANOX 1098, RIANOX 1135, RIANOX 1790, RIANOX 3114 (all manufactured by Rianlon Corporation), etc., catechols (e.g., p-tert-bub Examples of known polymerization inhibitors include tylcatechol, amines (e.g., N,N-diethylhydroxylamine), 1,1-diphenyl-2-picrylhydrazyl, tri-p-nitrophenylmethyl, phenothiazine, piperidine 1-oxyls (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl), and Polystop 7300P (manufactured by Hakuto Co., Ltd.). One of the polymerization inhibitors may be used alone, or two or more may be used in combination.

[0073] The amount of polymerization inhibitor used is not particularly limited, but is preferably 0.01 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass, and even more preferably 0.01 to 0.2 parts by mass, per 100 parts by mass of the α-(allyloxymethyl) acrylic acid ester.

[0074] In the above transesterification reaction, a solvent may be used. The solvent used is not particularly limited as long as it does not affect the reaction, and examples include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, octane, and cyclohexane, and ether solvents such as dioxane and tetrahydrofuran. One of the above solvents may be used, or two or more may be used in combination.

[0075] The reaction conditions for the above transesterification reaction are not particularly limited and can be carried out under known reaction conditions. For example, the reaction temperature is preferably 50 to 120°C, more preferably 50 to 110°C. The above transesterification reaction may be carried out under normal pressure or under reduced pressure.

[0076] The above-described method for producing polymerizable monomers may further include other steps. Examples of these other steps include washing with water, purification, dilution, drying, concentration, solvent replacement, dissolution, solvent removal, thin-film distillation, and steam distillation. These steps can be carried out by known methods.

[0077] <Inorganic Particles> The polymerizable composition preferably contains inorganic particles. By including inorganic particles, a patterned film with a higher refractive index can be formed. The inorganic particles are not particularly limited as long as they are particles mainly composed of an inorganic component, and the inorganic component may be a single metal or a metal compound, but it is preferable that it be a metal compound.

[0078] The metal compound content in the inorganic particles is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass, based on 100% by mass of the inorganic particles.

[0079] The inorganic component content in inorganic particles can be determined as follows: (Method for measuring inorganic component content) Inorganic particles are subjected to a heat treatment in which they are heated from room temperature at a heating rate of 10°C / min, heated and held at 900°C for 2 hours, and then cooled to room temperature. When the mass of the inorganic particles subjected to the heat treatment is Sb (g) and the mass of the residue (ash) after the heat treatment is Sa (g), the inorganic oxide content can be determined by the following formula. The above heat treatment is usually performed under a nitrogen atmosphere from room temperature to 200°C, then switched to an air atmosphere at 200°C, and thereafter performed under an air atmosphere. However, if the inorganic particles contain metal oxides or metal nitrides that change into metal oxides, etc., whose valence changes and consequently their composition changes when heated under an air atmosphere, the above heat treatment should be performed under a nitrogen atmosphere for the entire process from the start of heating to cooling. Inorganic component content (mass%) = {Sa (g) / Sb (g)} × 100

[0080] The metal compound in the inorganic particles is not particularly limited, but a compound containing one or more elements from groups 2 to 15 of the periodic table or lanthanide elements as a metal element is preferred. Preferred metal elements include Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. A metal compound containing at least one element selected from the group consisting of these metal elements is more preferred.

[0081] Examples of the above-mentioned metal compounds include metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal sulfides, and metal hydroxides. From the viewpoint of ease of controlling optical and electronic functions, metal oxides and metal hydroxides are preferred, and metal oxides are more preferred.

[0082] The inorganic component is preferably a metal oxide having a refractive index of 2 or more for NaD lines (589 nm). Among these, metal oxides with no or little characteristic absorption in the visible light region are preferred. Such metal oxides include zirconium oxide (ZrO). ２ ), titanium oxide (TiO ２ ), barium titanate (BaTiO ３ ), strontium titanate (SrTiO ３ ), bismuth titanate (BiTiO ３ ), calcium titanate (CaTiO ３ ), niobium oxide (Nb ２ O ５ ), tantalum oxide (Ta ２ O ５ ), indium oxide (In ２ O ３ ), tin(SnO) ２ ), bismuth oxide (Bi ２ O ３ ), lanthanum oxide (La ２ O ３ ), zinc oxide (ZnO), etc. are preferred, and zirconium oxide (ZrO) ２ ), titanium oxide (TiO ２ ) is particularly preferred. When the above metal oxide is included as inorganic particles, the resulting patterned film tends to have a high refractive index and be colorless (white).

[0083] From the viewpoint of having no or little characteristic absorption in the visible light region, in one embodiment, the above inorganic component is silicon dioxide (SiO ２ ), aluminum oxide (Al ２ O ３ ), zirconium oxide (ZrO ２ ), titanium oxide (TiO ２ ), barium titanate (BaTiO ３ ), strontium titanate (SrTiO ３ ), bismuth titanate (BiTiO ３ ), calcium titanate (CaTiO ３ ), niobium oxide (Nb ２ O ５ ), tantalum oxide (Ta ２ O ５), hafnium oxide (HfO ２ ), cerium oxide (CeO ２ ), tungsten oxide (WO ２ WO ３ ), indium oxide (In ２ O ３ ), tin(SnO) ２ ), bismuth oxide (Bi ２ O ３ ), lanthanum oxide (La ２ O ３ Preferably, it is at least one metal oxide selected from the group consisting of ), and zinc oxide (ZnO). When the above metal oxide is included as inorganic particles, it is also preferable from the viewpoint that the polymerizable composition tends to be colorless (white).

[0084] From the perspective that (photo)semiconductor properties can be exhibited by solid-solving dissimilar elements or having oxygen vacancies, and that light absorption characteristics in the infrared region and electronic conductivity can be controlled by the solid-solving metal elements, in one embodiment, the inorganic component is titanium oxide (TiO2). ２ ), indium oxide (In ２ O ３ ), tin(SnO) ２ Preferably, the solid solution oxide is obtained by solid-solving a different element in at least one metal oxide selected from the group consisting of ), and zinc oxide (ZnO). When the above metal oxide is included as inorganic particles, the resulting pattern film can preferably be used as a conductive film such as a transparent conductive film or an antistatic film, or an infrared shielding film. Preferred solid solution oxides include indium oxide obtained by solid-solving tin or titanium, stannous oxide obtained by solid-solving antimony or fluorine, and zinc oxide obtained by solid-solving aluminum, indium, or fluorine.

[0085] From the viewpoint of excellent ultraviolet absorption, in one embodiment, the above inorganic component is titanium dioxide (TiO ２ ), cerium oxide (CeO ２ Preferably, it is at least one metal oxide selected from the group consisting of ), and zinc oxide (ZnO). When the above metal oxide is included as inorganic particles, the resulting patterned film can preferably be used as an ultraviolet absorbing film or the like.

[0086] In one embodiment, it is also preferable that the inorganic component is an inorganic component used in pigments. Examples of inorganic pigments include zinc oxide (ZnO) and basic lead carbonate (2PbCO2). ３ Pb(OH) ２ ), barium sulfate (BaSO ４ ), zinc sulfide (ZnS), titanium dioxide (TiO ２ ) White pigments such as lead trioxide (Pb ３ O ４ ), ferric oxide (Fe ２ O ３ ) Red pigments such as lead chromate (PbCrO ４ ), zinc chromate (ZnCrO ４ Yellow pigments such as ) and iron(III) hexacyanoferrate(II) (Fe ４ [Fe(CN)] ６ ] ３ 15H ２ O), YInMn Blue (YIn １－ｘ Mn ｘ O ３ Blue pigments such as 0 < x < 1, iron(Fe)(0) ３ O ４ Examples include black pigments such as titanium black.

[0087] From the viewpoint of excellent insulating properties, in one embodiment, the inorganic component is silicon dioxide (SiO ２ ), aluminum oxide (Al ２ O ３ ), zirconium oxide (ZrO ２ ), titanium oxide (TiO ２ Preferably, it is at least one metal compound selected from the group consisting of ), boron nitride (BN), and silicon dioxide (SiO ２ It is more preferable that it be silicon dioxide (SiO ２ The material may be crystalline or amorphous, but amorphous is preferred. When the above metal compound is included as inorganic particles, the resulting patterned film can preferably be used as a film with excellent insulating properties.

[0088] The inorganic particles described above may be crystalline or amorphous, but from the viewpoint of easily obtaining a patterned film with a high refractive index, crystalline inorganic particles are preferred.

[0089] The inorganic particles described above preferably have a crystallinity of 80% or more, more preferably 85% or more, even more preferably 90% or more, even more preferably 94% or more, and particularly preferably 98% or more. The crystallinity can be determined by powder X-ray diffraction measurement, similar to the crystallite size described later, and the value obtained by powder X-ray diffraction measurement can be adopted as the crystallinity of the inorganic particles.

[0090] The form of the inorganic particles described above is not particularly limited; they may be primary particles or may include secondary particles formed by the aggregation of primary particles.

[0091] The dispersed particle size (Dd) of the inorganic particles in the polymerizable composition is preferably 5 to 60 nm, more preferably 8 to 50 nm, and even more preferably 10 to 45 nm. The dispersed particle size (Dd) is the 50% particle size in the volume-based particle size distribution measured by a particle size distribution measurement method using dynamic light scattering (DLS).

[0092] As the device for measuring the dispersed particle size (Dd) mentioned above, it is preferable to use the concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.). In the above measurement method, if the polymerizable composition is a liquid containing a solvent, the composition is used as is, or diluted with the solvent as necessary, as the measurement sample. If the polymerizable composition is a solid, it is preferable to use a sample prepared by mixing and stirring with a solvent (e.g., cyclopentanone, N-methylpyrrolidone, benzyl alcohol). In either case, it is preferable that the concentration of inorganic particles in the measurement sample be about 1 to 2% by mass, and the concentration can be adjusted as appropriate during measurement depending on the amount of scattered light and the presence or absence of multiple scattering.

[0093] The average primary particle diameter (D1) of the inorganic particles is preferably 1 to 50 nm. The resulting patterned film provides a coating with excellent transparency. The average primary particle diameter (D1) of the inorganic particles is more preferably 5 to 40 nm, even more preferably 7 to 30 nm, and particularly preferably 10 to 25 nm.

[0094] The average primary particle diameter (D1) described above is the crystallite diameter Dc if the inorganic particles contain crystalline inorganic components, and the specific surface area diameter Ds if they do not contain crystalline inorganic components. When inorganic particles contain crystalline inorganic components, the aggregates are also referred to as crystalline inorganic particles; when they do not contain crystalline inorganic components, the aggregates are also referred to as amorphous inorganic particles. Whether or not crystalline inorganic components are present can be confirmed by powder X-ray diffraction measurement. For example, inorganic particles or their aggregates can be used as a sample, and the resulting X-ray diffraction pattern can be analyzed using analysis software (PDXL2, Rigaku Corporation) to determine this.

[0095] The crystallite size Dc is determined by performing powder X-ray diffraction measurements on inorganic particles or aggregates thereof, measuring the full width at half maximum of the diffraction line with the highest diffraction intensity (strongest line) in the obtained X-ray diffraction chart, and using Scherrer's formula. Here, diffraction intensity refers to the height of the peak top of the diffraction line. For analysis software, for example, analysis software (PDXL2, manufactured by Rigaku Corporation) can be used.

[0096] The apparatus and conditions for performing the above powder X-ray diffraction measurement are not particularly limited, but for example, a fully automated multi-purpose X-ray diffractometer SmartLab (manufactured by Rigaku Corporation) can be used as the apparatus, and it is preferable to adopt the conditions shown in the examples for the measurement conditions.

[0097] The specific surface area diameter Ds can be calculated using the specific surface area and true density of inorganic particles or aggregates thereof by the following formula: Ds(m) = 6 / (ρ・S) ρ[g / m] ３ ]: True density of inorganic particles or aggregates thereof, which can be determined by a pycnometer. S [m ２ [ / g]: Specific surface area of ​​inorganic particles or aggregates thereof, which can be measured by the BET method.

[0098] The ratio of the dispersed particle diameter (Dd) to the average primary particle diameter (D1) of the above inorganic particles is preferably 0.5 to 2.3, more preferably 0.8 to 2, even more preferably 1 to 1.8, and particularly preferably 1 to 1.5.

[0099] The shape of the inorganic particles described above is not particularly limited and may be irregular, granular, plate-like, columnar, needle-like, etc., but granular is preferred, and among granular shapes, spherical is preferred. The granular shape described above means an unbiased shape with an aspect ratio of 1.5 or less. As for the shape of the inorganic particles, the aspect ratio obtained by dividing the longest diameter within the particle by the shortest diameter is preferably 5 or less, more preferably 2 or less, and most preferably 1.5 or less.

[0100] The content of the inorganic particles is preferably 8 to 90% by mass, more preferably 35 to 80% by mass, and even more preferably 50 to 80% by mass, based on 100% by mass of the total solid content of the polymerizable composition.

[0101] <Dispersant> The polymerizable composition preferably contains a dispersant. By including a dispersant, the dispersibility of the inorganic particles is improved, and a patterned film with a high refractive index and excellent transparency can be obtained.

[0102] The above-mentioned dispersant is not particularly limited as long as it is a compound that exhibits dispersibility with respect to the inorganic particles, but it is preferable that it contains a compound having a polar functional group. The above-mentioned polar functional group is preferably a neutral or acidic polar functional group. Examples of the above-mentioned neutral or acidic functional group are sulfinyl group, sulfonic acid group, phosphate group, phosphate ester group, carboxyl group, alkoxysilyl group, hydroxyl group, etc., and preferably sulfinyl group, phosphate group, phosphate ester group, carboxyl group, alkoxysilyl group.

[0103] In particular, the above-mentioned dispersant preferably includes at least one dispersant selected from the group consisting of sulfur-based dispersants, phosphoric acid-based dispersants, carboxylic acid-based dispersants, and silane-based dispersants.

[0104] (Sulfur-based dispersant) There are no particular restrictions on the sulfur-based dispersant, but the following formula (2):

[0105]

[0106] (In the formula, X ２ A sulfur-containing polymer having a constituent unit (U1) represented by formula (2) is preferred. The presence of the above sulfur-containing polymer can further increase the refractive index. The above sulfur-containing polymer is not particularly limited as long as it has a constituent unit represented by formula (2) above, and may have one or more constituent units (U1), but may have multiple, and more preferably may have the constituent unit (U1) as a repeating unit, and more preferably may have multiple repeating units.

[0107] In the above equation (2), X ２ represents a divalent aromatic hydrocarbon group which may have substituents. Examples of the above-mentioned divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, anthreylene group, a triphenylene group, a biphenylene group, and a phenanthrylene group. In particular, the above-mentioned divalent aromatic hydrocarbon group is preferably a phenylene group, a naphthylene group, anthreylene group, a biphenylene group, or a triphenylene group, and more preferably a phenylene group, in that it reduces the photodispersion of the polymer.

[0108] The above X ２ The substituents that the above-mentioned divalent aromatic hydrocarbon group represented by the above-mentioned formula may have (also referred to as "substituent α") are not particularly limited, but preferably include reactive functional groups, halogen atoms, or alkyl groups, alkoxy groups, aryl groups, aralkyl groups, or sulfur-containing hydrocarbon groups that may have a substituent (also referred to as "substituent β").

[0109] Examples of the above-mentioned reactive functional groups include acidic functional groups, basic functional groups, curable functional groups, and groups containing these functional groups. Examples of the above-mentioned acidic functional groups include carboxyl groups (-COOH) and phosphate groups (-OPO(OH)). ２ ), hydroxyl group (-OH), sulfo group (-SO ３ H), phosphonic acid group (-PO(OH) ２Examples include ), phosphinic acid groups (-PO(OH)-), etc. Examples of basic functional groups include amino groups, ammonium groups, imino groups, amide groups, imide groups, maleimide groups, etc. Examples of curable functional groups include groups having reactive unsaturated bonds such as vinyl groups, (meth)acryloyl groups, allyl groups, methallyl groups, etc.; groups having reactive ionic bonds such as epoxy groups, oxetane groups, etc.; mercapto groups (-SH), etc.

