The composite contains components

Abstract

To provide a polymer-containing composition that enables a sulfur-containing polymer to be uniformly dissolved or dispersed and can give a film having excellent transparency.SOLUTION: A polymer-containing composition contains a sulfur-containing polymer and a compound (M). The compound (M) is a benzene aromatic compound (M1) having an electron-withdrawing group as a substituent, an unsaturated heterocyclic compound (M2) having an unsaturated 6-membered ring, an unsaturated heterocyclic compound (M3) having a substituted unsaturated 5-membered ring, a compound (M4) having an amide group, or a compound (M5) having an imino group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition containing a sulfur-containing polymer. More specifically, the present invention relates to a polymer-containing composition that can be suitably used for producing a film or the like having excellent transparency. [Background technology]

[0002] While high-refractive-index materials such as polycarbonates with aromatic rings and polymeric materials with fluorene structures are well known, materials with a high Abbe number, i.e., low optical dispersion, are required for refractive index adjustment materials to improve the light extraction efficiency of LEDs and for lens materials in imaging systems. Materials with high refractive index and low optical dispersion have been developed, including those incorporating sulfur or halogen molecules and those containing metal oxide nanoparticles. Polyarylene sulfides, particularly polyphenylene sulfide, are sulfur-containing materials known for their excellent heat resistance, corrosion resistance, and electrical insulation properties. In recent years, their application to optical materials with high refractive indexes has been attracting attention.

[0003] For example, Patent Document 1 discloses that a polymer having a repeating unit of a phenylene sulfide skeleton in which hydrogen atoms at specific positions on the benzene ring are substituted with methyl groups has a high refractive index and excellent formability in a solution state, and therefore a molding material containing the polymer is useful as a molding material for producing optical components. As a method for processing the molding material into a film, the document describes a method in which the polymer is dissolved in a solvent and a thin film is formed by spin coating or casting. Dichloromethane and the like are described as solvents. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2017-52834 Summary of the Invention [Problem to be solved by the invention]

[0005] Sulfur-containing polymers such as polyarylene sulfide have poor solubility in solvents, but their solubility can be increased by introducing methyl groups as described in Patent Document 1. Although they are relatively soluble in some of the chlorine-based solvents described in Patent Document 1, the use of chlorine-based solvents is becoming more and more restricted. It has been difficult to uniformly dissolve or disperse sulfur-containing polymers such as polyarylene sulfide in solvents other than chlorine-based solvents, making it difficult to produce films with excellent transparency. Therefore, an object of the present invention is to provide a polymer-containing composition that can uniformly dissolve or disperse sulfur-containing polymers such as polyarylene sulfide, thereby producing films with excellent transparency. [Means for solving the problem]

[0006] The present inventors have discovered that the above-mentioned problems can be solved by adding a specific compound to a composition containing a sulfur-containing polymer such as polyarylene sulfide, and have thus completed the present invention. Specifically, the polymer-containing composition of the present invention is a polymer-containing composition containing a sulfur-containing polymer and a compound (M), wherein the compound (M) is a benzene-based aromatic compound (M1) having an electron-withdrawing group as a substituent, an unsaturated six-membered ring-containing unsaturated heterocyclic compound (M2), a substituted five-membered ring-containing unsaturated heterocyclic compound (M3), an amide group-containing compound (M4), or an imino group-containing compound (M5). [Effects of the Invention]

[0007] The polymer-containing composition according to the present invention contains a specific compound, which enables the sulfur-containing polymer to be uniformly dissolved or dispersed, and also enables the formation of a film having excellent transparency. Therefore, the polymer-containing composition according to the present invention is useful as a raw material for optical thin films, lenses, etc. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described in detail below. A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment 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.

[0009] 1. Polymer-containing composition The present invention provides a polymer-containing composition comprising a sulfur-containing polymer and a compound (M), wherein the compound (M) is a benzene-based aromatic compound (M1) having an electron-withdrawing group as a substituent, an unsaturated heterocyclic compound (M2) containing an unsaturated six-membered ring, an unsaturated heterocyclic compound (M3) containing an unsaturated five-membered ring having a substituent, a compound (M4) having an amide group, or a compound (M5) having an imino group.

[0010] <Sulfur-containing polymer> The sulfur-containing polymer constituting the polymer-containing composition of the present invention will be described in detail below. The sulfur-containing polymer is not particularly limited as long as it has a sulfur-containing bond in its main chain, but a polymer having at least one sulfur-containing group selected from the group consisting of a sulfide group (-S-), a sulfinyl group (-S(=O)-), and a sulfonyl group (-S(=O)2-) in its main chain is preferred. The sulfur-containing polymer preferably further has an aromatic ring structure in its main chain. By having the sulfur-containing group and an aromatic ring structure in the main chain of the polymer, it is possible to obtain a polymer with a higher refractive index. In the sulfur-containing polymer, the aromatic ring structure preferably has a substituent. By having a substituent, the crystallinity of the sulfur-containing polymer is reduced, tending to improve processability.

[0011] The aromatic ring structure is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, a biphenyl ring, a diphenyl ring, and a triphenyl ring. Among these, a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, and a triphenyl ring are preferred, and a benzene ring is particularly preferred. In the present invention, the phrase "having an aromatic ring structure in the main chain" means that the aromatic ring structure itself is on the main chain. In addition, examples of the substituents possessed by the aromatic ring structure include reactive functional groups, polar functional groups, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aralkyl groups, and sulfur-containing substituents. The respective substituents such as the reactive functional groups and the polar functional groups are described below with reference to X in general formula (1). 1 The substituents are the same as the substituents (substituent A) that may be possessed by the divalent aromatic hydrocarbon group represented by the formula (1) below, and will be described in detail later. Among the substituents possessed by the aromatic ring structure, the alkyl group, alkoxy group, aryl group, aralkyl group, and sulfur-containing substituent may further possess a substituent. The substituents are also the same as the substituents (substituent A) that may be possessed by the divalent aromatic hydrocarbon group represented by the formula (1) below. 1 The substituents are the same as the substituents (substituent B) that may be possessed by an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a sulfur-containing substituent, which may be possessed by a divalent aromatic hydrocarbon group represented by the following formula:

[0012] The sulfur-containing polymer is preferably a sulfur-containing polymer having at least one structural unit selected from the group consisting of a structural unit (A) represented by the following general formula (1), a structural unit (B) represented by the following general formula (2), and a structural unit (C) represented by the following general formula (3):

[0013] [ka]

[0014] [ka]

[0015] [ka]

[0016] (In formulas (1) to (3), X 1 , X 2 and X 3 are the same or different and represent divalent aromatic hydrocarbon groups which may have a substituent. Each structural unit contained in the sulfur-containing polymer will be described below.

[0017] <<Constituent Unit (A)>> In the structural unit (A) represented by the general formula (1), 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 reducing the light dispersion of the polymer.

[0018] X 1 The substituent (also referred to as "substituent A") that the divalent aromatic hydrocarbon group represented by the formula (I) may have is preferably a reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent that may have a substituent (also referred to as "substituent B").

