Method for producing patterned film

Abstract

To provide a method for producing a patterned film which, in comparison with conventional production methods, suppresses a decrease in the thickness of the film after pattern formation relative to the thickness of the composition before patterning, and enables the transfer of a high-resolution pattern (possessed by a mold).SOLUTION: A method for producing a patterned film, the method including the step of pressing, by means of a mold, a polymerizable composition comprising inorganic particles and a polymerizable monomer, wherein the content proportion of the polymerizable monomer in the polymerizable composition is 15 mass% or more based on a total of 100 mass% of the polymerizable monomer and the inorganic particles, and the surface tension on the surface of the mold exceeds 30 mN / m.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a patterned film, and more particularly to a method for producing a patterned film useful for producing optical materials, semiconductor devices, and the like. [Background technology]

[0002] The imprinting method is a technique for transferring a fine pattern onto a material such as a resin by directly pressing a mold (metal mold) with a fine concave-convex pattern onto the material. Because the imprinting method makes it easy to create fine patterns, it is expected to be applied to various fields such as semiconductor devices. In particular, nanoimprinting technology, which can form fine patterns at the nano-order level, is attracting attention.

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

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-238416 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-191800 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, although various methods for forming patterned films using nanoimprinting have been disclosed, there is a demand for a technology for forming patterns with higher resolution. Furthermore, if a patterned film that maintains the film thickness of the composition (precursor) before pattern formation is obtained during pattern formation, the film thickness of the patterned film can be more easily controlled. Therefore, there is a demand for a technology that can prevent the film thickness after pattern formation from decreasing relative to the film thickness of the composition before pattern formation.

[0006] The present invention has been made in view of the above-mentioned current situation, and aims to provide a method for producing a patterned film that can suppress a decrease in film thickness after pattern formation relative to the film thickness of the composition before pattern formation, as compared to conventional production methods, and that can transfer a high-resolution pattern (having a mold). [Means for solving the problem]

[0007] The present inventors have conducted various studies on methods for producing patterned films and have found that by setting the content of the polymerizable monomer in a polymerizable composition containing inorganic particles and a polymerizable monomer to a predetermined amount or more and pressing such a composition using a mold having a surface tension of more than 30 mN / m on the mold surface, it is possible to prevent the film thickness after pattern formation from decreasing relative to the film thickness of the composition before pattern formation, and to transfer a high-resolution pattern (of the mold). These findings led to the present invention, which successfully solved the above-mentioned problems.

[0008] The present invention includes the following method for producing a patterned film. [1] A method for producing a patterned film, the method comprising: pressing a polymerizable composition containing inorganic particles and a polymerizable monomer using a mold; a content of the polymerizable monomer in the polymerizable composition is 15% by mass or more relative to 100% by mass of the total of the polymerizable monomer and the inorganic particles; and a surface tension on the mold surface is more than 30 mN / m. [2] The method for producing a patterned film according to [1] above, wherein the polymerizable composition has a solid viscosity of 100 to 10,000 cps at 25°C when the polymerizable composition is used as a solid content. [3] The method for producing a patterned film according to [1] or [2] above, wherein the inorganic particles have an average primary particle size of 1 to 50 nm. [4] The polymerizable composition is a polymerizable compound represented by the following formula (1): [ka] (In the formula, X 1 represents a divalent aromatic hydrocarbon group which may have a substituent. The method for producing a patterned film according to any one of the above [1] to [3], comprising at least one dispersant selected from the group consisting of a sulfur-based dispersant, a phosphoric acid-based dispersant, a carboxylic acid-based dispersant, and a silane-based dispersant, having a structural unit (U1) represented by the following formula: [5] The phosphoric acid-based dispersant is represented by the following formula (2): [ka] (In the formula, R 1 R may be the same or different and represent a hydrogen atom or an organic group. 2 are the same or different and represent an alkylene group having 2 to 20 carbon atoms. a is an integer of 1 to 3. and n is an integer of 0 to 20. The method for producing a patterned film according to [4] above, comprising a compound represented by the formula: [6] The method for producing a patterned film according to [4] or [5] above, wherein the phosphoric acid-based dispersant has a molecular weight of 98 to 2,000. [7] The method for producing a patterned film according to any one of [4] to [6] above, wherein the content of the dispersant is 1 to 30% by mass relative to 100% by mass of the inorganic particles. [Effects of the Invention]

[0009] The method for producing a patterned film of the present invention has the above-mentioned configuration, and can suppress a decrease in film thickness after pattern formation relative to the film thickness of the composition before pattern formation, and can transfer a high-definition pattern (having a mold), so that the method can be suitably used for producing optical materials, semiconductor devices, etc. DETAILED DESCRIPTION OF THE INVENTION

[0010] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope of the present invention. A combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of preferred embodiments of the present invention. Furthermore, in this specification, "(meth)acrylate" means "acrylate" or "methacrylate," "(meth)acrylic" means "acrylic" or "methacrylic," and "(meth)acryloyl" means "acryloyl" or "methacryloyl." Furthermore, (meth)acrylate is sometimes referred to as a (meth)acrylic acid ester.

[0011] [Method for producing patterned film] The method for producing a patterned film of the present invention includes a step of pressing a polymerizable composition containing inorganic particles and a polymerizable monomer using a mold, wherein the content of the polymerizable monomer in the polymerizable composition is 15% by mass or more relative to 100% by mass of the total of the polymerizable monomer and the inorganic particles, and the surface tension of the mold is greater than 30 mN / m. By using a mold with a surface tension greater than a predetermined value for a polymerizable composition of a predetermined composition, the polymerizable composition is prevented from flowing outside the pressed area during the pressing step, preventing a decrease in film thickness after pattern formation relative to the film thickness of the composition before pattern formation, and enabling the transfer of a high-resolution pattern (held by the mold).

[0012] The polymerizable composition used in the method for producing a patterned film of the present invention contains inorganic particles and a polymerizable monomer, and the content of the polymerizable monomer is 15% by mass or more relative to 100% by mass of the total of the polymerizable monomer and the inorganic particles, which allows the viscosity of the polymerizable composition to fall within a suitable range, enabling the formation of a high-resolution pattern. A preferred embodiment of the polymerizable composition will be described later.

[0013] The method for producing a patterned film of the present invention includes a step of pressing the polymerizable composition using the mold. The method for producing the pattern film may include a step of pressing a composition made from the polymerizable composition using the mold, but preferably includes a step of applying the polymerizable composition to a substrate to form a coating film (precursor film), a step of pressing a mold against the coating film obtained in the coating film forming step, and a step of peeling the mold from the pattern film obtained in the pressing step.

[0014] The method for applying the polymerizable composition in the coating film forming step is not particularly limited, and any conventionally known method can be used. Among these, spin coating, bar coating, squeegee coating, inkjet coating, spraying, roll coating, rotary coating, etc. are preferred. The coating thickness is not particularly limited and may be appropriately selected depending on the intended use of the resulting film, etc. 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.

[0015] In the coating film forming step, the viscosity of the polymerizable composition when applied is not particularly limited, but the viscosity at 25°C is preferably 1 to 10,000 cps. This makes application easier and makes it 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.

[0016] In the coating film forming step, the applied film (coating film) is preferably heated and / or irradiated with active energy rays. When heated, the solvent contained in the coating film can be evaporated and removed. Furthermore, heating or irradiating with active energy rays promotes the reaction of polymerizable monomers contained in the coating film, allowing a cured film to be efficiently obtained.

[0017] When heating is performed in the coating film forming step, the heating temperature is not particularly limited, but is preferably 50 to 400° C., and more preferably 100 to 300° C. The heating time is not particularly limited, but is preferably 0.01 to 10 hours, and more preferably 0.1 to 2 hours.

[0018] In the method using active energy rays, ultraviolet rays or electron beams are preferred as the active energy rays, and ultraviolet rays are more preferred. When ultraviolet rays are used, the amount of ultraviolet rays to be irradiated (cumulative exposure amount) is not particularly limited, but is preferably 0.001 to 100 J / cm 2 2 It is preferable to irradiate so that the radiation dose is in the range of 0.01 to 50 J / cm. 2 , and more preferably 0.05 to 10 J / cm 2 As the light source, various mercury lamps, LEDs, etc. can be used, but ultra-high pressure mercury lamps, metal halide lamps, and LEDs are preferred.

[0019] In the coating film forming step, the viscosity of the formed coating film (precursor film subjected to the pressing step) is not particularly limited, but the viscosity at 25°C is preferably 100 to 10,000 cps. This results in better transferability at low pressure. The viscosity is more preferably 100 to 6,000 cps, and even more preferably 100 to 3,500 cps. It is also preferable to control the composition of the polymerizable composition used for coating so that the solid content viscosity of the polymerizable composition, which will be described later, becomes a preferred viscosity for the precursor film.

[0020] In the coating film forming step, the formed coating film (precursor film subjected to the pressing step) may contain a solvent. The content of the solvent in the precursor film is preferably 0.01 to 20 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.1 to 3 mass %, relative to 100 mass % of the solid content of the precursor film.

[0021] The viscosity of the precursor film and the content of the solvent in the precursor film are preferably the viscosity of the precursor film and the content of the solvent in the precursor film immediately before being pressed in the pressing step. In some cases, the viscosity and the content of the solvent in the precursor film after the coating film forming step may be adjusted before the pressing step.

[0022] The substrate to which the polymerizable composition is applied is not particularly limited, and examples thereof include light-transmitting substrates such as glass plates, quartz plates, organic resin films, organic resin molded products, and films, sheets, and plates having a transparent inorganic oxide layer on the surface thereof; 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).

[0023] The mold used in the above pressing step is not particularly limited as long as the surface tension of the mold surface is 35 to 55 mN / m and a transfer pattern consisting of projections and recesses is formed on the surface; however, the surface tension is preferably 30 to 60 mN / m, more preferably 35 to 55 mN / m, and even more preferably 35 to 50 mN / m. The surface tension of the mold surface can be measured by the wetting tension test method in accordance with JIS K 6768. The measurement is performed and evaluated in a standard laboratory atmosphere of 23°C and a relative humidity of 50%.

[0024] The material of the surface of the mold used in the pressing step is not particularly limited as long as the surface tension of the mold surface is 30 mN / m or more, and examples thereof include silicone-based resins, fluorine-based resins, epoxy-based resins, acrylic-based resins, polyurethane-based resins, phenol-based resins, melamine-based resins, polyester resins, propylene resins, vinyl chloride resins, polystyrene, cycloolefin polymers, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, quartz, glass, etc. Preferred materials for the mold surface are epoxy-based resins, acrylic-based resins, polyurethane-based resins, phenol-based resins, melamine-based resins, polyester resins, cycloolefin polymers, polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, and more preferred are epoxy-based resins and acrylic resins.

[0025] When the material of the mold surface is an epoxy resin, the content of oxygen atoms in the epoxy groups in the epoxy resin before polymerization is preferably 1 to 35 mass% relative to 100 mass% of the resin. This ensures a more preferable range for the surface tension of the mold surface. The content of epoxy groups in the epoxy resin is more preferably 4 to 30 mass%, and even more preferably 6 to 25 mass%.

[0026] The shape of the pattern on the mold surface is not particularly limited, and examples thereof include a line-and-space shape, a pillar shape, a hole shape, a honeycomb shape, a slanted shape, a moth-eye shape, a cone shape, a square prism shape, a square pyramid shape, a triangular prism shape, a triangular pyramid shape, a polygonal prism shape, a polygonal pyramid shape, a lattice shape, etc. The line-and-space shape is preferred as the pattern shape.

[0027] When the pattern has a line and space shape, the line width is preferably 20 to 20,000 nm, more preferably 40 to 600 nm, and even more preferably 60 to 3,000 nm. The width of the space is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0028] The width of the upper surfaces of the convex portions 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.

[0029] The height of the convex portions on the surface of the mold is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0030] The width of the bottom of the recess on the surface of the mold is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0031] The depth of the grooves in the recesses on the surface of the mold is preferably 20 to 20,000 nm, more preferably 40 to 6,000 nm, and even more preferably 60 to 3,000 nm.

[0032] In the pressing step, the pressure used to press the mold against the coating film obtained in the coating film forming step 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.

[0033] In the pressing step, it is preferable to cure the coating film obtained in the coating film forming step while pressing the mold against the coating film. The curing method is not particularly limited, but it is preferable to perform heating and / or irradiation with active energy rays. As the curing method, irradiation with active energy rays is more preferable, and irradiation with ultraviolet rays is even more preferable. The amount of ultraviolet light irradiation (cumulative exposure amount) is not particularly limited, but is preferably 0.001 to 100 J / cm 2 It is preferable to irradiate so that the radiation dose is in the range of 0.01 to 50 J / cm. 2 , and more preferably 0.05 to 10 J / cm 2 is.

[0034] More specifically, in the pressing step, it is preferable to fill the mold with the precursor coating (resin) obtained in the coating film forming step in a light-shielded environment without exposing the mold to light. When the precursor coating is filled into the mold, the mold may be heated before filling, but it is preferable to heat the mold at room temperature. In the pressing step, it is preferable to fill the mold with the precursor coating at room temperature under light-shielding conditions, and then maintain the pressing pressure for a predetermined period of time. It is preferable to maintain the pressing pressure for a predetermined time at room temperature under light-shielded conditions, and then to perform curing by irradiating the composition with light while maintaining the pressing pressure. In one preferred embodiment of the present invention, the pressing step includes a step of filling a mold with a coating film of the precursor (filling step) and a step of curing (solidifying and molding) the coating film (curing step). In the above-mentioned filling step, it is preferable to maintain the pressing pressure at room temperature under light-shielded conditions. In the curing step, it is preferable to perform light irradiation while maintaining the pressing pressure.

[0035] The method for producing the patterned film preferably includes a step of further curing the patterned film obtained after the step of peeling the mold from the patterned film obtained in the pressing step. As a curing method, heating and / or irradiation with active energy rays is preferred, and heating is more preferred. 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 60 minutes, more preferably 15 to 45 minutes.

[0036] <<Polymerizable composition>> The polymerizable composition used in the method for producing a patterned film of the present invention contains inorganic particles and a polymerizable monomer, and the content of the polymerizable monomer is 15% by mass or more, preferably 18 to 90% by mass, more preferably 20 to 65% by mass, and even more preferably 20 to 40% by mass, relative to 100% by mass of the total of the polymerizable monomer and the inorganic particles.

[0037] The content of inorganic particles in the polymerizable composition is preferably 10% by mass or more, based on 100% by mass of the total of the polymerizable monomer and inorganic particles. This makes it easier to obtain a patterned film with a high refractive index, for example. The content of inorganic particles is more preferably 35 to 80% by mass, and even more preferably 60 to 80% by mass.

[0038] The polymerizable composition preferably contains a dispersant, and the content is not particularly limited, but is preferably 1 to 30% by mass relative to 100% by mass of inorganic particles. When the content of the dispersant is 1% by mass or more, the dispersibility of the inorganic particles can be further improved. Furthermore, the smaller the amount of organic dispersant in the composition, the more easily a patterned film with a high refractive index can be obtained. When the content of the dispersant is 30% by mass or less, the more easily a patterned film with a high refractive index can be obtained. The content of the dispersant is more preferably 2 to 25% by mass, even more preferably 5 to 22% by mass, and particularly preferably 8 to 20% by mass.

[0039] An embodiment in which the polymerizable composition contains a sulfur-containing polymer as a dispersant is one of the preferred embodiments of the present invention. When the composition contains a sulfur-containing polymer, its content is not particularly limited, but is preferably 1 to 30% by mass relative to 100% by mass of the inorganic particles. When the content of the sulfur-containing polymer is 1% by mass or more, the dispersibility of the inorganic particles can be further improved. When the content of the sulfur-containing polymer is 30% by mass or less, for example, a patterned film with a high refractive index is more easily obtained. The content of the sulfur-containing polymer is more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, and particularly preferably 5 to 15% by mass.

[0040] An embodiment in which the polymerizable composition contains a phosphoric acid compound as a dispersant is also one of the preferred embodiments of the present invention. When the composition contains a phosphoric acid compound, its content is not particularly limited, but is preferably 0.5 to 10% by mass relative to 100% by mass of the inorganic particles. When the content of the phosphoric acid compound is 0.5% by mass or more, the dispersibility of the inorganic particles can be further improved, and when the content of the phosphoric acid compound is 10% by mass or less, for example, a patterned film with a high refractive index can be easily obtained. The content of the phosphoric acid compound is more preferably 1 to 9% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass.

