Inorganic particle-containing composition

Abstract

The purpose of the present invention is to provide an inorganic particle-containing composition which is excellent in terms of dispersion stability. The present invention provides an inorganic particle-containing composition which contains a dispersant, zinc chalcogenide, and at least one substance that is selected from the group consisting of zirconium oxide, titanium oxide, and titanate.

Description

Inorganic particle-containing composition

[0001] The present invention relates to an inorganic particle-containing composition, and more particularly to an inorganic particle-containing composition useful for forming coating films such as optical materials, paints, coating agents, and inks.

[0002] Inorganic particles such as metal oxides obtained by dry methods such as gas phase methods or by firing at high temperatures generally tend to have excellent crystallinity and other physical properties inherent to inorganic substances, but because the particles tend to aggregate, they need to be crushed and dispersed to a level of primary particles or close to primary particles in order to be used in optical materials, etc. In response to this problem, various techniques for dispersing inorganic particles have been developed, and methods of performing crushing treatment in the presence of dispersants such as siloxane polymers, silane compounds such as silane coupling agents, carboxylic acid-based dispersants, and phosphorus-based dispersants have been reported (see, for example, Patent Documents 1 to 3).

[0003] JP 2006-316264 A JP 2006-1775 A International Publication No. 2019 / 240154

[0004] As described above, various techniques have been developed to disintegrate inorganic particle agglomerates. However, inorganic particles tend to agglomerate, and therefore, even if the agglomerates are disintegrated once, they tend to agglomerate again over time, resulting in a decrease in dispersibility. Therefore, there has been a demand for inorganic particle-containing compositions with excellent dispersion stability in order to form more uniform coating films.

[0005] The present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide an inorganic particle-containing composition having excellent dispersion stability.

[0006] The present inventors have conducted extensive research into compositions containing inorganic particles and have found that excellent dispersion stability can be achieved by using zinc chalcogenide and a dispersant with zirconium oxide, titanium oxide, and titanate as inorganic particles. This led to the realization that the above-mentioned problems can be successfully solved, and has led to the present invention.

[0007] The present invention encompasses the following inorganic particle-containing compositions, etc. [1] An inorganic particle-containing composition comprising at least one selected from the group consisting of zirconium oxide, titanium oxide, and titanates, zinc chalcogenide, and a dispersant. [2] The inorganic particle-containing composition according to [1] above, wherein the dispersant comprises a compound having a polar functional group. [3] The inorganic particle-containing composition according to [2] above, wherein the polar functional group is at least one selected from the group consisting of 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. [4] The dispersant is represented by the following formula (1); (In the formula, X １ represents a divalent aromatic hydrocarbon group which may have a substituent. [5] The inorganic particle-containing composition according to any one of [1] to [4] above, wherein the dispersant contains a phosphoric acid compound having a phosphoric acid group and / or a phosphoric acid ester group. [6] The phosphoric acid compound is a compound represented by the following formula (2); (In the formula, R １ are the same or different and represent a hydrogen atom or an organic group. ２are 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. The inorganic particle-containing composition according to [5] above, wherein the compound is a compound represented by the formula (I). [7] The inorganic particle-containing composition according to [5] or [6] above, wherein the phosphoric acid compound has a molecular weight of 98 to 2000. [8] The inorganic particle-containing composition according to [4] above, wherein the content of the sulfur-containing polymer is 1 to 30 mass% relative to a total of 100 mass% of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide. [9] The inorganic particle-containing composition according to any one of [5] to [7] above, wherein the content of the phosphoric acid compound is 0.5 to 10 mass% relative to a total of 100 mass% of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide.

[10] A polymerizable composition comprising the inorganic particle-containing composition according to any one of [1] to [9] above and a polymerizable monomer.

[11] A method for producing an inorganic particle-containing composition, the method comprising a step of disintegrating aggregates of particles of at least one type selected from the group consisting of zirconium oxide, titanium oxide, and titanates in the presence of zinc chalcogenide and a dispersant.

[12] The method for producing an inorganic particle-containing composition according to

[11] above, wherein the dispersant contains a compound having a polar functional group.

[13] The method for producing an inorganic particle-containing composition according to

[11] above or

[12] above, wherein the polar functional group is at least one selected from the group consisting of 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.

[14] The dispersant is a compound represented by the following formula (1); (In the formula, X １ represents a divalent aromatic hydrocarbon group which may have a substituent.

[15] The method for producing an inorganic particle-containing composition according to any one of

[11] to

[14] above, wherein the dispersant comprises a phosphoric acid compound having a phosphoric acid group and / or a phosphoric acid ester group.

[0008] The inorganic particle-containing composition of the present invention has the above-mentioned constitution and is excellent in dispersion stability, and therefore can be suitably used in optical materials, paints, coating agents, inks, and the like.

[0009] 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 that does not change the gist 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.

[0010] The inorganic particle-containing composition of the present invention contains at least one selected from the group consisting of zirconium oxide, titanium oxide, and titanate (hereinafter also referred to as Zr- or Ti-containing oxide), zinc chalcogenide, and a dispersant, and has excellent dispersion stability, so that the use of such a composition makes it possible to form a uniform coating film. In the inorganic particle-containing composition, it is believed that the zinc chalcogenide increases the absolute value of the zeta potential of the zirconium oxide, titanium oxide, and titanate, thereby improving the dispersion stability of the zirconium oxide, titanium oxide, and titanate.

[0011] The content of zinc chalcogenide in the composition is not particularly limited, but is preferably 1 to 150 mass% relative to 100 mass% of the total of zirconium oxide, titanium oxide, and titanate, more preferably 2 to 100 mass%, even more preferably 3 to 50 mass%, and particularly preferably 5 to 35 mass%.

[0012] The content of the dispersant in the composition is not particularly limited, but is preferably 1 to 30% by mass relative to 100% by mass of the total of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide. When the content of the dispersant is 1% by mass or more, the dispersibility of zirconium oxide, titanium oxide, and titanate can be further improved. Furthermore, the smaller the amount of organic dispersant in the composition, the higher the refractive index of the coating film when formed. When the content of the dispersant is 30% by mass or less, the refractive index of the coating film when formed can be further increased. The content of the dispersant is more preferably 2 to 25% by mass, even more preferably 5 to 22% by mass, and particularly preferably 10 to 20% by mass.

[0013] A preferred embodiment of the present invention is one in which the inorganic particle-containing composition contains a sulfur-containing polymer as a dispersant. 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 total of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide. When the sulfur-containing polymer content is 1% by mass or more, the dispersibility of zirconium oxide, titanium oxide, and titanate can be further improved. When the sulfur-containing polymer content is 30% by mass or less, the refractive index of the coating film formed can be further increased. The sulfur-containing polymer content is more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, and particularly preferably 5 to 15% by mass.

[0014] A preferred embodiment of the present invention also includes a phosphoric acid compound as a dispersant in the inorganic particle-containing composition. When the composition includes 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 total of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide. When the phosphoric acid compound content is 0.5% by mass or more, the dispersibility of zirconium oxide, titanium oxide, and titanate can be further improved. When the phosphoric acid compound content is 10% by mass or less, the refractive index of the resulting coating film can be further increased. The phosphoric acid compound content is more preferably 1 to 9% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass.

[0015] The total content of zirconium oxide, titanium oxide, and titanate in the composition is not particularly limited, but is preferably 10 to 99% by mass relative to 100% by mass of the solids content in the composition. When the total content of zirconium oxide, titanium oxide, and titanate is 10% by mass or more, the refractive index of the formed coating film can be further increased. The total content of zirconium oxide, titanium oxide, and titanate is more preferably 25 to 95% by mass, even more preferably 40 to 90% by mass, and particularly preferably 60 to 85% by mass.

[0016] The total content of zirconium oxide, titanium oxide, and titanate in the composition is preferably 5 to 99 mass%, more preferably 10 to 70 mass%, and even more preferably 10 to 45 mass%, relative to 100 mass% of the composition.

[0017] The inorganic particle-containing composition of the present invention has excellent dispersion stability. For example, dispersion stability can be evaluated by filling 10 g of the inorganic particle-containing composition immediately after production into a 10 mL sample bottle and leaving it at 40°C for 30 days, and visually checking for layer separation, solidification, and changes in viscosity of the inorganic particle-containing composition after leaving it at rest. Furthermore, the dispersed particle diameter (Dd) of the inorganic particle-containing composition after leaving it at rest is evaluated, and when the change in particle diameter is taken as 100% of the original dispersed particle diameter (immediately after production), it is also preferable that the dispersed particle diameter after leaving it at 40°C for 30 days is 500% or less. More preferably, it is 300% or less, even more preferably 200% or less, even more preferably 150% or less, and particularly preferably 120% or less.

[0018] The essential components and optional components contained in the inorganic particle-containing composition of the present invention will be further described below.

[0019] <Zirconium oxide, titanium oxide, and titanate> The zirconium oxide and titanium oxide contained in the inorganic particle-containing composition of the present invention are not particularly limited as long as they are oxides of zirconium and titanium, respectively. ３ (wherein A is a metal element other than Ti, and B is Ti) may be used.

[0020] The zirconium oxide, titanium oxide, and titanate preferably have a crystallinity of 80% or more. The crystallinity is more preferably 85% or more, even more preferably 90% or more, even more preferably 94% or more, and particularly preferably 98% or more. The crystallinity can be determined by powder X-ray diffraction measurement, as with the crystallite size, and the value obtained by powder X-ray diffraction measurement can be used as the crystallinity of zirconium oxide, titanium oxide, or titanate.

[0021] The titanate ABO ３In the formula, A may be any metal element other than titanium, and examples of the metal include alkali metals such as Li, Na, and K; alkaline earth metals such as Mg, Ca, Sr, and Ba; transition metals such as V, Cr, Mn, Fe, Co, Ni, Al, Ri, Zr, Sn, Nb, and W; and rare earth metals such as Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Pm, Sm, Sc, Tb, Tm, Y, and Yb. A is preferably an alkaline earth metal, more preferably barium or strontium, and even more preferably barium.

[0022] The form of the zirconium oxide, titanium oxide, and titanate is not particularly limited, and may be primary particles or may contain secondary particles formed by aggregation of primary particles.

[0023] The dispersed particle diameter (Dd) of the Zr- or Ti-containing oxide in the inorganic particle-containing composition of the present invention is preferably 5 to 60 nm, more preferably 8 to 50 nm, even more preferably 10 to 45 nm, and particularly preferably 10 to 35 nm. The dispersed particle diameter (Dd) is the 50% particle diameter in a 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 inorganic particle-containing composition is a liquid containing a solvent, the measurement sample is the composition as is, or diluted with the solvent as necessary. When the inorganic particle-containing composition is solid, the measurement sample is prepared by mixing and stirring a solvent capable of dissolving the dispersant contained in the composition, preferably a preferred solvent among the solvents described below in the method for producing the inorganic particle-containing composition (e.g., cyclopentanone, N-methylpyrrolidone, benzyl alcohol). In either case, the concentration in the measurement sample is usually about 1 to 2 mass % as the total concentration of zirconium oxide, titanium oxide, and titanate contained in the inorganic particle-containing composition, but the concentration can be adjusted appropriately during measurement depending on the amount of scattered light and the presence or absence of multiple scattering.