[0110] Examples of groups containing these functional groups include, for example, groups having a bonding chain with the aforementioned acidic functional group, basic functional group, or curable functional group. In other words, in the present invention, the reactive functional group includes not only the acidic functional group, basic functional group, and curable functional group mentioned above, but also groups containing a bonding chain with these functional groups. Examples of the bonding chain include divalent hydrocarbon groups such as alkylene groups and arylene groups, bonding groups such as ethers, esters, carbonyls, and amides, and combinations thereof. For example, when it is stated that a carboxyl group is preferred as the reactive functional group, it means that a carboxyl group and / or a group containing a carboxyl group is preferred as the reactive functional group.

[0111] Examples of the halogen atoms mentioned above include fluorine, chlorine, bromine, and iodine atoms, with bromine being the preferred choice.

[0112] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, and heptyl group. C1 to C18 alkyl groups are preferred, C1 to C6 alkyl groups are more preferred, and methyl groups are even more preferred.

[0113] Examples of the alkoxy groups mentioned above include methoxy, ethoxy, propoxy, isopropoxy, s-butoxy, t-butoxy, pentyloxy, phenoxy, cyclohexyloxy, and benzyloxy groups. Preferably, the alkoxy group has 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably a methoxy group.

[0114] Examples of the aryl group mentioned above include phenyl, naphthyl, anthryl, biphenyl, and triphenyl groups. Among these, the phenyl group is preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 18, and even more preferably 6 to 12.

[0115] Examples of the above-mentioned aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, and phenyloctyl groups. The number of carbon atoms in the above-mentioned aralkyl group is preferably 7 to 14, and more preferably 7 to 9.

[0116] Examples of the sulfur-containing hydrocarbon group include alkylthio groups and arylthio groups. The number of carbon atoms in the sulfur-containing hydrocarbon group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0117] The alkyl groups, alkoxy groups, aryl groups, aralkyl groups, and sulfur-containing hydrocarbon groups described above may further have substituents (substituents β). Examples of substituents β include alkyl groups and halogen atoms, and their preferred forms are the same as those of substituents α, such as alkyl groups and halogen atoms.

[0118] Among the substituents α described above, alkyl groups are preferred, C1-C18 alkyl groups are more preferred, C1-C6 alkyl groups are even more preferred, and methyl groups are particularly preferred, from the viewpoint of easily obtaining excellent solubility of the sulfur-containing polymer in the solvent described later. Furthermore, the above-mentioned curable functional groups are preferred as substituents α, and among these, mercapto groups are preferred. When a sulfur-containing polymer has a mercapto group as substituent α, it tends to have excellent reactivity such as curing reactivity and a high refractive index. When a sulfur-containing polymer has these functional groups or groups containing these functional groups as substituents, it tends to be easier to obtain a cured film with excellent heat resistance and solvent resistance. As groups containing mercapto groups, thioalkyl groups and thioaryl groups are preferred, and thioalkyl groups are more preferred.

[0119] When the above sulfur-containing polymer has mercapto groups, the amount is not particularly limited, but the amount of mercapto groups is preferably 1 to 300 mol% per 100 mol% of the total aromatic rings (total constituent units). More preferably it is 5 to 200 mol%, and even more preferably 10 to 50 mol%. The amount of mercapto groups in the sulfur-containing polymer is １ It can be measured by H-NMR, ICP, GPC, IR, and elemental analysis.

[0120] X ２ The number of substituents α that the above-mentioned divalent aromatic hydrocarbon group represented by may have is not particularly limited. It can be appropriately selected for purposes such as adjusting the solubility of the sulfur-containing polymer in the solvent used in the production of the polymerizable composition described later, or for subtly controlling the refractive index. The number of substituents is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. The position to which the substituents α are attached to the above-mentioned divalent aromatic hydrocarbon group is not particularly limited. If there are two or more substituents α in the above-mentioned structural unit (U1), the types of substituents α may be the same or different.

[0121] When the above sulfur-containing polymer has multiple constituent units (U1), the type of divalent aromatic hydrocarbon group, the type, number, and bonding position of the substituent α that the divalent aromatic hydrocarbon group may have in each constituent unit (U1) may be the same or different. In the above constituent unit (U1), the position where the sulfinyl group (-S(=O)-) is bonded to the divalent aromatic hydrocarbon group, the bonding position of the other main chain to the divalent aromatic hydrocarbon group, and the positional relationship between these are not particularly limited.

[0122] If the above sulfur-containing polymer has multiple constituent units (U1), the positions in which the sulfinyl group (-S (=O)-) is bonded to the divalent aromatic hydrocarbon group in each constituent unit (U1) may be the same or different, and the bond positions of the other main chain to the divalent aromatic hydrocarbon group may be the same or different. Furthermore, the positional relationship between the position in which the sulfinyl group is bonded to the divalent aromatic hydrocarbon group and the bond position of the other main chain to the divalent aromatic hydrocarbon group in each constituent unit (U1) may be the same or different.

[0123] One preferred embodiment of the above-mentioned structural unit (U1) is, for example, the above-mentioned X ２ One example is a form in which the divalent aromatic hydrocarbon group represented by is a phenylene group. ２ A constituent unit (U1) in which the divalent aromatic hydrocarbon group represented is a phenylene group is also referred to as constituent unit (U1-1). The phenylene group may or may not have a substituent (also referred to as "substituent α-1"). The type of substituent α-1 is the same as that of substituent α, and the preferred form is also the same.

[0124] The total number of substituents α-1 bonded to the phenylene group is an integer from 0 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The position of substituents α-1 is not particularly limited; when the carbon atom of the phenylene group to which the sulfinyl group is bonded is considered to be position 1, the position of substituent α-1 may be position 2, position 3, or position 4 of the phenylene group. Among these, position 4 or position 2 is preferred, and position 4 is more preferred.

[0125] In the above structural unit (U1-1), when the carbon atom of the phenylene group to which the sulfinyl group is bonded is designated as position 1, the bonding position of the other main chain to the phenylene group is not particularly limited. It may be position 2, position 3, or position 4 of the phenylene group. Among these, position 2 or 3 is preferred, and position 3 is more preferred.

[0126] The above sulfur-containing polymer preferably contains a plurality of the above constituent units (U1-1), and more preferably contains them as repeating units. When the above sulfur-containing polymer contains a plurality of the above constituent units (U1-1), X in each constituent unit (U1-1) ２ The type, number, and position of substituent α-1 attached to the phenylene group represented by , the position of the sulfinyl group attached to the phenylene group, and the position of the other main chain attached may be the same or different.

[0127] The above sulfur-containing polymer may have at least one of the above-mentioned constituent units (U1) as a constituent unit. Therefore, the above sulfur-containing polymer may be a polymer consisting of only one or more constituent units (U1), or it may be a polymer containing the above-mentioned constituent unit (U1) and constituent units other than the above-mentioned constituent unit (U1). The constituent units other than the above-mentioned constituent unit (U1) are also referred to as other constituent units. There may be one type of other constituent unit or two or more types.

[0128] The content ratio of the above-mentioned constituent unit (U1) in the above-mentioned sulfur-containing polymer is not particularly limited, but it is preferable that the content of the constituent unit (U1) is 1 to 100 moles per 100 moles of the total content of all constituent units in the sulfur-containing polymer. More preferably it is 5 moles or more, and even more preferably 10 moles or more. On the other hand, the upper limit is more preferably 98 moles or less, even more preferably 95 moles or less, and particularly preferably 90 moles or less. That is, the content of the above-mentioned constituent unit (U1) is more preferably 5 to 98 moles, even more preferably 10 to 95 moles, and particularly preferably 10 to 90 moles per 100 moles of the total content of all constituent units in the above-mentioned sulfur-containing polymer. The same applies to the content of the constituent unit (U1-1) in one preferred embodiment of the above-mentioned sulfur-containing polymer.

[0129] The other constituent units mentioned above are not particularly limited, but are preferably the constituent unit (U2) represented by the following general formula (3) and / or the constituent unit (U3) represented by the following general formula (4).

[0130]

[0131] (In the formula, X ３ (This represents a divalent aromatic hydrocarbon group which may have substituents.)

[0132]

[0133] (In the formula, X ４ (wherein represents a divalent aromatic hydrocarbon group which may have substituents.) In other words, one preferred embodiment of the sulfur-containing polymer is that the sulfur-containing polymer contains the above-mentioned structural unit (U1) and further contains the above-mentioned structural unit (U2) and / or the above-mentioned structural unit (U3).

[0134] X in the above structural unit (U2) ３ X in the above constituent unit (U3) ４ The types of divalent aromatic hydrocarbon groups represented by each, the types, number, and bond positions of substituents that the divalent aromatic hydrocarbon groups may have, including these preferred forms, are all part of the X of the above-mentioned structural unit (U1). ２ The types of divalent aromatic hydrocarbon groups represented, the types, number, and bond positions of substituents α that the divalent aromatic hydrocarbon group may have, etc., are the same as described in the explanation for the constituent unit (U1).

[0135] In the above-mentioned structural unit (U2) and the above-mentioned structural unit (U3), as one of the preferred embodiments, the above-mentioned X ３ , the above X ４ One example is a form in which the divalent aromatic hydrocarbon group represented by each of the symbols is a phenylene group. ３ , X ４The constituent units in which the divalent aromatic hydrocarbon group represented by each is a phenylene group are also referred to as constituent unit (U2-1) and constituent unit (U3-1). The types, number, and bonding positions of substituents attached to the phenylene group in constituent unit (U2-1) and constituent unit (U3-1), the bonding positions of sulfide groups and sulfonyl groups on the phenylene group, and the bonding positions of the other main chain, including these preferred forms, are the same as those in constituent unit (U1-1) in terms of the types, number, and bonding positions of substituent α-1 attached to the phenylene group, the bonding position of sulfinyl groups on the phenylene group, and the bonding positions of the other main chain, and the explanation for constituent unit (U1-1) can be applied mutatis mutandis.

[0136] The above sulfur-containing polymer may contain multiple of the above constituent units (U2-1) and / or the above constituent units (U3-1), or may contain them as repeating units, or may contain multiple repeating units. When the above sulfur-containing polymer contains multiple of the above constituent units (U2-1) and / or the above constituent units (U3-1), in each constituent unit (U2-1), (U3-1), X ３ , X ４ The types, number, and positions of substituents attached to the phenylene group represented by each, the positions of the sulfide group and sulfonyl group attached to the phenylene group, and the positions of the other main chain may be the same or different.

[0137] In the above sulfur-containing polymer, the total content of the constituent units (U1), (U2), and (U3) is not particularly limited, but it is preferable that the total content is 1 to 100 moles relative to 100 moles of the total content of all constituent units. More preferably it is 30 moles or more, even more preferably 50 moles or more, and even more preferably 80 moles or more. That is, the total content of the constituent units (U1), (U2), and (U3) is more preferably 30 to 100 moles, even more preferably 50 to 100 moles, and even more preferably 80 to 100 moles, relative to 100 moles of the total content of all constituent units.

[0138] In the above sulfur-containing polymer, the preferred range for the content of the constituent unit (U1) relative to 100 moles of the total content of all constituent units is as described above, but it is preferable that the remainder is the total content of the constituent units (U2) and (U3). When the constituent units (U1), (U2), and (U3) in the above sulfur-containing polymer are constituent units (U1-1), (U2-1), and (U3-1), respectively, the preferred range for the total content of the constituent units (U1-1), (U2-1), and (U3-1) relative to 100 moles of the total content of all constituent units is the same as in the case of the total content of the constituent units (U1), (U2), and (U3).

[0139] In the above sulfur-containing polymer, the content of the above constituent unit (U2) is not particularly limited, but is preferably 0 to 9900 moles per 100 moles of the content of the above constituent unit (U1). More preferably it is 0.01 moles or more, even more preferably 1.0 mole or more, and particularly preferably 5 moles or more. On the other hand, the upper limit is more preferably 900 moles or less, even more preferably 500 moles or less, even more preferably 100 moles or less, and particularly preferably 95 moles or less. That is, the content of the above constituent unit (U2) is more preferably 0.01 to 900 moles, even more preferably 1.0 to 500 moles, even more preferably 5 to 100 moles, and particularly preferably 5 to 95 moles per 100 moles of the content of the above constituent unit (U1). When the above sulfur-containing polymer is composed of the constituent unit (U2) and is composed of the constituent unit (U2-1), the preferred range for the content of the above constituent unit (U2-1) is the same as for the content of the above constituent unit (U2).

[0140] In the above sulfur-containing polymer, the content of the above constituent unit (U3) is not particularly limited, but is preferably 0 to 9900 moles per 100 moles of the content of the above constituent unit (U1). More preferably it is 0.01 moles or more, even more preferably 1.0 mole or more, and particularly preferably 5 moles or more. On the other hand, the upper limit is more preferably 900 moles or less, even more preferably 500 moles or less, even more preferably 100 moles or less, and particularly preferably 95 moles or less. That is, the content of the above constituent unit (U3) is more preferably 0.01 to 900 moles, even more preferably 1.0 to 500 moles, even more preferably 5 to 100 moles, and particularly preferably 5 to 95 moles per 100 moles of the content of the above constituent unit (U1). When the above sulfur-containing polymer contains constituent unit (U3) as constituent unit (U3-1), the preferred range for the content of the above constituent unit (U3-1) is the same as for the content of the above constituent unit (U3).

[0141] The method for producing the above-mentioned sulfur-containing polymer is not particularly limited. For example, a production method including a polymerization step of oxidative polymerization of monomer components containing an aromatic disulfide compound and / or an aromatic thiol compound is preferred, and among these, a production method including an oxidation step of oxidizing the polymer obtained by the polymerization step after the polymerization step is more preferred. The above production method allows for the efficient production of a sulfur-containing polymer having the above-mentioned constituent unit (U1).

[0142] The above polymerization step is a step of oxidative polymerization of monomer components containing an aromatic disulfide compound and / or an aromatic thiol compound. This step can yield a polymer containing at least multiple constituent units (U2) as repeating units. The above oxidative polymerization can be carried out with the monomer components heated and melted, but it is preferable to carry it out in a composition in which the monomer components are dispersed or dissolved in a solvent. The above composition, that is, the composition containing the monomer components and the solvent, is also called the raw material composition, and the composition from the start of the polymerization reaction until the end of the polymerization reaction is also called the reaction composition. The composition obtained by the polymerization reaction is also called the polymer composition.

[0143] The monomer components include aromatic disulfide compounds and / or aromatic thiol compounds. Among these, it is preferable to include aromatic disulfide compounds. Diaryl disulfide compounds represented by the following general formula (5) are more preferable as aromatic disulfide compounds, and thioaryl compounds represented by the following general formula (6) are more preferable as aromatic thiol compounds.

[0144]

[0145] (In equations (5) and (6), A １ and A ２ (This represents a monovalent aromatic hydrocarbon group that may have substituents, either identical or different.) A １ and A ２ Examples of the monovalent aromatic hydrocarbon group represented above include phenyl, naphthyl, anthryl, triphenyl, biphenyl, and phenanthryl groups. Among these, phenyl, naphthyl, anthryl, biphenyl, or triphenyl groups are preferred, and phenyl groups are more preferred. A １ and A ２ The substituents that the above monovalent aromatic hydrocarbon group represented by the above general formula (2) may have include X ２ A group similar to the substituent α that may be present on the divalent aromatic hydrocarbon group represented by the above general formula (2) can be given, and the number of substituents and the bond position to the aromatic hydrocarbon group are the same as X in the above general formula (2). ２ This is similar to the case where a divalent aromatic hydrocarbon group represented by may have substituents.

[0146] Diphenyl disulfide compounds are preferred as the diaryl disulfide compounds, and benzenethiol compounds are preferred as the thioaryl compounds. Diphenyl disulfide compounds are particularly preferred. These compounds may have substituents, and the types of substituents are the same as those in the diaryl disulfide compounds and thioaryl compounds.