[0041] The polymerizable composition preferably has flowability, and is more preferably in a liquid state. The viscosity of the polymerizable composition is not particularly limited, but is preferably 1 to 10,000 cps at 25° C. The viscosity of the polymerizable composition is more preferably 2 to 2,000 cps, and even more preferably 3 to 200 cps. Furthermore, the polymerizable composition preferably has a solid viscosity at 25° C. when the polymerizable composition is in the solid state (hereinafter also referred to as the solid viscosity of the polymerizable composition) of 100 to 10,000 cps. This makes it easier to control the viscosity of the precursor film to be subjected to the pressing step within the above-mentioned preferred range. The solid content viscosity of a polymerizable composition when the polymerizable composition is the solid content means the viscosity of the polymerizable composition when the polymerizable composition does not contain a solvent, and means the viscosity of the composition obtained by removing the solvent from the polymerizable composition when the polymerizable composition contains a solvent. The solid viscosity of the polymerizable composition is more preferably 100 to 6000 cps, and even more preferably 100 to 3500 cps. The viscosity of the polymerizable composition can be a value measured at 25° C. using an R100 type viscometer in accordance with JIS Z 8803. In measuring the solid content viscosity of a polymerizable composition, a composition may be prepared using only the solid components contained in the polymerizable composition, and the obtained composition may be used as a measurement sample. When the polymerizable composition contains a solvent, the solvent may be removed from the polymerizable composition using an evaporator or the like, and the resulting composition may be used as a measurement sample.

[0042] The essential components and optional components contained in the polymerizable composition of the present invention will be further described below.

[0043] <Inorganic particles> The inorganic particles contained in the polymerizable composition are not particularly limited as long as they are particles containing an inorganic component as a main component, and the inorganic component may be a simple metal or a metal compound. The inorganic component is preferably a metal compound. The inorganic particles preferably contain a metal compound in an amount of 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. The content of the inorganic component in the inorganic particles can be determined as follows. (Method for measuring inorganic component content) The inorganic particles are subjected to a heat treatment in which the temperature is increased from room temperature at a rate of 10°C / min, heated to 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 calculated using the following formula. The heat treatment is typically carried out in a nitrogen atmosphere from room temperature to 200°C, switched to an air atmosphere at 200°C, and continued in an air atmosphere thereafter. However, if the inorganic particles contain metal oxides or metal nitrides that change into metal oxides and undergo a change in valence and composition upon heating in an air atmosphere, the entire heat treatment process, from the start of the temperature increase to cooling, is carried out in a nitrogen atmosphere. Inorganic component content (mass%) = {Sa(g) / Sb(g)}×100

[0044] The metal compound in the inorganic particles is not particularly limited, but is preferably a compound containing, as a metal element, one or more elements included in Groups 2 to 15 of the periodic table and the lanthanoid elements. 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. The metal compound is more preferably a metal compound containing at least one selected from the group consisting of these metal elements.

[0045] Examples of the metal compound include metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal sulfides, metal hydroxides, etc. From the viewpoint of easy control of optical functions and electronic functions, metal oxides and metal hydroxides are preferred, and metal oxides are more preferred.

[0046] In one embodiment, the inorganic component is preferably at least one metal oxide selected from the group consisting of silicon oxide (SiO), aluminum oxide (AlO), zirconium oxide (ZrO), titanium oxide (TiO), barium titanate (BaTiO), niobium oxide (NbO), tantalum oxide (TaO), hafnium oxide (HfO), cerium oxide (CeO), tungsten oxide (WO, WO), indium oxide (InO), stannic oxide (SnO), and zinc oxide (ZnO), because the inorganic component has little or no characteristic absorption in the visible light region. The inclusion of the metal oxide as inorganic particles is also preferred because it tends to result in a colorless (white) composition.

[0047] In one embodiment, the inorganic component is preferably a metal oxide having a refractive index of 2 or greater for the NaD line (589 nm). Among these, metal oxides with little or no characteristic absorption in the visible light region are preferred. Examples of such metal oxides include zirconium oxide (ZrO), titanium oxide (TiO), barium titanate (BaTiO), niobium oxide (NbO), tantalum oxide (TaO), indium oxide (InO), stannic oxide (SnO), and zinc oxide (ZnO). Zirconium oxide (ZrO) and titanium oxide (TiO) are particularly preferred. When the metal oxide is included as inorganic particles, the resulting patterned film tends to have a high refractive index and be colorless (white).

[0048] The incorporation of heterogeneous elements or the inclusion of oxygen vacancies can impart (optical) semiconductor properties, enabling the control of optical absorption characteristics in the infrared region and electronic conductivity, etc., depending on the metal element in the solid solution. Therefore, in one embodiment, the inorganic component is preferably a solid solution oxide formed by dissolving heterogeneous elements in at least one metal oxide selected from the group consisting of titanium oxide (TiO), indium oxide (InO), stannic oxide (SnO), and zinc oxide (ZnO). When the metal oxide is contained as inorganic particles, the resulting patterned film can be suitably used as a transparent conductive film, a conductive film such as an antistatic film, an infrared blocking film, etc. Preferred examples of the solid solution oxide include indium oxide with tin or titanium as a solid solution, stannic oxide with antimony or fluorine as a solid solution, and zinc oxide with aluminum, indium, or fluorine as a solid solution.

[0049] From the viewpoint of excellent ultraviolet absorption, in one embodiment, the inorganic component is preferably at least one metal oxide selected from the group consisting of titanium oxide (TiO), cerium oxide (CeO), and zinc oxide (ZnO). When the inorganic particles contain the metal oxide, the resulting patterned film can be preferably used as an ultraviolet absorbing film, etc.

[0050] In one aspect, it is also preferable that the inorganic component is an inorganic component used in pigments. Examples of inorganic pigments include white pigments such as zinc oxide (ZnO), basic lead carbonate (2PbCO3·Pb(OH)2), barium sulfate (BaSO4), zinc sulfide (ZnS), titanium dioxide (TiO2), etc., red pigments such as lead tetroxide (Pb3O4), ferric oxide (Fe2O3), etc., yellow pigments such as lead chromate (PbCrO4), zinc chromate (ZnCrO4), etc., iron(III) hexacyanoferrate(II) (Fe4[Fe(CN)6]3·15H2O), YIn 1-x Mn x O3, 0 < x < 1), etc. blue pigments, black pigments such as magnetite (Fe3O4), titanium black, etc.

[0051] From the viewpoint of excellent insulation properties, in one aspect, it is preferable that the inorganic component is at least one metal compound selected from the group consisting of silicon oxide (SiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), titanium oxide (TiO2), and boron nitride (BN), and silicon oxide (SiO2) is more preferable. The silicon oxide (SiO2) may be crystalline or amorphous, but is preferably amorphous. When the metal compound is included as inorganic particles, the obtained pattern film can be preferably used as a film with excellent insulation properties.

[0052] The inorganic particles may be crystalline inorganic particles or amorphous inorganic particles, but from the viewpoint of easily obtaining a pattern film with a high refractive index, it is preferable that they are crystalline inorganic particles.

[0053] It is preferable that the crystallinity of the inorganic particles is 80% or more, more preferably 85% or more, further 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 in the same manner as the crystallite size, and the value obtained by powder X-ray diffraction measurement can be adopted as the crystallinity of the inorganic particles.

[0054] The form of the inorganic particles is not particularly limited, and may be primary particles or may include secondary particles formed by aggregation of primary particles.

[0055] The dispersed particle diameter (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 diameter (Dd) is the 50% particle diameter in the volume-based particle size distribution measured by a particle size distribution measurement method using dynamic light scattering (DLS). The device used to measure the dispersed particle diameter (Dd) is preferably a concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.). In the above measurement method, when the polymerizable composition is a liquid containing a solvent, the measurement sample is the composition as is, or diluted with the solvent as necessary. When the polymerizable composition is a solid, the measurement sample is preferably prepared by mixing and stirring a preferred solvent (e.g., cyclopentanone, N-methylpyrrolidone, benzyl alcohol) described below. In either case, the concentration of inorganic particles in the measurement sample is preferably about 1 to 2 mass %, and the concentration can be adjusted appropriately during measurement depending on the amount of scattered light and the presence or absence of multiple scattering.

[0056] The inorganic particles preferably have an average primary particle diameter (D1) of 1 to 50 nm. This allows the patterned film to be a coating film with 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 average primary particle diameter (D1) is the crystallite diameter Dc when the inorganic particles contain a crystalline inorganic component, and the specific surface area diameter Ds when the inorganic particles do not contain a crystalline inorganic component. When the inorganic particles contain a crystalline inorganic component, the aggregates are also referred to as crystalline inorganic particles, and when the inorganic particles do not contain a crystalline inorganic component, the aggregates are also referred to as amorphous inorganic particles. Whether or not a crystalline inorganic component is contained can be confirmed by powder X-ray diffraction measurement. For example, inorganic particles or their aggregates can be used as a sample, and the determination can be made from the obtained X-ray diffraction pattern using analysis software (PDXL2, manufactured by Rigaku Corporation).

[0057] The crystallite diameter Dc is determined by measuring the full width at half maximum of the diffraction line with the highest diffraction intensity (the strongest line) among the diffraction lines in the obtained X-ray diffraction chart by powder X-ray diffraction measurement of the inorganic particles or their aggregates, and then using the Scherrer equation. Here, the diffraction intensity refers to the height of the peak top of the diffraction line. For example, analytical software (PDXL2, manufactured by Rigaku Corporation) can be used. The apparatus and conditions for the powder X-ray diffraction measurement are not particularly limited, but for example, a fully automatic multipurpose X-ray diffractometer SmartLab (manufactured by Rigaku Corporation) can be used, and the measurement conditions are preferably those shown in the Examples. The specific surface area diameter Ds can be calculated using the specific surface area and true density of the inorganic particles or their aggregates according to the following formula: Ds(m)=6 / (ρ·S) ρ [g / m 3 ]: true density of inorganic particles or their aggregates, which can be determined by a pycnometer. S[m 2 / g]: specific surface area of ​​inorganic particles or their aggregates, which can be measured by the BET method.

[0058] The dispersed particle size (Dd) / average primary particle size (D1) of the 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.

[0059] The shape of the inorganic particles is not particularly limited and may be any of amorphous, granular, plate-like, columnar, needle-like, etc., but granular is preferred, and among granular, spherical is preferred. The granular shape refers to a uniform shape with an aspect ratio of 1.5 or less. The shape of the inorganic particles is preferably 5 or less, more preferably 2 or less, and most preferably 1.5 or less, when the aspect ratio is the value obtained by dividing the longest diameter by the shortest diameter within the particle.

[0060] <Polymerizable monomer> The polymerizable monomer is not particularly limited as long as it is a monomer having a polymerizable functional group, and examples thereof include a compound having an ethylenically unsaturated group, a compound having two or more ring-opening polymerizable groups in the molecule, a compound containing two or more isocyanate groups in the molecule, and a compound containing two or more oxazoline groups in the molecule.

[0061] The compound having an ethylenically unsaturated group is not particularly limited, and examples thereof include compounds having a radical curable group and / or an addition curable group such as an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, an allyl group, or a vinyl group or a maleimide group. Specific examples thereof 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; vinyl thioethers such as bis(4-vinylthiophenyl) sulfide and phenyl vinyl 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 di(meth)acrylates having a fluorene skeleton such as tris[2-(meth)acryloyloxyethyl]triazinebenzyl(meth)acrylate, phenoxyethyl(meth)acrylate, (1-naphthyl)methyl(meth)acrylate, 2-naphthalene(meth)acrylic acid, (decahydro-1,4:5,8-dimethanonaphthalen)-2-yl(meth)acrylate, 4-phenylbenzyl(meth)acrylate, biphenylmethyl such as 2-phenylbenzyl(meth)acrylate Bisphenol A (meth)acrylate, bisphenol A-(EO)-(meth)acrylate, bisphenol S (meth)acrylate, bisphenol S-(EO)-(meth)acrylate Examples of the (meth)acrylic monomers include sulfur-containing (meth)acrylates such as bis(4-methacryloylthiophenyl)sulfide, 1H,1H,2H,2H-heptafluorodecyl (meth)acrylate, and (meth)acrylic monomers having an adamantyl skeleton; triallyl cyanurate; glycidyl (meth)acrylate; and 3,4-epoxycyclohexylmethyl methacrylate.

[0062] The compound having two or more ring-opening polymerizable groups in the molecule is not particularly limited, and examples thereof include compounds having ring-opening polymerizable groups such as an epoxy group, an oxetane group, an ethylene sulfide group, and an aziridine group. Specific examples thereof include aromatic epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene-based epoxy compounds, and aromatic epoxy compounds having a bromo substituent; aliphatic epoxy compounds such as those obtained by a condensation reaction of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol (PEG600) with epihalohydrin; alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epsilon-caprolactone-modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, and bis-(3,4-epoxycyclohexyl)adipate; hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, and hydrogenated bisphenol F type epoxy compounds. hydrogenated epoxy compounds such as epoxide compounds, aliphatic oxetane compounds such as 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane and dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether; phenol novolak oxetane, dioxetane compounds having a biphenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) OXBP), dioxetane compounds having a phenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) OXTP), dioxetane compounds having a fluorene skeleton, aromatic oxetane compounds such as tungstate compounds; aliphatic episulfide compounds such as bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, and 1,3-bis(2,3-epithiopropylthio)cyclohexane; aromatic episulfide compounds such as 1,2-bis(2,3-epithiopropylthio)benzene and 1,3-bis(2,3-epithiopropylthio)benzene; and mercapto group-containing epithio compounds such as 3-mercaptopropylene sulfide and 4-mercaptobutene sulfide.

[0063] The compound containing two or more isocyanate groups in the molecule is not particularly limited, and examples thereof include aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine triisocyanate, and xylylene diisocyanate; alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and 4,9-bis(isocyanatomethyl)tricyclodecane; aromatic polyisocyanate compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenylsulfide-4,4-diisocyanate, and phenylene diisocyanate; and heterocyclic polyisocyanate compounds such as 4,5-bis(isocyanatomethyl)-1,3-dithiolane. Examples include aliphatic polyisothiocyanate compounds such as bis(isothiocyanatoethyl) disulfide; alicyclic polyisothiocyanate compounds such as 3,9-bis(isothiocyanatomethyl)tricyclodecane and 4,8-bis(isothiocyanatomethyl)tricyclodecane; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate; and sulfur-containing heterocyclic polyisothiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-bis(isothiocyanatomethyl)thiophene.

[0064] Examples of compounds containing two or more oxazoline groups in the molecule include 2,2'-(1,3-phenylene)bis-(2-oxazoline) and oxazoline group-containing polymers such as EPOCROS (registered trademark) manufactured by Nippon Shokubai.

[0065] The polymerizable monomer is preferably a compound having an ethylenically unsaturated group, more preferably a compound having a (meth)acrylic group, and even more preferably a (meth)acrylic monomer having an aromatic group.

[0066] The surface tension of the polymerizable monomer is not particularly limited, but is preferably 20 to 60 mN / m, more preferably 25 to 55 mN / m, and even more preferably 30 to 45 mN / m. The surface tension of the polymerizable monomer can be measured, for example, using an automatic surface tensiometer DY-300 (manufactured by Kyowa Interface Science Co., Ltd.), and the surface tension can be calculated by the Wilhelmy method. Measurement is performed at 25°C and evaluation is performed. When the polymerizable composition contains only one type of polymerizable monomer, the surface tension refers to the surface tension of that polymerizable monomer. When the polymerizable composition contains two or more types of polymerizable monomers, the surface tension refers to the surface tension of the mixture of the polymerizable monomers contained. The same applies to the surface tension (y) of the polymerizable monomers described below.

[0067] In the above-mentioned method for producing a patterned film, when the surface tension of the polymerizable monomer in the polymerizable composition is x mN / m, the surface tension (y) of the mold surface is preferably x+1 mN / m or more. This provides better affinity with the mold surface, allowing the effects of the present invention to be more fully exhibited. y is more preferably x+2 to x+20 mN / m, and even more preferably x+5 to x+15 mN / m.

[0068] <Dispersant> The dispersant contained in the polymerizable composition is not particularly limited as long as it is a compound that exhibits dispersibility in inorganic particles, but it is preferable that the dispersant contains a compound having a polar functional group.