[0024] The Zr- or Ti-containing oxide preferably has an average primary particle diameter (D1) of 1 to 50 nm. When such an inorganic particle-containing composition is used to form a film, a coating film with excellent transparency can be obtained. The average primary particle diameter (D1) of the Zr- or Ti-containing oxide is more preferably 3 to 45 nm, even 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 measured by the crystallite diameter Dc when the crystalline Zr- or Ti-containing oxide is contained, and by the specific surface area diameter Ds when the crystalline Zr- or Ti-containing oxide is not contained. The presence or absence of a crystalline Zr- or Ti-containing oxide can be confirmed by powder X-ray diffraction measurement. For example, the Zr- or Ti-containing oxide and / or its 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).

[0025] The crystallite diameter Dc is determined by performing powder X-ray diffraction measurement on the Zr- or Ti-containing oxide or its aggregate, 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, and using the Scherrer formula. Here, diffraction intensity refers to the height of the peak top of the diffraction line. As analysis software, for example, analysis software (PDXL2, manufactured by Rigaku Corporation) can be used. The apparatus and conditions for performing 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 as the apparatus, and the measurement conditions are preferably those shown in the Examples. The specific surface area diameter Ds can be determined using the specific surface area and true density values ​​of the target particle (the Zr- or Ti-containing oxide or its aggregate) according to the following formula: Ds (m) = 6 / (ρ·S) ρ [g / m ３ ]: the true density of the particles or their aggregates, which can be determined by a pycnometer. S [m ２ / g]: specific surface area of ​​the particles or their aggregates, which can be measured by the BET method.

[0026] In the inorganic particle-containing composition, the ratio of dispersed particle size (Dd) to average primary particle size (D1) of the Zr- or Ti-containing oxide 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.

[0027] The shape of the Zr- or Ti-containing oxide 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. Note that 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.

[0028] <Zinc Chalcogenide> The zinc chalcogenide contained in the inorganic particle-containing composition of the present invention is not particularly limited as long as it is a zinc chalcogenide, and may be a compound containing zinc element and a Group 16 element (oxygen, sulfur, selenium, tellurium, polonium, livermorium). Preferred examples of the zinc chalcogenide include zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), and zinc telluride (ZnTe), more preferably zinc oxide and zinc sulfide, and even more preferably zinc oxide.

[0029] The average primary particle diameter of the zinc chalcogenide is not particularly limited, but is preferably 1 to 50 nm. The average primary particle diameter of the zinc chalcogenide 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 of the zinc chalcogenide can be measured as follows. As with the Zr- or Ti-containing oxides, when the zinc chalcogenide contains crystalline zinc chalcogenide, the crystallite diameter Dc can be used, and when it does not contain crystalline zinc chalcogenide, the specific surface area diameter Ds can be used. The crystallite diameter Dc and specific surface area diameter Ds can be measured in the same manner as for zirconium oxide, titanium oxide, and titanate.

[0030] The shape of the zinc chalcogenide is not particularly limited, and may be any of amorphous, granular, plate-like, columnar, needle-like, etc., but granular is preferred, and among granular, spherical is preferred. The granular shape means a uniform shape with an aspect ratio of 1.5 or less. 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.

[0031] <Dispersant> The dispersant contained in the inorganic particle-containing composition of the present invention is not particularly limited as long as it is a compound that exhibits dispersibility for the Zr- or Ti-containing oxide, but it is preferable that it contains a compound having a polar functional group.

[0032] 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. A preferred embodiment of the present invention is one in which the dispersant contains a compound having, as the polar functional group, at least one selected from the group consisting of 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. More preferred examples of the polar functional group are a sulfinyl group, a phosphoric acid group, and a phosphoric acid ester group. A preferred embodiment of the present invention is one in which the inorganic particle-containing composition of the present invention contains, as the dispersant, a dispersant having a sulfinyl group and a dispersant having a phosphoric acid group and / or a phosphoric acid ester group.

[0033] 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 5000. More preferably, it is 150 to 3500, and even more preferably, it is 200 to 3000. When the dispersant is a polymer, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0034] (Dispersant Having a Sulfonic Acid Group) The dispersant having a sulfonic acid group is not particularly limited, and 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, allylsulfonic acid, methallyl sulfonic acid, allyloxybenzenesulfonic acid, and 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid. Examples of derivatives include conventionally known compounds such as esters and salts.

[0035] (Dispersant Having a Carboxy Group) The dispersant having a carboxy group is not particularly limited, and examples thereof include polyacrylic acid; a copolymer of an unsaturated carboxylic acid monomer such as (meth)acrylic acid or maleic acid and an unsaturated polyalkylene glycol monomer; a copolymer of an unsaturated carboxylic acid monomer and an aromatic monomer such as styrene; a copolymer of an unsaturated carboxylic acid monomer and an acrylic acid ester, and ammonium salts, organic amine salts, and alkali metal salts thereof.

[0036] (Dispersant Having an Alkoxysilyl Group) The 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.

[0037] (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.

[0038] (Dispersant Having a Sulfinyl Group) In one preferred embodiment of the present invention, the inorganic particle-containing composition contains a dispersant having a sulfinyl group. The dispersant having a sulfinyl group is not particularly limited, but may be a dispersant represented by the following formula (1):

[0039]

[0040] (In the formula, X １ represents a divalent aromatic hydrocarbon group which may have a substituent. The sulfur-containing polymer is preferably a polymer having a structural unit (U1) represented by the following formula (1): The sulfur-containing polymer is not particularly limited as long as it has a structural unit represented by the above formula (1), and may have one or more structural units (U1), but preferably has a plurality of structural units (U1), and more preferably has the structural unit (U1) as a repeating unit, and more preferably has a plurality of repeating units.

[0041] In the above formula (1), X １ represents 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.

[0042] 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").

[0043] 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) ２ ), hydroxyl group (-OH), sulfo group (-SO ３ H), phosphonic acid group (-PO(OH) ２), phosphinic acid group (—PO(OH)—), etc. Examples of the basic functional group include basic functional groups such as amino group, ammonium group, imino group, amide group, imide group, maleimide group, etc. Examples of the curable functional group include groups having a reactive unsaturated bond such as groups having a reactive double bond such as vinyl group, (meth)acryloyl group, allyl group, methallyl group, etc.; groups having a reactive ionic bond such as groups having a reactive cyclic ether group such as epoxy group, oxetane group, etc.; and mercapto group (—SH).

[0044] Examples of the groups containing these functional groups include the above-mentioned acidic functional group, basic functional group, or curable functional group, and a group having 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.

[0045] 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, and a heptyl group. 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.

[0046] 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, and a benzyloxy group. 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 aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms.

[0047] Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, and a phenyloctyl group. The number of carbon atoms in the aralkyl group is preferably 7 to 14, and more preferably 7 to 9. Examples of the sulfur-containing hydrocarbon group include an alkylthio group and an arylthio group. The number of carbon atoms in the sulfur-containing hydrocarbon group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0048] 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 and a halogen atom, and preferred forms thereof are the same as those of the alkyl group, halogen atom, etc. as the substituent α.

[0049] Among the above-mentioned substituents α, from the viewpoint of easily improving the solubility of the sulfur-containing polymer in the solvents described below, alkyl groups are preferred, alkyl groups having 1 to 18 carbon atoms are more preferred, alkyl groups having 1 to 6 carbon atoms are even more preferred, and methyl groups are particularly preferred. Furthermore, the above-mentioned curable functional groups are preferred as the substituent α, and a mercapto group is particularly preferred. By having a mercapto group as the substituent α, the sulfur-containing polymer 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, the inorganic particle-containing composition of the present invention tends to easily produce a cured film having excellent heat resistance and solvent resistance. As the group containing a mercapto group, a thioalkyl group or a thioaryl group is preferred, and a thioalkyl group is more preferred.

[0050] 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.

[0051] 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 inorganic particle-containing 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 are no particular limitations on the position at 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.

[0052] When the sulfur-containing polymer has a plurality of structural units (U1), the type of the divalent aromatic hydrocarbon group, 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), the position at which the sulfinyl group (—S(═O)—) is bonded to the divalent aromatic hydrocarbon group, the bonding position of the other main chain to the divalent aromatic hydrocarbon group, and the positional relationship thereof are not particularly limited.

[0053] 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.

[0054] One preferred embodiment of the structural unit (U1) is, for example, the structural unit represented by the formula (I) above. 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 formula (I) is a phenylene group is also referred to as structural unit (U1-1). The phenylene group may or may not have a substituent (also referred to as "substituent α-1"). The type of the substituent α-1 is the same as that of the substituent α, and the preferred forms are also the same.

[0055] 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 taken as the 1st position, the position of the substituent α-1 may be the 2nd, 3rd, or 4th position of the phenylene group. Of these, the 4th or 2nd position is preferred, and the 4th position is more preferred.

[0056] 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, the 3-position, or the 4-position of the phenylene group. Of these, the 2-position or the 3-position is preferred, and the 3-position is more preferred.

[0057] 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.

[0058] 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.

[0059] 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. On the other hand, it 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.

[0060] 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).

[0061]

[0062] (In the formula, X ２ represents a divalent aromatic hydrocarbon group which may have a substituent.

[0063]

[0064] (In the formula, X ３ represents a divalent aromatic hydrocarbon group which may have a substituent.) In other words, one preferred embodiment of the sulfur-containing polymer is a polymer which contains the structural unit (U1) and further contains the structural unit (U2) and / or the structural unit (U3).

[0065] X in the 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.

[0066] 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 each of the following formulas 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 on 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 on 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.

[0067] 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, or may contain a plurality of repeating units. 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) 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.

[0068] 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.

[0069] The preferred range of the content of the structural unit (U1) relative to 100 moles of the total content of all structural units in the sulfur-containing polymer 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 unit (U1-1), the structural unit (U2-1), and the structural unit (U3-1) relative to 100 moles of the total content of all structural units is the same as in the case of the total content of the structural unit (U1), the structural unit (U2), and the structural unit (U3).

[0070] 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. On the other hand, it 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).

[0071] 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. On the other hand, it 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).

[0072] 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 efficient production of a sulfur-containing polymer having the structural unit (U1).

[0073] The polymerization step is a step of oxidatively polymerizing a monomer component containing an aromatic disulfide compound and / or an aromatic thiol compound. This step can produce a polymer containing at least a plurality of repeating units of the structural unit (U2). The oxidative polymerization can be carried out in a heated and molten state of the monomer component, but is preferably carried out in a composition in which the monomer component is dispersed or dissolved in a solvent. The composition, i.e., a composition containing the monomer component 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.