[0019] Examples of the reactive functional group include an acidic functional group, a basic functional group, a curable functional group, and groups containing these functional groups. Examples of the acidic functional group include a carboxyl group (-COOH), a phosphate group (-OPO(OH)), a hydroxyl group (-OH), a sulfo group (-SOH), a phosphonic acid group (-PO(OH)), a phosphinic acid group (-PO(OH)-), and a mercapto group (-SH). Examples of the basic functional group include an amino group, an ammonium group, an imino group, an amide group, an imide group, and a maleimide group. Examples of the curable functional group include a group having a reactive unsaturated bond, such as a group having a reactive double bond, such as a vinyl group, a (meth)acryloyl group, an allyl group, or a methallyl group; and a group having a reactive ionic bond, such as a group having a reactive cyclic ether group, such as an epoxy group or an oxetane group.

[0020] Examples of the groups containing these functional groups include groups having the above-mentioned acidic functional group, basic functional group, or curable functional group and a hydrocarbon chain or a bonding group. That is, in the present invention, the reactive functional group includes not only the above-mentioned acidic functional group, basic functional group, or curable functional group, but also groups containing these functional groups and a bonding chain. Examples of the bonding chain include divalent hydrocarbon groups such as alkylene groups and arylene groups, bonding groups such as ethers, esters, carbonyls, and amides, and combinations thereof. For example, when it is said that a carboxy group is preferred as the reactive functional group, it means that the reactive functional group is preferably a carboxy group and / or a group containing a carboxy group.

[0021] The preferred form of the reactive functional group varies depending on the various physical properties of the sulfur-containing polymer. For example, from the viewpoint of improving the dispersibility of inorganic particles in the sulfur-containing polymer, an acidic functional group, a basic functional group, or a group containing these functional groups is preferred, and a carboxyl group, a phosphate group, a phosphonic acid group, a hydroxyl group, or a group containing these functional groups is more preferred. From the viewpoint of making the sulfur-containing polymer more likely to have a low linear expansion coefficient, a carboxyl group, a phosphate group, a phosphonic acid group, a hydroxyl group, or a group containing these functional groups is preferred, and a hydroxyl group or a group containing a hydroxyl group is more preferred. From the viewpoint of improving the adhesion of the sulfur-containing polymer to the substrate, a carboxyl group, a phosphate group, a phosphonic acid group, or a group containing these functional groups is preferred, and a phosphate group, a phosphonic acid group, or a group containing these functional groups is more preferred. In addition, examples of substrates to which adhesion can be improved include inorganic substrates such as inorganic particle substrates (coatings), metal oxide particle substrates (coatings), glass substrates, silicone substrates, and copper substrates, and organic substrates such as organic particle substrates (coatings), and polymer film substrates. From the viewpoint of improving heat resistance, mechanical strength, and solvent resistance, a carboxy group, a hydroxy group, an amino group, a maleimide group, a curable functional group, or a group containing these functional groups is preferred, and a carboxy group, a hydroxy group, an amino group, a maleimide group, a vinyl group, a (meth)acryloyl group, an allyl group, a methallyl group, an epoxy group, an oxetane group, or a group containing these functional groups is more preferred.

[0022] Among these, the reactive functional group is preferably a carboxyl group, a phosphate group, a phosphonic acid group, a hydroxyl group, a curable functional group, or a group containing these functional groups, from the viewpoint of being able to impart a higher refractive index along with excellent physical properties to the sulfur-containing polymer, more preferably a carboxyl group, a phosphate group, a hydroxyl group, a vinyl group, an epoxy group, or a group containing these functional groups, and even more preferably a phosphate group, a hydroxyl group, a vinyl group, or a group containing these functional groups. Furthermore, from the viewpoint of being able to improve adhesion to the substrate with a low linear expansion coefficient in addition to a high refractive index, the reactive functional group is preferably a carboxyl group, a phosphate group, or a group containing these functional groups.

[0023] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a bromine atom is 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. Among these, an alkyl group having 1 to 18 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is even more preferred.

[0024] Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, a phenoxy group, a cyclohexyloxy group, a benzyloxy group, etc. Among these, an alkoxy group having 1 to 18 carbon atoms is preferred, an alkoxy group having 1 to 6 carbon atoms is more preferred, and a methoxy group is more preferred.

[0025] 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. 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 aralkyl group preferably has 7 to 14 carbon atoms, and more preferably 7 to 9 carbon atoms. Examples of the sulfur-containing substituent include a thioalkyl group, a thioaryl group, and an alkylthio group. Of these, a thioalkyl group is preferred. The sulfur-containing substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 4 carbon atoms.

[0026] The alkyl group, alkoxy group, aryl group, aralkyl group, and sulfur-containing substituent may further have a substituent (substituent B), and examples of the substituent (substituent B) include alkyl groups, halogen atoms, etc. Among these, alkyl groups are preferred from the viewpoint of the solubility of the resulting sulfur-containing polymer, and halogen atoms are preferred from the viewpoint of the dispersibility of inorganic particles.

[0027] In terms of further increasing the refractive index and Abbe number, the substituent (substituent A) that the divalent aromatic hydrocarbon group may have is more preferably the alkyl group having 1 to 18 carbon atoms or a sulfur-containing substituent, even more preferably a methyl group or a thioalkyl group, and particularly preferably a methyl group. In terms of improving the dispersibility of inorganic particles, the substituent that the divalent aromatic hydrocarbon group may have is more preferably a hydroxyl group or a sulfur-containing substituent, even more preferably a hydroxyl group, a thioalkyl group or a thioaryl group, and particularly preferably a hydroxyl group.

[0028] The substituent (substituent A) that the divalent aromatic hydrocarbon group may have is preferably a functional group that effectively enhances the dispersibility of inorganic particles. In the present invention, such a group is also referred to as a polar functional group. Examples of the polar functional group include an ester group (e.g., a methyl ester group: -COOCH3), a carbonyl group (e.g., an acetyl group: -COCH3), a thiocarbonyl group (e.g., a thioacetyl group: -CSCH3), a nitro group (-NO2), a sulfonyl group (e.g., a methanesulfonyl group: -SO2CH3), a cyano group (-CN), an alkoxy group (e.g., a methoxy group: -OCH3), a sulfonate group (e.g., -OSO2CH3), a phosphonate group (e.g., -PO(OCH3)2), an alkylthio group (e.g., -SCH3), and a halogenated alkyl group (-CH2Br). When the substituent A is a polar functional group, the sulfur-containing polymer effectively enhances the dispersibility of inorganic particles. From the same viewpoint, an acidic functional group or a basic functional group is also preferred as the substituent A. From the above viewpoint, an ester group, a carbonyl group, an alkoxy group (—OCH3), an alkylthio group, a halogenated alkyl group, etc. are more preferred.