[0069] The polar functional group is not particularly limited, but is preferably a neutral or acidic polar functional group. Preferred examples of the neutral or acidic polar functional group include a sulfinyl group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group, a carboxy group, an alkoxysilyl group, and a hydroxyl group, and more preferred examples are a sulfinyl group, a phosphoric acid group, a phosphoric acid ester group, a carboxy group, and an alkoxysilyl group. In one embodiment, the dispersant preferably comprises at least one selected from the group consisting of sulfur-based dispersants having a sulfinyl group, phosphate-based dispersants having a phosphate group and / or phosphate ester group, carboxylic acid-based dispersants having a carboxy group, and silane-based dispersants having an alkoxysilyl group. More preferred examples of the polar functional group include a sulfinyl group, a phosphate group, and a phosphate ester group. In one preferred embodiment of the present invention, the polymerizable composition contains, as the dispersant, a dispersant having a sulfinyl group and a dispersant having a phosphate group and / or a phosphate ester group.

[0070] The molecular weight of the dispersant (weight average molecular weight when the dispersant is a polymer) is not particularly limited, but is preferably, for example, 98 to 5,000. It is more preferably 150 to 3,500, and even more preferably 200 to 3,000. When the dispersant is a polymer, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0071] (Sulfonic acid dispersant) The sulfonic acid dispersant having the sulfonic acid group is not particularly limited, but examples thereof include polymers of sulfonic acid group-containing monomers and derivatives thereof, such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidoethanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-methacrylamidopropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, allyloxybenzenesulfonic acid, and 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid. Derivatives include conventionally known compounds such as esters and salts.

[0072] (carboxylic acid dispersant) The carboxylic acid dispersant having a carboxy group is not particularly limited, but examples thereof 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 esters, and ammonium salts, organic amine salts, and alkali metal salts thereof.

[0073] (Dispersant having a hydroxyl group) The dispersant having a hydroxyl group is not particularly limited, and examples thereof include polyvinyl alcohol, polyethylene glycol, and polyethylene glycol monoalkyl ethers such as polyethylene glycol monomethyl ether.

[0074] (Silane-based dispersant) The silane-based dispersant having an alkoxysilyl group is not particularly limited, and examples thereof include 3-(trimethoxysilyl)propyl methacrylate, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and γ-glycidoxypropyltrimethoxysilane.

[0075] (sulfur-based dispersant) An embodiment in which the polymerizable composition contains a sulfur-based dispersant having a sulfinyl group is one of the preferred embodiments of the present invention. The sulfur-based dispersant having a sulfinyl group is not particularly limited, but may be selected from the group consisting of sulfur-based dispersants having the following formula (1):

[0076] [ka]

[0077] (In the formula, X 1 represents a divalent aromatic hydrocarbon group which may have a substituent. A sulfur-containing polymer having a structural unit (U1) represented by: is preferred. The sulfur-containing polymer is not particularly limited as long as it has a structural unit represented by the above formula (1). It may have one or more structural units (U1), but it preferably has a plurality of structural units (U1). It is more preferable that the structural unit (U1) is a repeating unit, and it is even more preferable that the structural unit (U1) is a repeating unit.

[0078] In the above formula (1), X 1represents a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a triphenylene group, a biphenylene group, and a phenanthrylene group. Among these, the divalent aromatic hydrocarbon group is preferably a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, or a triphenylene group, and more preferably a phenylene group, in terms of further reducing the light dispersion of the polymer.

[0079] Above X 1 The substituent (also referred to as "substituent α") that the divalent aromatic hydrocarbon group represented by the formula (I) may have is not particularly limited, but preferably includes a reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing hydrocarbon group that may have a substituent (also referred to as "substituent β").

[0080] Examples of the reactive functional group include an acidic functional group, a basic functional group, a curable functional group, and groups containing these functional groups. Examples of the acidic functional group include a carboxyl group (-COOH), a phosphate group (-OPO(OH)), a hydroxyl group (-OH), a sulfo group (-SOH), a phosphonic acid group (-PO(OH)), and a phosphinic acid group (-PO(OH)-). Examples of the basic functional group include an amino group, an ammonium group, an imino group, an amide group, an imide group, and a maleimide group. Examples of the curable functional group include a group having a reactive unsaturated bond, such as a group having a reactive double bond, such as a vinyl group, a (meth)acryloyl group, an allyl group, or a methallyl group; a group having a reactive ionic bond, such as a group having a reactive cyclic ether group, such as an epoxy group or an oxetane group; and a mercapto group (-SH).

[0081] Examples of the groups containing these functional groups include groups having the above-mentioned acidic functional group, basic functional group, or curable functional group and a hydrocarbon chain or a bonding group. That is, in the present invention, the reactive functional group includes not only the above-mentioned acidic functional group, basic functional group, or curable functional group, but also groups containing these functional groups and a bonding chain. 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 said that a carboxy group is preferred as the reactive functional group, it means that a carboxy group and / or a group containing a carboxy group is preferred as the reactive functional group.

[0082] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a bromine atom being preferred. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a heptyl group, etc. The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0083] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, a phenoxy group, a cyclohexyloxy group, a benzyloxy group, etc. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and even more preferably a methoxy group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a triphenyl group. Of these, a 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.

[0084] Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenyloctyl group, etc. The aralkyl group preferably has 7 to 14 carbon atoms, and more preferably 7 to 9 carbon atoms. Examples of the sulfur-containing hydrocarbon group include an alkylthio group, an arylthio group, etc. The sulfur-containing hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0085] The alkyl group, alkoxy group, aryl group, aralkyl group, and sulfur-containing hydrocarbon group may further have a substituent (substituent β). Examples of the substituent β include an alkyl group, a halogen atom, and the like, and preferred forms thereof are the same as those of the alkyl group, halogen atom, and the like as the substituent α.

[0086] Among the above-mentioned substituents α, from the viewpoint of easily improving the solubility of the sulfur-containing polymer in the solvent described later, an alkyl group is preferred, an alkyl group having 1 to 18 carbon atoms is more preferred, an alkyl group having 1 to 6 carbon atoms is even more preferred, and a methyl group is particularly preferred. Furthermore, as the substituent α, the above-mentioned curable functional groups are preferred, and a mercapto group is particularly preferred. When a sulfur-containing polymer has a mercapto group as the substituent α, it is likely to have excellent reactivity such as curing reactivity and a high refractive index. When a sulfur-containing polymer having these functional groups or groups containing these functional groups as substituents is used, a cured film having excellent heat resistance and solvent resistance tends to be easily obtained. As the group containing a mercapto group, a thioalkyl group or a thioaryl group is preferred, and a thioalkyl group is more preferred.

[0087] When the sulfur-containing polymer has mercapto groups, the amount thereof is not particularly limited, but the amount of mercapto groups is preferably 1 to 300 mol % relative to 100 mol % of all aromatic rings (all structural units), more preferably 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.

[0088] X 1 There is no particular limitation on the number of substituents α that the divalent aromatic hydrocarbon group represented by the formula (I) may have. The number may be appropriately selected for purposes such as adjusting the solubility of the sulfur-containing polymer in a solvent used in producing the polymerizable composition described below, or finely controlling the refractive index, etc. The number of the substituents is, for example, preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. There is no particular limitation on the position to which the substituent α is bonded in the divalent aromatic hydrocarbon group. When the structural unit (U1) has two or more substituents α, the types of the substituents α may be the same or different.

[0089] When the sulfur-containing polymer has a plurality of structural units (U1), the type of the divalent aromatic hydrocarbon group, and the type, number, bonding position, etc. of the substituent α that the divalent aromatic hydrocarbon group may have in each structural unit (U1) may be the same or different. In the structural unit (U1), there are no particular restrictions on the position at which the sulfinyl group (—S(═O)—) is bonded to the divalent aromatic hydrocarbon group, the position at which the other main chain is bonded to the divalent aromatic hydrocarbon group, or the positional relationship between these.

[0090] When the sulfur-containing polymer has a plurality of structural units (U1), the position at which the sulfinyl group (-S(=O)-) in each structural unit (U1) is bonded to the divalent aromatic hydrocarbon group may be the same or different, and the position at which the other main chain is bonded to the divalent aromatic hydrocarbon group may be the same or different. Furthermore, the positional relationship between the position at which the sulfinyl group is bonded to the divalent aromatic hydrocarbon group in each structural unit (U1) and the position at which the other main chain is bonded to the divalent aromatic hydrocarbon group may be the same or different.

[0091] One preferred embodiment of the structural unit (U1) is, for example, the structural unit X 1 In one embodiment, the divalent aromatic hydrocarbon group represented by X is a phenylene group. 1 The structural unit (U1) in which the divalent aromatic hydrocarbon group represented by the following formula is a phenylene group is also referred to as a structural unit (U1-1). The phenylene group may or may not have a substituent (also referred to as "substituent α-1"). The type and preferred form of the substituent α-1 are the same as those of the substituent α.

[0092] The total number of substituents α-1 bonded to the phenylene group is an integer of 0 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. The position of the substituent α-1 is not particularly limited, and when the carbon atom of the phenylene group to which the sulfinyl group is bonded is considered to be position 1, the position of the substituent α-1 may be position 2, 3, or 4 of the phenylene group. Of these, position 4 or position 2 is preferred, and position 4 is more preferred.

[0093] In the structural unit (U1-1), when the carbon atom of the phenylene group to which the sulfinyl group is bonded is defined as the 1-position, the bonding position of the other main chain to the phenylene group is not particularly limited. It may be the 2-position, 3-position, or 4-position of the phenylene group. Of these, the 2-position or 3-position is preferred, and the 3-position is more preferred.

[0094] The sulfur-containing polymer preferably contains a plurality of the structural units (U1-1), preferably as repeating units, and more preferably as repeating units. When the sulfur-containing polymer contains a plurality of the structural units (U1-1), X in each structural unit (U1-1) 1 The type, number, and bonding position of the substituent α-1 bonded to the phenylene group represented by the formula (I), the bonding position of the sulfinyl group in the phenylene group, and the bonding position of the other main chain may be the same or different.

[0095] The sulfur-containing polymer may have at least one of the structural units (U1) as a structural unit. Thus, the sulfur-containing polymer may be a polymer consisting of only one or more structural units (U1), or may be a polymer containing the structural unit (U1) and a structural unit other than the structural unit (U1). The structural unit other than the structural unit (U1) is also referred to as an "other structural unit." The other structural units may be one type or two or more types.

[0096] The content of the structural unit (U1) in the sulfur-containing polymer is not particularly limited, but the content of the structural unit (U1) is preferably 1 to 100 moles per 100 moles of the total content of all structural units in the sulfur-containing polymer. It is more preferably 5 moles or more, and even more preferably 10 moles or more. Meanwhile, the upper limit is more preferably 98 moles or less, even more preferably 95 moles or less, and particularly preferably 90 moles or less. The same applies to the content of the structural unit (U1-1) in a preferred embodiment of the sulfur-containing polymer.

[0097] The other structural unit is not particularly limited, but is preferably a structural unit (U2) represented by the following formula (3) and / or a structural unit (U3) represented by the following formula (4).

[0098] [ka]

[0099] (In the formula, X2 represents a divalent aromatic hydrocarbon group which may have a substituent.

[0100] [ka]

[0101] (In the formula, X 3 represents a divalent aromatic hydrocarbon group which may have a substituent. That is, one preferred embodiment of the sulfur-containing polymer is a polymer that contains the structural unit (U1) and further contains the structural unit (U2) and / or the structural unit (U3).

[0102] X in the above structural unit (U2) 2 , X in the structural unit (U3) 3 The type of divalent aromatic hydrocarbon group represented by each of the following formulae, the type, number, bonding position, etc. of the substituent that the divalent aromatic hydrocarbon group may have, including preferred embodiments thereof, are determined by the X 1 and the type, number, bonding position, etc. of the substituent α that the divalent aromatic hydrocarbon group may have, and the explanation for the structural unit (U1) can be applied mutatis mutandis.

[0103] In one preferred embodiment of the structural unit (U2) and the structural unit (U3), the X 2 , the above X 3 In one embodiment, the divalent aromatic hydrocarbon group represented by X is a phenylene group. 2 , X 3Structural units in which the divalent aromatic hydrocarbon group represented by the following formula (I) is a phenylene group are also referred to as structural units (U2-1) and (U3-1). In structural units (U2-1) and (U3-1), the type, number, and bonding position of the substituent bonded to the phenylene group, the bonding position of the sulfide group or sulfonyl group in the phenylene group, and the bonding position of the other main chain, including preferred embodiments thereof, are the same as the type, number, and bonding position of the substituent α-1 bonded to the phenylene group, the bonding position of the sulfinyl group in the phenylene group, and the bonding position of the other main chain, in structural unit (U1-1), and the explanation for structural unit (U1-1) can be applied mutatis mutandis.

[0104] The sulfur-containing polymer may contain a plurality of the structural units (U2-1) and / or the structural units (U3-1), or may contain them as a repeating unit. When the sulfur-containing polymer contains a plurality of the structural units (U2-1) and / or the structural units (U3-1), X in each of the structural units (U2-1) and (U3-1) may be substituted or unsubstituted. 2 , X 3 The types, numbers, and bonding positions of the substituents bonded to the phenylene groups represented by the following formula (I), the bonding positions of the sulfide group and sulfonyl group in the phenylene group, and the bonding positions of the other main chain may be the same or different.

[0105] In the sulfur-containing polymer, the total content of the structural units (U1), (U2), and (U3) is not particularly limited, but the total content is preferably 1 to 100 moles per 100 moles of the total content of all structural units, more preferably 30 moles or more, even more preferably 50 moles or more, and even more preferably 80 moles or more.

[0106] In the sulfur-containing polymer, the preferred range of the content of the structural unit (U1) relative to the total content of all structural units (100 moles) is as described above, but it is preferable that the remainder be the total content of the structural units (U2) and (U3). When the structural units (U1), (U2), and (U3) in the sulfur-containing polymer are structural units (U1-1), (U2-1), and (U3-1), respectively, the preferred range of the total content of the structural units (U1-1), (U2-1), and (U3-1) per 100 moles of all structural units is the same as the preferred range of the total content of the structural units (U1), (U2), and (U3).

[0107] In the sulfur-containing polymer, the content of the structural unit (U2) is not particularly limited, but is preferably 0 to 9,900 moles per 100 moles of the structural unit (U1). It is more preferably 0.01 mole or more, even more preferably 1.0 mole or more, and particularly preferably 5 moles or more. Meanwhile, 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. When the structural unit (U2) in the sulfur-containing polymer is the structural unit (U2-1), the preferred range for the content of the structural unit (U2) is the same as that for the content of the structural unit (U2).

[0108] In the sulfur-containing polymer, the content of the structural unit (U3) is not particularly limited, but is preferably 0 to 9,900 moles per 100 moles of the structural unit (U1). It is more preferably 0.01 mole or more, even more preferably 1.0 mole or more, and particularly preferably 5 moles or more. Meanwhile, 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. When the structural unit (U3) in the sulfur-containing polymer is the structural unit (U3-1), the preferred range for the content of the structural unit (U3-1) is the same as that for the content of the structural unit (U3).

[0109] The method for producing the sulfur-containing polymer is not particularly limited. For example, a production method including a polymerization step of oxidatively polymerizing a monomer component containing an aromatic disulfide compound and / or an aromatic thiol compound is preferred. 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 production method allows for efficient production of a sulfur-containing polymer having the structural unit (U1).

[0110] The polymerization step is a step of oxidatively polymerizing a monomer component containing an aromatic disulfide compound and / or an aromatic thiol compound, and can produce a polymer containing at least a plurality of structural units (U2) as repeating units. The oxidative polymerization can be carried out in a state in which the monomer components are heated and melted, but is preferably carried out in a composition in which the monomer components are dispersed or dissolved in a solvent. The composition, i.e., a composition containing the monomer components and a solvent, is also referred to as a raw material composition, and the composition from the start of the polymerization reaction to the end of the polymerization reaction is also referred to as a reaction composition. The composition obtained by the polymerization reaction is also referred to as a polymer composition.

[0111] The monomer component includes an aromatic disulfide compound and / or an aromatic thiol compound, and among these, it is preferable to include an aromatic disulfide compound. The aromatic disulfide compound is more preferably a diaryl disulfide compound represented by the following formula (5), and the aromatic thiol compound is more preferably a thioaryl compound represented by the following formula (6).