[0074] The monomer component includes an aromatic disulfide compound and / or an aromatic thiol compound. Among these, an aromatic disulfide compound is preferred. As the aromatic disulfide compound, a diaryl disulfide compound represented by the following formula (5) is more preferred, and as the aromatic thiol compound, a thioaryl compound represented by the following formula (6) is more preferred.

[0075]

[0076] (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. 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. Among 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.

[0077] 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.

[0078] 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 to which the disulfide group is bonded (1st position). 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 to 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 to which the mercapto group is bonded (1st position).

[0079] 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'-hexamethyldiphenyl disulfide 2,2',3,3',6,6'-hexaethyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-octaethyldiphenyl disulfide, 2,2'-dipropyldiphenyl disulfide, 3,3'-dipropyldiphenyl disulfide, 2,2',6,6'-tetrapropyldiphenyl disulfide, 2,2',3,3'-tetrapropyldiphenyl disulfide, 2,2',5,5'-tetrapropyldiphenyl disulfide, 3,3',5,5'-tetrapropyldiphenyl disulfide, 2,2 ',3,3',5,5'-hexapropyldiphenyl disulfide, 2,2',3,3',6,6'-hexapropyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-octapropyldiphenyl disulfide, 2,2'-diisopropyldiphenyl disulfide, 3,3'-diisopropyldiphenyl disulfide, 2,2',6,6'-tetraisopropyldiphenyl disulfide, 2,2',3,3'-tetraisopropyldiphenyl disulfide, 2,2',5,5'-tetraisopropyldiphenyl disulfide, 3,3',Examples include 5,5'-tetraisopropyldiphenyl disulfide, 2,2',3,3',5,5'-hexaisopropyldiphenyl disulfide, 2,2',3,3',6,6'-hexaisopropyldiphenyl disulfide, and 2,2',3,3',5,5',6,6'-octaisopropyldiphenyl disulfide.

[0080] 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.

[0081] 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.

[0082] 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. As for oxidative polymerization using a catalyst, it is more preferred to carry out the polymerization reaction by, for example, 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.

[0083] Among the substances containing the above metal elements, substances containing vanadium or iron as a metal element (these are also referred to as vanadium-containing substances and iron-containing substances, respectively) are preferred in terms of their high catalytic activity for oxidative polymerization, with iron-containing substances being more preferred. As the vanadium-containing substance, metals containing vanadium and oxovanadium compounds having a V=O bond in the vanadium compound molecule are preferred. Examples of the oxovanadium compound include vanadyl acetylacetonate, oxovanadium salen complex, N,N'-bissalicylideneethylenediamine oxovanadium, phthalocyanine oxovanadium, and tetraphenylporphyrin oxovanadium. As the iron-containing substance, iron compounds having chlorine in the molecule are preferred. Furthermore, compounds containing iron 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, iron(III) trifluoromethanesulfonate, and the like.

[0084] 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%, and 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, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less; and from the viewpoint that a sulfur-containing polymer having 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.

[0085] 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.

[0086] The oxygen-containing gas is oxygen molecules (O ２ The oxygen-containing gas is preferably a gas containing oxygen molecules (O ２ The oxygen-containing gas may contain gas components other than oxygen molecules (O ２ The gas components other than the above are not particularly limited, but are preferably rare gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn); nitrogen (N ２ In addition to the above inert gases, carbon dioxide gas (CO ２ ), water vapor, etc. in the oxygen-containing gas. ２ The content of oxygen molecules (O ２ The volume ratio of the oxygen-containing gas is preferably 0.1 to 100% by volume, more preferably 1 to 60% by volume, and even more preferably 10 to 30% by volume, relative to 100% by volume of the oxygen-containing gas. The remainder of the oxygen-containing gas is, for example, an inert gas.

[0087] 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 Preferably, 10 g / m or less ３ More preferably, 1 g / m or less ３ More preferably, 0.1 g / m or less ３ The amount of oxygen-containing gas supplied is preferably 1 / 3 of the total volume of the reaction composition from the viewpoint of accelerating the reaction rate and being easy to control. ３ per minute, oxygen (O ２ ) as the supply amount (supply rate) of 0.00002 m ３ / min~2m ３ / min, and more preferably 0.0001 to 0.2 m ３ / min or more, and more preferably 0.0002 to 0.02 m ３ / minutes or more.

[0088] In the polymerization step, it is preferable to further use an acid and / or a salt thereof. By using an 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 period of time. As the acid, a Brønsted acid is preferable, and in particular, an acid having an acid dissociation constant of −19 to 4 is preferable. 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.

[0089] 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 above acids 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 above acids and / or salts 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 %, relative to 100 mol % of the monomer component.

[0090] A solvent may be used in the polymerization. The solvent is not particularly limited, but 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. The amount of the solvent used is not particularly limited, but 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 listed above, it is preferred to use non-halogen solvents such as N-methylpyrrolidone, tetrahydrofuran, ethyl acetate, and cyclopentyl methyl ether.

[0091] 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, while more 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.

[0092] When the diaryl disulfide compound represented by the formula (5) and / or the thioaryl compound represented by the 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.

[0093] When oxidative polymerization is carried out under the preferred conditions described above in the polymerization step, a polymer containing a relatively high proportion of the structural unit (U2) is likely to be obtained. Similarly, when the diphenyl disulfide compound and / or benzenethiol compound described above is used as the monomer component, a polymer containing the structural unit (U2-1) as the main structural unit can be obtained.

[0094] If the polymer obtained by the polymerization step is a polymer having a structural unit (U1), such as the structural unit (U1-1), the polymer can be used as the sulfur-containing polymer. For the purpose of increasing the proportion of the structural units (U1) and (U1-1) in the polymer obtained by the polymerization step, it is preferable to subject the polymer to an oxidation step. The oxidation step is a step in which the polymer obtained by the polymerization step is oxidized.

[0095] 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.

[0096] 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 is possible to moderately 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, per mol of sulfur atoms in the polymer (P).

[0097] 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.

[0098] Sulfonyl group (-S(-O) ２ When it is desired to increase the content of sulfur atoms, the reaction can be carried out for a longer time than the above-mentioned reaction time. In this case, the amount of the oxidizing agent to be added is not particularly limited as long as the desired oxidation reaction of sulfur atoms proceeds, but is usually preferably 0.01 to 1,000 mol, more preferably 0.05 to 500 mol, still more preferably 0.1 to 100 mol, and particularly preferably 0.5 to 20 mol, per mol of sulfur atoms in the polymer.

[0099] A solvent may be used in the oxidation reaction. Examples of the solvent used include the same solvents as those used in the polymerization step. The oxidation step can produce 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.

[0100] 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 sulfur-containing polymers include those in which at least one of the divalent aromatic hydrocarbon groups constituting the main chain, such as a divalent aromatic hydrocarbon group represented by the formula (I), has a reactive functional group as a substituent. Methods for producing such sulfur-containing polymers 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 reactive properties, 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.

[0101] 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.

[0102] 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. Of these, chlorosulfonic acid is preferred. The amount of the sulfonating agent used is not particularly limited, but it is preferable to use 0.1 to 10,000 mass% of the sulfonating agent relative to 100 mass% of the polymer. The amount is more preferably 1 mass% or more, even more preferably 10 mass% or more, and more preferably 1,000 mass% or less, even more preferably 500 mass% or less.

[0103] 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 complex compounds thereof (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 0.01 to 1000% by mass of the reducing substance 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.

[0104] In the mercapto group introduction step, a sulfonyl group is introduced into a divalent aromatic hydrocarbon group contained in the polymer using 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 such as (1) mixing the polymer with a sulfonating agent to introduce a sulfonyl group into the divalent aromatic hydrocarbon group, and then mixing the polymer with a reducing substance to reduce the introduced sulfonyl group to a mercapto group; (2) mixing the polymer with a sulfonating agent and a reducing substance substantially simultaneously; and (3) mixing the polymer with a reducing substance first, followed by the sulfonating agent. Among these, method (1) is preferred.

[0105] The reaction in the mercapto group introduction step is preferably carried out in a solvent, and preferred 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, and 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.

[0106] 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.

[0107] The sulfur-containing polymer can be obtained by the above-mentioned production method, but the polymer composition obtained by the polymerization step contains impurities such as the solvent used in the polymerization step and the residue of the catalyst used (catalyst residue). Furthermore, the polymer or polymer-containing composition obtained by the oxidation step may contain residual acids. These impurities may affect the heat resistance, etc., of the inorganic particle-containing composition of the present invention, so it is preferable to isolate the sulfur-containing polymer and reduce these impurities. Therefore, it is preferable that the production method of the sulfur-containing polymer further includes a purification step.

[0108] 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.

[0109] 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.

[0110] (Dispersant Having Phosphate Group and / or Phosphate Ester Group) In one preferred embodiment of the present invention, the inorganic particle-containing composition contains a dispersant having a phosphate group and / or a phosphate ester group (hereinafter also referred to as a phosphate compound or a phosphate dispersant). The phosphate compound is not particularly limited as long as it has a phosphate group and / or a phosphate ester group, but may be a compound represented by the following formula (2):

[0111]

[0112] (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.

[0113] In the above formula (2), R １ are the same or different and are 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 heteroatoms. 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.

[0114] 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 a 2-ethylbutyl group, a 2-ethyl-2-methylpropyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 1,5-dimethylhexyl group, a t-octyl group, a branched nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and an icosyl group; and alicyclic alkyl groups such as a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexylpropyl group, a cyclododecyl group, a norbornyl group (C7), an adamantyl group (C10), and a cyclopentylethyl group.

[0115] Examples of the alkenyl group include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecenyl, and icosenyl groups.

[0116] 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.

[0117] 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 or an ester group. １ has a carbonyl structure, and R ２ In one preferred embodiment, the linking moiety to the alkyl group is an ester structure. In another preferred embodiment, the organic group is a (meth)acryloyl group. The number of carbon atoms in the hydrocarbon group includes the number of carbon atoms in the substituent.

[0118] 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, a t-octyl group, or a 1-ethylpentyl group; or an alkenyl group such as a vinyl group, an allyl group, or an isopropenyl group.

[0119] The above R １ The organic group having a polyester structure is also one of the preferred embodiments of the present invention. １ is represented by the following formula: -(R１’ -COO) ｍ -R １’’ (In the formula, R １’ represents an alkylene group having 1 to 10 carbon atoms. １’’ represents an alkyl group having 1 to 4 carbon atoms, and m is a number from 1 to 10.

[0120] -(R ２ The oxyalkylene group represented by -(R)- 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. ２ The oxyalkylene group represented by (O)- is preferably an oxyalkylene group having 2 to 8 carbon atoms, 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, and styrene oxide. Ethylene oxide, propylene oxide, and butylene oxide are more preferred, and ethylene oxide and propylene oxide are even more preferred.