[0029] The number of substituents A that the divalent aromatic hydrocarbon group may have is not particularly limited, but a smaller number is preferable in terms of further increasing the refractive index of the resulting sulfur-containing polymer, and specifically, it is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. In the divalent aromatic hydrocarbon group, the position to which the substituent A is bonded is not particularly limited. The same applies when the divalent aromatic hydrocarbon group is a phenyl group, and when the substituent A is, for example, an alkyl group, the bonding position is not particularly limited, but it is preferably bonded to the 4-position of the phenyl group.

[0030] The structural unit (A) is preferably a structural unit (A-1) represented by the following general formula (1-1), in that the refractive index becomes higher.

[0031] [ka]

[0032] (In the formula, R 1 are the same or different and represent a reactive functional group, a halogen atom, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent, each of which may have a substituent. 1 represents the number of digits, and is an integer between 0 and 4.) R 1 When there are multiple R, they may be the same or different. 1 The reactive functional group, halogen atom, or optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent represented by the formula (1) is the same as the substituent that the divalent aromatic hydrocarbon group in the formula (1) may have, including preferred embodiments.

[0033] In general formula (1-1), the bonding position of the other main chain relative to the carbon atom (position 1) to which the sulfide group is bonded is not particularly limited, and may be position 2, 3, or 4. Of these, position 2 or 3 is preferred, and position 3 is more preferred. Furthermore, when the sulfur-containing polymer contains the structural unit (A-1), it may contain multiple structural units (A-1) bonded at different bonding positions.

[0034] In the general formula (1-1), a represents a substituent R 1 and is an integer of 0 to 4. In order to further increase the refractive index, a is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. In the above general formula (1-1), the above substituent R 1 The position of is not particularly limited, and may be the 2-position, 3-position, or 4-position of the phenylene group. Among these, the 4-position or 2-position is preferred, and the 4-position is more preferred.

[0035] <<Constituent Unit (B)>> In the structural unit (B) represented by the general formula (2), 2 represents a divalent aromatic hydrocarbon group which may have a substituent. 2 The divalent aromatic hydrocarbon group represented by the formula (I) includes the above-mentioned X 1 Preferred examples of the divalent aromatic hydrocarbon group include the same groups as those represented by X 2 The substituent that the divalent aromatic hydrocarbon group represented by the formula (I) may have is, for example, the above-mentioned X 1 Preferred examples of the substituents include the same groups as those that may be contained in the divalent aromatic hydrocarbon group represented by the formula: X 2 The divalent aromatic hydrocarbon group represented by X and its substituents are 1 and the substituents thereof may be the same as or different from the divalent aromatic hydrocarbon group represented by the following formula:

[0036] The structural unit (B) is preferably a structural unit (B-1) represented by the following general formula (2-1), in that it increases the refractive index.

[0037] [ka]

[0038] (In the formula, R 2 are the same or different and represent a reactive functional group, a halogen atom, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent, each of which may have a substituent. 2 represents the number of digits, and is an integer between 0 and 4.) R 2 When there are a plurality of, they may be the same or different.

[0039] R 2 The reactive functional group, halogen atom, or optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent represented by the formula (I) can be any of the above-mentioned R 1 Examples of such groups include the same groups as those represented by R 2 A preferred embodiment in R 1 This is similar to what is expressed as

[0040] In general formula (2-1), the bonding position of the other main chain relative to the carbon atom (position 1) to which the sulfinyl group is bonded is not particularly limited, and may be position 2, 3, or 4. Of these, position 2 or 3 is preferred, and position 3 is more preferred. Furthermore, when the sulfur-containing polymer contains the structural unit (B-1), it may contain multiple structural units (B-1) bonded at different bonding positions.

[0041] In the general formula (2-1), b is a substituent R 2 and is an integer of 0 to 4. In order to further increase the refractive index, b is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. In the above general formula (2-1), the substituent R 2 The bonding position of R 1 This is the same as in the case of

[0042] <<Constituent Unit (C)>> In the structural unit (C) represented by the general formula (3), 3 represents a divalent aromatic hydrocarbon group which may have a substituent. 3 The divalent aromatic hydrocarbon group represented by the formula (I) includes the above-mentioned X 1 Preferred examples of the divalent aromatic hydrocarbon group include the same groups as those represented by X 3 The substituent that the divalent aromatic hydrocarbon group represented by the formula (I) may have is, for example, the above-mentioned X 1 Preferred examples of the substituents include the same groups as those that may be contained in the divalent aromatic hydrocarbon group represented by the formula: X 3 The divalent aromatic hydrocarbon group represented by X and its substituents are 1 or X 2 and the substituents thereof may be the same as or different from the divalent aromatic hydrocarbon group represented by the following formula:

[0043] The structural unit (C) is preferably a structural unit (C-1) represented by the following general formula (3-1), since this increases the refractive index.

[0044] [ka]

[0045] (In the formula, R 3 are the same or different and represent a reactive functional group, a halogen atom, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent, each of which may have a substituent. 3 represents the number of digits, and is an integer between 0 and 4.) R 3 When there are a plurality of, they may be the same or different.

[0046] R 3 The reactive functional group, halogen atom, or optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent represented by the formula (I) can be any of the above-mentioned R 1 Examples of such groups include the same groups as those represented by R 3 A preferred embodiment in R 1This is similar to what is expressed as

[0047] In general formula (3-1), the bonding position of the other main chain relative to the carbon atom (position 1) to which the sulfonyl group is bonded is not particularly limited, and may be position 2, 3, or 4. Of these, position 2 or 3 is preferred, and position 3 is more preferred. Furthermore, when the sulfur-containing polymer contains the structural unit (C-1), it may contain multiple structural units (C-1) bonded at different positions.

[0048] In the general formula (3-1), c represents a substituent R 3 and is an integer of 0 to 4. c is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, in order to further increase the refractive index. 3 The bonding position of R 1 This is the same as in the case of

[0049] The sulfur-containing polymer may be an alternating copolymer, a block copolymer, or a random copolymer of the structural units (A), (B), and (C). The sulfur-containing polymer may contain only one of the structural units (A), (B), and (C), or may contain two or three structural units. The structural units (A), (B), and (C) constituting the sulfur-containing polymer may each be one type or two or more types.

[0050] The form and content ratio of these can be appropriately selected depending on the purpose and application of the sulfur-containing polymer and the polymer-containing composition of the present invention. For example, from the viewpoint of easily obtaining a composition with a relatively high refractive index, it is preferable to use a sulfur-containing polymer with a high content of the structural unit (A). Furthermore, since the dissolution rate of the sulfur-containing polymer tends to be high, it is preferable to use a sulfur-containing polymer containing the structural unit (B) and / or (C). From the viewpoint of both excellent refractive index and dissolution rate, it is preferable to use a sulfur-containing polymer mainly composed of the structural unit (B).

[0051] From the viewpoint of prioritizing a high refractive index, the content of the structural unit (A) in the sulfur-containing polymer is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 95 to 100 mol%, relative to 100 mol% of all structural units in the polymer. In this case, the total content of the structural units (B) and (C) in the polymer is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 to 5 mol%, relative to 100 mol% of all structural units.