[0112] [ka]

[0113] (In formulas (5) and (6), A 1 and A 2 are the same or different and represent monovalent aromatic hydrocarbon groups which may have a substituent. A 1 and A 2Examples of the monovalent aromatic hydrocarbon group represented by the formula (I) include a phenyl group, a naphthyl group, an anthryl group, a triphenyl group, a biphenyl group, and a phenanthryl group. Of these, a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, or a triphenyl group is preferred, and a phenyl group is more preferred. 1 and A 2 The substituent that the monovalent aromatic hydrocarbon group represented by the formula (1) may have is, for example, X 1 The number of the substituents and the bonding positions to the aromatic hydrocarbon group can be determined by the same factors as those of X in the above formula (1). 1 The same applies to the substituents that the divalent aromatic hydrocarbon group represented by the following formula may have.

[0114] The diaryl disulfide compound is preferably a diphenyl disulfide compound, and the thioaryl compound is preferably a benzenethiol compound. Among these, a diphenyl disulfide compound is preferred. These compounds may have a substituent, and the type of the substituent is the same as that of the diaryl disulfide compound and the thioaryl compound.

[0115] The number of substituents that the diphenyl disulfide compound can have is 0 to 10, preferably 1 to 8, more preferably 2 to 6, and even more preferably 2 to 4. The bonding position of the substituent to the phenyl group in the diphenyl disulfide compound is not particularly limited, but preferably includes the para-position (4th position) relative to the carbon atom (1st position) to which the disulfide group is bonded. The number of substituents that the benzenethiol compound can have is 0 to 5, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. The bonding position of the substituent to the phenyl group in the benzenethiol compound is not particularly limited, but preferably includes the para-position (4th position) relative to the carbon atom (1st position) to which the mercapto group is bonded.

[0116] Specific examples of the diphenyl sulfide compound include 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, 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'-hexa Ethyl diphenyl disulfide, 2,2',3,3',6,6'-hexaethyl diphenyl disulfide, 2,2',3,3',5,5',6,6'-octaethyl diphenyl disulfide, 2,2'-dipropyl diphenyl disulfide, 3,3'-dipropyl diphenyl disulfide, 2,2',6,6'-tetrapropyl diphenyl disulfide, 2,2',3,3'-tetrapropyl diphenyl disulfide, 2,2',5,5'-tetrapropyl diphenyl disulfide, 3,3',5,5'-tetrapropyl diphenyl 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',5,Examples include 5'-tetraisopropyldiphenyl disulfide, 2,2',3,3',5,5'-hexaisopropyldiphenyl disulfide, 2,2',3,3',6,6'-hexaisopropyldiphenyl disulfide, and 2,2',3,3',5,5',6,6'-octaisopropyldiphenyl disulfide.

[0117] Specific examples of the benzenethiol compound include 3-methylbenzenethiol, 2-methylbenzenethiol, 4-methylbenzenethiol, thiophenol (benzenethiol), 2,3-dimethylbenzenethiol, 2,5-dimethylbenzenethiol, 2,6-dimethylbenzenethiol, and 3,5-dimethylbenzenethiol.

[0118] The disulfide compound can also be prepared by oxidation of a thiol compound. Therefore, in the polymerization step, a thiol compound can also be used as a precursor of the disulfide compound. A disulfide compound can be obtained by oxidatively bonding two molecules of a thiol compound. The method for oxidatively bonding is not particularly limited, and known methods can be used.

[0119] The oxidative polymerization is not particularly limited, but is preferably oxidative polymerization using a quinone compound or oxidative polymerization using a catalyst. From the viewpoint of reducing the amount of waste liquid, oxidative polymerization using a catalyst is more preferred. For oxidative polymerization using a catalyst, for example, it is more preferred 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 catalyst is not particularly limited, but is preferably a substance containing a metal element such as vanadium (V), zirconium (Zr), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), or iron (Fe), and one or more of these may be used in combination.

[0120] Among the above-mentioned substances containing metal elements, substances containing vanadium or iron as a metal element (also referred to as vanadium-containing substances and iron-containing substances, respectively) are preferred due to their high catalytic activity toward oxidative polymerization, with iron-containing substances being more preferred. Preferred vanadium-containing substances include vanadium-containing metals and oxovanadium compounds having a V=O bond within the vanadium compound molecule. Examples of the oxovanadium compounds include vanadyl acetylacetonate, oxovanadium salen complex, N,N'-bissalicylideneethylenediamine oxovanadium, phthalocyanine oxovanadium, and tetraphenylporphyrin oxovanadium. Preferred iron-containing substances are iron compounds having chlorine atoms within the molecule. Furthermore, iron-containing compounds with an oxidation number of 3 or more are preferred. Examples of such iron-containing substances include ferric chloride (Fe(Cl)3), 5,10,15,20-tetraphenyl-21H,23H-porphine iron(III) chloride, and iron(III) trifluoromethanesulfonate.

[0121] The amount of the catalyst used in the polymerization 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 %. From the viewpoint that the influence of catalyst residue on physical properties tends to be small, the amount is preferably 30 mol % or less, more preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less. From the viewpoint that a sulfur-containing polymer with a high molecular weight is easily obtained, the amount is more preferably 0.01 mol % or more, even more preferably 0.1 mol % or more, and particularly preferably 1 mol % or more.

[0122] The polymerization is preferably carried out in the presence of oxygen. By carrying out the polymerization in the presence of oxygen, the oxidative polymerization reaction is promoted. Therefore, the polymerization is preferably carried out under the supply of an oxygen-containing gas. For example, a method of supplying an oxygen-containing gas to the gas phase during the polymerization reaction, or a method of bubbling an oxygen-containing gas into the reaction composition during the polymerization reaction, etc., can be adopted. From the viewpoint of easily promoting the oxidative polymerization, a method of continuously supplying an oxygen-containing gas to the reaction composition during the polymerization reaction is preferred, and among these, a bubbling method is preferred.

[0123] The oxygen-containing gas is preferably a gas containing oxygen molecules (O2). The oxygen-containing gas may contain gas components other than oxygen molecules (O2). The gas components other than oxygen molecules (O2) contained in the oxygen-containing gas are not particularly limited, but preferably include rare gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn); and inert gases such as nitrogen (N2). In addition to the above inert gases, carbon dioxide gas (CO2), water vapor, etc. may also be contained. The content of oxygen molecules (O2) in the oxygen-containing gas is not particularly limited, but at room temperature (25°C) and under 1 atmosphere, the volume ratio of oxygen molecules (O2) in 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, it is 10 to 30% by volume. The remainder of the oxygen-containing gas is, for example, an inert gas.

[0124] The oxygen-containing gas is not particularly limited, but examples thereof include oxygen gas, a mixed gas of oxygen and nitrogen, and air. From the viewpoint of economical efficiency, air is preferably used. The water vapor concentration in the oxygen-containing gas is not particularly limited, but is preferably 1000 g / m 3 Less than 10 g / m 3 Less than 1g / m is more preferable. 3 More preferably, 0.1 g / m or less 3 The following is most preferred, with dry air being preferred: The supply amount of the oxygen-containing gas is set to 1 / 3 of the total volume of the reaction composition from the viewpoint of accelerating the reaction rate and making it easy to control. 3 The oxygen (O2) supply rate per minute is 0.00002 m 3 / min~2m 3 / min, more preferably 0.0001 to 0.2 m 3 / min or more, and more preferably 0.0002 to 0.02 m 3 / min or more.

[0125] In the polymerization step, it is preferable to further use an acid and / or a salt thereof. By using the acid and / or a salt thereof 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 even in a short time. The acid is preferably a Bronsted acid, and particularly, an acid having an acid dissociation constant of -19 to 4 is preferred. More preferably, the acid dissociation constant is 3 or less and -8 or more. Examples of acids having 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. Of these, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, and persulfuric acid are preferred.

[0126] The salt of the acid is not particularly limited as long as it is a salt of the acid, but for example, salts of the acid with metal elements of Group 1 of the periodic table such as sodium and potassium, metal elements of Group 2 of the periodic table such as magnesium and calcium, ammonium, etc. are preferred. Among these, for example, sodium persulfate, ammonium persulfate, sodium toluenesulfonate, sodium trifluoromethanesulfonate, etc. are preferred. The acid and / or salt thereof may be used alone or in combination of two or more. The amount of the acid and / or salt thereof 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.

[0127] A solvent may be used in the polymerization. While the solvent is not particularly limited, preferred examples include 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. While the amount of the solvent used is not particularly limited, 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 components used as raw materials. Among the solvents, it is preferred to use non-halogen solvents such as N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, and cyclopentyl methyl ether.

[0128] The polymerization may be carried out at atmospheric pressure at a temperature below the boiling point of the solvent, under reflux conditions, or under pressure while heating to a temperature above the boiling point. The polymerization temperature is not particularly limited as long as it is a temperature at which oxidative polymerization proceeds. However, in terms of ease of carrying out the oxidative polymerization reaction using inexpensive equipment, it is preferably 0 to 250°C, more preferably 30°C or higher, and even more preferably 50°C or higher. The upper limit is preferably 200°C or lower, and even more preferably 180°C or lower. The polymerization time is not particularly limited, but 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.

[0129] When the diaryl disulfide compound represented by the above formula (5) and / or the thioaryl compound represented by the above formula (6) is used as a monomer component by the above-mentioned oxidative polymerization, the main chain is usually 1 , A 2 In other words, it is possible to obtain a composition (polymer composition) containing a polymer having one or more structural units selected from the group consisting of the structural units (U1), (U2), and (U3) above as structural units.

[0130] When oxidative polymerization is carried out under the above-mentioned preferred conditions in the polymerization step, a polymer having a relatively high content of the structural unit (U2) is likely to be 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.

[0131] If the polymer obtained by the above polymerization step is a polymer having a structural unit (U1) such as the structural unit (U1-1), then the polymer can be used as the above sulfur-containing polymer. For the purpose of increasing the proportion of the structural units (U1) and (U1-1) in the polymer obtained in the polymerization step, it is preferable to subject the polymer obtained in the polymerization step to an oxidation step. The oxidation step is a step in which the polymer obtained in the polymerization step is oxidized.

[0132] The oxidation step is a step of carrying out an oxidation reaction using an oxidizing agent. The oxidizing agent is not particularly limited, and known oxidizing agents can be used, such as quinone compounds, perbenzoic acid, metachloroperbenzoic acid, lead tetraacetate, thallium acetate, tetracyanoquinodimethane, tetracyanoethylene, cerium (IV) acetylacetonate, manganese (III) acetylacetonate, peroxides, chloric acid, hypochlorous acid, hypochlorite, and compounds capable of generating hypochlorous acid.

[0133] Among these, it is more preferable to use at least one compound selected from the group consisting of peroxides, chloric acid, hypochlorous acid, hypochlorites, and compounds capable of generating hypochlorous acid, because it can appropriately oxidize sulfur atoms (sulfide groups, -S-) contained on the main chain to form sulfinyl groups (-S(=O)-). Examples of the peroxides include metachloroperbenzoic acid, hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, and t-butyl hydroperoxide. The oxidizing agents may be used alone or in combination of two or more. The amount of the oxidizing agent added is preferably 0.01 to 1,000 mol, more preferably 0.05 to 500 mol, more preferably 0.1 to 100 mol, and even more preferably 0.2 to 20 mol, relative to 1 mol of sulfur atoms in the polymer (P).

[0134] The reaction temperature of the 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 progress of the oxidation reaction, and is more preferably 180°C or lower, and even more preferably 150°C or lower, from the viewpoint of facilitating the suppression of side reactions. The reaction time of the 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.

[0135] When it is desired to increase the content of sulfonyl groups (-S(-O)2-), the reaction can be carried out for a longer time than the above-mentioned reaction time. In this case, the amount of oxidizing agent added is not particularly limited as long as the desired oxidation reaction of sulfur atoms proceeds, but is usually preferably 0.01 to 1000 mol, more preferably 0.05 to 500 mol, still more preferably 0.1 to 100 mol, and even more preferably 0.5 to 20 mol, per mol of sulfur atoms in the polymer.

[0136] In the oxidation reaction, a solvent may be used, and preferred examples of the solvent used include the same solvents as those used in the polymerization step. The oxidation step makes it possible to obtain a polymer having a higher proportion of the structural unit (U1) than the polymer obtained in the polymerization step, and this polymer can be used as the sulfur-containing polymer.

[0137] As described above, a preferred embodiment of the sulfur-containing polymer is a polymer in which X in the structural unit (U1) 1 Examples of such a sulfur-containing polymer include a sulfur-containing polymer having a reactive functional group as a substituent at least one of which is a divalent aromatic hydrocarbon group constituting the main chain, such as a divalent aromatic hydrocarbon group represented by the formula (I). Methods for producing such a sulfur-containing polymer include a method using a diaryl disulfide compound or a thioaryl compound having a reactive functional group as a substituent as a monomer component in the polymerization step, and a production method including a step of introducing a reactive functional group (reactive functional group introduction step) before or after the oxidation step. From the viewpoint of producing a sulfur-containing polymer having a higher refractive index and 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 (mercapto group introduction step) before or after the oxidation step.

[0138] The mercapto group introduction step may be carried out by any method as long as it can introduce a mercapto group into the sulfur-containing polymer obtained in the polymerization step or further in the oxidation step. For example, a step of reacting a sulfonating agent with a reducing substance is preferred.

[0139] The sulfonating agent that can be used in the mercapto group introduction step is not particularly limited as long as it is a compound that can introduce a sulfonyl group into 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 the sulfonating agent used is not particularly limited, but it is preferably used in an amount of 0.1 to 10,000% by mass relative to 100% by mass of the polymer. The amount is more preferably 1% by mass or more, even more preferably 10% by mass or more, and more preferably 1,000% by mass or less, even more preferably 500% by mass or less.

[0140] The reducing substance that can be used in the mercapto group introduction step is not particularly limited, but preferred examples include metal or semimetal hydrides and their complex compounds (ate complexes), 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 ions and divalent tin ions; acid-based organic compounds such as formic acid and oxalic acid; phosphine-based 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 in the polymerization step remain, the heavy metals are easily removed, and a sulfur-containing polymer with reduced coloration 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 preferably used in an amount of 0.01 to 1000% by mass relative to 100% by mass of the polymer. It is more preferably 0.1% by mass or more, even more preferably 5% by mass or more, and more preferably 100% by mass or less, even more preferably 50% by mass or less.

[0141] In the mercapto group introduction step, the reaction is thought to proceed through a mechanism in which a sulfonyl group is introduced into 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 of mixing the sulfonating agent and reducing substance with the polymer is not particularly limited. For example, there are methods (1) in which a sulfonating agent is mixed with the polymer to introduce sulfonyl groups into the divalent aromatic hydrocarbon groups, and then a reducing substance is mixed with the polymer into which sulfonyl groups have been introduced to reduce the introduced sulfonyl groups to mercapto groups; a method in which the sulfonating agent and reducing substance are mixed with the polymer substantially simultaneously; and a method in which the reducing substance is first mixed with the polymer, and then the sulfonating agent is mixed. Among these, method (1) is preferred.

[0142] The reaction in the mercapto group introduction step is preferably carried out in a solvent, and examples of the solvent include 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 may be used. Among these, sulfoxide solvents are more preferred, and sulfolane is even more preferred. The amount of the solvent used is not particularly limited, but 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 the polymer used in the mercapto group introduction step.

[0143] The reaction temperature in the mercapto group introduction step is not particularly limited as long as it is a temperature at which the sulfonation reaction and reduction reaction proceed, but is preferably −20 to 250° C., more preferably −5° C. or higher, and even more preferably 5° C. or higher. From the viewpoint of suppressing side reactions, it is more preferably 150° C. or lower, and even more preferably 80° C. or lower. The reaction time for the reaction is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.5 hours or higher, and even more preferably 2 hours or higher. From the viewpoint of excellent productivity, it is more preferably 50 hours or lower, and even more preferably 20 hours or lower.

[0144] The sulfur-containing polymer can be obtained by the above-mentioned production method. However, the polymer composition obtained by the polymerization step contains impurities, such as the solvent used in the polymerization step and the catalyst residue (catalyst residue). Furthermore, the polymer or polymer-containing composition obtained by the oxidation step may contain residual acids. Because these impurities can affect the heat resistance of the patterned film of the present invention, it is preferable to isolate the sulfur-containing polymer and reduce these impurities. Therefore, the production method of the sulfur-containing polymer preferably further includes a purification step.

[0145] As the purification method used in the purification step, a conventionally known purification method can be used. For example, it is preferable to use a reprecipitation method. The reprecipitation method is not particularly limited, but examples include a method in which the polymer composition is dropped into hydrochloric acid-acidified methanol to precipitate the polymer, which is then filtered to obtain a precipitate, and the obtained precipitate is washed with water or a lower alcohol such as methanol. As the purification step, a method using a conventionally known 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 a combination of the reprecipitation method and a method using an adsorbent.