[0121] -(R ２ When the oxyalkylene group represented by (O)- contains an oxyethylene group to which ethylene oxide is added, the oxyethylene group content is preferably 50 to 100 mol %, 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 %, based on 100 mol % of all oxyalkylene groups.

[0122] In the formula (2), a is an integer of 1 to 3. Preferably, a is 1 or 2. The inorganic particle-containing composition may contain two or more of a phosphoric acid monoester in which a is 1 in formula (2), a phosphoric acid diester in which a is 2, and a phosphoric acid triester in which a is 3, and an embodiment containing a phosphoric acid monoester and a phosphoric acid diester is one of the preferred embodiments of the present invention.

[0123] In the above formula (2), n is an integer of 0 to 20. n is preferably 1 to 15, more preferably 2 to 10, even more preferably 3 to 8, and particularly preferably 3 to 6. In one aspect, an embodiment in which n is 1 is also one of the preferred embodiments. When the above phosphoric acid compound has an oxyalkylene group, affinity with the solvent is further improved, thereby further increasing the dispersibility of the zirconium oxide particles, titanium oxide particles, and titanate particles.

[0124] The phosphate compound preferably has a molecular weight of 98 to 2000. When the molecular weight of the phosphate compound is within this range, it can penetrate more fully into the fine gaps between the zirconium oxide, titanium oxide, or titanate particles, further improving dispersibility. The molecular weight of the phosphate compound is more preferably 180 to 1800, even more preferably 200 to 1500, even more preferably 220 to 1200, and particularly preferably 240 to 1000. The molecular weight of the phosphate compound can be measured by high performance liquid chromatography (HPLC) or gel permeation chromatography (GPC).

[0125] [Method for producing an inorganic particle-containing composition] The present invention is also a method for producing an inorganic particle-containing composition, which includes a step of disintegrating aggregates of particles of at least one type selected from the group consisting of zirconium oxide, titanium oxide, and titanates in the presence of zinc chalcogenide and a dispersant.

[0126] The method for producing the inorganic particle-containing composition is not particularly limited as long as it includes a step of disintegrating agglomerates of at least one type of particles selected from the group consisting of zirconium oxide, titanium oxide, and titanates in the presence of zinc chalcogenide and a dispersant. However, it is preferable that the disintegration step includes disintegrating a mixture containing agglomerates of particles of the Zr- or Ti-containing oxide, zinc chalcogenide, and a dispersant.

[0127] The dispersant used in the production of the inorganic particle-containing composition can be the same as the dispersant described for the inorganic particle-containing composition, and the preferred form of the dispersant is also as described above.

[0128] The amount of zinc chalcogenide used in the disintegration step is not particularly limited, but is preferably 1 to 150% by mass relative to 100% by mass of the aggregates of zirconium oxide particles, titanium oxide particles, and titanate particles in total, more preferably 2 to 100% by mass, even more preferably 3 to 50% by mass, and particularly preferably 5 to 35% by mass.

[0129] The amount of dispersant used in the disintegration step is not particularly limited, but is preferably 1 to 30% by mass relative to 100% by mass of the total of the aggregates of zirconium oxide particles, titanium oxide particles, and titanate particles. When the amount of dispersant used is 1% by mass or more, the disintegration property of the aggregates of Zr- or Ti-containing oxide particles can be further improved. When the amount of dispersant used is 30% by mass or less, the refractive index of the coating film formed using the resulting composition can be further increased. The amount of dispersant used is more preferably 2 to 25% by mass, even more preferably 5 to 22% by mass, and particularly preferably 10 to 20% by mass.

[0130] In the method for producing the inorganic particle-containing composition, the sulfur-containing polymer is used as a dispersant, which is one of the preferred embodiments of the present invention. The amount of the sulfur-containing polymer used is not particularly limited, but is preferably 1 to 30% by mass relative to 100% by mass of the aggregate of the zirconium oxide particles, titanium oxide particles, and titanate particles. The amount of the sulfur-containing polymer used is more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, and particularly preferably 5 to 15% by mass.

[0131] In the method for producing an inorganic particle-containing composition, the use of the phosphoric acid compound as a dispersant is one preferred embodiment of the present invention. The amount of the phosphoric acid compound used in the disintegration step is not particularly limited, but is preferably 0.5 to 10 mass% relative to 100 mass% of the aggregates of zirconium oxide particles, titanium oxide particles, and titanate particles. The amount of the phosphoric acid compound used is more preferably 1 to 9 mass%, even more preferably 2 to 8 mass%, and particularly preferably 3 to 7 mass%.

[0132] The disintegration step may be carried out without using a solvent, but is preferably carried out in the presence of a solvent. That is, the mixture containing the aggregates of at least one particle selected from the group consisting of zirconium oxide, titanium oxide, and titanates, zinc chalcogenide, and a dispersant preferably further contains 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 solvent is not particularly limited, but is preferably one that has excellent solubility for the dispersant. Examples of such solvents 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, and sulfolane. These solvents may be used singly or in combination. Among these, non-halogenated solvents are preferred, and it is more preferred to use at least one solvent selected from the group consisting of cyclohexanone, cyclopentanone, propylene glycol monomethyl ethyl ether acetate, methyl ethyl ketone, toluene, xylene, tetrahydrofuran, and N-methylpyrrolidone.

[0133] The amount of solvent used in the disintegration step 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 Zr- or Ti-containing oxide particle agglomerates, zinc chalcogenide, and dispersant. The same applies to the preferred range of the content of the solvent relative to 100 parts by mass of the total content of the Zr- or Ti-containing oxide particle agglomerates, zinc chalcogenide, and dispersant in the mixture.

[0134] The crushing method in the above-mentioned production method (also referred to as a crushing method) is not particularly limited as long as it includes an operation (crushing operation) of crushing the aggregates of the Zr- or Ti-containing oxide particles into inorganic particles that are primary particles. Although it may include an operation of further pulverizing the inorganic particles finer, it is preferable to crush the aggregates to a size close to the primary particle size.

[0135] The Zr- or Ti-containing oxide particle agglomerates used in the disintegration step refer to particles formed by agglomeration of at least one type of particles selected from the group consisting of zirconium oxide, titanium oxide, and titanates. In the Zr- or Ti-containing oxide particle agglomerates, a plurality of Zr- or Ti-containing oxide particles are present as primary particles, which are agglomerated together. The Zr- or Ti-containing oxide particle agglomerates used in the production method are preferably particles having an agglomeration 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: Agglomeration 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 (e.g., nm).

[0136] The average secondary particle diameter (D2) is the 50% particle diameter in a volume-based particle size distribution measured by a particle size distribution measurement method using dynamic light scattering (DLS). A concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.) is preferably used as a measuring device for the average secondary particle diameter (D2). In the above measurement method, a measurement sample prepared as follows is used. That is, 0.04 g of the aggregate (powder) of Zr- or Ti-containing oxide particles to be measured is weighed into a 10 cc screw tube, and 8 g of benzyl alcohol is added. The mixture is shaken at room temperature for 2 minutes, ultrasonically irradiated for 1 minute, shaken for 2 minutes, ultrasonically irradiated for 1 minute, and shaken for 2 minutes, in this order, and the resulting liquid is used as a measurement sample. The shaking treatment is carried out using a shaker (TUBE MIXER TRIO, product number: HM-1N, manufactured by AS ONE Corporation), and the ultrasonic irradiation treatment is carried out using an ultrasonic device (BRANSONIC, product number: 5510J-DTH, manufactured by Branson Corporation). However, before the measurement, the concentration may be appropriately adjusted using benzyl alcohol depending on the amount of scattered light and the presence or absence of multiple scattering.

[0137] In the above production method, the crushing is preferably carried out so that the dispersed particle size (Dd) in the resulting inorganic particle-containing composition is smaller than the average secondary particle size (D2) of the agglomerates of the Zr- or Ti-containing oxide particles used, and so that the degree of crushing (r) represented by the following formula is less than 5. It is more preferable to carry out the crushing until the degree of crushing (r) becomes 3 or less, and even more preferably until the degree of crushing (r) becomes 2 or less. Degree of crushing (r) = Dd / D1 In the above formula, Dd is the dispersed particle size (Dd) (unit: nm) in the inorganic particle-containing composition, and D1 is the average primary particle size (D1) (unit: nm) of the agglomerates of the Zr- or Ti-containing oxide particles used.

[0138] The average primary particle diameter (D1) of the Zr- or Ti-containing oxide particle agglomerates used in the above-mentioned crushing step is not particularly limited, but the average primary particle diameter (D1) is preferably 1 to 50 nm. When such Zr- or Ti-containing oxide particle agglomerates are crushed to a diameter close to the average primary particle diameter (D1), the resulting inorganic particle-containing composition, when used to form a coating film, exhibits superior transparency. The average primary particle diameter (D1) of the Zr- or Ti-containing oxide particles is more preferably 3 to 45 nm, even more preferably 5 to 40 nm, even more preferably 7 to 30 nm, and particularly preferably 10 to 25 nm.

[0139] The aggregates of Zr- or Ti-containing oxide particles used in the crushing step preferably contain crystalline zirconium oxide and / or titanium oxide. The preferred ranges of the crystallinity of the crystalline zirconium oxide and titanium oxide are as described above for the zirconium oxide, titanium oxide, and titanate contained in the inorganic particle-containing composition. The crystallinity can be determined by powder X-ray diffraction measurement.

[0140] The average secondary particle diameter (D2) of the aggregates of Zr- or Ti-containing oxide particles is not particularly limited, but is preferably 5 to 25,000 nm. By setting the average secondary particle diameter (D2) within the above range, the resulting inorganic particle-containing composition 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.

[0141] The definitions of the average primary particle diameter (D1) of the Zr- or Ti-containing oxide particle agglomerates used in the disintegration step, the average primary particle diameter (D1) of the Zr- or Ti-containing oxide particles in the inorganic particle-containing composition obtained by the production method, the definition of the dispersed particle diameter (Dd), and the measurement methods thereof are the same as the average primary particle diameter (D1) and dispersed particle diameter (Dd) of the Zr- or Ti-containing oxide contained in the inorganic particle-containing composition described above, and the measurement methods thereof.

[0142] As described above, the Zr- or Ti-containing oxide particle aggregates preferably have an agglomeration degree (R) of 5 or more, 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.

[0143] The specific surface area of ​​the aggregate of the Zr- or Ti-containing oxide particles is not particularly limited, but is preferably 1 to 300 m ２ / g, more preferably 10 to 200m ２ / g, and more preferably 15 to 150m ２ The specific surface area of ​​the aggregate of Zr- or Ti-containing oxide particles is a value measured by the BET method, and specifically, can be measured by the method described in the examples.