[0147] The number of substituents that the above diphenyl disulfide compound may have is 0 to 10, preferably 1 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The bonding positions of the substituents to the phenyl group in the above diphenyl disulfide compound are not particularly limited, but it is preferable that the substituents include the para position (position 4) relative to the carbon atom to which the disulfide group is bonded (position 1).

[0148] The number of substituents that the above benzenethiol compound may have is 0 to 5, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2. The bonding position of the substituent to the phenyl group in the above benzenethiol compound is not particularly limited, but it is preferable that it includes the para position (position 4) relative to the carbon atom to which the mercapto group is bonded (position 1).

[0149] Specific examples of the above diphenyl sulfide compounds include, for example, 3,3'-dimethyldiphenyl disulfide, 2,2'-dimethyldiphenyl disulfide, 4,4'-dimethyldiphenyl disulfide (bis(4-methylphenyl) disulfide), 2,2',3,3'-tetramethyldiphenyl disulfide, 2,2',5,5'-tetramethyldiphenyl disulfide, 2,2',6,6'-tetramethyldiphenyl disulfide, 3,3',5,5'-tetramethyldiphenyl disulfide, and 2,2',3,3',5,5'-hexamethyldiphenyl disulfide. Ludisulfide, 2,2',3,3',6,6'-hexamethyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-octamethyldiphenyl disulfide, 2,2'-diethyldiphenyl disulfide, 3,3'-diethyldiphenyl disulfide, 2,2',6,6'-tetraethyldiphenyl disulfide, 2,2',3,3'-tetraethyldiphenyl disulfide, 2,2',5,5'-tetraethyldiphenyl disulfide, 3,3',5,5'-tetraethyldiphenyl disulfide, 2,2',3,3',5,5'-hex 2,2',3,3',6,6'-Hexaethyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-Octaethyldiphenyl disulfide, 2,2'-Dipropyldiphenyl disulfide, 3,3'-Dipropyldiphenyl disulfide, 2,2',6,6'-Tetrapropyldiphenyl disulfide, 2,2',3,3'-Tetrapropyldiphenyl disulfide, 2,2',5,5'-Tetrapropyldiphenyl disulfide, 3,3',5,5'-Tetrapropyldiphenyl disulfide, 2,2 ',3,3',5,5'-Hexapropyldiphenyl disulfide, 2,2',3,3',6,6'-Hexapropyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-Octapropyldiphenyl disulfide, 2,2'-Diisopropyldiphenyl disulfide, 3,3'-Diisopropyldiphenyl disulfide, 2,2',6,6'-Tetraisopropyldiphenyl disulfide, 2,2',3,3'-Tetraisopropyldiphenyl disulfide, 2,2',5,5'-Tetraisopropyldiphenyl disulfide, 3,3',Examples include 5,5'-tetraisopropyldiphenyl disulfide, 2,2',3,3',5,5'-hexisopropyldiphenyl disulfide, 2,2',3,3',6,6'-hexisopropyldiphenyl disulfide, and 2,2',3,3',5,5',6,6'-octaisopropyldiphenyl disulfide.

[0150] Specific examples of the above-mentioned benzenethiol compounds include 3-methylbenzenethiol, 2-methylbenzenethiol, 4-methylbenzenethiol, thiophenol(benzenethiol), 2,3-dimethylbenzenethiol, 2,5-dimethylbenzenethiol, 2,6-dimethylbenzenethiol, 3,5-dimethylbenzenethiol, and the like.

[0151] The above disulfide compound can also be prepared by oxidation of a thiol compound. Therefore, in the polymerization step described above, a thiol compound can also be used as a precursor to the disulfide compound. The disulfide compound can be obtained by oxidatively bonding two molecules of the thiol compound. The method of oxidative bonding is not particularly limited, and known methods can be used.

[0152] The above oxidative polymerization is not particularly limited, but oxidative polymerization using quinone compounds or oxidative polymerization using a catalyst is preferred. From the viewpoint of reducing the amount of waste liquid, oxidative polymerization using a catalyst is more preferred. As for oxidative polymerization using a catalyst, for example, it is more preferable to carry out the polymerization reaction by heating a composition in which the monomer components and the catalyst are dissolved or dispersed in a solvent. The above catalyst is not particularly limited, but substances containing metal elements such as vanadium (V), zirconium (Zr), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe) are preferred, and one or more of them can be used in combination.

[0153] Among the substances containing the above metal elements, substances containing vanadium and iron as metal elements (referred to as vanadium-containing substances and iron-containing substances, respectively) are preferred due to their high catalytic activity for oxidative polymerization, and iron-containing substances are more preferred. Preferred vanadium-containing substances include vanadium-containing metals and oxovanadium compounds having a V=O bond in the vanadium compound molecule. Examples of oxovanadium compounds include vanadylacetylacetonate, oxovanadium salen complex, N,N'-bissalicylideneethylenediamine oxovanadium, phthalocyanine oxovanadium, and tetraphenylporphyrin oxovanadium. Preferred iron-containing substances include iron compounds having chlorine in the molecule. Compounds containing iron with an oxidation state of 3 or higher are also preferred. Examples of such iron-containing substances include ferric chloride (Fe(Cl)). ３ Examples include 5,10,15,20-tetraphenyl-21H,23H-porphyrin iron chloride (III), iron trifluoromethanesulfonate (III), etc.

[0154] The amount of the catalyst used in the polymerization described above is not particularly limited, but the total content of metal elements contained in the catalyst relative to 100 mol% of the monomer component is preferably in the range of 0.001 to 50 mol%, and from the viewpoint of minimizing the influence of catalyst residuals on physical properties, it is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 5 mol% or less. From the viewpoint of easily obtaining a sulfur-containing polymer with a high molecular weight, it is more preferably 0.01 mol% or more, even more preferably 0.1 mol% or more, and particularly preferably 1 mol% or more. In other words, the amount of the catalyst is preferably 0.01 to 30 mol%, more preferably 0.1 to 20 mol%, even more preferably 1 to 10 mol%, and even more preferably 1 to 5 mol% relative to 100 mol% of the monomer component.

[0155] The above polymerization is preferably carried out in the presence of oxygen. Carrying it out in the presence of oxygen promotes the oxidative polymerization reaction. Therefore, the above polymerization is preferably carried out under the supply of an oxygen-containing gas. For example, methods such as supplying an oxygen-containing gas to the gas phase during the polymerization reaction, or bubbling an oxygen-containing gas into the reaction composition during the polymerization reaction are employed. From the viewpoint of easily promoting oxidative polymerization, a method of continuously supplying an oxygen-containing gas to the reaction composition during the polymerization reaction is preferred, and among these, the bubbling method is preferred.

[0156] Oxygen-containing gases are oxygen molecules (O ２ It is preferable that the gas contains oxygen molecules (O). ２ It may also contain gaseous components other than ). Oxygen molecules (O) contained in oxygen-containing gases ２ Other gaseous components are not particularly limited, but preferably include noble gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn); nitrogen (N ２ Examples of inert gases include carbon dioxide (CO2). ２ ), may contain water vapor, etc.

[0157] Oxygen molecules in oxygen-containing gases (O ２ The content of oxygen molecules (O) in an oxygen-containing gas is not particularly limited, but at room temperature (25°C) and 1 atmosphere, ２ The volume percentage of the oxygen-containing gas is preferably 0.1 to 100% by volume relative to 100% by volume of the oxygen-containing gas. More preferably, it is 1 to 60% by volume, and even more preferably 10 to 30% by volume. The residue in the oxygen-containing gas is, for example, an inert gas.

[0158] The oxygen-containing gas is not particularly limited, but examples include oxygen gas, a mixture of oxygen and nitrogen, and air. From the viewpoint of economic efficiency, it is preferable to use air. The water vapor concentration in the oxygen-containing gas is not particularly limited, but 1000 g / m³ is preferable. ３ The following is preferable: 10 g / m ３ The following is more preferable: 1 g / m ３ The following is even more preferable: 0.1 g / m ３The following is most preferred, and dry air is preferred.

[0159] The amount of oxygen-containing gas supplied is determined from the viewpoint of accelerating the reaction rate and being easy to control, so that it is 1 m³ of the total volume of the reaction composition. ３ per minute, oxygen (O ２ The supply amount (supply rate) of ) is 0.00002 to 2 m ３ It is preferably 0.0001 to 0.2 m / min. ３ This is per minute, and more preferably 0.0002 to 0.02 m ３ It is per minute.

[0160] In the polymerization step described above, it is preferable to further use an acid and / or its salt. By using an acid and / or its salt in combination with the catalyst, it becomes easier to control the molecular weight of the polymer obtained by the polymerization reaction to a high range, and it becomes easier to obtain a high molecular weight sulfur-containing polymer in a short time.

[0161] As the above-mentioned acid, Brønsted acids are preferred, and among them, acids with an acid dissociation constant of -19 to 4 are preferred. More preferably, acids with an acid dissociation constant of -8 to 3 are preferred. Examples of acids with an acid dissociation constant of -19 to 4 include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, persulfuric acid, sulfurous acid, hydrochloric acid, and hydrobromic acid; sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, and 1,1,2,2-tetrafluoroethanesulfonic acid; chlorocarboxylic acids such as chloroacetic acid, dichloroacetic acid, and trichloroacetic acid; and fluorocarboxylic acids such as fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, perfluoropropionic acid, perfluorobutyric acid, and 4-fluorobenzoic acid. Among these, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, and persulfuric acid are preferred.

[0162] The salt of the above acid is not particularly limited as long as it is a salt of the above acid, but salts of the above acid with Group 1 metal elements of the periodic table such as sodium and potassium, Group 2 metal elements of the periodic table such as magnesium and calcium, and ammonium are preferred. Among these, sodium persulfate, ammonium persulfate, sodium toluenesulfonate, and sodium trifluoromethanesulfonate are preferred. Only one of the above acid and / or its salt may be used, or two or more may be used. The amount of acid and / or its salt used is preferably 0.01 to 100 mol%, more preferably 0.1 to 10 mol%, and even more preferably 0.5 to 5 mol%, based on 100 mol% of the monomer component.

[0163] In the polymerization described above, a solvent may be used. The solvent is not particularly limited, but preferred solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, nitrobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, and cyclopentyl methyl ether. The amount of solvent used is not particularly limited, but it is preferably 1 to 10,000 parts by mass, and more preferably 10 to 1,000 parts by mass, per 100 parts by mass of the monomer component used as a raw material. Among the solvents, it is preferable to use non-halogenated solvents such as N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, and cyclopentyl methyl ether.

[0164] The polymerization described above may be carried out at atmospheric pressure at a temperature below the boiling point of the solvent, under flux conditions, or under pressure while being heated to a temperature above the boiling point. In the polymerization described above, the polymerization temperature is not particularly limited as long as it is a temperature at which oxidative polymerization proceeds, but it is preferably 0 to 250°C, more preferably 30°C or higher, even more preferably 50°C or higher, while it is more preferably 200°C or lower, and even more preferably 180°C or lower, as it is easier to carry out the oxidative polymerization reaction with inexpensive equipment. The polymerization time is not particularly limited, but it is preferably 0.1 to 100 hours, more preferably 1 to 80 hours, even more preferably 5 to 50 hours, and particularly preferably 10 to 24 hours.

[0165] When the above-described oxidative polymerization uses a diaryl disulfide compound represented by the above general formula (5) and / or a thioaryl compound represented by the above general formula (6) as monomer components, the main chain is usually A １ A ２ A polymer having a structure in which aromatic hydrocarbon groups represented by are bonded by sulfide groups (-S-), etc., that is, a composition (polymer composition) can be obtained that contains a polymer having one or more constituent units selected from the group consisting of the above constituent units (U1), (U2), and (U3).

[0166] When oxidative polymerization is carried out under the preferred conditions described above in the polymerization process, a polymer with a relatively high content of the above-mentioned structural unit (U2) is easily obtained. Similarly, when the above-mentioned diphenyl disulfide compound and / or benzenethiol compound is used as the monomer component, a polymer containing the above-mentioned structural unit (U2-1) as the main structural unit can be obtained.

[0167] If the polymer obtained by the polymerization step described above is a polymer having a constituent unit (U1) such as (U1-1), then the polymer can be used as the sulfur-containing polymer. It is preferable to subject the polymer obtained by the polymerization step to an oxidation step in order to increase the proportion of constituent units (U1) and (U1-1). The oxidation step described above is a step of oxidizing the polymer obtained in the polymerization step described above.

[0168] The above oxidation step is a step in which an oxidation reaction is carried out using an oxidizing agent. The above oxidizing agent is not particularly limited and known ones can be used, for example, quinone compounds, perbenzoic acid, metachloroperbenzoic acid, lead tetraacetate, thallium acetate, tetracyanoquinodimethane, tetracyanoethylene, cerium(IV) acetylacetonate, manganese(III) acetylacetonate, peroxides, chloric acid, hypochlorous acid, hypochlorite salts, and compounds that can generate hypochlorous acid.

[0169] In particular, it is more preferable to use at least one compound selected from the group consisting of peroxides, chloric acid, hypochlorous acid, hypochlorite salts, and compounds that can generate hypochlorous acid, as it can appropriately oxidize the sulfur atoms (sulfide groups, -S-) contained in the main chain to form sulfinyl groups (-S(=O)-). Examples of the above peroxides include metachloroperbenzoic acid, hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, and t-butyl hydroperoxide. The above oxidizing agent may be used alone or in combination of two or more. The amount of the above oxidizing agent added is preferably 0.01 to 1000 moles, more preferably 0.05 to 500 moles, more preferably 0.1 to 100 moles, and even more preferably 0.2 to 20 moles per mole of sulfur atoms in the polymer (P).

[0170] The reaction temperature for the above oxidation reaction is preferably 0 to 200°C, more preferably 10°C or higher, and even more preferably 15°C or higher, from the viewpoint of facilitating the oxidation reaction. From the viewpoint of easily suppressing side reactions, it is more preferably 180°C or lower, and even more preferably 150°C or lower. The reaction time for the above oxidation reaction is usually 0.1 to 100 hours, preferably 1 to 80 hours, more preferably 5 to 50 hours, and even more preferably 10 to 24 hours.

[0171] Sulfonyl group (-S (-O) ２If you want to increase the content of (-), you can simply allow the reaction to proceed for a longer time than described above. In this case, the amount of oxidizing agent added is not particularly limited as long as the oxidation reaction of the desired sulfur atoms proceeds, but it is usually preferably 0.01 to 1000 moles, more preferably 0.05 to 500 moles, even more preferably 0.1 to 100 moles, and even more preferably 0.5 to 20 moles per mole of sulfur atoms in the polymer.

[0172] A solvent may be used in the above oxidation reaction. Preferably, the solvent used is the same as the solvent used in the polymerization step. The oxidation step yields a polymer with a higher proportion of constituent units (U1) compared to the polymer obtained in the polymerization step, and this polymer can be used as the sulfur-containing polymer.

[0173] As described above, a preferred form of the sulfur-containing polymer is X in the above-mentioned structural unit (U1). ２ Examples of sulfur-containing polymers include those in which at least one of the divalent aromatic hydrocarbon groups constituting the main chain, such as a divalent aromatic hydrocarbon group represented by , has a reactive functional group as a substituent. Methods for producing sulfur-containing polymers in this form include using diaryl disulfide compounds and thioaryl compounds having a reactive functional group as a substituent as monomer components in the polymerization step, and production methods that include a step of introducing a reactive functional group before or after the oxidation step (reactive functional group introduction step). From the viewpoint of producing a sulfur-containing polymer with a higher refractive index and higher reactivity, it is preferable to introduce a mercapto group (-SH) as the reactive functional group. When producing a sulfur-containing polymer having a mercapto group as a substituent, it is preferable to include a step of introducing a mercapto group before or after the oxidation step (mercapto group introduction step).

[0174] The above mercapto group introduction step is not limited in terms of the method used, as long as it can introduce mercapto groups into the sulfur-containing polymer obtained in the polymerization step or further in the oxidation step. However, it is preferable, for example, to react a sulfonating agent with a reducing substance.