[0146] The method for producing the sulfur-containing polymer may include other steps in addition to the polymerization step, oxidation step, reactive functional group introduction step, and purification step. Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a solvent substitution step, and a dissolution step. These steps can be carried out by known methods. The sulfur-containing polymer can be obtained by the above-mentioned production method.

[0147] (Phosphate-based dispersants having phosphate groups and / or phosphate ester groups) An embodiment in which the polymerizable composition contains a phosphoric acid-based dispersant (hereinafter also referred to as a phosphoric acid-based compound) having a phosphoric acid group and / or a phosphoric acid ester group is one of the preferred embodiments of the present invention. The phosphoric acid compound is not particularly limited as long as it has a phosphoric acid group and / or a phosphoric acid ester group, but may be selected from compounds represented by the following formula (2):

[0148] [ka]

[0149] (In the formula, R 1 are the same or different and represent a hydrogen atom or an organic group. 2 are the same or different and represent an alkylene group having 2 to 20 carbon atoms. a is an integer of 1 to 3. n is an integer of 0 to 20. Preferably, the compound is a compound represented by the following formula:

[0150] In the above formula (2), R 1 are the same or different and each represents a hydrogen atom or an organic group, preferably an organic group. The organic group is not particularly limited, but examples thereof include hydrocarbon groups which may have a heteroatom. The number of carbon atoms in the organic group is not particularly limited, but is preferably 1 to 20. It is more preferably 1 to 16, even more preferably 1 to 12, still more preferably 1 to 8, and particularly preferably 1 to 4. Examples of the hydrocarbon group in the organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms.

[0151] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, a neopentyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a t-amyl group, a 1,3-dimethylbutyl group, and a 3,3-dimethylbutyl group. 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 icosyl 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.

[0152] Examples of the alkenyl group include a vinyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, and an icosenyl group. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group, and an icosynyl group.

[0153] Examples of the aryl group include a phenyl group, an o-, m- or p-tolyl group, a 2,3- or 2,4-xylyl group, a mesityl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, and a benzhydryl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group.

[0154] The hydrocarbon group may have a heteroatom and may have a substituent such as a carbonyl group, an amide group, an ether group, an ester group, a hydroxyl group, or a thioether group. The substituent is preferably a carbonyl group, an amide group, an ether group, an ester group, or a hydroxyl group, and more preferably a carbonyl group. An embodiment 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.

[0155] The organic group is preferably an alkyl group or an alkenyl group, and more preferably a linear alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, or an n-octyl group; a branched alkyl group having 1 to 8 carbon atoms, such as an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, a neopentyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a t-amyl group, a 1,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a 2-ethyl-2-methylpropyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 1,5-dimethylhexyl group, or a t-octyl group; or an alkenyl group, such as a vinyl group, an allyl group, or an isopropenyl group.

[0156] In the above formula (2), −(R 2 The oxyalkylene group represented by (O)- is an oxyalkylene group having 2 to 20 carbon atoms, and when two or more types of oxyalkylene groups are present, they may be added in any form such as random addition, block addition, or alternating addition. Above -(R 2 The oxyalkylene group represented by — is preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 4 carbon atoms. 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, styrene oxide, etc. Ethylene oxide, propylene oxide, and butylene oxide are more preferred, and ethylene oxide and propylene oxide are even more preferred.

[0157] In the above formula (2), −(R 2 When the oxyalkylene group represented by (O)- contains an oxyethylene group to which ethylene oxide is added, the content of oxyethylene groups is preferably 50 to 100 mol % relative to 100 mol % of all oxyalkylene 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 %.

[0158] In the above formula (2), a is an integer of 1 to 3. Preferably, a is 1 or 2. The polymerizable composition may contain two or more of a phosphoric acid monoester in which a is 1, a phosphoric acid diester in which a is 2, and a phosphoric acid triester in which a is 3 in formula (2), and an embodiment containing a phosphoric acid monoester and a phosphoric acid diester is one of the preferred embodiments of the present invention.

[0159] In the above formula (2), n is an integer of 0 to 20. n is preferably 1 to 15, more preferably 2 to 10, still more preferably 3 to 8, and particularly preferably 3 to 6. When the phosphoric acid compound has an oxyalkylene group, the affinity with the solvent is further improved, and the dispersibility of the inorganic particles is further increased.

[0160] The phosphoric acid compound preferably has a molecular weight of 98 to 2000. When the molecular weight of the phosphoric acid compound is within this range, it can penetrate more thoroughly into the fine gaps between the inorganic particles, further improving dispersibility. The molecular weight of the phosphoric acid compound is more preferably 150 to 1500, and even more preferably 200 to 1000. The molecular weight of the phosphoric acid compound can be measured by high performance liquid chromatography (HPLC) or gel permeation chromatography (GPC).

[0161] <Solvent> The polymerizable composition may contain a solvent. While the solvent is not particularly limited, it is preferable to use one that has excellent solubility for the dispersant. Examples of the solvent 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 solvents may be used. Among these, non-halogenated solvents are preferred, and among these, it is more preferred to include at least one solvent selected from the group consisting of cyclohexanone, cyclopentanone, propylene glycol monomethyl ethyl ether acetate, methyl ethyl ketone, toluene, xylene, tetrahydrofuran, N-methylpyrrolidone, etc.

[0162] The amount of the solvent in the polymerizable composition is not particularly limited, but is preferably 20 to 1,000 parts by mass, more preferably 60 to 400 parts by mass, and even more preferably 100 to 250 parts by mass, relative to 100 parts by mass of the total content of the inorganic particles and dispersant.

[0163] <Other ingredients> The polymerizable composition may contain other components in addition to the inorganic particles, polymerizable monomer, dispersant, and solvent. Other ingredients include the above-mentioned surface conditioners, polymerization initiators, photosensitizers, UV absorbers, light stabilizers, pigments, dyes, antioxidants, resins, reactive diluents, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, adhesion improvers such as coupling agents, heat stabilizers, antibacterial and anti-mold agents, flame retardants, matting agents, defoaming agents, leveling agents, wetting and dispersing agents, anti-settling agents, thickeners and anti-sagging agents, anti-color separation agents, emulsifiers, anti-slip and anti-scratch agents, anti-skinning agents, drying agents, anti-fouling agents, anti-static agents, conductive agents (electrostatic aids), etc. The polymerization initiator is not particularly limited, and a conventionally known thermal polymerization initiator or photopolymerization initiator can be appropriately selected and used. Examples thereof include aminobenzoate-based initiators, acetophenone-based initiators, benzoin-based initiators, benzophenone-based initiators, acylphosphine oxide-based initiators, oxime ester-based initiators, and cationic initiators. The polymerization initiator may be commercially available, and examples thereof include aminobenzoate-based initiators such as "Esacure A198," "Omnipol ASA," "Omnirad EDB," and "Omnirad EHA" manufactured by IGM Resins, and "GENOPOL AB-1" and "GENOPOL AB-2" manufactured by Rahn AG; acetophenone-based initiators such as "Omnirad 1173," "Omnirad 127," "Esacure KIP 150," "Esacure KIP 160," and "Omnirad 184" manufactured by IGM Resins; acylphosphine oxide-based initiators such as "Omnirad TPO," "Omnirad TPO-L," and "Omnirad 819" manufactured by IGM Resins; and Omnirad 1312, Omnirad 1314, and Omnirad 1315 manufactured by IGM Resins. Examples of initiators include oxime ester initiators such as "Omnicat 1316" manufactured by IGM Resins, and cationic initiators such as "Omnicat 250" and "Omnicat 432" manufactured by IGM Resins. The content of the polymerization initiator is not particularly limited, but 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, relative to 100% by mass of the polymerizable monomer.

[0164] The photosensitizer is not particularly limited, and any conventionally known photosensitizer can be appropriately selected and used. Examples include thioxanthone-based photosensitizers such as "Omnirad ITX," "Omnirad DETX," and "Omnirad DETX," manufactured by IGM RESINS, and coumarin-based photosensitizers such as "Esacure3644." The content of the photosensitizer is not particularly limited, but 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, relative to 100% by mass of the polymerizable monomer.

[0165] The ultraviolet absorber is not particularly limited, and any conventionally known ultraviolet absorber can be appropriately selected and used. Examples thereof 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.

[0166] The light stabilizer is not particularly limited, and a conventionally known light stabilizer can be appropriately selected and used. Examples thereof include ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77, ADK STAB LA-81, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-402XP, ADK STAB LA-502XP (all manufactured by ADEKA Corporation), and TINUVIN 11. Examples of such an agent 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-piperidylsebacate), and Tinuvin 5100 (all manufactured by BASF).

[0167] <<Method of producing polymerizable composition>> The method for producing the polymerizable composition used in the method for producing a patterned film of the present invention is not particularly limited, but it is preferable to carry out a step of crushing aggregates of inorganic particles (hereinafter also referred to as a crushing step) and a step of mixing the inorganic particle-containing composition obtained in the crushing step with a polymerizable monomer.

[0168] The above-mentioned disintegration step is not particularly limited as long as it disintegrates aggregates of inorganic particles, but is preferably carried out in the presence of a dispersant. The preferred form of the dispersant in the disintegration step is as described for the polymerizable composition, and the preferred amount of the dispersant used is the same as the preferred range of the content ratio of the dispersant to the inorganic particles in the polymerizable composition.

[0169] The disintegration step may be carried out without using a solvent, but is preferably carried out in the presence of a solvent. In this case, there is a tendency that the temperature rise due to disintegration is suppressed and disintegration can be carried out under mild temperature conditions. The preferred form of the solvent is as described in the polymerizable composition, and the preferred amount of the solvent to be used is the same as the preferred range of the content ratio of the solvent to the inorganic particles and dispersant in the polymerizable composition.

[0170] The inorganic particle agglomerates used in the disintegration step refer to particles formed by agglomeration of inorganic particles. In the inorganic particle agglomerates, a plurality of inorganic particles exist as primary particles, and these particles are agglomerated. The inorganic particles contained in the aggregate of inorganic particles (the inorganic particles constituting the aggregate of inorganic particles) are not particularly limited as long as they are particles containing an inorganic component as a main component. The inorganic components are the same as those described in the polymerizable composition, and the preferred forms are also the same as those described in the polymerizable composition.

[0171] The inorganic particle aggregates used in the above-mentioned crushing step preferably have an average primary particle diameter (D1) of 1 to 50 nm. When such inorganic particle aggregates are crushed to a diameter close to the average primary particle diameter (D1), the resulting patterned film has better 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) of the aggregates of inorganic particles used in the above-mentioned disintegration step are the same as those for the inorganic particles described in the polymerizable composition.

[0172] The average secondary particle diameter (D2) of the inorganic particle aggregates 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 obtained inorganic particle-containing composition tends 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.

[0173] The inorganic particle aggregates preferably have an aggregation degree (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, but the aggregation degree (R) is more preferably 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. Cohesion degree (R) = average secondary particle diameter (D2) / average primary particle diameter (D1) In the above formula, the average primary particle diameter (D1) and the average secondary particle diameter (D2) use the same unit (for example, nm).

[0174] The specific surface area of ​​the aggregate of the inorganic particles is not particularly limited, but is preferably 1 to 300 m 2 / g, more preferably 10 to 200m 2 / g, more preferably 15 to 150m 2 / g. The specific surface area of ​​the aggregate of inorganic particles is a value measured by the BET method, and specifically, can be measured by the method described in the examples.

[0175] The structure of the inorganic particle aggregate is not particularly limited and may be a porous structure or a dense structure. It may also be hollow. The shape of the inorganic particle aggregate is not particularly limited and may be any of amorphous, granular, plate-like, columnar, needle-like, etc., but granular is preferred, and among granular shapes, spherical is preferred. The granular shape refers to a uniform shape with an aspect ratio of 1.5 or less.

[0176] The method for producing the aggregates of inorganic particles used in the above-mentioned crushing step is not particularly limited, and they can be produced by, for example, a conventionally known wet method, dry method, or the like. Specific examples of preferred methods include solid-phase synthesis methods in which metal oxide particles are obtained by thermally decomposing a solid raw material, such as the thermal decomposition of oxalates; liquid-phase synthesis methods such as a method in which a metal alkoxide is subjected to hydrolysis and condensation reaction in an organic solvent, or a method in which a metal hydroxide or oxide is precipitated in an alkaline aqueous solution from an inorganic metal salt, such as a metal nitrate, sulfate, or chloride; a method in which the metal hydroxide or metal oxide obtained by the liquid-phase synthesis method is calcined at a high temperature; and gas-phase reaction methods such as a method in which heated vapor of a metal chloride, such as SiCl4 or TiCl4, is reacted with heated oxygen to form particles made of metal oxide in a high-temperature gas phase. Of these, gas-phase reaction methods are preferred.

[0177] When the inorganic particle aggregates contain titanium dioxide as the inorganic component, preferred production methods include hydrothermal treatment of a hydrolysis product of titanium alkoxide in aqueous alcohol or organic acid, a chlorine method in which heated vapor of TiCl4 is reacted with heated oxygen to form TiO2 particles in a high-temperature gas phase, and a sulfuric acid method in which anatase-type TiO2 fine particles, which are precipitates obtained by thermally hydrolyzing an aqueous solution of TiOSO4, are baked at 800-1000°C to grow. Of these, the chlorine method and sulfuric acid method are preferred.

[0178] As the aggregate of inorganic particles, commercially available products can also be used. Examples of commercially available products include, when the inorganic particle aggregates contain titanium dioxide as the inorganic component, AEROXIDE® TiO2 P-25, AEROXIDE® TiO2 P-90, AEROXIDE® TiO2 T-805, and AEROXIDE® TiO2 NKT-90 manufactured by Nippon Aerosil Co., Ltd.; fine particle titanium dioxide MT-05, MT-100SA, MT-100HD, and MT-500B manufactured by Teika Corporation; high-purity titanium dioxide PT-601A and TTO-51(A) manufactured by Ishihara Sangyo Kaisha, Ltd.; titania for catalyst carriers SSP-M, SSP-N, and STR-100N manufactured by Sakai Chemical Industry Co., Ltd.; microtitanium TAF-1500J and TAF-500J manufactured by Fuji Titanium Industry Co., Ltd.; and Super Titania F-2, F-4A, and F-6A manufactured by Resonaq Holdings Co., Ltd. When the inorganic particle aggregate contains alumina as the inorganic component, examples thereof include AEROXIDE® Al2O3 AluC manufactured by Nippon Aerosil Co., Ltd. When the aggregate of inorganic particles contains zirconia as an inorganic component, examples thereof include zirconium oxide UEP-100, UEP-50, and UEP manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., zirconium oxide PCS-90 and PCS-60 manufactured by Nippon Denko Co., Ltd., and Zirconeo-Cp and Zirconeo-Rp manufactured by ITEC Corporation.

[0179] Examples of the crushing method include a method using a planetary mill, a method using an attritor, a method using a jet mill, a method using a vibration ball mill, a method using a ball mill, and a method using beads. Among these, the method using beads is preferred because it tends to enable crushing in a short time.

[0180] The crushing treatment time in the crushing step is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours, and even more preferably 1 to 6 hours.

[0181] In the method using beads, the material and hardness of the beads to be used are not particularly limited. They may be appropriately selected depending on the material of the inorganic particles to be used (type of inorganic component), the size of the inorganic particles as primary particles, the strength of aggregation, etc. Examples of the material of the beads include inorganic materials such as glass, alumina, zircon (zirconia-silica ceramics), zirconia, silicon nitride, and steel, as well as resin materials. When the aggregates of inorganic particles to be disintegrated are aggregates of crystalline inorganic particles, the material of the beads is preferably zirconia, and the Mohs hardness of the beads is preferably in the range of 8 to 10.

[0182] The average particle size of the beads is not particularly limited. It may be appropriately selected depending on the material of the inorganic particles used (type of inorganic component), the size of the inorganic particles (primary particles), cohesive force, etc., but beads with an average particle size in the range of 0.01 mm to 2 mm are usually used. It is preferably 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. It is preferable to use beads such that the ratio of the average particle size of the beads to the average primary particle size (D1) of the aggregates of inorganic particles to be disintegrated is in the range of 100 to 10,000. The ratio is more preferably 200 to 8,000, and even more preferably 500 to 5,000.