[0144] The structure of the aggregate of Zr- or Ti-containing oxide particles is not particularly limited, and may be a porous structure or a dense structure. It may also be hollow. The shape of the aggregate of Zr- or Ti-containing oxide particles is not particularly limited, and may be any of amorphous, granular, plate-like, columnar, and needle-like shapes, but granular shapes are preferred, and among granular shapes, spherical shapes are preferred. The granular shape refers to a uniform shape with an aspect ratio of 1.5 or less.

[0145] The method for producing the aggregate of Zr- or Ti-containing oxide particles used in the above-mentioned crushing step is not particularly limited, and can be produced by, for example, a conventionally known wet method, dry method, etc. Specific examples include solid-phase synthesis methods in which Zr- or Ti-containing oxide particles are obtained by thermally decomposing a solid raw material such as oxalate, 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 an oxide is precipitated in an alkaline aqueous solution from a metal inorganic salt such as a metal nitrate, sulfate, or chloride, and a method in which the metal hydroxide or metal oxide obtained by the liquid-phase synthesis method is calcined at a high temperature; ４Among these, a gas phase reaction method is preferred, for example, a method in which heated vapor of a metal chloride such as the above is reacted with heated oxygen to form particles of the metal oxide in a high-temperature gas phase.

[0146] Titanium dioxide can be produced by hydrothermally treating the hydrolysis product of titanium alkoxide in aqueous alcohol or organic acid, or by TiCl ４ The heated steam is reacted with heated oxygen to form TiO in the high-temperature gas phase. ２ Chlorine method for forming particles, TiOSO ４ Anatase-type TiO, which is a precipitate obtained by thermal hydrolysis of an aqueous solution of ２ A preferred example is a sulfuric acid method in which fine particles are baked at 800 to 1000° C. to grow. Of these, the chlorine method and sulfuric acid method are preferred.

[0147] Commercially available products can also be used as the agglomerates of Zr- or Ti-containing oxide particles. Commercially available products of the zirconium oxide particles 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 Co., Ltd. Commercially available products of the titanium oxide particles include AEROXIDE® TiO2 P-25, AEROXIDE® TiO2 P-90, AEROXIDE® TiO2 T-805, and AEROXIDE® TiO2 manufactured by Nippon Aerosil Co., Ltd. Examples of commercially available titanate particles include NKT-90 manufactured by Teika Corporation; fine particle titanium oxide MT-05, MT-100SA, MT-100HD, and MT-500B manufactured by Ishihara Sangyo Kaisha, Ltd.; high-purity titanium oxide PT-601A and TTO-51(A) manufactured by Sakai Chemical Industry Co., Ltd.; titania for catalyst carriers SSP-M, SSP-N, and STR-100N manufactured by Fuji Titanium Industry Co., Ltd.; Micro Titanium TAF-1500J and TAF-500J manufactured by Resonac Holdings Co., Ltd.; and Super Titania F-2, F-4A, and F-6A. Examples of commercially available titanate particles include barium titanate nanoparticles manufactured by Merck.

[0148] The zinc chalcogenide used in the disintegration step may be an aggregate or a dispersion of zinc chalcogenide particles. For example, the zinc chalcogenide aggregate can be produced by a wet method, a dry method, or the like, similar to the zirconium oxide, titanium oxide, and titanate described above.

[0149] The zinc chalcogenide used in the disintegration step is not particularly limited as long as it is a zinc chalcogenide, and may be a compound containing zinc and a Group 16 element (oxygen, sulfur, selenium, tellurium, polonium, livermorium). Preferred examples of the zinc chalcogenide include zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), and zinc telluride (ZnTe), with zinc oxide and zinc sulfide being more preferred, and zinc oxide being even more preferred. The average primary particle size of the zinc chalcogenide used in the disintegration step is not particularly limited, but is preferably 1 to 50 nm. The average primary particle size of the zinc chalcogenide 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 size has the same meaning as the average primary particle size of the zinc chalcogenide in the inorganic particle-containing composition and can be determined by the same measurement method. Commercially available zinc oxide aggregates or dispersions can be used as the zinc oxide. Commercially available zinc oxide aggregates include FINEX-50, FINEX-30, FINEX-50LP, FINEX-33W, FINEX-52W-LP2, FINEX-33W-LP2, FINEX-50S-LP2, FINEX-30S-LPT, and FINEX-50-OTS, all manufactured by Sakai Chemical Industry Co., Ltd., and ultrafine zinc oxide FZO-50, all manufactured by Ishihara Sangyo Kaisha, Ltd. Examples of zinc oxide dispersions include DIF-5CS and DIF-AW4OP-3W, all manufactured by Sakai Chemical Industry Co., Ltd.

[0150] 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.

[0151] 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 type of particles to be used (Zr- or Ti-containing oxide), the size of the primary particles, the strength of aggregation, and the like. Examples of materials for 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 to be disintegrated are aggregates of crystalline zirconium oxide particles and / or titanium oxide particles, the material for the beads is preferably zirconia, and the Mohs hardness of the beads is preferably in the range of 8 to 10.

[0152] The average particle size of the beads is not particularly limited. It may be selected appropriately depending on the type of particles (Zr- or Ti-containing oxide) used, the size of the primary particles, the cohesive strength, 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. It 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 Zr- or Ti-containing oxide particles to be disintegrated is in the range of 100 to 10,000. This ratio is more preferably 200 to 8,000, and even more preferably 500 to 5,000.

[0153] The average particle size of the beads is the average particle size based on the number of beads. Typically, the particle size (diameter) of each bead is measured using 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 as the beads. Examples include 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.).

[0154] In the method using beads, the amount of beads used is not particularly limited, but it is preferable to use beads so that the ratio of beads to 1 part by mass of the aggregates of Zr- or Ti-containing oxide particles is 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 20 parts by mass.

[0155] 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 a paint shaker, there are no particular restrictions on the conditions as long as the beads can be used to break down agglomerates of Zr- or Ti-containing oxide 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 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 devices that can be used in the method include commercially available devices, such as the No. 488 Test Disperser (Paint Shaker / Paint Conditioner) (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and the Standard Model Disperser (manufactured by Seiwa Giken Co., Ltd.).

[0156] 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 break down agglomerates of Zr- or Ti-containing oxide particles, and it is preferable to select conditions that reduce the dispersed particle size without reducing the average primary particle size as much as possible. From this viewpoint, 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 apparatuses, 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.).

[0157] In the method using the beads, it is preferable to mix a mixture of the Zr- or Ti-containing oxide particle agglomerates, zinc chalcogenide, and a dispersant with the beads and disintegrate them, and it is more preferable to mix a mixture of the Zr- or Ti-containing oxide particle agglomerates, zinc chalcogenide, a dispersant, and the solvent with the beads and disintegrate them.

[0158] In the disintegration step, other components may be present in addition to the Zr- or Ti-containing oxide particle agglomerates, zinc chalcogenide, dispersant, and solvent. Other components may also be present in the mixture. Examples of such other components include carboxylic acid compounds such as oleic acid, alcohol compounds such as benzyl alcohol and cyclohexyl alcohol, silane compounds such as 3-(trimethoxysilyl)propyl methacrylate, and surface conditioners (surface tension modifiers) such as BYK-307 and BYK-378. The content of the other components is preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the total of the Zr- or Ti-containing oxide particle agglomerates. 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, it is more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more.

[0159] In the method using beads, it is preferable to remove the beads from the obtained composition after crushing. Examples of means for removing the beads include filtration and centrifugation. The above-mentioned production method produces an inorganic particle-containing composition, but the production method may further include another step after the crushing step. Examples of the other step include a purification step. For example, if abrasion powder from the beads generated in the method using beads or some of the agglomerates of Zr- or Ti-containing oxide particles used as the raw material remain without being crushed, a purification step such as filtration can be performed to remove the residue.

[0160] [Polymerizable Composition] The inorganic particle-containing composition of the present invention can be used as it is for various applications, such as a functional coating agent that can exhibit the functions of inorganic particles. However, it can also be used for the above applications by adding a conventionally known polymerizable monomer or resin component to further increase added value, for example, to form the resulting film into a cured film (coating film) or to improve adhesion to a substrate. For example, the inorganic particle-containing composition can be used for adjusting film-forming properties and imprint moldability by adding a conventionally known surface tension modifier used in paints and inks. The present invention also relates to a polymerizable composition containing an inorganic particle-containing composition and a polymerizable monomer. Using the above polymerizable composition to form a coating film is one preferred embodiment of the present invention.

[0161] The proportion of the polymerizable monomer in the polymerizable composition is not particularly limited, but is preferably 0.5 to 200% by mass, more preferably 2 to 100% by mass, even more preferably 5 to 75% by mass, and particularly preferably 10 to 50% by mass, relative to 100% by mass of the total of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide.

[0162] The total content of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide in the polymerizable composition is not particularly limited, but is preferably 1 to 99% by mass relative to 100% by mass of the polymerizable composition. When the total content of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide is 1% by mass or more, the refractive index of the formed coating film can be further increased. The total content of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide is more preferably 5 to 90% by mass, even more preferably 5 to 75% by mass, and particularly preferably 10 to 50% by mass.

[0163] The total content of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide in the polymerizable composition is preferably 15 to 95 mass%, more preferably 35 to 90 mass%, and even more preferably 50 to 82 mass%, based on 100 mass% of the solid content in the composition.

[0164] The polymerizable monomer contained in the polymerizable composition 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.

[0165] 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 bis(meth)acrylate, 4,4'-bis(meth)acryloxymethylbiphenyl, o-phenylphenolethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, o-phenylphenol-(EO)-addition-(meth)acrylate, o-phenylphenol-(EO)2-(meth)acrylate, bisphenol A (meth)acrylate, bisphenol A-(EO)-addition-(meth)acrylate, bisphenol S (meth)acrylate, bisphenol S-(EO)-addition (meth)acrylic monomers such as sulfur-containing (meth)acrylates such as bis(4-methacryloylthiophenyl)sulfide, 1H,1H,2H,2H-heptafluorodecyl (meth)acrylate, and (meth)acrylates having an adamantyl skeleton; triallyl cyanurate; glycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl methacrylate;

[0166] 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.

[0167] 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; and aromatic polyisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenylsulfide-4,4-diisocyanate, and phenylene diisocyanate. cyanate compounds; heterocyclic polyisothiocyanate compounds such as 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane; 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.

[0168] 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.

[0169] 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.

[0170] The polymerizable composition may contain other components in addition to the Zr- or Ti-containing oxide particle aggregates, zinc chalcogenide, dispersant, solvent, and polymerizable monomer. Examples of other components include the surface conditioner, polymerization initiator, photosensitizer, UV absorber, light stabilizer, pigment, dye, antioxidant, resin, reactive diluent, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization initiator, polymerization inhibitor, inorganic filler, organic filler, adhesion improver such as coupling agent, heat stabilizer, antibacterial / anti-fungal agent, flame retardant, matting agent, defoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-color separation agent, emulsifier, slip / scratch inhibitor, anti-skinning agent, drying agent, antifouling agent, antistatic agent, conductive agent (electrostatic assistant), etc.