[0052] From the viewpoint of increasing the dissolution rate, the total content of the structural units (B) and (C) in the sulfur-containing polymer is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 95 to 100 mol%, based on 100 mol% of all structural units in the polymer. In this case, the content of the structural unit (A) in the polymer is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 to 5 mol%, based on 100 mol% of all structural units.

[0053] From the viewpoint of increasing the dissolution rate and increasing the refractive index, the content of the structural unit (B) in the sulfur-containing polymer is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 95 to 100 mol%, relative to 100 mol% of all structural units in the polymer. In this case, the total content of the structural units (A) and (C) in the polymer is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 to 5 mol%, relative to 100 mol% of all structural units.

[0054] In the sulfur-containing polymer, the total content of the structural units (A), (B), and (C) is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%, based on 100 mol% of all structural units in the polymer.

[0055] The sulfur-containing polymer may have a structural unit (D) other than the structural unit (A), the structural unit (B), and the structural unit (C). Examples of the structural unit (D) include structural units having at least the reactive functional group described above.

[0056] Examples of monomers that can introduce the structural unit (D) include monomers having a polymerizable double bond and the reactive functional group. Examples of the polymerizable double bond include vinyl, (meth)acryloyl, allyl, and methallyl groups, with (meth)acryloyl being preferred. Examples of monomers having a polymerizable double bond and the reactive functional group include carboxyl group-containing (meth)acrylates such as 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, and 4-carboxybutyl (meth)acrylate; phosphate group-containing (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate; and vinyl ether group-containing (meth)acrylates such as 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. The content of the structural unit (D) is preferably 0 to 80 mol%, more preferably 0 to 50 mol%, even more preferably 0 to 20 mol%, even more preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%, relative to 100 mol% of all structural units of the polymer.

[0057] The sulfur-containing polymer may have a chain structure, a cyclic structure, or a mixture thereof. Among these, the sulfur-containing polymer preferably has a chain structure as a main component, from the viewpoint of excellent solubility and mechanical strength. Specifically, the sulfur-containing polymer preferably has a chain structure content of 50% by mass or more, more preferably 80% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on 100% by mass of the sulfur-containing polymer.

[0058] The sulfur-containing polymer preferably has an elemental ratio (O / S) of the oxygen atom O bonded to the sulfur atom S in the main chain to the sulfur atom S in the main chain of 0.1 to 1.5. The elemental ratio (O / S) is more preferably 0.3 or more, and even more preferably 0.5 or more. In terms of further increasing the refractive index, it is more preferably 1.3 or less, and even more preferably 1.1 or less. The elemental ratio can be determined by evaluating and measuring the peak intensities of the oxygen atom 1s orbital (O1s), the carbon atom 1s orbital (C1s), and the sulfur atom 2p orbital (S2p) using an X-ray photoelectron spectrometer (XPS). Specifically, the sulfur atom S in the main chain refers to the sulfur atom S of -SO- in the main chain in the structural unit (B). In the structural unit (A), it refers to the sulfur atom S of -S- in the main chain, and in the structural unit (C), it refers to the sulfur atom S of -SO2- in the main chain. The oxygen atom bonded to the sulfur atom S in the main chain specifically means, for example, the oxygen atom O of —SO— in the main chain in the structural unit (B), and the oxygen atom O of —SO— in the main chain in the structural unit (C).

[0059] The weight-average molecular weight (Mw) of the sulfur-containing polymer is preferably 500 to 10,000,000. When the weight-average molecular weight is within the above range, the polymer can be suitably used as an optical material. From the viewpoint of improving mechanical properties, the weight-average molecular weight is more preferably 1,000 or more, more preferably 1,100 or more, and even more preferably 1,500 or more. It is more preferably 3,000 or more, and even more preferably 10,000 or more, and from the viewpoint of reducing melt viscosity, it is more preferably 1,000,000 or less, and even more preferably 100,000 or less.

[0060] The polydispersity (weight average molecular weight / number average molecular weight) of the sulfur-containing polymer is preferably 1 or more and 10 or less. When the polydispersity is within the above range, molding becomes easy. In terms of further improving moldability, the polydispersity is more preferably 5 or less, and even more preferably 3 or less. The weight average molecular weight and number average molecular weight can be determined by measurement using gel permeation chromatography (GPC), specifically, by the method described in the examples below. The polydispersity can be determined by dividing the weight average molecular weight by the number average molecular weight.

[0061] The sulfur-containing polymer preferably has a glass transition temperature (Tg) of 80 to 250°C. When the glass transition temperature is in the above range, molding and processing can be easily performed. From the viewpoint of increasing heat resistance, the glass transition temperature is more preferably 90°C or higher, and even more preferably 100°C or higher, and from the viewpoint of facilitating molding and processing, it is more preferably 200°C or lower. The glass transition temperature can be determined by a method using a differential scanning calorimeter (DSC) in a nitrogen gas atmosphere, by heating from room temperature to 250°C (heating rate 10°C / min), and evaluating the intersection of the baseline and the tangent at the inflection point from a DSC curve obtained by heating.

[0062] The sulfur-containing polymer preferably has a refractive index of 1.69 or higher. When the refractive index is within the above range, the polymer can be suitably used in a wide variety of applications, including optical materials (members), machine component materials, electric and electronic component materials, automobile component materials, civil engineering and construction materials, molding materials, as well as paints and adhesives. The refractive index is more preferably 1.7 or higher, and even more preferably 1.71 or higher. The refractive index can be determined by forming a 50 nm thick film from the polymer as a measurement sample and measuring it using a spectroscopic ellipsometer UVISEL (manufactured by HORIBA Scientific) with NaD radiation (589 nm).

[0063] The sulfur-containing polymer preferably has an Abbe number of 10 or more. When the Abbe number is within the above range, light dispersion is small and the material can be an optical material suitable for lenses. The Abbe number is more preferably 15 or more, even more preferably 18 or more, and even more preferably 20 or more. From the viewpoint of adjusting light dispersion, the Abbe number is preferably 60 or less, more preferably 55 or less. The Abbe number can be calculated using the following formula by forming a film using the polymer in the same manner as in measuring the refractive index, and measuring the refractive indexes at D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm) using the spectroscopic ellipsometer. Abbe number (vD) = (nD-1) / (nF-nC) In the formula, nD, nF, and nC represent the refractive indices at the Fraunhofer D line (589.3 nm), F line (486.1 nm), and C line (658.3 nm), respectively.

[0064] The sulfur-containing polymer preferably has a heavy metal content of 0.0001 ppm or more and 1200 ppm or less based on the sulfur-containing polymer (solid content). Heavy metals in the sulfur-containing polymer tend to cause the polymer-containing composition of the present invention to discolor upon heating. From this perspective, the heavy metal content is more preferably 500 ppm or less, even more preferably 200 ppm or less, and even more preferably 100 ppm or less based on the sulfur-containing polymer (solid content). On the other hand, from the viewpoint that molded articles obtained using the polymer-containing composition of the present invention containing the sulfur-containing polymer tend to have higher toughness, the heavy metal content is more preferably 0.001 ppm or more, even more preferably 0.01 ppm or more based on the sulfur-containing polymer (solid content). The heavy metal content can be determined by ICP atomic emission spectroscopy.