[0175] The sulfonating agent that can be used in the above mercapto group introduction step is not particularly limited as long as it is a compound that can introduce a sulfonyl group to an aromatic hydrocarbon group. Examples include concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, and chlorosulfonyl. Among these, chlorosulfonic acid is preferred. The amount of sulfonating agent used is not particularly limited, but it is preferable to use 0.1 to 10,000% by mass of the sulfonating agent per 100% by mass of the polymer. More preferably it is 1% by mass or more, even more preferably 10% by mass or more, and even more preferably 1,000% by mass or less, and even more preferably 500% by mass or less. That is, the amount of sulfonating agent used is more preferably 1 to 1,000% by mass, and even more preferably 10 to 500% by mass, per 100% by mass of the polymer.

[0176] The reducing substances that can be used in the above mercapto group introduction step are not particularly limited, but examples of preferred substances include: hydrides or complexes (art complexes) of metals or metalloids such as sodium hydride, sodium borohydride, lithium aluminum hydride, butyllithium, diborane, sodium cyanoborohydride, lithium triethylborohydride, lithium tri(sec-butyl)borohydride, potassium tri(sec-butyl)borohydride, diisobutylaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, tributyltin hydride, lithium hexamethyldisilazide, and lithium diisopropylamide; metals such as metallic tin and metallic zinc; compounds containing low-valent metal ions such as divalent iron and divalent tin; acidic organic compounds such as formic acid and oxalic acid; phosphine organic compounds such as triphenylphosphine; and inorganic compounds such as hydrazine. One or more of these can be used. Among these, metals are preferred, and metallic zinc is more preferred. When zinc is used, even if heavy metals used as catalysts remain in the polymerization process, these heavy metals are easily removed, and a sulfur-containing polymer with suppressed discoloration is easily obtained. Furthermore, when a metal is used as the reducing substance, its form is not particularly limited, but it is preferably in the form of fine particles. The amount of the reducing substance used is not particularly limited, but it is preferable to use 0.01 to 1000% by mass of the reducing substance per 100% by mass of the polymer. More preferably 0.1% by mass or more, even more preferably 5% by mass or more, and even more preferably 100% by mass or less, and even more preferably 50% by mass or less. That is, the amount of the reducing substance used is more preferably 0.1 to 100% by mass, and even more preferably 5 to 50% by mass, per 100% by mass of the polymer.

[0177] In the mercapto group introduction step described above, it is believed that the reaction proceeds by a mechanism in which a sulfonyl group is introduced to a divalent aromatic hydrocarbon group contained in the polymer used by a sulfonating agent, and the sulfonyl group is reduced to a mercapto group by the action of a reducing substance. The order in which the sulfonating agent and the reducing substance are mixed with the polymer is not particularly limited. For example, there are methods (1) in which the sulfonating agent is mixed with the polymer to introduce a sulfonyl group to the divalent aromatic hydrocarbon group, and then the reducing substance is mixed with the polymer to which the sulfonyl group has been introduced to reduce the introduced sulfonyl group to a mercapto group; (2) in which the sulfonating agent and the reducing substance are mixed with the polymer substantially simultaneously; and (3) in which the reducing substance is mixed with the polymer first, and then the sulfonating agent is mixed. Among these, method (1) is preferred.

[0178] The reaction in the mercapto group introduction step described above is preferably carried out in a solvent. Suitable solvents include, for example, sulfoxide or sulfone solvents such as dimethyl sulfoxide and sulfolane; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylformamide, and 1,3-dimethyl-2-imidazolidinone; ethers such as tetrahydrofuran, diethyl ether, and cyclopentyl methyl ether; chlorinated hydrocarbons such as chloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, and 1,3-dichlorobenzene; carbonyl compounds such as cyclohexanone; esters such as ethyl acetate; and water. One or more of these can be used. Among these, sulfoxide solvents are more preferred, and sulfolane is even more preferred. The amount of the above solvent used is not particularly limited, but it is preferably 0.5 to 50,000 parts by mass, and more preferably 10 to 5,000 parts by mass, per 100 parts by mass of polymer used in the mercapto group introduction step.

[0179] The reaction temperature in the above mercapto group introduction step is not particularly limited as long as it is within the temperature at which the sulfonation and reduction reactions proceed, but is preferably -20 to 250°C, more preferably -5°C or higher, even more preferably 5°C or higher, and more preferably 150°C or lower, and even more preferably 80°C or lower, in terms of suppressing side reactions. The reaction time for the above reaction is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.5 hours or higher, even more preferably 2 hours or higher, and even more preferably 50 hours or lower, and even more preferably 20 hours or lower, from the viewpoint of excellent productivity.

[0180] The above-described manufacturing method can yield the above-described sulfur-containing polymer. However, the polymer composition obtained in the polymerization step contains substances such as the solvent used in the polymerization step and the residue of the catalyst used (catalyst residue), in other words, impurities. Furthermore, the polymer or the composition containing the polymer obtained in the oxidation step may contain residual acids, etc. Since these impurities may affect the heat resistance of the pattern film of the present invention, it is preferable to isolate the sulfur-containing polymer and reduce these impurities. Therefore, it is preferable that the method for producing the above-described sulfur-containing polymer further includes a purification step.

[0181] The purification method used in the above purification step can be a conventionally known purification method. For example, the reprecipitation method is preferred. The reprecipitation method is not particularly limited, but examples include a method in which the polymer composition is dropped dropwise into hydrochloric acid-acidified methanol to precipitate the polymer, the precipitate is filtered to obtain a precipitate, and the obtained precipitate is washed with water or a lower alcohol such as methanol. As the above purification step, a conventionally known method using an adsorbent can also be used to remove components derived from the oxidizing agent used in the oxidation step and impurity components derived from the polymerization step. It is also preferable to use the above reprecipitation method in combination with the method using an adsorbent.

[0182] The above-described method for producing the sulfur-containing polymer may include, in addition to the polymerization step, oxidation step, reactive functional group introduction step, and purification step, other steps. Examples of these other steps include a maturation step, neutralization step, dilution step, drying step, concentration step, solvent replacement step, and dissolution step. These steps can be carried out by known methods. The above-described method can be used to obtain the sulfur-containing polymer.

[0183] (Phosphate-based dispersants) The phosphate-based dispersant is not particularly limited as long as it is a compound having a phosphate group and / or a phosphate ester group, but the following general formula (7):

[0184]

[0185] (In the formula, R ７１ R represents a hydrogen atom or an organic group, either identical or distinct. ７２ (where a represents an alkylene group having 2 to 20 carbon atoms, either identical or different; a is an integer from 1 to 3; and n is an integer from 0 to 20.) is preferably a compound represented by ( ).

[0186] In the above general formula (7), R ７１ These are, either the same or different, a hydrogen atom or an organic group, preferably an organic group. The above organic group is not particularly limited, but examples include hydrocarbon groups which may have a heteroatom.

[0187] The number of carbon atoms in the above organic group is not particularly limited, but it is preferably 1 to 20. More preferably 1 to 16, even more preferably 1 to 12, even more preferably 1 to 10, and particularly preferably 1 to 8.

[0188] Examples of hydrocarbon groups in the above organic group include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 6 to 20 carbon atoms.

[0189] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, and 3,3-dimethylbutyl group. Examples include aliphatic alkyl groups such as 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and eicosyl group; and alicyclic alkyl groups such as cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group (C7), adamantyl group (C10), and cyclopentylethyl group.

[0190] Examples of the above alkenyl groups include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups.

[0191] Examples of the alkynyl groups mentioned above include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desinyl group, dodecynyl group, octadecynyl group, and icosinyl group.

[0192] Examples of the aryl groups mentioned above include phenyl groups, o-, m- or p-tolyl groups, 2,3- or 2,4-xylyl groups, mesityl groups, naphthyl groups, anthryl groups, phenanthryl groups, biphenylyl groups, and benzhydryl groups.

[0193] Examples of the above-mentioned aralkyl groups include benzyl groups, phenethyl groups, and phenylpropyl groups.

[0194] The hydrocarbon group may have a heteroatom, and may have substituents such as a carbonyl group, amide group, ether group, ester group, hydroxyl group, or thioether group. Preferably, the substituent is a carbonyl group, amide group, ether group, ester group, or hydroxyl group, and more preferably a carbonyl group. A form in which the organic group is a (meth)acryloyl group is also one of the preferred embodiments of the present invention. The number of carbon atoms in the hydrocarbon group includes the number of carbon atoms in the substituent.

[0195] Preferably, the above organic groups are alkyl groups and alkenyl groups, and more preferably linear alkyl groups having 1 to 8 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, and n-octyl group; i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, and t-octyl group; and alkenyl groups such as vinyl group, allyl group, and isopropenyl group.

[0196] In the above general formula (7), -(R ７２ The oxyalkylene group represented by O)- is an oxyalkylene group having 2 to 20 carbon atoms, and if there are two or more types of oxyalkylene groups, any of the addition forms such as random addition, block addition, or alternating addition may be used.

[0197] Above - (R ７２ The oxyalkylene group represented by O)- is preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 4 carbon atoms.

[0198] These oxyalkylene groups are alkylene oxide adducts, and examples of such alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. More preferably, ethylene oxide, propylene oxide, and butylene oxide are used, and even more preferably, ethylene oxide and propylene oxide are used.

[0199] In the above general formula (7), -(R ７２ When the oxyalkylene group represented by O)- includes an oxyethylene group to which ethylene oxide has been added, it is preferable that the total oxyalkylene group contains 50 to 100 mol% oxyethylene groups. More preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, particularly preferably 80 to 100 mol%, and most preferably 90 to 100 mol%.

[0200] In the above general formula (7), a is an integer from 1 to 3. Preferably, a is 1 or 2. The polymerizable composition may contain two or more of the following: a monophosphate ester in the above general formula (7) where a is 1, a diphosphate ester where a is 2, and a triester phosphate ester where a is 3. A form containing a monophosphate ester and a diphosphate ester is one of the preferred embodiments of the present invention.

[0201] In the above general formula (7), n is an integer from 0 to 20. Preferably, n is 1 to 15, more preferably 2 to 10, even more preferably 3 to 8, and particularly preferably 3 to 6.

[0202] When the above-mentioned phosphate-based dispersant contains an oxyalkylene group, its affinity for the solvent is further improved, resulting in better dispersibility of inorganic particles.

[0203] The above-mentioned phosphate-based dispersant preferably has a molecular weight of 98 to 2000. Having a molecular weight within this range allows the phosphate-based dispersant to penetrate sufficiently into the fine gaps between inorganic particles, further improving dispersibility. More preferably, the molecular weight of the phosphate-based dispersant is 150 to 1500, and even more preferably 200 to 1000. The molecular weight of the above-mentioned phosphate-based dispersant can be measured by high-performance liquid chromatography (HPLC) or gel permeation chromatography (GPC).

[0204] (Carboxylic Acid Dispersants) Carboxylic acid dispersants are not particularly limited as long as they are compounds having a carboxyl group, but examples include: polyacrylic acid; copolymers of unsaturated carboxylic acid monomers such as (meth)acrylic acid and maleic acid with unsaturated polyalkylene glycol monomers; copolymers of unsaturated carboxylic acid monomers with aromatic monomers such as styrene; copolymers of unsaturated carboxylic acid monomers with acrylic acid esters, and ammonium salts, organic amine salts, and alkali metal salts thereof; 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl succinic acid Examples include unsaturated carboxylic acids having a (meth)acryloyl group, such as liloyloxyethyl phthalic acid and 2-(meth)acryloyloxymonomethyltetrahydrophthalic acid; carboxylic acids having an ether linkage, such as methoxyacetic acid, ethoxyacetic acid, 3-ethoxypropionic acid, 2-methoxyethoxyacetic acid, and 2-methoxyethoxyethoxyacetic acid; secondary carboxylic acids such as isobutyric acid, 2-methylbutyric acid, 2-ethylbutyric acid, and 2-ethylhexanoic acid; and unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid, crotonic acid, cinnamic acid, 2-hexenoic acid, phthalic acid, isophthalic acid, and trimellitic acid.

[0205] (Silane-based dispersants) Silane-based dispersants are not particularly limited as long as they are compounds having an alkoxysilyl group, but examples include 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-glycidoxypropyltrimethoxysilane, and the like.

[0206] The molecular weight (or weight-average molecular weight if the dispersant is a polymer) of the above-mentioned dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 98 to 5000, more preferably 150 to 3500, and even more preferably 200 to 3000. If the above-mentioned dispersant is a polymer, the weight-average molecular weight can be measured by gel permeation chromatography (GPC).

[0207] The polymerizable composition may contain one or more of the dispersants. The content of the dispersants in the polymerizable composition is preferably 2 to 35% by mass, more preferably 4 to 30% by mass, and even more preferably 5 to 22% by mass, based on 100% by mass of the total solid content of the polymerizable composition. If the polymerizable composition contains two or more of the dispersants, it is preferable that the total amount of the two or more dispersants is within the above range.

[0208] When the polymerizable composition contains a sulfur-based dispersant, its content is not particularly limited, but is preferably 1 to 30% by mass per 100% by mass of inorganic particles. When the content of the sulfur-based dispersant is 1% by mass or more, the dispersibility of the inorganic particles can be further improved. When the content of the sulfur-based dispersant is 30% by mass or less, it becomes easier to obtain a patterned film with a high refractive index. The content of the sulfur-based dispersant is more preferably 1 to 25% by mass, even more preferably 2 to 15% by mass, and particularly preferably 5 to 15% by mass, per 100% by mass of inorganic particles.

[0209] When the polymerizable composition contains a phosphate-based dispersant, its content is not particularly limited, but is preferably 0.5 to 10% by mass per 100% by mass of inorganic particles. When the content of the phosphate-based dispersant is 0.5% by mass or more, the dispersibility of the inorganic particles can be further improved, and when the content of the phosphate-based dispersant is 10% by mass or less, it is easier to obtain a patterned film with a high refractive index. The content of the phosphate-based dispersant is more preferably 1 to 9% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass, per 100% by mass of inorganic particles.

[0210] When the polymerizable composition contains a carboxylic acid-based dispersant, its content is not particularly limited, but is preferably 0.5 to 10% by mass per 100% by mass of inorganic particles. When the content of the carboxylic acid-based dispersant is 0.5% by mass or more, the dispersibility of the inorganic particles can be further improved, and when the content of the carboxylic acid-based dispersant is 10% by mass or less, it is easier to obtain a patterned film with a high refractive index. The content of the carboxylic acid-based dispersant is more preferably 1 to 9% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass, per 100% by mass of inorganic particles.

[0211] <Solvent> The polymerizable composition may contain a solvent. The solvent is not particularly limited, but one that has excellent solubility for the dispersant is preferred. Examples include halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, and 1,3-dichlorobenzene; and non-halogenated solvents such as nitromethane, nitrobenzene, N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, cyclopentyl methyl ether, cyclohexanone, cyclopentanone, cycloheptanone, toluene, xylene, propylene glycol monomethyl ethyl ether acetate, methyl ethyl ketone, sulfolane, benzyl alcohol, benzyl acetate, and dibenzyl ether. One or more of these can be used. Among these, non-halogenated solvents are preferred, and more preferably, the solvent contains at least one solvent selected from the group consisting of cyclohexanone, cyclopentanone, propylene glycol monomethyl ethyl ether acetate, methyl ethyl ketone, toluene, xylene, tetrahydrofurene, N-methylpyrrolidone, and the like.

[0212] The amount of solvent in the polymerizable composition is not particularly limited, but it is preferably 20 to 1000 parts by mass, more preferably 60 to 400 parts by mass, and even more preferably 100 to 250 parts by mass, based on 100 parts by mass of the total content of the inorganic particles and dispersant.

[0213] In the method for producing a patterned film of the present invention, one preferred embodiment is in which the polymerizable composition comprises a polymerizable monomer represented by the general formula (1), inorganic particles, and at least one dispersant selected from the group consisting of sulfur-based dispersants, phosphoric acid-based dispersants, carboxylic acid-based dispersants, and silane-based dispersants, wherein the sulfur-based dispersant comprises a polymer having a constituent unit (U1) represented by the general formula (2).