[0171] 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; and acetophenone-based initiators such as "Omnirad TPO" and "Omnirad Examples of the initiator include acylphosphine oxide initiators such as "TPO-L" and "Omnirad 819," oxime ester initiators such as "Omnirad 1312," "Omnirad 1314," and "Omnirad 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.

[0172] The photosensitizer is not particularly limited, and conventionally known photosensitizers can be appropriately selected and used, and examples thereof include thioxanthone-based photosensitizers such as "Omnirad ITX," "Omnirad DETX," and "Omnirad DETX," manufactured by IGM RESINS, and coumarin-based photosensitizers such as "Esacure 3644." 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.

[0173] 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.

[0174] The light stabilizer is not particularly limited, and a conventionally known light stabilizer can be appropriately selected and used, for example, 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), TINUVIN 11 Examples of suitable terpolymers include 1FDL, TINUVIN 123, TINUVIN 144 (bis(1,2,2,6,6-pentamethyl-4-piperidyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butyl malonate), 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).

[0175] The method for curing the polymerizable composition is not particularly limited, and conventionally known methods such as a method using heating (thermal curing) or a method using active energy rays can be used. In the case of a method using heating, 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. In the case of a method using active energy rays, the active energy rays are preferably ultraviolet rays or electron beams, and more preferably ultraviolet rays. When ultraviolet irradiation is performed, the ultraviolet irradiation amount (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 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.

[0176] The method for forming a coating film using the polymerizable composition is not particularly limited, but it is preferable to form a coating film by applying the composition to a substrate or the like. When forming a coating film by coating, the coating method is not particularly limited, and conventionally known methods can be used. Among these, spin coating, bar coating, squeegee coating, inkjet coating, spraying, roll coating, rotary coating, and the like are preferred. The coating thickness is not particularly limited, and may be appropriately selected depending on the application of the resulting film, etc. For example, when used as an optical material, it is preferable to adjust the coating thickness so that the resulting film has a thickness of 0.01 to 1000 μm. The coating thickness is more preferably 0.1 to 100 μm, and even more preferably 0.5 to 10 μm.

[0177] In forming the coating film, it is preferable to heat the applied film (coating film) and / or irradiate it with active energy rays. The solvent contained in the coating film can be evaporated and removed by heating. Furthermore, by heating or irradiating it with active energy rays, the reaction of the polymerizable monomers contained in the coating film can be promoted, and a cured film can be obtained.

[0178] When heating is performed in forming the coating film, 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.

[0179] The active energy rays are preferably ultraviolet rays or electron beams, and more preferably ultraviolet rays. When ultraviolet rays are irradiated, the amount of ultraviolet rays (cumulative exposure amount) is not particularly limited, but the preferred amount is as described above.

[0180] 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).

[0181] In one preferred embodiment of the present invention, a coating film is formed using the polymerizable composition, and then a pattern is formed using a metal mold, a resin mold, or the like by nanoimprint molding, etc. The pattern formation method is not particularly limited, but preferably includes a step of forming a coating film by applying the polymerizable composition to a substrate by the above-mentioned method, etc., and a step of pressing a mold having a concave-convex pattern against the coating film obtained in the coating film formation step to form a pattern.

[0182] The mold used in the pattern formation step is not particularly limited as long as it has a transfer pattern consisting of projections and recesses formed on its surface. Examples of the material for the mold surface include silicone-based resins, fluorine-based resins, epoxy resins, quartz, and glass.

[0183] The surface tension of the mold surface is not particularly limited, but is preferably 40 mN / m or less, more preferably 35 mN / m or less, even more preferably 30 mN / m or less, and particularly preferably 25 mN / m or less.

[0184] [Uses] The inorganic particle-containing composition and polymerizable composition of the present invention are preferably used as molding materials or raw materials for molding materials, coating agents or raw materials for coating agents, nanoparticle inks for nanoimprint lithography and the like, in various applications including optical applications such as optical materials, optical device members, and display device members, as well as machine part materials, electric / electronic part materials, automobile part materials, and civil engineering and construction materials.

[0185] For example, the inorganic particle-containing composition and the polymerizable composition may contain zirconium oxide (ZrO ２ ), titanium oxide (TiO ２) and titanates, and therefore can be suitably used in the manufacture of optical materials, optical device members, and display device members. Specific applications include, for example, spectacle 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 bonding materials, filters, diffraction gratings, diffractive optical elements, prisms, light guides, watch glasses, and transparent glasses and cover glasses for display devices; photosensors (optical sensors (CMOS sensors, TOF sensors, etc.)), photoswitches, LEDs, Examples of such optical device components include micro-LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, disconnectors, optical splitters, and optical fiber adhesives; display device components such as substrates for display elements such as LCDs, organic ELs, and PDPs, substrates for color filters, touch panel substrates, index matching materials used in touch panels, etc., display protective films, display backlights, light guide plates, anti-reflection films, anti-fogging films, and light extraction enhancers for LEDs and organic ELs; applications in which imprint molding can be applied to form diffractive optical elements, lenses, etc. that can be precisely thinned on inorganic, glass, or resin substrates; wafer-level optics, etc. Among these, imaging lenses, digital glasses, goggles, and displays that enable VR (virtual reality), AR (augmented reality), and MR (mixed reality), filters, diffraction gratings, diffractive optical elements, prisms, light guides, LEDs, micro-LEDs, light-emitting elements, color filters, and touch panels are more preferred.

[0186] The inorganic particle-containing composition and the polymerizable composition may further contain zirconium oxide (ZrO ２ ), titanium oxide (TiO ２) and titanates, and has a high refractive index, and therefore can be preferably used as 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, or a raw material for a coating agent for forming a high refractive index film for the above-mentioned applications, particularly for producing the above-mentioned optical materials, optical device members, display device members, and nanoparticle inks for nanoimprint lithography and the like.

[0187] 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."

[0188] [Evaluation of Zirconium Oxide, Titanium Oxide, Titanate, and Zinc Chalcogenide] The crystal structure, degree of crystallinity, average primary particle diameter (D1), specific surface area, and composition of the zirconium oxide particles, titanium oxide particles, aggregates of titanate particles, and zinc chalcogenide used in each of the Examples and Comparative Examples were measured as follows.

[0189] <Method for Evaluating Crystal Structure> The zirconium oxide particles, titanium oxide particles, titanate particle aggregates, and zinc chalcogenide used in each Example and Comparative Example were used as samples, and the crystal structure and crystallinity were measured using an X-ray diffractometer SmartLab (manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray source: CuKα (0.154 nm); X-ray output settings: 45 kV, 200 mA; sampling width: 0.0200°; scan speed: 5.0000° / min; measurement range: 5 to 90°; measurement temperature: 25°C. The crystal structure was determined from the obtained X-ray diffraction pattern using the zirconium oxide particles, titanium oxide particles, titanate particle aggregates, and zinc chalcogenide used in each Example and Comparative Example.

[0190] <Average primary particle diameter (D1)> In each example and comparative example, when the inorganic particle aggregates used were those containing zirconium oxide (crystalline) as an inorganic component, X-ray diffraction measurements were performed, and the crystallite diameter was determined from the full width at half maximum of the diffraction line (strongest line) with the largest diffraction intensity in the obtained X-ray diffraction pattern, and the obtained value was taken as the average primary particle diameter (D1). In each inorganic particle aggregate used in examples other than Examples 5 and 6, the diffraction line of the lattice plane (11-1) was the strongest line, and the full width at half maximum of the diffraction line of the lattice plane (11-1) was measured, and the value of the crystallite diameter Dc (11-1) was calculated using analysis software (PDXL2) from the obtained value, and the obtained value was taken as the average primary particle diameter (D1) of each inorganic particle aggregate used. In Examples 5 and 6, when the aggregates of inorganic particles used contained titanium oxide (crystalline) as the inorganic component, the diffraction line of the lattice plane (101) was 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 taken as the average primary particle diameter (D1) of each aggregate of inorganic particles used. The apparatus and conditions for X-ray diffraction measurement were the same as those for the crystalline structure. In Examples 1 to 7, when the zinc chalcogenide used contained zinc oxide (crystalline) as the inorganic component, the diffraction line of the lattice plane (101) was 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 taken as the average primary particle diameter (D1) of each inorganic particle used. The apparatus and conditions for X-ray diffraction measurement were the same as those for the crystalline structure.

[0191] <Specific Surface Area> The specific surface area of ​​the inorganic particle aggregates and zinc chalcogenide used in each Example and Comparative Example was measured by the BET method using a BELSORP-MR6 (manufactured by Microtrac-Bell). The measurement sample was prepared by vacuum-drying the inorganic particle aggregates for 20 hours in a vacuum dryer at 25°C.

[0192] <Composition> The zirconium oxide particles, titanium oxide particles, titanate particle aggregates, and zinc chalcogenide used in each example and comparative example were subjected to X-ray fluorescence analysis (XRF) to evaluate the contents of metal elements, sulfur, and chlorine. Specifically, the ratio of the mass content of each element to the total mass content of each metal element, sulfur, and chlorine detected by X-ray fluorescence analysis (XRF) for the zirconium oxide particles, titanium oxide particles, titanate particle aggregates, and zinc chalcogenide was calculated.

[0193] [Evaluation of Inorganic Particle-Containing Composition] The dispersed particle diameter (Dd) of the inorganic particle-containing composition obtained in each of the Examples and Comparative Examples was measured as follows.

[0194] <Dispersed Particle Diameter (Dd)> Samples were prepared using the inorganic particle-containing compositions obtained in each Example and Comparative Example as follows, and the volumetric particle size distribution was measured using a concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.). The 10% particle diameter was defined as D10, the 50% particle diameter as D50, and the 99% particle diameter as D99, and the 50% particle diameter (D50) was defined as the dispersed particle diameter (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 (D) used in each Example so that the concentration of inorganic particles contained in each composition was approximately 3 mass %, and these were used as measurement samples. Note that, during the measurement, the concentration was adjusted appropriately depending on the amount of scattered light and the presence or absence of multiple scattering.