[0183] The average particle size of the beads is the average particle size based on the number of beads. Usually, the particle size (diameter) of each bead 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 used as the average particle size of the beads. Commercially available beads can be used, such as YTZ® balls (Φ0.015 mm, 0.03 mm, 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm), alumina balls HD, HD-11, SSA-995, SSA-999W, and SSA-999S (all manufactured by Nikkato Corporation), and NZ10, NZ30, NZ50, NZ30HLC, and NZ50HLC (all manufactured by Niimi Sangyo Co., Ltd.).

[0184] In the method using beads, the amount of beads used is not particularly limited, but the ratio of beads to 1 part by mass of the inorganic particle aggregates is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 20 parts by mass.

[0185] Examples of the method using beads include a method using a paint shaker and a method using a bead mill. In the case of the method using the paint shaker, there are no particular restrictions on the conditions as long as the inorganic particle aggregates can be disintegrated using beads, 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 perspective, the preferred vibration speed is 100 to 1000 cpm, the preferred vibration amplitude is 750 cpm, and the preferred treatment time is 1 to 24 hours. Examples of equipment that can be used in the above method include commercially available equipment, such as No. 488 Test Disperser (Paint Shaker / Paint Conditioner) (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and Disperser Standard Model (manufactured by Seiwa Giken Co., Ltd.).

[0186] In the case of the method using the bead mill, there are no particular restrictions on the conditions as long as the beads can be used to disintegrate the 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 perspective, the preferred rotation speed is 500 rpm to 8000 rpm, the preferred peripheral speed is 5 to 20 m / s, the preferred treatment time is 1 to 24 hours, the preferred number of passes in the case of a circulation system is 5 to 500 times, and the preferred flow rate is 0.1 to 100 L / min. Apparatus that can be used in the above method include commercially available apparatus, such as Ready Mill RMB, Easy Nano RMB, Easy Nano RMB II type, Neo-Alpha Mill NAM, Sand Grinder BSG, Sand Grinder ESG (all manufactured by Imex Co., Ltd.), Labostar Mini LMZ015, Labostar Mini DMS65, Labostar Mini HFM02, Labostar LMZ06, Labostar LME075, Nano Getter, and MAX Nano Getter (all manufactured by Ashizawa Finetech Co., Ltd.).

[0187] In the method using the beads, it is preferable to mix a mixture of the inorganic particle agglomerates and the dispersant with the beads and then disintegrate the particles, and it is more preferable to mix a mixture of the inorganic particle agglomerates, the dispersant, and the solvent with the beads and then disintegrate the particles.

[0188] In the disintegration step, other components may be present in addition to the aggregates of inorganic particles, the dispersant, and the solvent. Other components may also be present in the mixture. Examples of the other components include carboxylic acid compounds such as oleic acid, alcohol compounds such as benzyl alcohol and cyclohexyl alcohol, and surface conditioners (surface tension adjusters) such as BYK-307 and BYK-378. The content of the other components is preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the inorganic particle aggregates. It is more preferably 0.005 to 5 parts by mass or less, and even more preferably 1 part by mass or less. On the other hand, the lower limit is more preferably 0.01 part by mass or more, and even more preferably 0.1 part by mass or more.

[0189] In the above method using beads, it is preferable to remove the beads from the resulting composition after crushing by means of filtration, centrifugation, etc. The above-described production method produces an inorganic particle-containing composition, but the production method may further include other steps after the disintegration step. Such other steps include a purification step. For example, in the case where abrasion powder from beads generated in the method using beads or a portion of the aggregates of inorganic particles used as raw materials remain without being disintegrated, a purification step such as filtration can be carried out to remove such residues.

[0190] The step of mixing the inorganic particle-containing composition obtained in the above-mentioned disintegration step with a polymerizable monomer (hereinafter also referred to as a mixing step) is not particularly limited as long as the inorganic particle-containing composition and the polymerizable monomer are mixed, but it is preferable to mix them so that the ratio of the inorganic particles to the polymerizable monomer is the preferred content ratio of the inorganic particles and the polymerizable monomer in the above-mentioned polymerizable composition.

[0191] In the mixing step, when the inorganic particle-containing composition and the polymerizable monomer are mixed, other components may be further mixed in addition to the inorganic particles, the polymerizable monomer, the dispersant, and the solvent. Specific examples of the other components are as described above.

[0192] [Patterned film] The patterned film obtained by the method for producing a patterned film of the present invention contains inorganic particles and a polymer (cured product of the polymerizable monomer) formed by polymerization of the polymerizable monomer. The inorganic particles contained in the pattern film are not particularly limited as long as they are particles mainly composed of an inorganic component. The inorganic component is the same as the inorganic component described above for the polymerizable composition, and the preferred form is also the same as that described above for the polymerizable composition. Particularly preferred inorganic components are titanium oxide and zirconium oxide.

[0193] The polymer contained in the pattern film and obtained by polymerizing a polymerizable monomer is not particularly limited as long as it is a polymer obtained by polymerizing the polymerizable monomer described above in relation to the polymerizable composition. Specific examples and preferred forms of the polymerizable monomer are as described above in relation to the polymerizable composition.

[0194] The patterned film obtained by the method for producing a patterned film of the present invention preferably further contains a dispersant. Specific examples and preferred forms of the dispersant are as described above for the polymerizable composition. A preferred embodiment of the patterned film obtained by the patterned film production method of the present invention includes at least one selected from the group consisting of a sulfur-based dispersant having a sulfinyl group, a phosphoric acid-based dispersant having a phosphoric acid group and / or a phosphoric acid ester group, a carboxylic acid-based dispersant having a carboxyl group, and a silane-based dispersant having an alkoxysilyl group. Particularly preferred dispersants are sulfur-containing polymers and phosphoric acid-based compounds.

[0195] The content of inorganic particles in the pattern film is not particularly limited, but is preferably 20 to 90% by mass relative to 100% by mass of the solid content of the pattern film. This makes it easier for the physical properties of the inorganic particles to be reflected in the pattern film, and makes it easier for the film to have excellent mechanical strength. The content of inorganic particles in the pattern film is more preferably 35 to 80% by mass, even more preferably 50 to 80% by mass, and particularly preferably 60 to 80% by mass.

[0196] The content of inorganic particles in the patterned film is preferably within a range of ±10%, more preferably ±7%, and even more preferably ±5%, of the content of inorganic particles relative to 100% by mass of the solid content of the polymerizable composition used in the method for producing the patterned film.

[0197] The content of the cured polymerizable monomer in the pattern film is not particularly limited, but is preferably 10 to 65 mass %, more preferably 15 to 50 mass %, and even more preferably 20 to 40 mass %, relative to 100 mass % of the solid content of the pattern film.

[0198] When the pattern film contains a dispersant, the content is not particularly limited, but is preferably 2 to 25 mass %, more preferably 3 to 22 mass %, and even more preferably 5 to 20 mass %, relative to 100 mass % of the solid content of the pattern film.

[0199] When the pattern film contains a sulfur-containing polymer, the content is not particularly limited, but is preferably 2 to 20 mass %, more preferably 4 to 18 mass %, and even more preferably 5 to 15 mass %, relative to 100 mass % of the solid content of the pattern film.

[0200] When the pattern film contains a phosphoric acid compound, its content is not particularly limited, but is preferably 1 to 10 mass %, more preferably 2 to 9 mass %, and even more preferably 3 to 7 mass %, relative to 100 mass % of the solid content of the pattern film.

[0201] The patterned film obtained by the method for producing a patterned film of the present invention is not particularly limited, but preferably has a residual film thickness of 1 to 20,000 nm, more preferably 1 to 1,000 nm, and even more preferably 1 to 500 nm. In one embodiment, the residual film thickness of the pattern film is more preferably 5 to 1000 nm, and even more preferably 10 to 500 nm. For example, the above residual film thickness is particularly preferred for a pattern film having a higher refractive index.

[0202] The patterned film obtained by the method for producing a patterned film of the present invention preferably has a cross-sectional film thickness of 60 to 5000 nm, more preferably 60 to 3000 nm, and even more preferably 60 to 2000 nm.

[0203] The patterned film obtained by the method for producing a patterned film of the present invention preferably has a haze of 0.01 to 5%, more preferably 0.01 to 1.5%, and even more preferably 0.01 to 0.8% at a film thickness of 1 μm. The haze of the pattern film can be measured by the method described in the Examples.

[0204] The patterned film obtained by the method for producing a patterned film of the present invention preferably has a refractive index at a wavelength of 589 nm of 1.65 to 2.4, more preferably 1.70 to 2.3, and even more preferably 1.75 to 2.2. The refractive index of the pattern film can be measured by the method described in the Examples.

[0205] In the patterned film obtained by the method for producing a patterned film of the present invention, when the pattern shape is a line and space, the line width of 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. The width of the space is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm.

[0206] The width of the upper surface of the convex portion of the pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. The height of the convex portions of the pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm.

[0207] The width of the bottom surface of the recesses in the pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm. The depth of the grooves in the recesses of the pattern shape is preferably 20 to 5000 nm, more preferably 40 to 3000 nm, and even more preferably 60 to 2000 nm.

[0208] When the upper surfaces of the convex portions of the lines of the pattern shape are needle-shaped, it can be said that the definition is higher. In the case of a needle-like shape, the width of the upper surface of the protrusion is preferably 1 to 500 nm, more preferably 3 to 100 nm, and even more preferably 5 to 50 nm.

[0209] When the pattern shape is a pillar shape, the width of the upper surface of the convex portion, which can be said to have higher definition, is preferably 20 to 3000 nm, more preferably 40 to 2000 nm, and even more preferably 60 to 1000 nm.

[0210] When the pattern shape is a hole shape, the width of the bottom of the recess, which can be said to have higher definition, is preferably 20 to 3000 nm, more preferably 40 to 2000 nm, and even more preferably 60 to 1000 nm.

[0211] [Application] The patterned film obtained by the production method of the present invention is highly precise and is a film in which the physical properties of the composition before pattern formation are sufficiently reflected, and therefore is preferably used for optical applications such as optical materials, optical device members, and display device members.

[0212] For example, when the inorganic particles in the polymerizable composition contain at least one metal oxide selected from the group consisting of silicon oxide (SiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), titanium oxide (TiO2), barium titanate (BaTiO3), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), hafnium oxide (HfO2), cerium oxide (CeO2), tungsten oxide (WO2, WO3), indium oxide (In2O3), stannic oxide (SnO2), and zinc oxide (ZnO), the method for producing a patterned film of the present invention can be particularly suitably used for producing optical materials, optical device components, and display device components. Specific applications include, for example, eyeglass lenses, digital eyeglasses, goggles, and displays that enable VR (virtual reality), AR (augmented reality), and MR (mixed reality), imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and in-vehicle cameras, lenses such as light beam condensing lenses and light diffusing lenses, LED encapsulants, optical adhesives, optical pressure-sensitive adhesives, optical transmission joining materials, filters, diffraction gratings, diffractive optical elements, prisms, light guides, watch glasses, and optical material applications such as transparent glass and cover glass for display devices; photosensors (optical sensors (CMOS sensors, TOF sensors, etc.)), photoswitches, LEDs, These include optical device 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 LCDs, OLEDs, and PDPs, color filter substrates, touch panel substrates, index matching materials used in touch panels, display protective films, display backlights, light guide plates, anti-reflection films, anti-fog films, and light extraction enhancers for LEDs and OLEDs; applications where imprint molding can be used to form precise, thin-film diffractive optical elements and lenses on inorganic, glass, or resin substrates; and wafer-level optics. Among these, imaging lenses, digital glasses, goggles, and displays that enable virtual reality (VR), augmented reality (AR), and mixed reality (MR), filters, diffraction gratings, diffractive optical elements, prisms, light guides, LEDs, micro-LEDs, light-emitting elements, color filters, and touch panels are particularly preferred.

[0213] For example, when the inorganic particles in the polymerizable composition contain zirconium oxide (ZrO2) or titanium oxide (TiO2), the method for producing a patterned film of the present invention can be preferably used for producing a high refractive index molding material, a raw material for a high refractive index molding material, a coating agent for forming a high refractive index film, etc., particularly the above-mentioned optical materials, optical device members, display device members, etc. [Example]

[0214] 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 weight" and "%" means "% by mass."

[0215] [Evaluation of inorganic particle aggregates] The crystal structure, degree of crystallinity, average primary particle diameter (D1), and composition of the aggregates of inorganic particles used in each of the Examples and Comparative Examples were measured as follows.

[0216] <Crystal structure evaluation method> The aggregates of inorganic particles used in each of the examples and comparative examples were used as samples, and the crystal structure and crystallinity were measured using an X-ray diffractometer SmartLab (manufactured by Rigaku Corporation) under the following measurement conditions. X-ray source: CuKα (0.154nm). X-ray power settings: 45kV, 200mA. Sampling width: 0.0200°. Scan speed: 5.0000° / min. Measuring range: 5~90° Measurement temperature: 25℃. The crystal structure was determined from the X-ray diffraction pattern obtained by using the aggregates of inorganic particles used in each of the Examples and Comparative Examples as samples.

[0217] <Average primary particle diameter (D1)> When the inorganic particle aggregates used in each example and comparative example contain zirconium oxide (crystalline) as an inorganic component, X-ray diffraction measurement is performed, and the crystallite diameter is determined from the full width at half maximum of the diffraction line with the highest diffraction intensity (strongest line) in the obtained X-ray diffraction pattern, and the obtained value is taken as the average primary particle diameter (D1). In each inorganic particle aggregate used in Example 1, the diffraction line of the lattice plane (11-1) is the strongest line, and the full width at half maximum of the diffraction line of the lattice plane (11-1) is measured, and the value obtained is used to calculate the crystallite diameter Dc (11-1) using analysis software (PDXL2), and the obtained value is taken as the average primary particle diameter (D1) of each inorganic particle aggregate used. In the case where the aggregates of each inorganic particle used in Example 2 contain titanium oxide (crystalline) as the inorganic component, the diffraction line of the lattice plane (101) is the strongest line, and the value of the crystallite diameter Dc(101) was calculated from the full width at half maximum of this diffraction line in the same manner as above, and the obtained value was used as the average primary particle diameter (D1) of each inorganic particle aggregate used. The apparatus and conditions for X-ray diffraction measurement were the same as those for the crystalline structure.

[0218] <Specific surface area> The specific surface area of ​​the inorganic particle aggregates used in each example and comparative example was measured by the BET method using a BELSORP-MR6 (Microtrack-Bell). The measurement samples were prepared by vacuum drying the inorganic particle aggregates for 20 hours in a vacuum dryer at 25°C.

[0219] [Evaluation of inorganic particle-containing compositions] The dispersed particle diameter (Dd) of the inorganic particle-containing composition obtained in each of the Examples and Comparative Examples was measured as follows.

[0220] <Dispersed particle diameter (Dd)> Using the inorganic particle-containing compositions obtained in each Example and Comparative Example, samples were prepared as follows, and the volume-based particle size distribution was measured using a concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.). The 10% particle size was defined as D10, the 50% particle size as D50, and the 99% particle size as D99, and the 50% particle size (D50) was defined as the dispersed particle size (Dd) of the measured inorganic particle-containing composition. (Method of preparing measurement samples) The inorganic particle-containing compositions obtained in each Example and Comparative Example were diluted with the solvent used in each Example so that the concentration of inorganic particles contained in each composition was about 3 mass %, and the diluted compositions were used as measurement samples. Note that the concentration was adjusted appropriately depending on the amount of scattered light and the presence or absence of multiple scattering.

[0221] <Crushing degree (r)> For each of the inorganic particle-containing compositions of the Examples and Comparative Examples, the degree of disintegration (r), which is the ratio of the average primary particle diameter (D1) of the inorganic particle aggregates to the dispersed particle diameter (Dd) of the inorganic particle-containing composition, was evaluated as shown in the following formula. Disintegration degree (r)=dispersed particle diameter (Dd) / average primary particle diameter (D1) The dispersed particle size (Dd) and the average primary particle size (D1) are measured by the methods described above.

[0222] [Evaluation of sulfur-containing polymers obtained in each synthesis example] The average molecular weight and other properties of the sulfur-containing polymer obtained in each synthesis example were measured as follows.

[0223] <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 polymer obtained in each synthesis example were determined by gel permeation chromatography (GPC) under the following conditions. Equipment 1: SHIMAZU, CBM-20A. Apparatus 2: Agilent Technologies 1260 Infinity. Detectors: Refractive index detector (RI) (SHIMAZU, SPD-20MA) and ultraviolet-visible-infrared spectrophotometer (SHIMAZU, SPD-20MA). Column: TOSOH, TSKgel SuperHM-N. Column temperature: 40°C. Flow rate: 0.3ml / min. Calibration curve: Polystyrene Standards. Eluent: chloroform, tetrahydrofuran.