[0214] <Other Components> The polymerizable composition described above may contain other components besides the inorganic particles, polymerizable monomers, dispersants, and solvents mentioned above. Examples of these other components include polymerizable compounds other than the polymerizable monomer represented by the general formula (1) above, surface modifiers, surface tension modifiers, polymerization initiators, photosensitizers, ultraviolet absorbers, light stabilizers, pigments, dyes, antioxidants, resins, reactive diluents, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, adhesion enhancers such as coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, defoaming agents, leveling agents, wetting and dispersing agents, settling inhibitors, thickeners and anti-sagging agents, color separation inhibitors, emulsifiers, slip and scratch inhibitors, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic additives), etc. These known components can be appropriately selected and used. Furthermore, the amount used can be appropriately selected from publicly available technologies.

[0215] Examples of polymerizable compounds other than the polymerizable monomer represented by the general formula (1) above (also called "other monomers") include aromatic vinyl monomers such as divinylbenzene; aromatic allyl monomers such as diallyl phthalate and diallylbenzene phosphonate; (meth)acrylamide monomers such as N-benzyl(meth)acrylamide and 4-acryloylmorpholine; vinyl ester monomers such as vinyl acetate; and vinyl thioethers such as bis(4-vinylthiophenyl) sulfide and phenylvinyl sulfide.(Di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, benzyl (meth)acrylate, 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, (9H-fluorene-9,9-diyl)bis( 4,1-phenylene) di(meth)acrylate and other di(meth)acrylates having a fluorene skeleton, tris[2-(meth)acryloyloxyethyl]triazinebenzyl(meth)acrylate, phenoxyethyl(meth)acrylate, (1-naphthyl)methyl (meth)acrylate, 2-naphthalene(meth)acrylate, (decahydro-1,4:5,8-dimethanonaphthalene)-2-yl (meth)acrylate, 4-phenylbenzyl(meth)acrylate, 2-f Biphenylmethyl (meth)acrylates such as phenylbenzyl (meth)acrylate, 4,4'-bis(meth)acryloyloxymethylbiphenyl, o-phenylphenolethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, o-phenylphenol-(EO)-addition-(meth)acrylate, o-phenylphenol-(EO)2-(meth)acrylate, bisphenol A (meth)acrylate, bisphenol A-(EO)-addition-(meth)acrylate, bisphenol S (meth)acrylate, bisphenol S-(EO)-addition-(meth)acrylate, urethane (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, sulfur-containing (meth)acrylates such as bis(4-methacryloylthiophenyl) sulfide, (meth)acrylic monomers such as 1H,1H,2H,2H-heptafluorodecyl (meth)acrylic acid, and (meth)acrylates having an adamantyl skeleton; triallyl cyanurates;Examples include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl methacrylate. Among these, compounds containing aromatic groups are preferred because they further increase the refractive index of the patterned film. Biphenylmethyl (meth)acrylates such as 4-phenylbenzyl (meth)acrylate and 2-phenylbenzyl (meth)acrylate, 4,4'-bis(meth)acrylooxymethylbiphenyl, o-phenylphenolethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, o-phenylphenol-(EO)-addition-(meth)acrylate, and o-phenylphenol-(EO)2-(meth)acrylate are particularly preferred.

[0216] The content of the above-mentioned other monomers is not particularly limited, but for example, it is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, particularly preferably 30 to 70% by mass, and most preferably 40 to 60% by mass, out of 100% by mass of the total of the polymerizable monomer represented by the above general formula (1) and the above-mentioned other monomers.

[0217] When the polymerizable composition contains the above-mentioned other monomers, the total content of the polymerizable monomer represented by the above-mentioned general formula (1) and the above-mentioned other monomers is preferably 5 to 100% by mass, more preferably 5 to 90% by mass, even more preferably 10 to 60% by mass, and particularly preferably 15 to 40% by mass, based on 100% by mass of the total solid content of the polymerizable composition. Furthermore, when the polymerizable composition contains a solvent, the content ratio of the polymerizable monomer is preferably 1 to 40% by mass, more preferably 2 to 25% by mass, and even more preferably 3 to 20% by mass, based on 100% by mass of the polymerizable composition.

[0218] The polymerization initiator is not particularly limited, and conventionally known thermal polymerization initiators and photopolymerization initiators can be appropriately selected and used. Examples include aminobenzoate initiators, acetophenone initiators, benzoin initiators, benzophenone initiators, acylphosphine oxide initiators, oxime ester initiators, and cationic initiators. The polymerization initiators mentioned above can be commercially available, such as aminobenzoate initiators like "Esacre A198," "Omnipol ASA," "Omnirad EDB," and "Omnirad EHA" from IGM Resins, and "GENOPOL AB-1" and "GENOPOL AB-2" from Rahn AG, as well as acetophenone initiators like "Omnirad 1173," "Omnirad 127," "Esacre KIP 150," "Esacre KIP 160," and "Omnirad 184" from IGM Resins, and "Omnirad TPO" and "Omnirad Examples of polymerization initiators include acylphosphine oxide-based initiators such as "TPO-L" and "Omnirad 819," oxime ester-based initiators such as "Omnirad 1312," "Omnirad 1314," and "Omnirad 1316" from IGM Resins, and cationic initiators such as "Omnicat 250" and "Omnicat 432" from IGM Resins. The content of the polymerization initiator is not particularly limited, but for example, it is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass, based on 100% by mass of the polymerizable monomer.

[0219] The photosensitizer is not particularly limited, and conventionally known photosensitizers can be appropriately selected and used. Examples include thioxanthone-based photosensitizers such as "Omnirad ITX" and "Omnirad DETX" manufactured by IGM RESINS, and coumarin-based photosensitizers such as "Esacre 3644". The content of the above photosensitizer is not particularly limited, but for example, it is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass, based on 100% by mass of the polymerizable monomer.

[0220] The ultraviolet absorber is not particularly limited, and conventionally known ultraviolet absorbers can be appropriately selected and used. Examples include triazine-based ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN 326, TINUVIN 360, TINUVIN 900, TINUVIN 928, and TINUVIN 1130.

[0221] The light stabilizer is not particularly limited, and conventionally known light stabilizers can be appropriately selected and used, for example, Adeka Stab LA-52, Adeka Stab LA-57, Adeka Stab LA-63P, Adeka Stab LA-68, Adeka Stab LA-72, Adeka Stab LA-77, Adeka Stab LA-81, Adeka Stab LA-82, Adeka Stab LA-87, Adeka Stab LA-402XP, Adeka Stab LA-502XP (all manufactured by ADEKA Corporation), Chinubin 11 Examples include 1FDL, Tinuvin 123, Tinuvin 144 (bis(1,2,2,6,6-pentamethyl-4-piperidyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butylmalonate), Tinuvin 292 (a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate), and Tinuvin 5100 (all manufactured by BASF).

[0222] The viscosity of the polymerizable composition is not particularly limited, but it is preferably 1 to 10,000 cps at 25°C. More preferably, the viscosity of the polymerizable composition is 2 to 2,000 cps, and even more preferably 3 to 200 cps.

[0223] Furthermore, it is preferable that the solid content viscosity of the polymerizable composition at 25°C (hereinafter also referred to as the solid content viscosity of the polymerizable composition) is 100 to 10,000 cps. This makes it easier to control the viscosity of the precursor film subjected to the pressing process within the above-mentioned preferred range. The solid content viscosity of the polymerizable composition, when the polymerizable composition is considered as the solid content, refers to the viscosity of the polymerizable composition if the polymerizable composition does not contain a solvent, and refers to the viscosity of the composition obtained by removing the solvent from the polymerizable composition if the polymerizable composition contains a solvent. The solid content viscosity of the polymerizable composition is more preferably 100 to 6,000 cps, and even more preferably 100 to 3,500 cps. The viscosity of the polymerizable composition can be determined in accordance with JIS Z 8803, and the value measured at 25°C using an R100 type viscometer can be adopted. In measuring the solid content viscosity of a polymerizable composition, the composition may be prepared using only the solid components contained in the polymerizable composition, and the resulting composition may be used as the measurement sample. Alternatively, if the polymerizable composition contains a solvent, the solvent may be removed from the polymerizable composition using an evaporator or the like, and the resulting sample may be used as the measurement sample.

[0224] <Method for preparing polymerizable composition> The method for preparing the polymerizable composition used in the method for producing patterned films of the present invention is not particularly limited, and examples include mixing the polymerizable monomer described above with other components other than the polymerizable monomer (for example, other polymerizable compounds, photopolymerization initiators, thermal polymerization initiators, surface tension modifiers, etc.) by known methods.

[0225] If the polymerizable composition contains inorganic particles as one of the other components, it is preferable that the method for preparing the polymerizable composition includes a step of crushing aggregates of inorganic particles (hereinafter also referred to as the crushing step) and a step of mixing the inorganic particle-containing composition obtained in the crushing step with a polymerizable monomer.

[0226] The above crushing step is not particularly limited as long as it crushes aggregates of inorganic particles, but it is preferable to carry it out in the presence of a dispersant. The preferred form of the dispersant in the crushing step is as described in the section on polymerizable compositions, and the preferred amount of dispersant used is the same as the preferred range of the dispersant content relative to inorganic particles in the polymerizable compositions.

[0227] The above crushing process may be carried out without a solvent, but it is preferable to carry it out in the presence of a solvent. In this case, the temperature rise due to crushing is suppressed, and crushing tends to be carried out under mild temperature conditions. The preferred form of the solvent is as described in the section on polymerizable compositions, and the preferred amount of solvent used is the same as the preferred range of solvent content relative to inorganic particles and dispersant in polymerizable compositions.

[0228] The aggregates of inorganic particles used in the above crushing process refer to particles formed by the aggregation of inorganic particles. In these aggregates of inorganic particles, multiple inorganic particles exist as primary particles, and these are aggregated. The inorganic particles contained in these aggregates of inorganic particles (inorganic particles constituting the aggregates of inorganic particles) are not particularly limited as long as they are particles whose main component is an inorganic component. The inorganic component is the same as the inorganic component described in the polymerizable composition, and the preferred form is also as described in the polymerizable composition.

[0229] The aggregates of inorganic particles used in the above crushing step preferably have an average primary particle diameter (D1) of 1 to 50 nm. When such aggregates of inorganic particles are crushed to near the average primary particle diameter (D1), the resulting patterned film exhibits superior transparency. The average primary particle diameter (D1) of the inorganic particles is more preferably 5 to 40 nm, even more preferably 7 to 30 nm, and particularly preferably 10 to 25 nm. The definition and measurement method of the average primary particle diameter (D1) in the aggregates of inorganic particles used in the above crushing step are the same as those for the inorganic particles contained in the polymerizable composition described above.

[0230] The average secondary particle diameter (D2) in the aggregate of the inorganic particles is not particularly limited, but is preferably 5 to 25,000 nm. By setting the average secondary particle diameter (D2) within the above range, the resulting inorganic particle-containing composition and polymerizable composition tend to have excellent light transmittance. The average secondary particle diameter (D2) is more preferably 20,000 nm or less, even more preferably 10,000 nm or less, and particularly preferably 8,000 nm or less. The lower limit is more preferably 25 nm or more, even more preferably 35 nm or more, and particularly preferably 50 nm or more. That is, the average secondary particle diameter (D2) is more preferably 25 to 20,000 nm, even more preferably 35 to 10,000 nm, and particularly preferably 50 to 8,000 nm.

[0231] As aggregates of the above inorganic particles, it is preferable to use those with a degree of aggregation (R), which is the ratio of the average secondary particle diameter (D2) to the average primary particle diameter (D1), of 5 or more, as shown in the following formula. More preferably, the degree of aggregation (R) is 10 or more, and even more preferably 15 or more. There is no particular upper limit, but it is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less. That is, the degree of aggregation (R) is preferably 5 to 1000, more preferably 10 to 500, and even more preferably 15 to 300. Degree of aggregation (R) = Average secondary particle diameter (D2) / Average primary particle diameter (D1) In the above formula, the same unit (e.g., nm) is used for the average primary particle diameter (D1) and the average secondary particle diameter (D2).

[0232] The specific surface area of ​​the aggregate of inorganic particles is not particularly limited, but is between 1 and 300 m. ２ It is preferable that it is / g. More preferably 10 to 200m ２ / g, and more preferably 15 to 150m ２ The value is / g. The specific surface area of ​​the inorganic particle aggregate is a value measured by the BET method, and can be measured specifically by the method described in the examples.

[0233] The structure of the aggregate of inorganic particles described above is not particularly limited and may be porous or dense. It may also be hollow. The shape of the aggregate of inorganic particles is not particularly limited and may be irregular, granular, plate-like, columnar, needle-like, etc., but granular is preferred, and among granular shapes, spherical is preferred. The above-mentioned granular shape means an unbiased shape with an aspect ratio of 1.5 or less.

[0234] The method for producing the aggregates of inorganic particles used in the above crushing process is not particularly limited, and can be produced by conventionally known wet methods, dry methods, etc. Specifically, for example, a solid-phase synthesis method to obtain metal oxide particles by thermal decomposition of solid raw materials such as oxalates; a liquid-phase synthesis method such as hydrolysis and condensation of metal alkoxides in an organic solvent or precipitation of metal hydroxides or oxides from metal inorganic salts such as metal nitrates, sulfates, and chlorides in an alkaline aqueous solution; and a method of calcining the metal hydroxides or metal oxides obtained by the liquid-phase synthesis method at high temperatures; SiCl ４ TiCl ４ Preferred methods include gas-phase reaction methods such as reacting heated vapor of metal chlorides with heated oxygen to form particles made of metal oxides in a high-temperature gas phase. Among these, gas-phase reaction methods are preferred.

[0235] When the aggregate of the above inorganic particles contains titanium dioxide as an inorganic component, the manufacturing method is to hydrothermally treat the hydrolysis product of titanium alkoxide in aqueous alcohol or organic acid, TiCl ４ The heated steam is reacted with heated oxygen, and TiO is produced in the high-temperature gas phase. ２ Chlorine method for forming particles, TiOSO ４ Anatase-type TiO2 is a precipitate obtained by thermal hydrolysis of an aqueous solution of TiO2. ２ A preferred method is the sulfuric acid method, in which fine particles are grown by calcining them at 800 to 1000°C. Among these, the chlorine method and the sulfuric acid method are preferred.

[0236] Commercially available products can also be used as aggregates of the above-mentioned inorganic particles. For example, when the aggregates of the above-mentioned inorganic particles contain titanium dioxide as the inorganic component, commercially available products include those manufactured by Nippon Aerosil Co., Ltd.: AEROXIDE(R)TiO2 P-25, AEROXIDE(R)TiO2 P-90, AEROXIDE(R)TiO2 T-805, AEROXIDE(R)TiO2 Examples include NKT-90, manufactured by Teika Co., Ltd.; fine particle titanium oxide MT-05, MT-100SA, MT-100HD, MT-500B, manufactured by Ishihara Sangyo Co., Ltd.; high-purity titanium oxide PT-601A, TTO-51(A), manufactured by Sakai Chemical Industry Co., Ltd.; titania for catalyst carriers SSP-M, SSP-N, STR-100N, manufactured by Fuji Titanium Industry Co., Ltd.; micro titanium TAF-1500J, TAF-500J, manufactured by Resonac Holdings Co., Ltd.; super titanium F-2, F-4A, F-6A, etc. When the aggregate of the above inorganic particles has alumina as the inorganic component, examples include AEROXIDE(R) Al2O3 AluC, manufactured by Nippon Aerosil Co., Ltd. When the aggregate of the above inorganic particles contains zirconia as an inorganic component, examples include zirconium oxide UEP-100, UEP-50, and UEP manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd.; zirconium oxide PCS-90 and PCS-60 manufactured by Shin Nippon Denko Co., Ltd.; and Zirconeo-Cp and Zirconeo-Rp manufactured by ITEC Co., Ltd.

[0237] The above-mentioned crushing methods include using a planetary mill, an attritor, a jet mill, a vibrating ball mill, a ball mill, and beads. Among these, the method using beads is preferred because it tends to crush materials in a short amount of time.