[0195] [Evaluation of Sulfur-Containing Polymers Obtained in Each Synthesis Example] The average molecular weight and other properties of the sulfur-containing polymers obtained in each Synthesis Example were measured as follows. <Weight-Average Molecular Weight (Mw), Number-Average Molecular Weight (Mn)> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the sulfur-containing polymers obtained in each Synthesis Example were determined by gel permeation chromatography (GPC) under the following conditions. Apparatus 1: CBM-20A, manufactured by Shimadzu Corporation Apparatus 2: 1260 Infinity, manufactured by Agilent Technologies Detector: Differential refractive index detector (RI) (SPD-20MA, manufactured by Shimadzu Corporation) and ultraviolet-visible-infrared spectrophotometer (SPD-20MA, manufactured by Shimadzu Corporation) Column: TSKgel Super HM-N, manufactured by Tosoh Corporation Column temperature: 40°C Flow rate: 0.3 ml / min Calibration curve: Polystyrene Standards Eluent: Chloroform, tetrahydrofuran

[0196] <MALDI (Time-of-Flight Mass Spectrometry)> The sulfur-containing polymers obtained in each Synthesis Example were subjected to MALDI measurement under the following conditions: Apparatus: Time-of-Flight Mass Spectrometer (Bruker Autoflex III) Sample Preparation: Approximately 2 mg of a measurement sample, 20 mg of 2,5-dihydroxybenzoic acid as a matrix agent, and 2.0 mg of sodium iodide as an ionizing agent were dissolved in 1.0 g of tetrahydrofuran, and the prepared solution was applied to a measurement target plate and then dried at room temperature for approximately 100 minutes.

[0197] < １ H-NMR> The sulfur-containing polymers obtained in each synthesis example were analyzed under the following conditions: １ H-NMR measurement was carried out. Apparatus: Nuclear magnetic resonance spectrometer (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 were dissolved in the measurement solvent.

[0198] < １３ C-NMR> The sulfur-containing polymers obtained in each synthesis example were analyzed under the following conditions: 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 to several hundreds of mg of the sulfur-containing polymer obtained in each synthesis example was dissolved in the measurement solvent.

[0199] <IR> IR measurement was carried out on the sulfur-containing polymers obtained in each synthesis example 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.

[0200] <Elemental 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 sample, a photoelectron spectrometer (JPS-9010TR, XPS device, light source: Mg, X-ray output: 400 W) manufactured by JEOL was used to measure the peak intensity derived from the 2p orbital of sulfur atoms and the peak intensity derived from the 1s orbital of oxygen atoms, and the O / S ratio was calculated by calculating their integral ratio. If necessary, the peak intensity derived from the 1s orbital of carbon atoms was also measured, and the O / S ratio was calculated taking the results into consideration. Furthermore, for sulfur atom peaks that could be separated into sulfide and disulfide peaks, the sulfide / disulfide ratio was also calculated. The measurement method, the position of the binding energy, etc. were determined with reference to Handbook of X-ray Photoelectron Spectroscopy (published by 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.

[0201] <Binding Energy> 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 on a silicon wafer to form a film. Using this sample, the binding energy was measured from the peak position of the 2p3 / 2 orbital of the sulfur atom using a photoelectron spectrometer (JPS-9010TR, XPS device) manufactured by JEOL.

[0202] <Organic Elemental Analysis> The sulfur-containing polymers obtained in each synthesis example were subjected to elemental analysis using the following apparatus: Apparatus: J Science Lab JM10

[0203] [Evaluation of Coating Films Prepared in Each Example and Comparative Example] Evaluations of the coating films prepared in each Example and Comparative Example were carried out as follows. <Method of Curing Coating Film by UV Irradiation> The cured films on the coated glass slides prepared in each Example and Comparative Example were prepared by irradiating the coating film on the coated glass slide with UV light using an area UV irradiator to harden the coating film. The equipment used was as follows: Equipment: Area UV Irradiation System (manufactured by CCS Inc.) Power source: PSCC-60048-NL (manufactured by CCS Inc.) Irradiation wavelength: 365 nm Irradiation intensity: 100 mW / cm ２

[0204] <Method for evaluating refractive index and film thickness of film> The refractive index and film thickness of the coating film obtained in each Example and Comparative Example were determined from the reflectance spectrum of the coating film on the slide glass with the coating film 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. The refractive index and film thickness of the cured film obtained in each Example and Comparative Example were also determined in the same manner. Device: Film Thickness Measurement System F-20, Standard Fiber Stage SS-1 (Spot diameter 1.5 mm), manufactured by Filmetrics

[0205] <Method for evaluating film transparency (haze)> Transparency was determined by measuring haze. The haze of the slide glass with the coating film prepared in each Example and Comparative Example was measured, and the haze of the coating film was determined by subtracting the haze measurement value of the slide glass substrate used as the substrate from the measured value. The haze of the cured film obtained in each Example and Comparative Example was also determined in the same manner. The following device was used for measuring haze. Device: HAZE METER NDH5000 turbidity meter manufactured by Nippon Denshoku Industries Co., Ltd.

[0206] (Synthesis of Sulfur-Containing Polymer) [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), Na ２ S ２ O ８ Sodium peroxodisulfate (2.57 g, 12.00 mmol) was added. The three-neck flask was then heated to 160°C with nitrogen flow (20 mL / min) for 10 minutes, then switched to air bubbling (150 mL / min), and stirred for 40 hours to carry out oxidative polymerization. After polymerization was completed, air bubbling was stopped, and 240 mL of N-methylpyrrolidone was added and stirred for 10 minutes. The reaction solution was then cooled to room temperature, and THF (2.2 L) was added as a solvent. After stirring for 10 minutes, 192 mL of purified water was added and stirred for 5 minutes. Next, while the eggplant-shaped flask was cooled on an ice bath, trichloroisocyanuric acid (122.11 g, 0.66 mol) was added, and after stirring for 2 hours, zinc powder (31.53 g, 0.48 mol) was added and stirred at room temperature for 14 hours. After the reaction was completed, methanol (12 L) was added to the reaction 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 a white sulfur-containing polymer (Po1a) powder. The yield was 92%. The structure of the resulting sulfur-containing polymer (Po1a) was as follows: １The product was identified by H-NMR, XPS, ICP, IR, GPC, elemental analysis, and MALDI measurement. １ H-NMR (CD ２ Cl ２ , 400 MHz, ppm): δ = 7.56 (m, 17H), δ = 7.19 (m, 6H), 2.35 (m, 3H). XPS confirmed that the ratio of sulfide groups: sulfoxide groups: sulfonic acid groups was 45:55:0 mol %. IR confirmed that the ratio was 2570 cm －１ A peak derived from mercapto was observed around 100 mol %, 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).

[0207] <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, and 1.1 L of sulfolane was added as a solvent. Next, the three-neck flask was heated to 130 ° C. while nitrogen flow (0.5 L / min) was performed for 10 minutes, and then allowed to cool to room temperature. After cooling, the three-neck flask was immersed in a water-cooled bath, and 98.3 g of chlorosulfuric acid was gradually added dropwise while nitrogen flow (0.25 L / min) was performed. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then 16.6 g of zinc was added while the three-neck flask was cooled again in a water-cooled bath, and the mixture was stirred for 14 hours. After completion of the reaction, the resulting reaction solution was added dropwise to 5.5 L of methanol to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum dried at room temperature to obtain polymer (Po1) powder. The yield was 90%. The structure of the obtained polymer (Po1) is １ The product was identified by H-NMR, ICP, GPC, IR, and elemental analysis. １ H-NMR (CDCl ３ , 600MHz, ppm): δ = 7.53 (m, 10H), δ = 7.24 (m, 12H), 2.34 (m, 3H), 2570cm from IR －１A peak derived from mercapto was observed near the nucleus, and GPC confirmed that Mw = 2370 and Mn = 1150, confirming the presence of 27.7 mol% of thiol (-SH) groups relative to all aromatic rings. Since the content of thiol (-SH) groups in polymer (Po1a) is thought to be 9.5 mol% relative to 100 mol% of all aromatic rings (all structural units), the amount of mercapto groups introduced in this reaction is thought to be 18.2 mol%. Elemental analysis confirmed that the sulfur atom weight ratio of the sulfur-containing polymer (Po1) was increased compared to the sulfur-containing polymer (Po1a) before the reaction.

[0208] <Quantification of SH groups in sulfur-containing polymer (Po1)> 2.0 g of sulfur-containing polymer (Po1) was added to a 20 mL test tube, followed by the addition of 5.0 g of 1,2-epoxycyclohexane, and stirring at 80°C for 2 hours. After completion of the reaction, 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 The product was identified by H-NMR, ICP, GPC, IR, and elemental analysis. １ H-NMR (CDCl ３ , 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 1000 mcg, and GPC confirmed that Mw was 2,410 and Mn was 1,150. Elemental analysis revealed that the chlorine atom content in the polymer was below the detection limit, and it was confirmed that the weight ratio of sulfur atoms in the polymer (Po1t) was increased compared to the sulfur-containing polymer (Po1) before the reaction. １H-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 possible to calculate 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.

[0209] [Example 1] In a 50 mL plastic bottle, 60 g of zirconia balls YTZ (0.05 mm) manufactured by Nikkato Corporation and zirconium oxide particles UEP-50 (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) (hereinafter referred to as ZrO ２ 5.51 g of a sulfur-containing polymer (Po1) obtained in Synthesis Example 1 as the sulfur-containing polymer, 0.70 g of zinc oxide particles FINEX-50 (manufactured by Sakai Chemical Industry Co., Ltd.) (hereinafter also referred to as ZnO(1)) as the zinc chalcogenide, 0.49 g of a mixture containing triethylene glycol monomethyl ether phosphate ester as the phosphoric acid compound (hereinafter also referred to as phosphoric acid-based dispersant (1)), and 13 g of cyclopentanone as the solvent were added, and the mixture was then crushed at room temperature for 5 hours using a paint shaker manufactured by Toyo Seiki Seisaku-sho, Ltd. After crushing, a dispersion composition was obtained. Zirconia balls YTZ (0.05 mm) contained in the dispersion composition were separated by filtration to obtain inorganic particle-containing composition (1), which is a milky white composition. The dispersed particle diameter (Dd) of the obtained inorganic particle-containing composition (1) was evaluated, and the results are shown in Table 3. The phosphoric acid dispersant (1) used is a compound represented by the above formula (2), and R １ , R ２ , a and n are shown in Table 1. ２ The evaluation results of the crystal structure, average primary particle diameter (D1), specific surface area, and composition (contents of metal elements, sulfur, and chlorine) of ZrO (1) and ZnO (1) are shown in Table 2. The contents of metal elements, sulfur, and chlorine shown in Table 2 are ２The mass content (mass%) of each element is the ratio of the mass content of each element to the total mass (total mass) of the metal elements, sulfur, and chlorine detected for (1) and ZnO (1) by X-ray fluorescence analysis (XRF). Table 3 also shows the raw materials and blending ratios used to prepare the inorganic particle-containing composition (1). In Table 3, the sulfur-containing polymer (Po1) (mass%), phosphate-based dispersant (1) (mass%), zirconium oxide particles (mass%), and zinc oxide (mass%) refer to the respective proportions (mass%) of the sulfur-containing polymer (Po1), phosphate-based dispersant (1), zirconium oxide particles, and zinc oxide (mass%) relative to the total mass of the sulfur-containing polymer (Po1), phosphate-based dispersant (1), zirconium oxide particles, and zinc oxide (mass%) used. The same applies to each example and comparative example other than Example 1. The dispersion stability of the inorganic particle-containing composition (1) was evaluated visually (presence or absence of thickening or solidification in the composition) for 90 days at 23° C., 10 days at 40° C., and 30 days at 40° C., and the dispersed particle diameter (Dd) of the inorganic particle-containing composition (1) after 30 days at 40° C. was confirmed. The results of the dispersion stability evaluation are shown in Table 4.