[0224] <Matrix-Assisted Laser Desorption / Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS)> For the sulfur-containing polymers obtained in each synthesis example, MALDI measurements were performed under the following conditions. Apparatus: Time-of-flight mass spectrometer (Bruker AutoflexIII) Sample preparation: Approximately 2 mg of the measurement sample was dissolved in 1.0 g of tetrahydrofuran. As a matrix agent, 20 mg of 2,5-dihydroxybenzoic acid and as an ionizing agent, 2.0 mg of sodium iodide were dissolved. The adjusted solution was applied to a measurement target plate and dried at room temperature for about 100 minutes.

[0225] < 1 1H-NMR For the sulfur-containing polymers obtained in each synthesis example, 1H-NMR measurements were performed under the following conditions. 1 1H-NMR measurement was carried out. Apparatus: Nuclear magnetic resonance apparatus (400 MHz) manufactured by JEOL Ltd. Measurement solvent: deuterated dichloromethane, deuterated chloroform Sample preparation: Several mg to several tens of mg of the obtained polymer was dissolved in the measurement solvent.

[0226] < 13 13C-NMR For the sulfur-containing polymers obtained in each synthesis example, 13C-NMR measurements were performed under the following conditions. 13 13C-NMR measurement was carried out. Apparatus: Nuclear magnetic resonance apparatus (400 MHz) manufactured by JEOL Ltd. Measurement solvent: deuterated chloroform Sample preparation: Several tens of mg to several hundreds of mg of the sulfur-containing polymers obtained in each synthesis example was dissolved in the measurement solvent.

[0227] <ir> The sulfur-containing polymers obtained in each synthesis example were subjected to IR measurement under the following conditions. Apparatus: JASCO Fourier transform infrared spectrophotometer (FT / IR-6100). Sample preparation: Approximately 2 mg of sample was diluted with approximately 300 mg of dry potassium bromide (KBr). The mixture was ground with a mortar and pestle and molded.

[0228] <Element content ratio O / S ratio> The sulfur-containing polymer obtained in each synthesis example was dissolved in cyclohexanone solvent to a concentration of 10% to prepare a polymer solution. 0.25 ml of the polymer solution was spin-coated onto a silicon wafer to form a film. Using a JEOL photoelectron spectrometer (JPS-9010TR, XPS device, light source: Mg, X-ray output: 400 W), the peak intensity derived from the sulfur atom 2p orbital and the peak intensity derived from the oxygen atom 1s orbital were measured, and the O / S ratio was calculated by calculating their integral ratio. If necessary, the peak intensity derived from the carbon atom 1s orbital was also measured, and the O / S ratio was calculated taking the results into consideration. For sulfur atom peaks that could be separated into sulfide and disulfide peaks, the sulfide / disulfide ratio was also calculated. The measurement method, bond energy positions, etc. were based on the Handbook of X-ray Photoelectron Spectroscopy (JEOL, March 1991). 1 For those in which the sulfide and sulfoxide peaks could be separated by H-NMR measurement, the O / S ratio was calculated by calculating the integral ratio of each peak.

[0229] <Binding energy> The sulfur-containing polymer obtained in each synthesis example was dissolved in cyclohexanone to a concentration of 10% to prepare a polymer solution. 0.25 ml of the polymer solution was spin-coated onto a silicon wafer to form a film. Using this film, the binding energy was measured from the peak position of the 2p3 / 2 orbital of the sulfur atom using a JEOL photoelectron spectrometer (JPS-9010TR, XPS device).

[0230] <Organic Elemental Analysis> For the sulfur-containing polymers obtained in each synthesis example, elemental analysis measurements were performed using the following apparatus. Apparatus: Jay Science Lab JM10

[0231] [Evaluation of the Polymerizable Composition] <Method for Curing the Coating Film by UV Irradiation> For the production of the cured film on the slide glass with the coating film prepared in each example and comparative example, the coating film on the slide glass with the coating film was cured and formed into a film by irradiating the coating film with UV using an area UV irradiator. The apparatus is as follows. Apparatus: Area UV Irradiation System (manufactured by CCS, Inc.). Power supply: PSCC-60048-NL (manufactured by CCS, Inc.). Irradiation wavelength: 365 nm. Irradiation intensity: 100 mW / cm 2 .

[0232] <Method for Measuring the Solid Content Viscosity of the Polymerizable Composition in the Polymerizable Composition> From the polymerizable compositions prepared in each example and comparative example, the solvent was distilled off using a rotary evaporator, and the resulting composition was used as a measurement sample. The viscosity of the obtained measurement sample at 25°C was measured using an R100 type viscometer in accordance with JIS Z 8803. The obtained measured value was taken as the solid content viscosity of the polymerizable composition.

[0233] <Method for Evaluating the Surface Tension of the Replica Mold> Regarding the surface tension of the replica molds produced in each example and comparative example, evaluation was performed by a wetting tension test in accordance with JIS K 6768. The measurement was carried out and evaluated in a standard test chamber atmosphere at 23°C and a relative humidity of 50%.

[0234] <Method for Evaluating the Refractive Index and Film Thickness of the Cured Film> The refractive index and film thickness of the cured film obtained in each Example and Comparative Example were determined from the reflectance spectrum of the cured film on the cured film-coated slide glass prepared in each Example and Comparative Example. The refractive index was evaluated by calculating the refractive index value at 589 nm and the film thickness value from the measured reflectance using the following device. Equipment: Filmetrics film thickness measurement system F-20. Standard fiber stage SS-1 (spot diameter 1.5 mm). The imprinted films obtained in each of the Examples and Comparative Examples were also evaluated in the same manner.

[0235] <Method for evaluating film transparency (haze)> Transparency was determined by measuring haze. The haze of the slide glass with the cured film prepared in each Example and Comparative Example was measured, and the haze of the cured film was determined by subtracting the haze measurement value of the slide glass substrate used as the substrate from the measured value. The haze was measured using the following device. Equipment: HAZE METER NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd. The imprinted films obtained in each of the Examples and Comparative Examples were also evaluated in the same manner.

[0236] <Method for evaluating cross-sectional film thickness and remaining film thickness> The cross-sectional film thickness and residual film thickness of the imprinted film obtained in each of the Examples and Comparative Examples were measured as follows. The imprinted film was cut perpendicular to the pattern shape in which the line and space shape was transferred in a striped shape using a glass cutter, and the resulting cut surface was observed using an FE-SEM (JEOL: JSM7600F) to obtain a cross-sectional image. In the cross-sectional image at a magnification of 10,000 times, the distance from the interface between the substrate glass and the imprint film to the top surface of the convex portion was measured for each of the 10 convex portions, and the simple average of the obtained measurements (10 portions) was calculated and used as the cross-sectional film thickness. Similarly, in the cross-sectional image at a magnification of 10,000 times, the distance from the interface between the substrate glass and the imprint film to the top surface of the recess (between the protrusions) was measured for 10 recesses, and the simple average of the obtained measurements (10) was calculated and used as the remaining film thickness.

[0237] <Imprint molding evaluation method> For the evaluation of imprint molding in the imprint films of each Example and Comparative Example, imprint moldability, which is the ratio of the height of the pattern shape of the imprint film to the height of the pattern shape of the replica mold used to mold the pattern shape of the imprint film, was evaluated as shown in the following formula, and when the imprint moldability value was 95% or more, it was evaluated that an imprint film that reflected the pattern shape of the replica mold was obtained.When the imprint moldability value was less than 95%, it was evaluated that an imprint film that did not reflect the pattern shape of the replica mold was obtained. Imprint formability = height of pattern shape of imprint film / height of pattern shape of replica mold × 100 (%) Imprint moldability value is 95% or more: ○ Imprint moldability value less than 95%: × Regarding the height of the pattern shape of the imprinted film, the value obtained by subtracting the measured value of the residual film thickness from the measured value of the cross-sectional film thickness in the cross-sectional image in the above <Method for evaluating cross-sectional film thickness and residual film thickness> was used as the height of the pattern shape of the imprinted film. The height of the pattern shape of the replica mold can be evaluated by measuring the pattern shape of the replica mold obtained in each example, and was measured using the same method as described above for the evaluation of cross-sectional film thickness and residual film thickness. For the portion of the replica mold where the convex portions were formed, the distance from the interface between the substrate and the replica mold to the top surface of the convex portions was measured for each of the ten convex portions, and the simple average of the obtained measurements (10) was calculated, which was used as the cross-sectional film thickness of the replica mold. Similarly, for the concave portions (between the convex portions) in the cross-sectional image at 10,000x magnification, the distance from the interface between the substrate and the replica mold to the top surface of the concave portions was measured for each of the ten concave portions, and the simple average of the obtained measurements (10) was calculated, which was used as the residual film thickness of the replica mold. The value obtained by subtracting the measured value of the residual film thickness of the replica mold from the measured value of the cross-sectional film thickness of the replica mold was used as the height of the pattern shape of the replica mold.

[0238] (Synthesis of sulfur-containing polymers) [Synthesis Example 1] <Production of sulfur-containing polymer (Po1a)> 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 sodium peroxodisulfate (NaSO) (2.57 g, 12.00 mmol) were added to a 3.0 L three-neck flask. The three-neck flask was then heated to 160 °C under nitrogen flow (20 mL / min) for 10 minutes, after which air bubbling was switched to (150 mL / min) and the mixture was stirred for 40 hours to carry out oxidative polymerization. After polymerization was complete, air bubbling was stopped, and 240 mL of N-methylpyrrolidone was added and stirred for 10 minutes. The reaction mixture was then cooled to room temperature, and THF (2.2 L) was added as a solvent. After stirring for 10 minutes, 192 mL of pure water was added and stirred for 5 minutes. Next, while the recovery flask was cooled on an ice bath, trichloroisocyanuric acid (122.11 g, 0.66 mol) was added and stirred for 2 hours. After stirring for 2 hours, zinc powder (31.53 g, 0.48 mol) was added and stirred at room temperature for 14 hours. After the reaction was completed, methanol (12 L) was added to the reaction mixture to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum dried at room temperature to obtain a white sulfur-containing polymer (Po1a) powder. The yield was 92%. The structure of the resulting sulfur-containing polymer (Po1a) was as follows: 1 The identification was carried out using H-NMR, XPS, ICP, IR, GPC, elemental analysis, and MALDI measurements. 1 H-NMR (CD2Cl2, 400 MHz, ppm): δ = 7.56 (m, 17H), δ = 7.19 (m, 6H), 2.35 (m, 3H). XPS confirmed that the sulfide group: sulfoxide group: sulfonic acid group ratio was 45:55:0 mol%. IR revealed that the peak at 2570 cm -1 A peak derived from mercapto was observed around this range, and GPC confirmed that Mw was 2400 and Mn was 1150, confirming that the terminal structure was -SH. From Mn = 1150, it was confirmed that the proportion of terminal aromatic rings (structural units) was 9.5 mol % relative to 100 mol % of all aromatic rings (all structural units).

[0239] <Production of sulfur-containing polymer (Po1)> 200.0 g of the sulfur-containing polymer (Po1a) was added to a 2.0 L three-neck flask, followed by 1.1 L of sulfolane as a solvent. The three-neck flask was then heated to 130°C while nitrogen flow (0.5 L / min) was applied for 10 minutes, and then allowed to cool to room temperature. After cooling, the three-neck flask was immersed in a water-cooled bath, and 98.3 g of chlorosulfuric acid was gradually added dropwise while nitrogen flow (0.25 L / min) was applied. After the addition was complete, the mixture was stirred at room temperature for 2 hours. Again, 16.6 g of zinc was added while the three-neck flask was cooled in the water-cooled bath, and the mixture was stirred for 14 hours. After the reaction was completed, the resulting reaction solution was added dropwise to 5.5 L of methanol to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum-dried at room temperature to obtain polymer (Po1) powder. The yield was 90%. The structure of the resulting polymer (Po1) was as follows: 1 Identification was carried out using H-NMR, ICP, GPC, IR, and elemental analysis. 1 H-NMR (CDCl3,600MHz,ppm): δ=7.53(m,10H),δ=7.24(m,12H),2.34(m,3H), 2570cm from IR -1 A peak derived from mercapto was observed near the mercapto atom range. GPC confirmed that Mw = 2370 and Mn = 1150, confirming the presence of 27.7 mol% thiol (-SH) groups relative to the total aromatic rings. Since the content of thiol (-SH) groups in the polymer (Po1a) is estimated to be 9.5 mol% relative to 100 mol% of the total aromatic rings (total structural units), the amount of mercapto groups introduced in this reaction is estimated to be 18.2 mol%. Elemental analysis confirmed that the sulfur atom weight ratio of the sulfur-containing polymer (Po1) was higher than that of the sulfur-containing polymer (Po1a) before the reaction.

[0240] <Quantitative determination of SH groups in sulfur-containing polymers (Po1)> 2.0 g of sulfur-containing polymer (Po1) was added to a 20 mL test tube, followed by 5.0 g of 1,2-epoxycyclohexane, and the mixture was stirred at 80°C for 2 hours. After the reaction was completed, THF (5 mL) was added, and the resulting solution was added dropwise to 50 mL of a hydrochloric acid-acidified methanol solution to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum dried at room temperature to obtain polymer (Po1t) powder. The yield was 89%. The structure of the resulting polymer (Po1t) is as follows: 1 Identification was carried out using H-NMR, ICP, GPC, IR, and elemental analysis. 1 H-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, 2570cm -1 A peak derived from mercapto was observed around this range, and GPC confirmed that Mw was 2410 and Mn was 1150. Elemental analysis confirmed that the chlorine atom content in the polymer was below the detection limit, and that the weight ratio of sulfur atoms in the polymer (Po1t) was higher than that in the sulfur-containing polymer (Po1) before the reaction. 1 H-NMR confirmed that mercapto groups were introduced into 27.7 mol% of all aromatic rings in the polymer (Po1t). From the above, it was found that mercapto groups were introduced into 27.7 mol% of all aromatic rings in the 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, confirming that 18.2 mol% of mercapto groups were introduced into side chains.

[0241] [Example 1] Using a batch-type ready mill RMB 02 vessel (nominal capacity 200 mL) manufactured by Imex Co., Ltd., 300 g of zirconia balls YTZ (0.05 mm) manufactured by Nikkato Corporation, 30.0 g of zirconium oxide particles UEP-50 (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) (hereinafter also referred to as ZrO2 (1)) as inorganic particle aggregates, 3.50 g of the sulfur-containing polymer (Po1) obtained in Synthesis Example 1 as a sulfur-containing polymer, 1.75 g of a mixture containing triethylene glycol monomethyl ether phosphate ester as a phosphoric acid compound (hereinafter also referred to as phosphoric acid-based dispersant (1)), and 65 g of cyclopentanone as a solvent were added, and the mixture was cooled to 10 ° C and 1910 rpm for 2 hours. After completion of the disintegration, a dispersion composition was obtained, and the zirconia balls YTZ (0.05 mm) contained in the dispersion composition were separated by filtration to obtain a milky white composition, inorganic particle-containing composition (1). The dispersion particle diameter (Dd) and the degree of crushing (r) of the obtained inorganic particle-containing composition (1) were evaluated, and the results are shown in Table 3. The phosphoric acid-based dispersant (1) used was a compound represented by the above formula (2), and R 1 , R 2 , a, and n are shown in Table 1. Table 2 also shows the evaluation results for the crystal structure, average primary particle diameter (D1), and specific surface area of ​​the ZrO2(1) used. Table 3 shows the raw materials and their blending ratios used to prepare the inorganic particle-containing composition (1). In Table 3, the sulfur-containing polymer (Po1) (mass%), phosphoric acid-based dispersant (1) (mass%), and inorganic particle aggregates (mass%) refer to the respective proportions (mass%) of the sulfur-containing polymer (Po1), phosphoric acid-based dispersant (1), and inorganic particle aggregates relative to the total mass of the sulfur-containing polymer (Po1), phosphoric acid-based dispersant (1), and inorganic particle aggregates used. The same applies to each of the examples and comparative examples other than Example 1.

[0242] <Evaluation of films using inorganic particle-containing composition (1)> BYK-307 (a surface tension modifier manufactured by BYK-Chemie) was added to and mixed with the obtained inorganic particle-containing composition (1) so that the ratio of BYK-307 was 0.05 parts by mass per 100 parts by mass of the solid content of the inorganic particle-containing composition (1), thereby preparing an inorganic particle-containing composition (1-2). The obtained inorganic particle-containing composition (1-2) was dropped onto a slide glass on a spin coater using a pipette, and spin-coated at a rotation speed of 1500 rpm for 90 seconds to obtain a coating film (1).