[0238] The crushing process time in the above crushing step is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours, and even more preferably 1 to 6 hours.

[0239] In the method using beads, the material and hardness of the beads used are not particularly limited. They can be appropriately selected depending on the material of the inorganic particles used (type of inorganic component), the size of the primary inorganic particles, the strength of aggregation, etc. Examples of bead materials include inorganic materials such as glass, alumina, zircon (zirconia-silica ceramics), zirconia, silicon nitride, and steel, as well as resin materials. When the aggregate of inorganic particles to be crushed is an aggregate of crystalline inorganic particles, zirconia is preferred as the bead material, and the Mohs hardness of the beads is preferably in the range of 8 to 10.

[0240] The average particle size of the beads described above is not particularly limited. It can be appropriately selected depending on the material of the inorganic particles used (type of inorganic component), the size of the primary inorganic particles, the cohesive force, etc., but usually beads with an average particle size in the range of 0.01 mm to 2 mm are used. Preferably it is 0.02 mm or more, more preferably 0.04 mm or more. The upper limit is preferably 1 mm or less, more preferably 0.5 mm or less, even more preferably 0.1 mm or less, and particularly preferably 0.08 mm or less. That is, the average particle size of the beads described above is preferably 0.02 to 1 mm, more preferably 0.04 to 0.5 mm, even more preferably 0.04 to 0.1 mm, and particularly preferably 0.04 to 0.08 mm.

[0241] It is preferable to use beads in which the ratio of the average particle size of the beads to the average primary particle size (D1) of the aggregate of inorganic particles to be crushed is in the range of 100 to 10000. This ratio is more preferably 200 to 8000, and even more preferably 500 to 5000.

[0242] The average particle size of the beads mentioned above is the average particle size based on the number of beads. Typically, the particle size (diameter) of individual beads is measured from an optical microscope image of the beads, the particle size distribution based on the number of beads is determined, and the 50% diameter is adopted as the average particle size of the beads.

[0243] Commercially available beads can be used as described above. Examples include YTZ(R) balls (Φ0.015mm, 0.03mm, 0.05mm, 0.1mm, 0.2mm, 0.3mm), alumina balls HD, HD-11, SSA-995, SSA-999W, SSA-999S (all manufactured by Nikkatoh Co., Ltd.), NZ10, NZ30, NZ50, NZ30HLC, NZ50HLC (all manufactured by Niimi Sangyo Co., Ltd.), etc.

[0244] In the method using the beads described above, the amount of beads used is not particularly limited, but it is preferable to use beads in such a ratio of 1 to 50 parts by mass per 1 part by mass of the aggregate of inorganic particles. More preferably, this ratio is 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass.

[0245] Examples of methods using the beads mentioned above include using a paint shaker and using a bead mill. In the case of using a paint shaker, there are no particular restrictions as long as the beads can break up aggregates of inorganic particles, and it is preferable to select conditions that reduce the dispersed particle size without reducing the average primary particle size as much as possible. From this viewpoint, a preferred vibration speed is 100 to 1000 cpm, a preferred vibration amplitude is 750 cpm, and a preferred processing time is 1 to 24 hours. Examples of equipment that can be used in the above method include commercially available equipment such as the No. 488 test disperser (paint shaker / paint conditioner) (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and the standard model disperser (manufactured by Seiwa Giken Co., Ltd.).

[0246] In the method using the bead mill described above, there are no particular limiting conditions as long as the aggregates of inorganic particles can be broken up using the beads. It is preferable to select conditions that reduce the dispersed particle size without reducing the average primary particle size as much as possible. From this viewpoint, the preferred rotation speed is 500 rpm to 8000 rpm, the preferred peripheral speed is 5 to 20 m / s, the preferred processing time is 1 to 24 hours, the preferred number of passes in the case of a circulating system is 5 to 500 times, and the preferred flow rate is 0.1 to 100 L / min.

[0247] Examples of commercially available devices that can be used in the above method include the ReadyMill RMB, EasyNano RMB, EasyNano RMB II, Neo-AlphaMill NAM, SandGrinder BSG, SandGrinder ESG (all manufactured by AIMEX Co., Ltd.), LabStar Mini LMZ015, LabStar Mini DMS65, LabStar Mini HFM02, LabStar LMZ06, LabStar LME075, Nano-Getter, and MAX Nano-Getter (all manufactured by Ashizawa Finetech Co., Ltd.).

[0248] In the method using the beads described above, it is preferable to mix the aggregate of inorganic particles and the dispersant mixture with the beads and then crush them, and it is more preferable to mix the aggregate of inorganic particles, the dispersant, and the solvent mixture with the beads and then crush them.

[0249] In the above crushing process, other components besides the aggregates of inorganic particles, dispersant, and solvent can be further included. Other components can also be included in the above mixture.

[0250] Examples of the other components mentioned above include carboxylic acid compounds such as oleic acid, alcohol compounds such as benzyl alcohol and cyclohexyl alcohol, and surface modifiers (surface tension modifiers) such as BYK-307 and BYK-378. The content of the other components is preferably 0.001 to 10 parts by mass per 100 parts by mass of the aggregate of inorganic particles. More preferably 0.005 to 5 parts by mass, and even more preferably 1 part by mass or less. On the other hand, the lower limit is even more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more. That is, the content of the other components is even more preferably 0.01 to 1 part by mass, and even more preferably 0.1 to 1 part by mass per 100 parts by mass of the aggregate of inorganic particles.

[0251] In the method using the beads described above, it is preferable to remove the beads from the resulting composition after crushing. Means for removing the beads include filtration and centrifugation.

[0252] An inorganic particle-containing composition can be obtained by the manufacturing method described above, but the manufacturing method may further include other steps after the crushing step. One example of such other steps is a purification step. For example, if wear particles from the beads generated in the method using the beads, or some aggregates of inorganic particles used as raw materials, remain without being crushed, a purification step such as filtration can be performed to remove the residue.

[0253] The step of mixing the inorganic particle-containing composition obtained in the above crushing step with the polymerizable monomer (hereinafter also referred to as the mixing step) is not particularly limited as long as it involves mixing the inorganic particle-containing composition with the polymerizable monomer, but it is preferable to mix them so that the ratio of inorganic particles to polymerizable monomers is the preferred ratio of inorganic particles to polymerizable monomers in the polymerizable composition described above.

[0254] In the above mixing step, when mixing the inorganic particle-containing composition with the polymerizable monomer, other components other than the inorganic particles, polymerizable monomer, dispersant, and solvent may also be added. Specific examples of these other components are as described above.

[0255] As described above, the method for producing a patterned film of the present invention uses a polymerizable composition containing a polymerizable monomer represented by the general formula (1) above. However, in order to form a patterned film with a high refractive index, high resolution, minimal change in pattern shape due to heating, and excellent transparency, it is preferable that the polymerizable composition contains a polymerizable monomer represented by the general formula (1), a sulfur-based dispersant containing a polymer having a constituent unit (U1) represented by the general formula (2), and inorganic particles. Such a polymerizable composition containing a polymerizable monomer represented by the general formula (1), a sulfur-based dispersant containing a polymer having a constituent unit (U1) represented by the general formula (2), and inorganic particles is also one of the present inventions.

[0256] [Patterned Film] The patterned film obtained by the method for manufacturing a patterned film of the present invention is formed using a polymerizable composition containing the polymerizable monomer represented by the general formula (1) above, as described above. The patterned film may be a film made of the polymerizable composition or a cured product of the polymerizable composition. When the patterned film is a cured product of the polymerizable composition, in the method for manufacturing the patterned film, it is preferable to cure the coating film while pressing a mold onto the coating film obtained in the coating film formation step during the pressing step.

[0257] The pattern film described above may contain a polymerizable monomer represented by the general formula (1) described above, or it may contain a polymer obtained by polymerizing the polymerizable monomer (a cured product of the polymerizable monomer). However, it is preferable to include a polymer obtained by polymerizing the polymerizable monomer in order to improve the heat resistance, mechanical properties, etc., of the pattern film.

[0258] The polymer formed by polymerizing the polymerizable monomers contained in the pattern film described above is not particularly limited as long as it is a polymer formed by polymerizing the polymerizable monomers described in the polymerizable composition described above. Specific examples and preferred forms of the polymerizable monomers are as described in the polymerizable composition described above.

[0259] The patterned film described above preferably further contains inorganic particles and a dispersant. Specific examples and preferred forms of the inorganic particles and dispersant are as described in the polymerizable composition section above.

[0260] The thickness of the pattern film described above is not particularly limited, but is preferably 1 to 20,000 nm, more preferably 1 to 1,000 nm, and even more preferably 1 to 500 nm. In another preferred embodiment of the pattern film described above, the thickness is preferably 0.01 to 1,000 μm, more preferably 0.01 to 100 μm, and even more preferably 0.08 to 10 μm.

[0261] The refractive index of the patterned film described above is preferably 1.55 or higher at a wavelength of 589 nm. The refractive index of the patterned film described above can be measured by the method described in the examples.

[0262] The haze of the pattern film at a thickness of 1 μm is preferably 0.01 to 5%, more preferably 0.01 to 1.5%, and even more preferably 0.01 to 0.8%. The haze of the pattern film can be determined by measuring the haze of a glass slide with a cured film and subtracting the haze measurement of the glass slide used as the substrate from the obtained measurement. The haze measurement can be performed using a turbidimeter (HAZE METER NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.).

[0263] In a patterned film obtained by the method for manufacturing a patterned film of the present invention, when the shape of the pattern is line and space, the width of the lines in the line and space of the pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. In another preferred embodiment of the patterned film, the width of the lines is preferably 20 to 20000 nm, more preferably 40 to 6000 nm, and even more preferably 60 to 3000 nm. The width of the spaces is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. In another preferred embodiment of the patterned film, the width of the spaces is preferably 20 to 20000 nm, more preferably 40 to 6000 nm, and even more preferably 60 to 3000 nm.

[0264] The width of the upper surface of the protrusions in the above pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. In another preferred embodiment of the pattern film, the width of the upper surface of the protrusions is preferably 20 to 20000 nm, more preferably 40 to 6000 nm, and even more preferably 60 to 3000 nm. The height of the protrusions in the above pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. In another preferred embodiment of the pattern film, the height of the protrusions is preferably 20 to 20000 nm, more preferably 40 to 6000 nm, and even more preferably 60 to 3000 nm.

[0265] The width of the bottom surface of the recess in the pattern shape described above is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. In another preferred embodiment of the pattern film described above, the width of the bottom surface of the recess is preferably 20 to 20000 nm, more preferably 40 to 6000 nm, and even more preferably 60 to 3000 nm. The depth of the groove in the recess in the pattern shape described above is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. In another preferred embodiment of the pattern film described above, the depth of the groove in the recess is preferably 20 to 20000 nm, more preferably 40 to 6000 nm, and even more preferably 60 to 3000 nm.

[0266] When the upper surface of the convex portion of the line in the pattern shape described above is needle-shaped, it can be said to be of higher resolution. In the case of a needle shape, the width of the upper surface of the convex portion is preferably 1 to 500 nm, more preferably 3 to 100 nm, and even more preferably 5 to 50 nm.

[0267] When the above pattern shape is pillar-shaped, the width of the upper surface of the protrusion, which can be said to be of higher resolution, is preferably 20 to 3000 nm, more preferably 40 to 2000 nm, and even more preferably 60 to 1000 nm.

[0268] When the above pattern shape is a hole shape, the width of the recessed bottom surface, which can be said to be of higher resolution, is preferably 20 to 3000 nm, more preferably 40 to 2000 nm, and even more preferably 60 to 1000 nm.

[0269] A cured product of such a polymerizable composition, a patterned film having a pattern, is also one of the present inventions. As described above, one preferred embodiment of the present invention is that the patterned film is a film in which a pattern shape is formed by curing the polymerizable composition after pressing it using a mold having a pattern shape. Another preferred embodiment of the present invention is that the patterned film is a film in which a pattern shape is formed by curing the polymerizable composition while pressing it using a mold having a pattern shape. Furthermore, as described above, one preferred embodiment of the present invention is that the refractive index of the patterned film at a wavelength of 589 nm is 1.55 or higher.

[0270] [Applications] The patterned film obtained by the manufacturing method of the present invention has a high refractive index, high resolution, minimal change in pattern shape due to heating, and fully reflects the physical properties of the composition before pattern formation. Therefore, it is preferably used in optical applications such as optical materials, optodevice components, and display device components.

[0271] The patterned film obtained by the manufacturing method of the present invention can preferably be suitably used as a high refractive index molding material, a raw material for high refractive index molding materials, or a coating agent for forming high refractive index films in the manufacture of optical materials, optodevice components, and display device components.

[0272] Specific applications include, for example, eyeglass lenses, digital eyeglasses, goggles, and displays enabling VR (virtual reality), AR (augmented reality), and MR (mixed reality); imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and in-car cameras; lenses such as light beam focusing lenses and light diffusion lenses; encapsulants for LEDs; optical adhesives; optical bonding materials for optical transmission; filters; diffraction gratings; diffractive optical elements; prisms; optical guides; transparent glass and cover glass for watch glass and display devices; and other optical materials; photosensors (optical sensors (CMOS sensors, TOF sensors, etc.)); photoswitches; LEDs. Applications include optodevice components such as micro-LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, disconnectors, optical splitters, and optical fiber adhesives; display device components such as substrates for display elements like LCDs, organic EL displays, and PDPs, substrates for color filters, substrates for touch panels, index matching materials used in touch panels, display protective films, display backlights, light guide plates, anti-reflective films, anti-fogging films, and light extraction enhancers for LEDs, organic EL displays, etc.; applications where imprint molding is applicable, enabling the formation of precisely thin films of diffractive optical elements, lenses, etc., on substrates made of inorganic materials, glass, or resin; and wafer-level optics. Among these, imaging lenses, digital glasses, goggles, and displays enabling VR (virtual reality), AR (augmented reality), and MR (mixed reality), filters, diffraction gratings, diffractive optical elements, prisms, optical guides, LEDs, micro-LEDs, light-emitting elements, color filters, and touch panels are more preferred.

[0273] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0274] The evaluation methods used in the examples are as follows: [Evaluation of sulfur-containing polymers obtained in the synthesis examples] <Weight-average molecular weight (Mw), number-average molecular weight (Mn)> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the sulfur-containing polymers obtained in each synthesis example were determined by gel permeation chromatography (GPC) under the following conditions. Apparatus 1: SHIMAZU, CBM-20A. Apparatus 2: Agilent Technologies 1260 Infinity. Detector: Differential refractive index detector (RI) (SHIMAZU, SPD-20MA), and UV-Vis-Infrared spectrophotometer (SHIMAZU, SPD-20MA). Column: TOSOH, TSKgel SuperHM-N. Column temperature: 40°C. Flow rate: 0.3 ml / min. Calibration curve: Polystyrene Standards. Eluents: Chloroform, tetrahydrofuran.

[0275] <MALDI (Time-of-Flight Mass Spectrometry)> MALDI measurements were performed on sulfur-containing polymers under the following conditions. Instrument: Time-of-flight mass spectrometer (Bruker Autoflex III) Sample preparation: Approximately 2 mg of the sample to be measured was dissolved in 1.0 g of tetrahydrofuran, 20 mg of 2,5-dihydroxybenzoic acid as a matrix agent, and 2.0 mg of sodium iodide as an ionizing agent. The prepared solution was then applied to a target plate for measurement and dried at room temperature for about 100 minutes.

[0276] < １ H-NMR > For sulfur-containing polymers, under the following conditions １ ¹H-NMR measurements were performed. Equipment: Nuclear magnetic resonance spectrometer (400 MHz), manufactured by JEOL Ltd. Measurement solvents: Deuterated dichloromethane, deuterated chloroform. Sample preparation: Several mg to several tens of mg of the obtained polymer were dissolved in the measurement solvents.

[0277] <IR> IR measurements were performed on sulfur-containing polymers under the following conditions. Apparatus: JASCO Fourier transform infrared spectrophotometer (FT / IR-6100). Sample preparation: Approximately 2 mg of the sample was diluted with approximately 300 mg of dried potassium bromide (KBr). The mixture was ground in a mortar and pestle and molded.