[0210] <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) in an amount of 0.05 parts by mass of BYK-307 per 100 parts by mass of the solids 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 mounted 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). The refractive index, film thickness, and haze of the obtained coating film (1) were evaluated, and the refractive index (refractive index relative to the NaD line (589 nm)) was 1.93, the film thickness was 1.10 μm, and the haze was 0.10%. A polymerizable composition (1) was prepared by mixing a UV-curable monomer and the like 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 30 parts by mass of a 9:1 (mass ratio) mixed solution of 1-naphthylmethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade 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), BYK-307 (manufactured by BYK-Chemie, surface tension modifier) ​​as a 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 Adekastab LA-81 as a light stabilizer relative to 100 parts by mass of the UV-curable monomer, and Omnipol ASA (IGM Resins) as a photopolymerization initiator. The components were added and mixed so that the ratio of Esacure 3644 (manufactured by IGM Resins B.V.) as a photosensitizer was 3.1 parts by mass relative to 100 parts by mass of the UV-curable monomer, and 1.0 part by mass of Esacure 3644 (manufactured by IGM Resins B.V.) as a photosensitizer was 1.0 part by mass relative to 100 parts by mass of the UV-curable monomer, thereby obtaining a polymerizable composition (1). The obtained polymerizable composition (1) was dropped onto a slide glass on a spin coater using a pipette, and spin-coated at 1500 rpm for 90 seconds.The prepared coating film on the slide glass was placed on a hot plate preheated to 50°C and dried by heating for 1 minute. The dried coating film was then irradiated with UV light in a nitrogen atmosphere for 90 seconds to cure the coating film. The UV-cured film was placed on a hot plate preheated to 80°C and heated for 10 minutes, and then placed on a hot plate preheated to 150°C and heated for 10 minutes to obtain a cured film (1). The refractive index, film thickness, and haze of the obtained cured film (1) were evaluated, and the refractive index (refractive index relative to the NaD line (589 nm)) was 1.82, the film thickness was 1.19 μm, and the haze was 0.09%. The evaluation results for the cured film (1) are shown in Table 4. The dispersion stability of the polymerizable composition (1) was evaluated for 90 days at 23° C., 10 days at 40° C., and 30 days at 40° C., and the dispersed particle size (Dd) of the polymerizable composition (1) after 30 days at 40° C. was confirmed. The results of the evaluation of the dispersion stability are shown in Table 4.

[0211] <Production of Imprint Film (1)> Imprint molding was performed using the polymerizable composition (1). Specifically, the process is as follows. The polymerizable composition (1) was dropped onto a glass slide on a spin coater using a pipette, and spin-coated at 2500 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 to obtain a dried film with a film thickness of 0.75 μm. The obtained dried film was pressed against a transparent replica film mold (1) having a striped line and space pattern with a spacing of 1.0 μm, a top surface width of 1 μm on the convex portions, a bottom surface width of 1 μm on the concave portions, and a height of 1 μm within a 1 cm × 1 cm area using a nanoimprinting device EITRE®3 (manufactured by Obducat) at a pressure of 0.5 MPa for 30 seconds, and the mold was then subjected to a pressure of 60 mW / cm. ２The imprinted film (1) was subjected to UV irradiation for 120 seconds to obtain an imprinted-cured film (1) to which the transparent replica film mold (1) was pressure-bonded. The transparent replica film mold (1) was then released from the imprinted-cured film (1), yielding a pattern-imprinted film (1-2) to which the shape of the transparent replica film mold (1) was transferred. 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 10 minutes, yielding an imprinted film (1). The resulting imprinted film (1) was cut perpendicular to the pattern shape in which the striped line and space shape had been transferred using a glass cutter, and the cross-section of the transferred pattern shape was observed at 10,000x magnification using an FE-SEM (JSM7600F manufactured by JEOL Ltd.). It was confirmed that the transfer pattern shape reflecting the shape of the transparent replica film mold (1) was reproduced to 95% or more, confirming the feasibility of imprint molding. Furthermore, it was confirmed by cross-sectional observation that the remaining thickness of the cured film underlying the striped line and space pattern was 0.04 μm. The refractive index, film thickness, and haze of the cured film in the region of the imprint film (1) to which the transfer pattern shape was not imparted were evaluated. The refractive index (refractive index for the NaD line (589 nm)) was 1.89, the film thickness was 0.50 μm, and the haze was 0.12%. The transparent replica film mold (1) used can be manufactured from a metal mold (1) having a striped line and space pattern 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 x 1 cm area of ​​a metal surface such as a silicone-based metal mold. 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 or heat curing is performed, and the film is released from the metal mold (1). This allows a transparent replica film mold (1) to be obtained that reflects the pattern shape of the metal mold (1) on the PET film.The UV-curable transparent resin (1) used in the production of the transparent replica film mold (1) is as follows. The transfer pattern shape was confirmed by the same method as in the evaluation of the imprinted cured 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. UV-curable transparent resin (1): ultraviolet-curable liquid silicone rubber (PDMS) KER-4690-A / B, manufactured by Shin-Etsu Chemical Co., Ltd.

[0212] Examples 2 to 14, Comparative Examples 1 to 5: A crushing treatment was carried out in the same manner as in Example 1, except that the zirconium oxide, titanium oxide, titanate, zinc chalcogenide, sulfur-containing polymer (Po1), phosphate-based dispersant, blending ratio, crushing time, etc. were as shown in Table 3. In Examples 2 to 14, inorganic particle-containing compositions (2) to (14) were produced, and in Comparative Examples (1 to (5), inorganic particle-containing compositions (c1) to (c5) were produced. Furthermore, polymerizable compositions were prepared using each of the obtained inorganic particle-containing compositions in the same manner as in Example 1, and these compositions were evaluated in the same manner as in Example 1. Furthermore, cured films were prepared using each of the polymerizable compositions in the same manner as in Example 1, and these films were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4. The phosphate-based dispersants, zirconium oxide, titanium oxide, titanate, and zinc oxide used in each Example and Comparative Example are as follows, and the results of evaluation of the crystal structure, etc. are shown in Table 2. Phosphate-based dispersant (1): A compound represented by the above formula (2), in which R in formula (2) １ , R ２ , a and n are shown in Table 1. Phosphate-based dispersant (2): A compound represented by the above formula (2), in which R １ , R ２ , a and n are shown in Table 1. Phosphate-based dispersant (3): Plysurf A208F, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Phosphate-based dispersant (4): DISPERBYK-111, manufactured by BYK Japan KK Phosphate-based dispersant (5): KAYAMER PM-21, manufactured by Nippon Kayaku Co., Ltd. ZrO ２ (1): UEP-50, zirconium oxide, TiO manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. ２ (1): TAF-1500J, titanium oxide, manufactured by Fuji Titanium Industry Co., Ltd. TiO２ (2): Titania SSP-M for catalyst carrier, titanium oxide, manufactured by Sakai Chemical Industry Co., Ltd. TiO ２ (3): Ultrafine particle titanium oxide STR-100N, titanium oxide, BaTiO manufactured by Sakai Chemical Industry Co., Ltd. ３ (1): Barium titanate nanoparticles, barium titanate, manufactured by Merck ZnO (1): FINEX-50, zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.

[0213]

[0214]

[0215]

[0216]

[0217] As shown in Table 4, in Examples 1 to 14, the dispersion stability of the inorganic particle-containing composition and the polymerizable composition were evaluated, and it was confirmed that there was no change in the dispersed particle size as dispersibility after 90 days at 23°C and after 30 days at 40°C. For Comparative Examples 1 to 5, it was confirmed that the viscosity increased, the dispersed particle size increased, and the inorganic particles aggregated after 90 days at 23°C and after 10 days at 40°C, and that the inorganic particle-containing composition and the polymerizable composition solidified after 30 days at 40°C. As a result, it was found that the inorganic particle-containing composition and the polymerizable composition obtained by mixing zinc oxide as zinc chalcogenide with zirconium oxide, titanium oxide, or titanate in Examples 1 to 14 had high dispersion stability, and it was confirmed that the zinc chalcogenide improved the dispersibility of zirconium oxide, titanium oxide, and titanate.

Claims

1. An inorganic particle-containing composition comprising at least one selected from the group consisting of zirconium oxide, titanium oxide, and titanates, zinc chalcogenide, and a dispersant.

2. The inorganic particle-containing composition according to claim 1, wherein the dispersant comprises a compound having a polar functional group.

3. The inorganic particle-containing composition according to claim 2, wherein the polar functional group is at least one selected from the group consisting of 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.

4. The dispersant is represented by the following formula (1): (In the formula, X １ represents a divalent aromatic hydrocarbon group which may have a substituent.

5. The inorganic particle-containing composition according to any one of claims 1 to 4, wherein the dispersant contains a phosphoric acid compound having a phosphoric acid group and / or a phosphoric acid ester group.

6. The phosphoric acid compound is represented by the following formula (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.

7. The inorganic particle-containing composition according to claim 5 or 6, wherein the phosphoric acid compound has a molecular weight of 98 to 2,000.

8. The inorganic particle-containing composition according to claim 4, wherein the content of the sulfur-containing polymer is 1 to 30 mass % relative to 100 mass % in total of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide.

9. The inorganic particle-containing composition according to any one of claims 5 to 7, wherein the content of the phosphate compound is 0.5 to 10 mass% relative to 100 mass% in total of zirconium oxide, titanium oxide, titanate, and zinc chalcogenide.

10. A polymerizable composition comprising the inorganic particle-containing composition according to any one of claims 1 to 9 and a polymerizable monomer.

11. A method for producing an inorganic particle-containing composition, the method comprising a step of disintegrating aggregates of at least one type of particle selected from the group consisting of zirconium oxide, titanium oxide, and titanates in the presence of zinc chalcogenide and a dispersant.

12. The method for producing an inorganic particle-containing composition according to claim 11, wherein the dispersant includes a compound having a polar functional group.

13. The method for producing an inorganic particle-containing composition according to claim 11 or 12, wherein the polar functional group is at least one selected from the group consisting of 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.

14. The dispersant is represented by the following formula (1): (In the formula, X １ represents a divalent aromatic hydrocarbon group which may have a substituent.

15. The method for producing an inorganic particle-containing composition according to any one of claims 11 to 14, wherein the dispersant contains a phosphoric acid compound having a phosphoric acid group and / or a phosphoric acid ester group.

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