[0065] The sulfur-containing polymer preferably has an iron content of 10,000 ppm or less, more preferably 1,000 ppm or less, even more preferably 500 ppm or less, and even more preferably 100 ppm or less, based on the sulfur-containing polymer (solid content). Meanwhile, for the same reasons as for the heavy metal content, the lower limit is more preferably 0.01 ppm or more, even more preferably 0.1 ppm or more, based on the sulfur-containing polymer (solid content). The iron content can be determined by the same analytical method as for the heavy metal content.

[0066] <<Method of producing sulfur-containing polymer>> The sulfur-containing polymer constituting the polymer-containing composition of the present invention has been described in detail. The method for producing the sulfur-containing polymer is not particularly limited, but a preferred method includes, for example, oxidative polymerization of a monomer component containing a disulfide compound and / or a thiol compound, and, if necessary, an oxidation step and / or purification step for oxidizing the polymer obtained by oxidative polymerization. In the above production method, the content ratios of the structural units (A), (B), and (C) in the sulfur-containing polymer can be adjusted by selecting the polymerization reaction conditions or by further performing an oxidation step.

[0067] The oxidative polymerization will be described in detail. The oxidative polymerization can be carried out in a state in which the monomer components are heated and melted, but is preferably carried out in a composition in which the monomer components are dispersed or dissolved in a solvent. The composition, i.e., a composition containing the monomer components and a solvent, is also referred to as a raw material composition, and the composition from the start of the polymerization reaction to the end of the polymerization reaction is also referred to as a reaction composition. The composition obtained by the polymerization reaction is also referred to as a polymer composition.

[0068] The monomer components used in the above polymerization step will be described. The monomer component includes a disulfide compound and / or a thiol compound, and among these, it is preferable to include a disulfide compound. The disulfide compound is preferably a diaryl disulfide compound represented by the following general formula (4), and the thiol compound is preferably a thioaryl compound represented by the following general formula (5). By using these compounds, it is usually possible to obtain a sulfur-containing polymer containing at least one structural unit selected from the group consisting of the structural units (A), (B), and (C) described above.

[0069] [ka]

[0070] [ka]

[0071] (In formulas (4) and (5), A 1 and A 2 are the same or different and represent monovalent aromatic hydrocarbon groups which may have a substituent. A 1 and A 2 The monovalent aromatic hydrocarbon group represented by the formula (1) is preferably X 1 Examples of aromatic hydrocarbon groups include monovalent aromatic hydrocarbon groups obtained by converting a divalent aromatic hydrocarbon group represented by the formula: 1 and A 2 The substituents that the monovalent aromatic hydrocarbon group represented by the formula (1) may have and the number of such substituents are as follows: 1 The same applies to the substituents that the divalent aromatic hydrocarbon group represented by the following formula may have.

[0072] The diaryl disulfide compound is preferably a compound represented by the following general formula (4-1): The thioaryl compound is preferably a compound represented by the following general formula (5-1): By using these compounds, it is usually possible to obtain a sulfur-containing polymer containing at least one structural unit selected from the group consisting of the structural units (A-1), (B-1), and (C-1).

[0073] [ka]

[0074] [ka]

[0075] (In formulas (4-1) and (5-1), R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are the same or different and represent a hydrogen atom or a substituent, R 4 , R 5 , R 6 , R 7 , R 8 At least one of these is a hydrogen atom, and R 9 , R 10 , R 11 , R 12 , R 13 At least one of these is a hydrogen atom.) The R in the general formula (4-1) 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 may be the same or different. The R in the general formula (5-1) 4 , R 5 , R 6 , R 7 and R 8 may be the same or different.

[0076] In the general formula (4-1), the R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 The substituent represented by the formula (1-1) is preferably a reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent, which may have a substituent. The reactive functional group, the halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent, which may have a substituent, is preferably a reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent, which may have a substituent, 1 The preferred embodiments are also the same as those of the groups represented by the general formula (5-1). Examples of the substituent that the alkyl group, alkoxy group, aryl group, aralkyl group, or sulfur-containing substituent may have include the same as those of the substituent B described above. 4 , R 5 , R 6 , R 7 and R 8 The same applies to the above-mentioned substituents represented by the following formula: In the general formula (4-1), the R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13The number of substituents is an integer of 0 to 8, but is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2, in that the refractive index of the resulting sulfur-containing polymer will be even higher.

[0077] In the general formula (4-1), the R 4 , R 5 , R 6 , R 7 and R 8 The number of substituents is an integer of 0 to 4, but is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, in order to further increase the refractive index of the resulting sulfur-containing polymer. 9 , R 10 , R 11 , R 12 and R 13 The same applies to the above general formula (5-1). 4 , R 5 , R 6 , R 7 and R 8 The same applies to the above R in the general formula (4-1). 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Among them, R 6 , R 11 is preferably a substituent. 4 , R 5 , R 6 , R 7 , and R 8 Among them, R 6 is preferably a substituent.

[0078] Specific examples of the diphenyl sulfide compound include 3,3'-dimethyldiphenyl disulfide, 2,2'-dimethyldiphenyl disulfide, 4,4'-dimethyldiphenyl disulfide (bis(4-methylphenyl) disulfide), 2,2',3,3'-tetramethyldiphenyl disulfide, 2,2',5,5'-tetramethyldiphenyl disulfide, 2,2',6,6'-tetramethyldiphenyl disulfide, 3,3',5,5'-tetramethyldiphenyl disulfide, and 2,2',3,3',5,5'-hexamethyldiphenyl Disulfide, 2,2',3,3',6,6'-hexamethyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-octamethyldiphenyl disulfide, 2,2'-diethyldiphenyl disulfide, 3,3'-diethyldiphenyl disulfide, 2,2',6,6'-tetraethyldiphenyl disulfide, 2,2',3,3'-tetraethyldiphenyl disulfide, 2,2',5,5'-tetraethyldiphenyl disulfide, 3,3',5,5'-tetraethyldiphenyl disulfide, 2,2',3,3',5,5'-hexa Ethyl diphenyl disulfide, 2,2',3,3',6,6'-hexaethyl diphenyl disulfide, 2,2',3,3',5,5',6,6'-octaethyl diphenyl disulfide, 2,2'-dipropyl diphenyl disulfide, 3,3'-dipropyl diphenyl disulfide, 2,2',6,6'-tetrapropyl diphenyl disulfide, 2,2',3,3'-tetrapropyl diphenyl disulfide, 2,2',5,5'-tetrapropyl diphenyl disulfide, 3,3',5,5'-tetrapropyl diphenyl disulfide, 2,2' ,3,3',5,5'-Hexapropyldiphenyl disulfide, 2,2',3,3',6,6'-Hexapropyldiphenyl disulfide, 2,2',3,3',5,5',6,6'-Octapropyldiphenyl disulfide, 2,2'-Diisopropyldiphenyl disulfide, 3,3'-Diisopropyldiphenyl disulfide, 2,2',6,6'-Tetraisopropyldiphenyl disulfide, 2,2',3,3'-Tetraisopropyldiphenyl disulfide, 2,2',5,5'-Tetraisopropyldiphenyl disulfide, 3,3',5,Examples include 5'-tetraisopropyldiphenyl disulfide, 2,2',3,3',5,5'-hexaisopropyldiphenyl disulfide, 2,2',3,3',6,6'-hexaisopropyldiphenyl disulfide, and 2,2',3,3',5,5',6,6'-octaisopropyldiphenyl disulfide.