[0278] <Organic Elemental Analysis> Elemental analysis of sulfur-containing polymers was performed using the following instrument: Instrument: JM10, manufactured by J-Science Lab Co., Ltd.

[0279] [Evaluation of Inorganic Particles] The crystal structure, degree of crystallinity, mean primary particle size (D1), and composition of the aggregates of inorganic particles used in each example and comparative example were measured as follows.

[0280] <Method for Evaluating Crystal Structure> The crystal structure and degree of crystallinity of the inorganic particle aggregates used in each example and comparative example were measured using an X-ray diffractometer SmartLab (manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray source: CuKα (0.154 nm). X-ray output setting: 45 kV, 200 mA. Sampling width: 0.0200°. Scan speed: 5.0000° / min. Measurement range: 5 to 90°. Measurement temperature: 25°C. The crystal structure was determined from the obtained X-ray diffraction pattern using the inorganic particle aggregates used in each example and comparative example as samples.

[0281] <Average Primary Particle Size (D1)> In each example and comparative example, if the aggregate of inorganic particles contained zirconium oxide (crystalline) as the inorganic component, X-ray diffraction measurements were performed, and the crystallite size was determined from the full width at half maximum of the diffraction line with the greatest diffraction intensity (strongest line) in the obtained X-ray diffraction pattern. This value was taken as the average primary particle size (D1). In the case where the aggregate of inorganic particles contained titanium oxide (crystalline) as the inorganic component, the diffraction line at the lattice plane (101) was the strongest line. The crystallite size Dc(101) was calculated from the full width at half maximum of this diffraction line in the same manner as above, and this value was taken as the average primary particle size (D1) of each aggregate of inorganic particles used. The apparatus and conditions for performing the X-ray diffraction measurements were the same as in the case of the crystal structure.

[0282] <Specific Surface Area> The specific surface area of ​​the inorganic particle aggregates was measured using the BET method with a BELSORP-MR6 (Microtrac-Bel). The sample used for measurement was an inorganic particle aggregate that had been vacuum-dried in a vacuum dryer at 25°C for 20 hours.

[0283] [Evaluation of polymerizable monomers] <Refractive index> Measured using an ATAGO DR-M4 multi-wavelength Abbe refractometer (measurement temperature 25°C, interference filter wavelength 589 (D) nm).

[0284] [Evaluation of Patterned Films] <Method for Evaluating the Refractive Index and Film Thickness of Films> The refractive index of the imprinted films (patterned films) obtained in each example and comparative example was determined by measuring the refractive index of the film without the transfer pattern shape in the imprinted film prepared in each example and comparative example, and the obtained value was taken as the refractive index of the imprinted film. The refractive index was determined from the reflectance at a wavelength of 589 nm by measuring the reflection spectrum using the following apparatus. Apparatus: Filmetrix F-20 film thickness measurement system. Standard fiber stage SS-1 (spot diameter 1.5 mm)

[0285] <Moldability of Imprint Films> The imprint film was cut in the thickness direction using a glass cutter, and the resulting cross-section was used for evaluation. The pattern shape was observed at a magnification of 10,000x using an FE-SEM (JEOL Ltd.: JSM7600F) to evaluate whether the pattern shape of the mold used was transferred. For example, in the case of an imprint film obtained using the replica mold (1), the cross-section perpendicular to the line direction of the stripe-like line and space pattern, which is the pattern shape of the metal mold (1), was evaluated. The evaluation criteria are as follows: Moldability of imprint film (%) = (Height of pattern shape of imprint film / Height of pattern shape of replica mold) × 100 ◎: The moldability value of the imprint film is 95% or more. 〇: The moldability value of the imprint film is 90% or more and less than 95%. △: The moldability value of the imprint film is greater than 75% and less than 90%. ×: The moldability value of the imprint film is 75% or less.

[0286] <Thermal Stability of Imprinted Films> For each example and comparative example, a heating test was performed on the imprinted films. The pattern shape of the sample after the heating test was observed, and the rate of change from the pattern shape before the heating test was determined and evaluated according to the evaluation criteria below. Note that the observation of the pattern shape, including the method of preparing the sample, was the same as in the case of <Moldability of Imprinted Films>. Rate of change (%) = [1 - (Height of pattern shape after heating test / Height of pattern shape before heating test)] × 100 ◎: The absolute value of the rate of change is 5% or less. ○: The absolute value of the rate of change is greater than 5% and less than 10%. △: The absolute value of the rate of change is 10% or more and less than 25%. ×: The absolute value of the rate of change is 25% or more.

[0287] (Heating Test) The sample after the heating test was obtained by placing it on a hot plate preheated to 80°C using the same method as for pattern shape transfer, heating and holding for 60 minutes, and then placing it on a hot plate preheated to 150°C and heating and holding for another 60 minutes.

[0288] <Synthesis Example 1> Synthesis of Polymerizable Monomer (1) A stirrer bar, 80.00 g (362 mmol) of 2-(2-biphenylyloxy)ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 85.70 g (543 mmol) of α-allyloxymethylacrylate, 86 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.) (an amount equivalent to 1000 ppm relative to α-allyloxymethylacrylate), 86 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.) (an amount equivalent to 1000 ppm relative to α-allyloxymethylacrylate), and 34.6 g of heptane were weighed into a 300 mL separable flask. 5.7 g of heptane was placed in a holder, and the system was heated and stirred at 90-100°C for 1 hour while the pressure was reduced to 300 Torr. The water and heptane accumulated in the holder were recovered, and the water in the system was removed. Then, heptane was placed in the holder, and a titanium solution mixed with 2.06 g (7.2 mmol) of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.06 g of heptane was added to a separable flask to carry out the transesterification reaction. The lower phase accumulated in the holder was removed as needed, and heating was continued until the area ratio of the target product to 2-(2-biphenylyloxy)ethanol was >97% by gas chromatography analysis. The internal temperature was adjusted to 70°C, 39.5 g of 7% oxalic acid aqueous solution was added, and the system was heated and stirred for 30 minutes. After standing for 30 minutes, the aqueous phase was removed. Next, 39.5 g of water was used, and the above washing procedure was performed a total of two times. This water washing operation removed the titanium tetraisopropoxide used as a catalyst. The pressure in the system was reduced to 300 Torr, and the internal temperature was raised to 110°C to remove heptane and water. Then, while maintaining the internal temperature at 100-105°C, the pressure in the system was reduced to 50 Torr, and once it reached 50 Torr, the internal temperature was raised to 110°C to remove any remaining trace amounts of heptane. The internal temperature was then lowered to around 50°C, and once it reached 50°C, the pressure in the system was reduced to 5 Torr. After reaching 5 Torr, the internal temperature was raised to 115°C, and α-allyloxymethylacrylate was distilled off to complete the removal of light-boiling components. The obtained liquid was filtered to obtain the following compound (polymerizable monomer (1)). The refractive index of the obtained compound was 1.564 (25°C), and the viscosity was 73 mPa·s.

[0289]

[0290] <Synthesis Example 2> Synthesis of Sulfur-Containing Polymer (Production of Sulfur-Containing Polymer (Po1a)) In a 3.0 L three-necked flask, combine diphenyl disulfide (218.33 g, 1.00 mol), bis(4-methylphenyl) disulfide (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), and Na ２ S ２ O ８ (Sodium peroxodisulfate) (2.57 g, 12.00 mmol) was added. Next, the three-necked flask was heated to 160°C while a nitrogen flow (20 mL / min) was applied for 10 minutes, then the flow was switched to air bubbling (150 mL / min), and oxidative polymerization was carried out by stirring for 40 hours. After polymerization was complete, the air bubbling was stopped, 240 mL of N-methylpyrrolidone was added, and the mixture was stirred for 10 minutes. Next, the reaction mixture was cooled to room temperature, and THF (2.2 L) was added as a solvent, and after stirring for 10 minutes, 192 mL of pure water was added and the mixture was stirred for 5 minutes. Next, while cooling the round-bottom flask in 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 the mixture was stirred at room temperature for 14 hours. After the reaction was complete, methanol (12 L) was added to the reaction solution to precipitate the product. The precipitated material was filtered and washed with methanol and pure water. The resulting powder was then vacuum-dried at room temperature to obtain a white sulfur-containing polymer (Po1a) powder. The yield was 92%. The structure of the obtained sulfur-containing polymer (Po1a) is as follows: １ Identification was performed using H-NMR, XPS, ICP, IR, GPC, elemental analysis, and MALDI measurement. As a result, １ H-NMR (CD) ２ Cl ２ (400 MHz, ppm): δ = 7.56 (m, 17H), δ = 7.19 (m, 6H), 2.35 (m, 3H). XPS confirmed that sulfide group:sulfoxide group:sulfonic acid group = 45:55:0 mol%, and IR showed 2570 cm⁻¹. －１A peak originating from mercapto was observed nearby, and GPC confirmed Mw = 2400 and Mn = 1150, confirming the terminal structure as -SH. From Mn = 1150, it was confirmed that the proportion of terminal aromatic rings (constituent units) is 9.5 mol% relative to 100 mol% of all aromatic rings (total constituent units).

[0291] (Preparation of sulfur-containing polymer (Po1)) 200.0 g of the above sulfur-containing polymer (Po1a) was added to a 2.0 L three-necked flask, and 1.1 L of sulfolane was added as a solvent. Next, the three-necked flask was heated to 130°C while a nitrogen flow (0.5 L / min) was applied for 10 minutes, and then allowed to cool to room temperature. After cooling, the three-necked flask was immersed in a water-cooled bath, and 98.3 g of chlorosulfuric acid was gradually added dropwise while a nitrogen flow (0.25 L / min) was applied. After the addition was complete, the mixture was stirred at room temperature for 2 hours, and then 16.6 g of zinc was added while the three-necked flask was cooled again in a water-cooled bath, and the mixture was stirred for 14 hours. After the reaction was complete, the product was precipitated by adding the obtained reaction solution dropwise to 5.5 L of methanol, and the precipitated precipitate was filtered and washed with methanol and pure water. Next, the obtained powder was vacuum-dried at room temperature to obtain polymer (Po1) powder. The yield was 90%. The structure of the obtained polymer (Po1) is: １ Identification was performed using H-NMR, ICP, GPC, IR, and elemental analysis. As a result, １ H-NMR (CDCl ３ , 600MHz, ppm): δ = 7.53 (m, 10H), δ = 7.24 (m, 12H), 2.34 (m, 3H), 2570cm from IR －１ A peak originating from mercapto was observed in the vicinity, and GPC confirmed Mw = 2370 and Mn = 1150, confirming the presence of 27.7 mol% thiol (-SH) groups relative to the total aromatic rings. Since the thiol (-SH) group content of polymer (Po1a) is thought to be 9.5 mol% relative to 100 mol% of the total aromatic rings (total constituent units), the amount of mercapto groups introduced in this reaction is thought to be 18.2 mol%. Elemental analysis confirmed that the sulfur atom weight ratio of the sulfur-containing polymer (Po1) was increased compared to the sulfur-containing polymer (Po1a) before the reaction.

[0292] (Determination of SH groups in sulfur-containing polymer (Po1)) 2.0 g of sulfur-containing polymer (Po1) was added to a 20 mL test tube, followed by the addition of 5.0 g of 1,2-epoxycyclohexane, and the mixture was stirred at 80°C for 2 hours. After the reaction was complete, 5 mL of THF was added, and the resulting solution was added dropwise to 50 mL of hydrochloric acid-acidified methanol solution to precipitate the product. The precipitated material was filtered and washed with methanol and pure water. The resulting powder was then vacuum-dried at room temperature to obtain polymer (Po1t) powder. The yield was 89%. The structure of the obtained polymer (Po1t) is as follows: １ Identification was performed using H-NMR, ICP, GPC, IR, and elemental analysis. As a result, １ ¹H-NMR (CDCl3, 600MHz, ppm): δ = 7.53 (m, 6H), δ = 7.24 (m, 8H), 3.16 (m, 1H), 2.69 (m, 1H), 2.34 (m, 2H), 1.79 (m, 4H), 1.32 (m, 4H). From IR, a peak originating from mercapto was observed around 2570 cm⁻¹. From GPC, Mw = 2410 and Mn = 1150 were confirmed. Elemental analysis showed that the chlorine atom content in the polymer was below the detection limit, and it was confirmed that the weight ratio of sulfur atoms in the polymer (Po1t) was increased compared to the sulfur-containing polymer (Po1) before the reaction. １ ¹H-NMR confirmed that mercapto groups were introduced into 27.7 mol% of the total aromatic rings in polymer (Po1t). From the above, it was found that mercapto groups were introduced into 27.7 mol% of the total aromatic rings in polymer (Po1), and from the Mn of GPC, it was calculated that 9.5 mol% of mercapto groups were present at the terminals of all structural units, and it was confirmed that 18.2 mol% of mercapto groups were introduced into the side chains.

[0293] <Preparation Example 1> Preparation of Inorganic Particle-Containing Composition (1) Using a batch-type ready mill RMB RMB 02 vessel (nominal capacity 200 mL) manufactured by AIMEX Co., Ltd., 300 g of zirconia balls YTZ (0.05 mm) manufactured by Nikkatoh Co., Ltd. were used, and zirconium oxide particles UEP-50 (manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd.) (hereinafter referred to as ZrO) were used as an aggregate of inorganic particles. ２30.0 g of (1), 3.50 g of the sulfur-containing polymer (Po1) obtained in Synthesis Example 2 as a sulfur-based dispersant, 1.75 g of a mixture containing triethylene glycol monomethyl ether phosphate ester as a phosphoric acid-based dispersant (hereinafter also referred to as phosphoric acid-based dispersant (1)), and 65 g of cyclopentanone as a solvent were added, and the mixture was dissolved at 1910 rpm for 2 hours in cooling water at 10°C. After the dissolution was complete, a dispersion composition was obtained, and by separating the zirconia balls YTZ (0.05 mm) contained in the dispersion composition by filtration, an inorganic particle-containing composition (1), which is a milky white composition, was obtained. The phosphoric acid-based dispersant (1) used is a compound represented by the above general formula (7), and in the above formula (7), R ７１ CH ３ , R ７２ is C ２ H ４ n was 3. a=1 was 50 mol%, a=2 was 50 mol%, and a=0 was 0.3 mass%. ZrO ２ The crystal structure of (1) is a mixture of monoclinic and tetragonal crystals, with an average primary particle size (D1) of 16 nm and a specific surface area of ​​53 m². ２ It was / g.

[0294] <Preparation Example 2> Preparation of Inorganic Particle-Containing Composition (2) Using a batch-type ready mill RMB RMB 02 vessel (nominal capacity 200 mL) manufactured by AIMEX Co., Ltd., 300 g of zirconia balls YTZ (0.05 mm) manufactured by Nikkatoh Co., Ltd. were used, and the same ZrO as used in Preparation Example 1 was used as the aggregate of inorganic particles. ２ 30.0 g of (1), 2.62 g of the same phosphoric acid-based dispersant (1) used in Preparation Example 1 as a phosphoric acid-based dispersant, 2.62 g of HOA-MS(N) (2-acryloyloxyethylhexahydrophthalic acid) (hereinafter also referred to as carboxylic acid-based dispersant (1)) manufactured by Kyoeisha Chemical Co., Ltd. as a carboxylic acid-based dispersant, and 65 g of cyclopentanone as a solvent were added, and the mixture was dissolved at 1910 rpm for 2 hours in cooling water at 10°C. After the dissolution was complete, a dispersion composition was obtained, and by separating the zirconia balls YTZ (0.05 mm) contained in the dispersion composition by filtration, an inorganic particle-containing composition (2), which is a milky white composition, was obtained.

[0295] <Preparation Example 3> Preparation of inorganic particle-containing composition (3) As an aggregate of inorganic particles, instead of zirconium oxide particles, titanium oxide particles TAF-1500J (manufactured by Fuji Titanium Industries Co., Ltd.) (hereinafter referred to as TiO ２ (1) Also known as (1). An inorganic particle-containing composition (3) was obtained in the same manner as in Preparation Example 1, except that (1) was used. TiO ２ The crystal structure of (1) is anatase, the average primary particle size (D1) is 19 nm, and the specific surface area is 65 m². ２ It was / g.