[0243] A polymerizable composition (1) was prepared by mixing a UV-curable monomer (polymerizable monomer) with the inorganic particle-containing composition (1), and a cured film (1) was obtained using the obtained polymerizable composition (1). Specifically, the process is as follows. The inorganic particle-containing composition (1) was treated with 33.3 parts by mass of a 9:1 (mass ratio) mixed solution (viscosity 49.0 cps) of 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate NMT-A) and OGSOL EA0200 (manufactured by Osaka Gas Chemicals Co., Ltd.) as a UV curable monomer relative to 100 parts by mass of the solid content of the inorganic particle-containing composition (1), 0.05 parts by mass of BYK-307 (manufactured by BYK-Chemie, surface tension modifier) ​​relative to 100 parts by mass of the solid content of the inorganic particle-containing composition (1), 1.4 parts by mass of Tinuvin 405 (manufactured by BASF) as an ultraviolet absorber relative to 100 parts by mass of the UV curable monomer, 1.4 parts by mass of Adeka STAB LA-81 as a light stabilizer relative to 100 parts by mass of the UV curable monomer, and Omnipol ASA (manufactured by IGM Resins) as a photopolymerization initiator. The components were added and mixed so that the ratio of Esacure 3644 (manufactured by IGM Resins BV) as a photosensitizer was 1.0 part by mass per 100 parts by mass of the UV-curable monomer, and polymerizable composition (1) was obtained. The resulting polymerizable composition (1) was dropped onto a glass slide mounted on a spin coater using a pipette and spin-coated at 1000 rpm for 90 seconds. The resulting coating film on the glass slide was placed on a hot plate preheated to 50°C and dried by heating for 1 minute to obtain a pre-cured coating film with a thickness of 1.50 μm. The dried pre-cured coating film was then cured by irradiating it with UV light in a nitrogen atmosphere for 90 seconds. The UV-cured film was then placed on a hot plate preheated to 80°C and heated for 10 minutes, after which it was placed on a hot plate preheated to 150°C and heated for another 10 minutes to obtain a cured film (1). The refractive index, film thickness, and haze of the resulting cured film (1) were evaluated. The refractive index (refractive index relative to the NaD line (589 nm)) was 1.82, the film thickness was 1.41 μm, and the haze was 0.10%. Table 4 shows the results of various evaluations of the cured film (1). The solid viscosity of the polymerizable composition was confirmed to be 2400 cps by evaluating the viscosity of the polymerizable composition (1-2) obtained by removing the solvent by drying the polymerizable composition (1) under reduced pressure using a rotary evaporator or the like. The solid viscosity of the polymerizable composition was also evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 5.

[0244] <Production of imprinted film (1)> Imprint molding was performed using the polymerizable composition (1). Specifically, the procedure is as follows: The polymerizable composition (1) was dropped onto a glass slide on a spin coater using a pipette, and spin-coated at 1000 rpm for 90 seconds. The prepared coating film on the glass slide was placed on a hot plate preheated to 50°C and dried by heating for 1 minute, yielding 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) at a pressure of 0.5 MPa for 30 seconds using a nanoimprinting device EITRE®3 (manufactured by Obducat) to form a transparent replica film mold with a line-and-space pattern imparted in a stripe shape with a spacing of 1.0 μm, a width of 1 μm on the top of the convex portions, a width of 1 μm on the bottom of the concave portions, and a height of 1 μm within a 1 cm × 1 cm area. The film was then pressed against the replica mold (1) at a pressure of 0.5 MPa for 30 seconds, yielding a power of 60 mW / cm. 2 The imprinted film (1) was then subjected to UV irradiation for 120 seconds to obtain an imprinted cured film (1) with the replica mold (1) pressed against it. The replica mold (1) was then released from the imprinted cured film (1), yielding an imprinted film (1-2) with the shape of the replica mold (1) transferred onto it. The imprinted film (1-2) was placed on a hot plate preheated to 80°C and maintained at this temperature for 10 minutes. The imprinted film (1-2) was then placed on a hot plate preheated to 150°C and maintained at this temperature for another 10 minutes to obtain an imprinted film (1). The resulting imprinted film (1) was cut perpendicular to the pattern shape with the transferred striped line-and-space shape using a glass cutter. The cross-section of the transferred pattern shape was observed at 10,000x magnification using a field emission scanning electron microscope (FE-SEM) (JEOL Ltd.: JSM7600F). It was confirmed that the transferred pattern shape, which reflected the shape of the replica mold (1), was reproduced to 95% or more, confirming the feasibility of imprint molding. Furthermore, cross-sectional observation confirmed that the cross-sectional film thickness, including the height of the top surfaces of the convex portions of the striped line-and-space configuration, was 1.39 μm, and that the remaining film thickness of the cured film in the lower layer, excluding the height of the top surfaces of the convex portions, was 0.39 μm. The refractive index, film thickness, and haze of the region of the cured film to which the transfer pattern shape of the obtained imprint film (1) was not imparted were evaluated. The refractive index (relative to the NaD line (589 nm)) was 1.82, the film thickness was 1.40 μm, and the haze was 0.10%. The replica mold (1) used can be manufactured from a metal mold (1) having a line-and-space pattern in stripes, with 1.0 μm spacing, 1 μm width on the top of the convex portions, 1 μm width on the bottom of the concave portions, and 1 μm height, within a 1 cm x 1 cm area on the metal surface of a silicon-based material or the like. A UV-curable transparent resin (1) is applied to a substrate such as a transparent PET film, the coated surface of the film is pressed against the metal mold (1), UV curing is performed, and the film is released from the metal mold (1), thereby obtaining the replica mold (1) as a transparent replica film mold that reflects the pattern shape of the metal mold (1) on the PET film. The UV-curable transparent resin (1) used to manufacture the replica mold (1) is as follows. The transfer pattern shape was confirmed using the same method as in the evaluation of the imprint film (1) described above, and it was confirmed that the transfer pattern shape reflecting the shape of the metal mold (1) was reproduced by 95% or more. The surface tension of the film surface of the replica mold (1) was evaluated, and it was confirmed to be 41 mN / m. This is shown in Table 5 along with the evaluation results of the imprint film. UV-curable transparent resin (1): UV-curable resin (epoxy type) OEX-028-X433-3, manufactured by Otex Co., Ltd.

[0245] [Example 2] An inorganic particle-containing composition (2) was produced by performing a crushing treatment in the same manner as in Example 1, except that the inorganic particle aggregates, sulfur-containing polymer (Po1), phosphate-based dispersant (1), compounding ratio, crushing time, etc. were as shown in Table 3. Furthermore, in the same manner as in Example 1, a UV-curable monomer, etc. was mixed with the inorganic particle-containing composition (2) to prepare a polymerizable composition (2), and a cured film (2) was obtained using this. The cured film (2) was evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 4. Furthermore, imprint molding evaluation, including the production of the imprinted film (2), was also performed in the same manner as in Example 1, and the evaluation results are shown in Table 5.

[0246] The inorganic particles used in Examples 1 and 2 and Comparative Examples 1 and 2 are as follows, and the results of evaluation of the crystal structure, etc. are shown in Table 2. ZrO2(1):UEP-50, zirconium oxide, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. TiO2(1):TAF-1500J, titanium oxide, manufactured by Fuji Titanium Industry Co., Ltd.

[0247] [Example 3] Instead of the inorganic particle-containing composition (1) of Example 1, zirconium oxide dispersion ZP-153 (manufactured by Nippon Shokubai Co., Ltd.) (hereinafter, zirconium oxide in the inorganic particle-containing composition (3) may be referred to as ZrO2(2)) was used as the inorganic particle-containing composition (3), which is a pre-dispersed zirconium oxide dispersion, and evaluations (including film evaluation using the inorganic particle-containing composition) were carried out in the same manner as in Example 1. The inorganic particle-containing composition (3) used is as follows: ZP-153: Zirconium oxide dispersion ZP-153 (manufactured by Nippon Shokubai Co., Ltd., Zircostar (registered trademark) "ZP-153"), MEK dispersion, particle content 70 mass%, dispersion refractive index 1.53, particle size 11 nm (dynamic light scattering method), tetragonal (main crystal system).

[0248] <Evaluation of films using inorganic particle-containing composition (3)> Propylene glycol monomethyl ether acetate (PGMEA) was added to the inorganic particle-containing composition (3) in an amount of 140 parts by mass of PGMEA per 100 parts by mass of the solid content of the inorganic particle-containing composition (3), and BYK-307 (a surface tension modifier manufactured by BYK-Chemie) was added to the inorganic particle-containing composition (3) in an amount of 0.05 parts by mass per 100 parts by mass of the solid content of the inorganic particle-containing composition (3), and the inorganic particle-containing composition (3-2) was prepared. The obtained inorganic particle-containing composition (3-2) was dropped onto a slide glass on a spin coater using a pipette, and the resulting mixture was spin-coated at 1500 rpm for 90 seconds to obtain a coating film (3).

[0249] A polymerizable composition (3) was prepared by mixing a UV-curable monomer and the like with the inorganic particle-containing composition (3) in the same manner as in Example 1. A cured film (3) was obtained using the obtained polymerizable composition (3) in the same manner as in Example 1, and the obtained cured film (3) was then evaluated. The results are shown in Table 4. The production of the imprinted film (3) and the imprint molding evaluation were also performed in the same manner as in Example 1, and the evaluation results are shown in Table 5.

[0250] [Example 4] Using the inorganic particle-containing composition (1) produced in Example 1, a polymerizable composition (4) was produced in the same manner as in Example 1, except that the UV-curable monomer was changed to 42.8 parts by mass of a 9:1 (mass ratio) mixed liquid of 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate NMT-A) and OGSOL EA0200 (manufactured by Osaka Gas Chemicals Co., Ltd.) per 100 parts by mass of the solid content of the inorganic particle-containing composition (1). A cured film (4) was obtained using the obtained polymerizable composition (4) in the same manner as in Example 1, and the cured film (4) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

[0251] The production of the imprint film in Example 1 was carried out in the same manner as in the production of the imprint film in Example 1, except that the replica mold used to produce the imprint film in Example 1 was changed.A replica mold (2) was used, which had a line and space pattern in stripes with a spacing of 0.15 μm, a width of 0.15 μm on the top surface of the convex portions, a width of 0.15 μm on the bottom surface of the concave portions, and a height of 0.15 μm, within a 1 cm x 1 cm area of ​​a metal surface such as a silicon-based metal.A replica mold (2) was produced and evaluated in the same manner as in the production of the imprint film (1) in Example 1.

[0252] [Comparative Example 1] The same procedures as in Example 1 were carried out except that the inorganic particle-containing composition (1) produced in Example 1 was used and the replica mold used in producing the imprint film in Example 1 was changed. A replica mold (c1) was produced and evaluated in the same manner as in Example 1 except that the UV-curable transparent resin (c1) used in producing the replica mold was changed. The UV-curable transparent resin (c1) used in producing the replica mold (c1) is as follows. The transfer pattern shape was confirmed in the same manner as in Example 1, and it was confirmed that the transfer pattern shape reflecting the shape of the metal mold (1) was reproduced by 95% or more. The surface tension of the film surface of the replica mold (c1) was evaluated, and it was confirmed to be 22 mN / m. This is shown in Table 5 together with the evaluation results of the imprint film. UV-curable transparent resin (c1): UV-curable liquid silicone rubber (PDMS) KER-4690-A / B, manufactured by Shin-Etsu Chemical Co., Ltd.

[0253] Comparative Example 2 A polymerizable composition (c2) was produced in the same manner as in Example 1, except that the inorganic particle-containing composition (1) of Example 1 was used and the UV-curable monomer of Example 1 was a 9:1 (mass ratio) mixed solution of 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate NMT-A) and OGSOL EA0200 (manufactured by Osaka Gas Chemicals Co., Ltd.) in an amount of 11.1 parts by mass per 100 parts by mass of the solids content of the inorganic particle-containing composition (1). A cured film (c2) was produced using the resulting polymerizable composition (c2) in the same manner as in Example 1, and the resulting cured film (c2) was then evaluated. The results are shown in Table 4. The production of the imprinted film (c2) and the imprint molding evaluation were also performed in the same manner as in Example 1, and the evaluation results are shown in Table 5.

[0254] Comparative Example 3 A polymerizable composition (c3) was produced in the same manner as in Example 3, except that the inorganic particle-containing composition (3) of Example 3 was used and the UV-curable monomer of Example 3 was a 9:1 (mass ratio) mixed solution of 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate NMT-A) and OGSOL EA0200 (manufactured by Osaka Gas Chemicals Co., Ltd.) in an amount of 11.1 parts by mass per 100 parts by mass of the solids content of the inorganic particle-containing composition (1). A cured film (c3) was produced using the resulting polymerizable composition (c3) in the same manner as in Example 1, and the resulting cured film (c3) was then evaluated. The results are shown in Table 4. The production of the imprinted film (c3) and the imprint molding evaluation were also performed in the same manner as in Example 1, and the evaluation results are shown in Table 5.

[0255] [Table 1]

[0256] [Table 2]

[0257] [Table 3]

[0258] [Table 4]

[0259] [Table 5]

[0260] As shown in Tables 4 and 5, in the examples, when imprint molding was performed using a replica mold with a surface tension of 41 mN / m, the differences in the values ​​of the film thickness of the cured film, the film thickness of the imprinted film, and the cross-sectional film thickness were small, demonstrating excellent film thickness controllability. In Comparative Example 1, when imprint molding was performed using a replica mold with a low surface tension of 22 mN / m, imprint molding was possible, but it was confirmed that there were large differences in the values ​​of the film thickness of the pre-cured coating film, the film thickness of the cured film, the film thickness of the imprinted film, and the cross-sectional film thickness. In Comparative Examples 2 and 3, it was confirmed that when the mass proportion of the polymerizable monomer in the polymerizable composition was low (less than 15 mass% relative to 100 mass% of the total of the polymerizable monomer and inorganic particles), the polymerizable composition was not filled into the pattern on the replica mold, and imprint molding was not possible. From the above, it was confirmed that in Examples 1 to 4, when a replica mold with a surface tension of more than 30 mN / m is used and the mass proportion of the polymerizable monomer in the polymerizable composition is high (15 mass% or more relative to 100 mass% of the total of the polymerizable monomer and inorganic particles), the fluidity of the polymerizable composition is obtained, making imprint molding possible, and a pattern film with excellent film thickness controllability can be obtained. Furthermore, it was confirmed that in Examples 1 to 4, films with excellent transparency and controlled refractive index were obtained.< / ir>

Claims

1. 1. A method for producing a patterned film, comprising: The production method includes a step of pressing a polymerizable composition containing inorganic particles and a polymerizable monomer using a mold, the content of the polymerizable monomer in the polymerizable composition is 15% by mass or more relative to 100% by mass of the total of the polymerizable monomer and the inorganic particles; The method for producing a patterned film, wherein the surface tension on the mold surface is greater than 30 mN / m.

2. 2. The method for producing a patterned film according to claim 1, wherein the polymerizable composition has a solid viscosity of 100 to 10,000 cps at 25° C. when the polymerizable composition is made up of only solids.

3. 2. The method for producing a patterned film according to claim 1, wherein the inorganic particles have an average primary particle size of 1 to 50 nm.

4. The polymerizable composition comprises a compound represented by the following formula (1): 【Chemical 1】 (In the formula, X １ represents a divalent aromatic hydrocarbon group which may have a substituent. The method for producing a patterned film according to claim 1, further comprising at least one dispersant selected from the group consisting of a sulfur-based dispersant, a phosphoric acid-based dispersant, a carboxylic acid-based dispersant, and a silane-based dispersant, the dispersant having a structural unit (U1) represented by the following formula:

5. The phosphate-based dispersant has the following formula (2): 【Chemistry 2】 (In the formula, R １ are the same or different and represent a hydrogen atom or an organic group. ２ are the same or different and represent an alkylene group having 2 to 20 carbon atoms; a is an integer of 1 to 3; and n is an integer of 0 to 20. The method for producing a patterned film according to claim 4, wherein the compound is represented by the following formula:

6. 5. The method for producing a patterned film according to claim 4, wherein the phosphoric acid-based dispersant has a molecular weight of 98 to 2,000.

7. 5. The method for producing a patterned film according to claim 4, wherein the content of the dispersant is 1 to 30% by mass with respect to 100% by mass of the inorganic particles.

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