[0079] Specific examples of the thiol compound include 3-methylbenzenethiol, 2-methylbenzenethiol, 4-methylbenzenethiol, thiophenol (benzenethiol), 2,3-dimethylbenzenethiol, 2,5-dimethylbenzenethiol, 2,6-dimethylbenzenethiol, and 3,5-dimethylbenzenethiol.

[0080] 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. The oxidative polymerization is not particularly limited, but oxidative polymerization using a quinone compound or oxidative polymerization using a catalyst is preferred. From the viewpoint of reducing the amount of waste liquid, oxidative polymerization using a catalyst is more preferred.

[0081] The oxidative polymerization using a catalyst will now be described. For example, it is more preferable to carry out the polymerization reaction by heating a composition in which the above-mentioned monomer components and 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).

[0082] The substances containing the metal elements may be used alone or in combination of two or more. The catalyst is not particularly limited in its form in the raw material composition. For example, it may be dispersed in the raw material composition in a particulate form or the like, or may be present in a dissolved state in the monomer component or, if a solvent is used, in the solvent. Similarly, the substance containing a metal element is not particularly limited in its form in the raw material composition. For example, it may be dispersed in the raw material composition in a particulate form or the like, or may be present in a dissolved state in the monomer component or, if a solvent is used, in the solvent. Solvents will be described later. The same applies to the form of the catalyst and the form of the substance containing a metal element in the reaction composition. Among the substances containing a metal element, 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 because of their high catalytic activity for oxidative polymerization.

[0083] The iron-containing substance preferably contains iron as the metal element as the main component. Specifically, the iron content relative to 100 mol% of the total content of metal elements contained in the iron-containing substance is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 95 mol% or more, even more preferably 98 mol% or more, and particularly preferably 100 mol%. The vanadium-containing substance also preferably contains vanadium as the metal element as the main component, and the preferred content of vanadium relative to the total amount of metal elements is the same as that of iron in the iron-containing substance. The specific and preferred forms of existence of the vanadium-containing substance and iron-containing substance in the raw material composition and reaction composition are as described above.

[0084] The vanadium-containing substance is preferably a metal containing vanadium or an oxovanadium compound having a V=O bond in the vanadium compound molecule, such as vanadyl acetylacetonate, oxovanadium salen complex, N,N'-bissalicylideneethylenediamine oxovanadium, phthalocyanine oxovanadium, or tetraphenylporphyrin oxovanadium. The iron-containing substance is preferably an iron compound having chlorine in the molecule. Compounds containing iron with an oxidation number of 3 or greater are also preferred. Particularly preferred examples of such iron-containing substances include ferric chloride (Fe(Cl)3), 5,10,15,20-tetraphenyl-21H,23H-porphine iron(III) chloride, and iron(III) trifluoromethanesulfonate.

[0085] The amount of the catalyst used in the polymerization is not particularly limited, but the total content of metal elements contained in the catalyst relative to 100 mol % of the monomer component is preferably in the range of 0.001 to 50 mol %. From the viewpoint that the influence of catalyst residue on physical properties tends to be small, the amount is preferably 30 mol % or less, more preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less. From the viewpoint that a sulfur-containing polymer with a high molecular weight is easily obtained, the amount is more preferably 0.01 mol % or more, even more preferably 0.1 mol % or more, and particularly preferably 1 mol % or more.

[0086] 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. In a specific embodiment, a method of supplying an oxygen-containing gas during the polymerization reaction is preferred. That is, 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, a method of bubbling an oxygen-containing gas into the reaction composition during the polymerization reaction, or the like is employed.

[0087] It is believed that carrying out the polymerization reaction in the presence of oxygen gas can promote the hydrogen elimination reaction from the carbon constituting the aromatic ring contained in the monomer component. Furthermore, in the polymerization step, the oxidation number of the metal contained in the catalyst usually changes, but by carrying out the polymerization reaction in the presence of oxygen gas, the valence of the metal contained in the catalyst can be maintained at a high oxidation number, which is thought to promote oxidative polymerization. From this perspective, 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.

[0088] The oxygen-containing gas is preferably a gas containing oxygen molecules (O2). The oxygen-containing gas may contain gas components other than oxygen molecules (O2). The gas components other than oxygen molecules (O2) contained in the oxygen-containing gas are not particularly limited, but preferred examples include rare gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and radon (Rn); and inert gases such as nitrogen (N2). In addition to the above inert gases, carbon dioxide gas (CO2), water vapor, etc. may also be contained.

[0089] The content of oxygen molecules (O2) in the oxygen-containing gas is not particularly limited, but at room temperature (25°C) and 1 atmosphere, the volume ratio of oxygen molecules (O2) in the oxygen-containing gas is preferably 0.1 to 100% by volume relative to 100% by volume of the oxygen-containing gas. More preferably, it is 1% by volume or more, and even more preferably, it is 10% by volume or more. The upper limit is more preferably 60% by volume or less, and even more preferably, it is 30% by volume or less.

[0090] The total content of oxygen molecules (O2) and inert gas in the oxygen-containing gas is not particularly limited, but at room temperature (25°C) and 1 atmosphere, the total volume ratio of oxygen molecules (O2) and inert gas in the oxygen-containing gas is preferably 80 to 100% by volume relative to 100% by volume of the oxygen-containing gas, more preferably 95% by volume or more, and even more preferably 98% by volume or more.

[0091] The oxygen-containing gas is not particularly limited, but examples thereof include oxygen gas, a mixed gas of oxygen and nitrogen, and air. From the viewpoint of economical efficiency, air is preferably used. The water vapor concentration in the oxygen-containing gas is not particularly limited, but is preferably 1000 g / m 3 Less than 10 g / m is preferred 3 Less than 1g / m is more preferable. 3 More preferably, 0.1 g / m or less 3 The following is most preferred, with dry air being preferred:

[0092] The amount of oxygen-containing gas to be supplied is not particularly limited, but is preferably 1 m3 of the total volume of the reaction composition. 3 The supply rate per minute is 0.0001m 3 / min~10m 3 From the viewpoint of increasing the reaction rate, it is more preferable that the reaction rate is 0.0005 m / min. 3 / min or more, and more preferably 0.001 m 3 The upper limit is more preferably 1 m / min from the viewpoint of easy control of the reaction temperature. 3 / min or less, and more preferably 0.1 m 3 / min or less.