[0296] <Preparation Example 4> Preparation of inorganic particle-containing composition (4) As an aggregate of inorganic particles, instead of zirconium oxide particles, the same TiO used in Preparation Example 3 is used. ２ An inorganic particle-containing composition (4) was obtained in the same manner as in Preparation Example 2, except that (1) was used.

[0297] <Preparation Example 5> Preparation of Inorganic Particle-Containing Composition (5) An inorganic particle-containing composition (5) was obtained in the same manner as in Preparation Example 1, except that a phosphate-based dispersant (2) was used instead of a phosphate-based dispersant (1) as the phosphate-based dispersant. The phosphate-based dispersant (2) used is a compound represented by the above general formula (7), and in the above formula (7), R ７１ is a 2-ethylhexanoyl group, R ７２ is C ２ H ４ n was 3. a=1 was 50 mol%, a=2 was 50 mol%, and a=0 was 0.5 mass%.

[0298] <Preparation Example 6> Preparation of inorganic particle-containing composition (6) An inorganic particle-containing composition (6) was obtained in the same manner as in Preparation Example 2, except that phosphoric acid-based dispersant (2) was used instead of phosphoric acid-based dispersant (1) as the phosphoric acid-based dispersant, and monohydroxyethyl acrylate phthalate (hereinafter also referred to as carboxylic acid-based dispersant (2)) was used instead of carboxylic acid-based dispersant (1) as the carboxylic acid-based dispersant.

[0299] <Preparation Example 7> Preparation of Inorganic Particle-Containing Composition (7) Using a batch-type ready mill RMB RMB 02 vessel (nominal capacity 200 mL) manufactured by AIMEX Co., Ltd., 300 g of zirconia balls YTZ (0.05 mm) manufactured by Nikkatoh Co., Ltd. were used, and the same ZrO used in Preparation Example 1 was used as the aggregate of inorganic particles. ２ 30.0 g of (1), 3.50 g of the sulfur-containing polymer (Po1) obtained in Synthesis Example 2 as a sulfur-based dispersant, 0.87 g of the same phosphoric acid-based dispersant (2) used in Preparation Example 6 as a phosphoric acid-based dispersant, 0.87 g of the same carboxylic acid-based dispersant (2) used in Preparation Example 6 as a carboxylic acid-based dispersant, and 65 g of cyclopentanone as a solvent were added, and the mixture was dissolved at 1910 rpm for 2 hours in cooling water at 10°C. After the dissolution was complete, a dispersion composition was obtained, and by separating the zirconia balls YTZ (0.05 mm) contained in the dispersion composition by filtration, an inorganic particle-containing composition (7), which is a milky white composition, was obtained.

[0300] <Preparation Example 8> Preparation of inorganic particle-containing composition (8) As an aggregate of inorganic particles, instead of zirconium oxide particles, titanium oxide particles STR-100N (manufactured by Sakai Chemical Industry Co., Ltd.) (hereinafter referred to as TiO ２ (2) Also known as (2). An inorganic particle-containing composition (8) was obtained in the same manner as in Preparation Example 7, except that (2) was used. TiO ２ The crystal structure of (2) is rutile, the average primary particle size (D1) is 16 nm, and the specific surface area is 90 m². ２ It was / g.

[0301] <Preparation Example 9> Preparation of Replica Mold (1) The replica mold (1) used in each example and comparative example was prepared as follows. A metal mold (1) was prepared on a silicon metal surface with a line and space pattern in a stripe shape, with a spacing of 1.0 μm, a width of 1 μm on the upper surface of the convex part, a width of 1 μm on the bottom surface of the concave part, and a height of 1 μm. UV-curable transparent resin (1) was applied to a substrate such as a transparent PET film, the film-coated surface was pressed against the metal mold (1), UV curing was performed while pressed, and then the film was released from the metal mold (1) to obtain a replica mold (1) as a transparent replica film mold in which the pattern shape of the metal mold (1) was reflected on the PET film. The UV-curable transparent resin (1) used in the manufacture of the replica mold (1) is as follows. UV-curable transparent resin (1): UV-curable liquid silicone rubber (PDMS) KER-4690-A / B, manufactured by Shin-Etsu Chemical Co., Ltd.

[0302] (Example 1) Preparation of polymerizable composition A polymerizable composition (1) was obtained by adding and mixing the following components to 100 parts by mass of the solid content of the polymerizable monomer (1) obtained in Synthesis Example 1: 0.1 parts by mass of BYK-307 (manufactured by BYK-Chemie, surface tension modifier) ​​as a surface tension modifier and 3.0 parts by mass of Omnirad 184 (manufactured by IGM Resins B.V.) as a photopolymerization initiator.

[0303] Manufacturing of Imprint Film (Pattern Film) The polymerizable composition (1) described above was dropped onto a glass slide on a spin coater using a pipette, and spin-coated at a rotation speed of 1500 rpm for 10 seconds. The prepared coating film on the glass slide was placed on a hot plate preheated to 50°C and heated for 1 minute to obtain a pre-cured coating film with a thickness of 1.50 μm. The obtained pre-cured coating film was pressed against the replica mold (1) obtained in Preparation Example 9 above at a pressure of 0.5 MPa for 30 seconds using a nanoimprint apparatus EITRE(R)3 (manufactured by obducat), which was a transparent replica film mold in which a line and space pattern was applied in a stripe shape with a spacing of 1.0 μm, a width of 1 μm on the upper surface of the convex part, a width of 1 μm on the bottom surface of the concave part, and a height of 1 μm, within a 1 cm × 1 cm area, at a pressure of 0.5 MPa for 30 seconds, at a pressure of 60 mW / cm². ２By irradiating with UV for 120 seconds, an imprint cured film (1a) to which the replica mold (1) was pressure-bonded was obtained. Thereafter, the replica mold (1) was removed from the imprint cured film (1a) to obtain an imprint film (1) having the shape of the replica mold (1) transferred thereto.

[0304] The refractive index, moldability, and thermal stability of the obtained imprint film (1) were evaluated by the above method. The results are shown in Table 1. Regarding the confirmation of the transfer pattern shape, it was performed in the same manner as in the case of <Moldability of imprint film>, and it was confirmed that the transfer pattern shape reflecting the shape of the metal mold (1) was sufficiently (95% or more) transferred and reproduced.

[0305] (Example 2) As the polymerizable monomer, instead of using 100 parts by mass of the above polymerizable monomer (1) in terms of solid content, 50 parts by mass of the above polymerizable monomer (1) and 50 parts by mass of the following other monomer (1) were used. A polymerizable composition (2) was prepared in the same manner as in Example 1, and an imprint film (2) was produced using this and evaluated. The results are shown in Table 1. (Other monomer (1))

[0306]

[0307] (Example 3) With respect to 100 parts by mass of the solid content of the inorganic particle-containing composition (1) obtained in Preparation Example 1, 0.1 part by mass of BYK-307 (manufactured by BYK-Chemie, surface tension regulator) as a surface tension regulator, 25 parts by mass of the polymerizable monomer (1) obtained in Synthesis Example 1, and 1.0 part by mass of Omnirad 184 (manufactured by IGM Resins B.V.) as a photoinitiator. Each component was added and mixed so as to have a ratio, and a polymerizable composition (3) was obtained. Using the obtained polymerizable composition (3), an imprint film (3) was produced in the same manner as in Example 1, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0308] (Example 4) A polymerizable composition (4) was prepared in the same manner as in Example 3, except that instead of using 100 parts by mass of the polymerizable monomer (1) as the polymerizable monomer, 50 parts by mass of the polymerizable monomer (1) and 50 parts by mass of the other monomer (1) were used. An imprint film (4) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0309] (Example 5) A polymerizable composition (5) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (2) obtained in Preparation Example 2 was used instead of the inorganic particle-containing composition (1). An imprint film (5) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0310] (Example 6) A polymerizable composition (6) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (3) obtained in Preparation Example 3 was used instead of the inorganic particle-containing composition (1). An imprint film (6) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0311] (Example 7) A polymerizable composition (7) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (4) obtained in Preparation Example 4 was used instead of the inorganic particle-containing composition (1). An imprint film (7) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0312] (Example 8) A polymerizable composition (8) was prepared in the same manner as in Example 3, except that a zirconium oxide dispersion ZP-153 (manufactured by Nippon Shokubai Co., Ltd., Zircostar® "ZP-153") was used instead of the inorganic particle-containing composition (1). An imprinted film (8) was then fabricated using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0313] (Example 9) A polymerizable composition (9) was prepared in the same manner as in Example 3, except that polymerizable monomer (2) shown below was used instead of polymerizable monomer (1). An imprint film (9) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0314]

[0315] (Example 10) A polymerizable composition (10) was prepared in the same manner as in Example 3, except that polymerizable monomer (3) shown below was used instead of polymerizable monomer (1). An imprint film (10) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0316]

[0317] (Example 11) A polymerizable composition (11) was prepared in the same manner as in Example 3, except that polymerizable monomer (4) shown below was used instead of polymerizable monomer (1). An imprint film (11) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0318]

[0319] (Example 12) A polymerizable composition (12) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (5) obtained in Preparation Example 5 was used instead of the inorganic particle-containing composition (1). An imprint film (12) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0320] (Example 13) A polymerizable composition (13) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (6) obtained in Preparation Example 6 was used instead of the inorganic particle-containing composition (1). An imprint film (13) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0321] (Example 14) A polymerizable composition (14) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (7) obtained in Preparation Example 7 was used instead of the inorganic particle-containing composition (1). An imprint film (14) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0322] (Example 15) A polymerizable composition (15) was prepared in the same manner as in Example 3, except that the inorganic particle-containing composition (8) obtained in Preparation Example 8 was used instead of the inorganic particle-containing composition (1). An imprint film (15) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 1.

[0323] (Comparative Example 1) A polymerizable composition (16) was prepared in the same manner as in Example 1, except that another monomer (1) was used instead of the polymerizable monomer (1). An imprint film (16) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0324] (Comparative Example 2) A polymerizable composition (17) was prepared in the same manner as in Example 3, except that the polymerizable monomer (1) was replaced with the above-mentioned other monomer (1). An imprint film (17) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0325] (Comparative Example 3) A polymerizable composition (18) was prepared in the same manner as in Example 6, except that the polymerizable monomer (1) was replaced with the above-mentioned other monomer (1). An imprint film (18) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0326] (Comparative Example 4) A polymerizable composition (19) was prepared in the same manner as in Example 3, except that another monomer (2) shown below was used instead of polymerizable monomer (1). An imprint film (19) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0327]

[0328] (Comparative Example 5) A polymerizable composition (20) was prepared in the same manner as in Example 3, except that another monomer (3) shown below was used instead of polymerizable monomer (1). An imprint film (20) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0329]

[0330] (Comparative Example 6) A polymerizable composition (21) was prepared in the same manner as in Example 3, except that the following other monomer (4) was used instead of the polymerizable monomer (1). Using this, an imprint film (21) was produced, and the refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0331]

[0332] (Comparative Example 7) A polymerizable composition (22) was prepared in the same manner as in Example 5, except that the following other monomer (1) was used instead of the polymerizable monomer (1). Using this, an imprint film (22) was produced, and the refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0333] (Comparative Example 8) A polymerizable composition (23) was prepared in the same manner as in Example 7, except that the following other monomer (1) was used instead of the polymerizable monomer (1). Using this, an imprint film (23) was produced, and the refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0334] (Comparative Example 9) A polymerizable composition (24) was prepared in the same manner as in Example 12, except that the following other monomer (1) was used instead of the polymerizable monomer (1). Using this, an imprint film (24) was produced, and the refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0335] (Comparative Example 10) A polymerizable composition (25) was prepared in the same manner as in Example 13, except that the following other monomer (1) was used instead of the polymerizable monomer (1). Using this, an imprint film (25) was produced, and the refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0336] (Comparative Example 11) A polymerizable composition (26) was prepared in the same manner as in Example 14, except that the following other monomer (1) was used instead of the polymerizable monomer (1). Using this, an imprint film (26) was produced, and the refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0337] (Comparative Example 12) A polymerizable composition (27) was prepared in the same manner as in Example 15, except that another monomer (1) shown below was used instead of polymerizable monomer (1). An imprint film (27) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0338] (Comparative Example 13) A polymerizable composition (28) was prepared in the same manner as in Example 1, except that another monomer (5) shown below was used instead of polymerizable monomer (1). An imprint film (28) was then made using this composition, and its refractive index, moldability, and thermal stability were evaluated. The results are shown in Table 2.

[0339]

[0340]

[0341]

[0342] Tables 1 and 2 show that the imprint films obtained by the manufacturing method of the examples have a high refractive index, can be molded by effectively transferring the high-definition pattern shape of the mold, and can produce pattern films that show little change in pattern shape even when heated.

Claims

1. A method for manufacturing a pattern film, the manufacturing method including a step of pressing a polymerizable composition containing a polymerizable monomer represented by the following general formula (1) using a mold, the method for manufacturing a pattern film. (In formula (1), R ４ , ４ , ５ , １ , １ , ３ , １ , １ , ２ , １ , ５ , １ represents an organic group having 1 to 30 carbon atoms and having an aromatic group. R ２ represents -O-, -S- or -NH-. R ３ represents a hydrogen atom or a methyl group. X １ , Y １ and Z １ are the same or different and represent -CR ４ R ５ - or an oxygen atom. R ４ and R ５ are the same or different and represent a hydrogen atom or a methyl group. X １ , Y １ and Z １ at least one of which is an oxygen atom. n represents an integer of 1 or more.) 2. The method for manufacturing a patterned film according to claim 1, wherein the refractive index of the patterned film at a wavelength of 589 nm is 1.55 or greater.

3. The polymerizable composition further comprises inorganic particles and at least one dispersant selected from the group consisting of sulfur-based dispersants, phosphoric acid-based dispersants, carboxylic acid-based dispersants, and silane-based dispersants, wherein the sulfur-based dispersant comprises a polymer having a constituent unit (U1) represented by the following general formula (2), the method for producing a patterned film according to claim 1 or 2. (In formula (2), X ２ (This represents a divalent aromatic hydrocarbon group which may have substituents.) 4. A polymerizable composition comprising a polymerizable monomer represented by the following general formula (1), a sulfur-based dispersant containing a polymer having a constituent unit (U1) represented by the following general formula (2), and inorganic particles. (In formula (1), R １ R represents an organic group having 1 to 30 carbon atoms and containing an aromatic group. ２ R represents -O-, -S-, or -NH-. ３ X represents a hydrogen atom or a methyl group. １ , Y １ and Z １ They are the same or different, -CR ４ R ５ - or represents an oxygen atom. R ４ and R ５ X represents a hydrogen atom or a methyl group, either identical or distinct. １ , Y １ and Z １ At least one of them is an oxygen atom. (n represents an integer greater than or equal to 1.) (In formula (2), X ２ (This represents a divalent aromatic hydrocarbon group which may have substituents.) 5. A patterned film, which is a cured product of a polymerizable composition containing a polymerizable monomer represented by the following general formula (1), and having a pattern. (In formula (1), R １ R represents an organic group having 1 to 30 carbon atoms and containing an aromatic group. ２ R represents -O-, -S-, or -NH-. ３ X represents a hydrogen atom or a methyl group. １ , Y １ and Z １ They are the same or different, -CR ４ R ５ - or represents an oxygen atom. R ４ and R ５ X represents a hydrogen atom or a methyl group, either identical or distinct. １ , Y １ and Z １ At least one of them is an oxygen atom. (n represents an integer greater than or equal to 1.) 6. The pattern film according to claim 5, wherein the pattern film is a film in which a pattern shape is formed by pressing the polymerizable composition using a mold having a pattern shape and then curing it.

7. The patterned film according to claim 5 or 6, wherein the refractive index at a wavelength of 589 nm is 1.55 or greater.

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