[0093] The amount of oxygen-containing gas fed is also determined based on the total volume of the reaction composition per m 3 The oxygen (O2) supply rate per minute is 0.00002 m 3 / min~2m 3 From the viewpoint of increasing the reaction rate, it is more preferable that the reaction rate is 0.0001 m / min. 3 / min or more, and more preferably 0.0002 m 3 The upper limit is more preferably 0.2 m / min from the viewpoint of easy control of the reaction temperature. 3 / min or less, and more preferably 0.02 m 3 / min or less.

[0094] 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.

[0095] The acid is preferably a Bronsted acid. Examples include inorganic acids such as phosphoric acid, phosphonic acid, nitric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, persulfuric acid, and sulfurous acid; sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, 10-camphorsulfonic acid, trifluoromethanesulfonic acid, and 1,1,2,2-tetrafluoroethanesulfonic acid; and carboxylic acids such as acetic acid, trifluoroacetic acid, perfluoropropionic acid, perfluorobutyric acid, and benzoic acid. The acid is preferably an acid having an acid dissociation constant of -19 to 4. More preferably, the acid dissociation constant is 3 or less and -8 or more.

[0096] The salt of the acid is not particularly limited as long as it is a salt of the acid, but for example, salts of the acid with a metal element of Group 1 of the periodic table such as sodium or potassium, a metal element of Group 2 of the periodic table such as magnesium or calcium, or ammonium are preferred. Among these, for example, sodium persulfate, ammonium persulfate, sodium toluenesulfonate, sodium trifluoromethanesulfonate, etc. are preferred. The salt of the acid preferably has a pH of 1 to 6.9, more preferably 2 to 6, at 25°C when dissolved in pure water.

[0097] 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. The above acids and / or salts thereof may be used alone or in combination of two or more.

[0098] The amount of acid and / or its salt used is preferably 0.01 to 100 mol%, more preferably 0.1 to 10 mol%, and even more preferably 0.5 to 5 mol%, based on 100 mol% of the monomer component. The amount of acid and / or its salt used is preferably 0.1 to 1000 mol%, more preferably 1 to 100 mol%, and even more preferably 5 to 50 mol%, based on 100 mol% of the total amount of metal elements contained in the metal element-containing substance. The pH of the entire reaction system (raw material composition containing acid and / or its salt) to which the acid and / or its salt has been added is preferably 0.1 to 7, more preferably 1 to 6, and most preferably 2 to 5, from the viewpoint of improving reaction efficiency. The pH is the value measured when the reaction system (raw material composition containing acid and / or its salt) is directly measured, using pH indicator paper and a pH meter.

[0099] The polymerization may be carried out at atmospheric pressure at a temperature below the boiling point of the solvent, under reflux conditions, or under pressure while heating to a temperature above the boiling point. The polymerization temperature is not particularly limited as long as it is a temperature at which oxidative polymerization proceeds. However, in terms of ease of carrying out the oxidative polymerization reaction using inexpensive equipment, it is preferably 0 to 250°C, more preferably 30°C or higher, and even more preferably 50°C or higher. The upper limit is preferably 200°C or lower, and even more preferably 180°C or lower. The polymerization time is not particularly limited, but is typically 0.1 to 100 hours, preferably 1 to 80 hours, more preferably 5 to 50 hours, and even more preferably 10 to 24 hours.

[0100] In the polymerization, the monomer components may be added sequentially during the polymerization reaction. In the polymerization, the polymerization may be performed in multiple stages, such as by oxidatively polymerizing the above-mentioned thiol compound to obtain a disulfide compound, and then oxidatively polymerizing the obtained disulfide compound. A composition (raw material composition) containing the monomer components, the solvent, and the catalyst is maintained preferably at the polymerization temperature for the polymerization time, whereby the polymerization reaction of the monomer components occurs, and a composition (polymer composition) containing a sulfur-containing polymer is produced.

[0101] The above-described oxidative polymerization can produce a sulfur-containing polymer whose main chain consists of a repeating structure in which hydrocarbon chains contained in a disulfide compound and / or a thiol compound are bonded via sulfide groups (-S-) or the like. When a diaryl disulfide compound represented by the above general formula (4) and / or a thioaryl compound represented by the above general formula (5) is used as the monomer component, a sulfur-containing polymer containing at least one structural unit selected from the group consisting of the structural units (A), (B), and (C) can usually be obtained. Under the above-described preferred conditions, a sulfur-containing polymer can be obtained in which the content of the structural unit (A) is relatively high among these structural units.

[0102] Further oxidation of the sulfur-containing polymer obtained by the oxidative polymerization can produce a sulfur-containing polymer having a high content of the structural units (B) and / or (C). Specifically, by oxidizing the polymer produced by the oxidative polymerization, sulfur atoms in the sulfide groups (-S-) in the main chain of the sulfur-containing polymer are oxidized to form "-SO-" or "-SO2-," resulting in a sulfur-containing polymer having a high content of the structural units (B) and / or (C). By containing or increasing the proportion of the structural units (B) and / or (C), the refractive index, dissolution rate, and other properties can be controlled. Therefore, it is also preferable that the sulfur-containing polymer used in the polymer-containing composition of the present invention be subjected to an oxidation step (oxidation step) after polymerization to adjust the content of the structural units (B) and / or (C).

[0103] Furthermore, the polymer composition containing the sulfur-containing polymer obtained in the polymerization step contains at least the solvent used in the polymerization step, as well as substances such as residues of the catalyst used (catalyst residues), i.e., so-called impurities. These impurities may affect the optical properties and heat resistance of the sulfur-containing polymer. Therefore, it is preferable to isolate the sulfur-containing polymer from the obtained polymer composition and reduce these impurities from the viewpoint of improving the quality of the sulfur-containing polymer and the polymer-containing composition of the present invention. Therefore, it is preferable that the sulfur-containing polymer used in the polymer-containing composition of the present invention is purified by being subjected to a purification step after the polymerization step.

[0104] As described above, a preferred method for producing the sulfur-containing polymer constituting the polymer-containing composition of the present invention may further include a purification step and / or an oxidation step in addition to the polymerization step. The oxidation step may be performed after the polymerization step and before the purification step or after the purification step, but is preferably performed after the purification step.

[0105] The purification step will be described. Conventionally known purification methods can be used as the purification method. 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. By performing the purification method after the oxidation step, components derived from the oxidizing agent used in the oxidation step can also be removed, which is preferable. 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.

[0106] The timing of the purification step is not particularly limited, and the purification step may be performed before or after the oxidation step. That is, the polymer obtained after the purification step may be subjected to the oxidation step, or the purification step may be performed on a composition containing the polymer obtained in the oxidation step. In particular, when the method for producing a sulfur-containing polymer includes the oxidation step, it is preferable to perform the purification step on a composition containing the polymer obtained after both the polymerization step and the oxidation step, since this allows the sulfur-containing polymer to be obtained with fewer impurities derived from the raw materials used in each step.

[0107] The oxidation step is a step of oxidizing the polymer obtained in the polymerization step. The oxidation of the polymer produced in the polymerization step can be carried out by 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.

[0108] Among these, it is more preferable to use at least one compound selected from the group consisting of peroxides, chloric acid, hypochlorous acid, hypochlorites, and compounds capable of generating hypochlorous acid, because it can moderately oxidize sulfur atoms (sulfide groups, -S-) contained in the main chain to form sulfoxides (sulfinyl groups) (-SO-). Examples of the peroxides include metachloroperbenzoic acid, hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, and t-butyl hydroperoxide.

[0109] Among these, the oxidizing agent is preferably a peroxide, and more preferably metachloroperbenzoic acid or hydrogen peroxide. From the viewpoint of preventing oxidation to sulfonyl (—SO2—) by an excess of oxidizing agent, the oxidizing agent is even more preferably metachloroperbenzoic acid. Furthermore, when hydrogen peroxide is used as the oxidizing agent, it is preferable to use a phase transfer catalyst such as trifluoroacetone while reducing the amount of water, in order to prevent precipitation of the sulfur-containing polymer. The oxidizing agent may be used alone or in combination with two or more. It is also preferable to use at least one compound selected from the group consisting of hypochlorous acid, hypochlorites, and compounds capable of generating hypochlorous acid as the oxidizing agent.

[0110] The amount of the oxidizing agent added is not particularly limited as long as the oxidation reaction of sulfur atoms proceeds to produce the desired polymer, but is typically preferably 1 to 1,000 moles, more preferably 10 to 500 moles, and even more preferably 100 to 400 moles, per mole of sulfur atoms in the sulfur-containing polymer. The reaction temperature of the oxidation reaction is not particularly limited as long as the desired oxidation reaction proceeds at that temperature, but is preferably 0 to 200°C, more preferably 10°C or higher, and even more preferably 15°C or higher, from the viewpoint of facilitating the oxidation reaction. Furthermore, from the viewpoint of suppressing side reactions, it is preferably 180°C or lower, and even more preferably 150°C or lower. The reaction time of the oxidation reaction is not particularly limited, but is typically 0.1 to 100 hours, preferably 1 to 80 hours, more preferably 5 to 50 hours, and even more preferably 10 to 24 hours.

[0111] When oxidation is to be carried out to -SO2-, the reaction may be carried out for a longer time than the above-mentioned reaction time. In this case, the amount of the oxidizing agent added is not particularly limited as long as the oxidation reaction of the desired sulfur atoms proceeds, but is usually preferably 1.5 to 100 mol, more preferably 2 to 50 mol, and even more preferably 2 to 10 mol, per mol of sulfur atoms in the polymer.

[0112] In the oxidation reaction, a solvent may be used, and preferred examples of the solvent used include the same solvents as those used in the polymerization step. The sulfur-containing polymer obtained by the oxidation step may contain residual acids, etc., and therefore it is preferable to carry out the purification step.

[0113] The method for producing the sulfur-containing polymer may include other steps in addition to the polymerization step, purification step, and oxidation 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.

[0114] The above-described production method preferably produces a sulfur-containing polymer containing at least one structural unit selected from the group consisting of the structural units (A), (B), and (C), and more preferably produces a sulfur-containing polymer containing at least one structural unit selected from the group consisting of the structural units (A-1), (B-1), and (C-1). Furthermore, by appropriately selecting the conditions in the polymerization step, the presence or absence of an oxidation step, and the conditions, a sulfur-containing polymer can be produced in which the content ratio of each structural unit is adjusted. Therefore, the sulfur-containing polymer produced by the above-described production method can be suitably used as the sulfur-containing polymer constituting the polymer-containing composition of the present invention.

[0115] <Compound (M)> The compound (M) is a benzene-based aromatic compound (M1) having an electron-withdrawing group as a substituent, an unsaturated heterocyclic compound containing an unsaturated six-membered ring (M2), an unsaturated heterocyclic compound containing an unsaturated five-membered ring having a substituent (M3), a compound having an amide group (M4), or a compound having an imino group (M5). The polymer-containing composition of the present invention contains one or more of these compounds.

[0116] In the polymer-containing composition of the present invention, the compound (M) has an excellent effect of uniformly dissolving or dispersing the sulfur-containing polymer, preferably an excellent effect of uniformly dissolving the sulfur-containing polymer. Therefore, in the polymer-containing composition of the present invention, the compound (M) is preferably used as a solvent or dispersion medium for the sulfur-containing polymer, and more preferably as a solvent.

[0117] The compound (M) may have a polymerizable group, preferably an unsaturated double bond group, such as a vinyl group, an allyl group, or a (meth)acryloyl group. In the present invention, a compound (M) having a polymerizable group is also referred to as a polymerizable compound (M), and a compound (M) not having a polymerizable group is also referred to as a non-polymerizable compound (M).

[0118] The polymerizable compound (M) can function as a polymerizable component. When the polymer-containing composition of the present invention contains the polymerizable compound (M) as the compound (M), the compound (M) can function not only as a solvent component or a dispersion medium component but also as a polymerizable component.

[0119] The benzene-based aromatic compound (M1) having the above electron-withdrawing group as a substituent will be described. This compound is also referred to as compound (M1). The electron-withdrawing group is not particularly limited, but preferred examples include a hydroxyl group, a formyl group, a cyano group, and a nitro group. Examples of the compound (M1) include benzaldehyde, 2-hydroxybenzaldehyde (salicylaldehyde), 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, benzonitrile, and nitrobenzene. Among these, benzaldehyde, 2-hydroxybenzaldehyde, and benzonitrile are preferred, and 2-hydroxybenzaldehyde is more preferred.

[0120] Compounds further having a polymerizable group are also preferred as the compound (M1). Among these, compounds having a polymerizable double bond group are more preferred. Such compounds are also referred to as polymerizable compounds (M1). Among the polymerizable compounds (M), the polymerizable compound (M1) is preferred. Among the polymerizable compounds (M1), compounds having a hydroxyl group as an electron-withdrawing group and a polymerizable double bond group are preferred. Examples of the polymerizable compounds include compounds having a hydroxyl group and a (meth)acryloyl group in the molecule, such as 1,3-bis(methacryloyloxy)-2-propanol and 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol; compounds having a hydroxyl group and an allyl group in the molecule, such as 2-allylphenol, 4-allyl-2-methoxyphenol, and 2-methoxy-4-propenylphenol; and compounds having a hydroxyl group and a vinyl group in the molecule, such as 2-vinylphenol.

[0121] The unsaturated heterocyclic compound (M2) containing an unsaturated 6-membered ring will now be described. This compound is also referred to as compound (M2). Examples of the compound (M2) include pyridine-based compounds. Specifically, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, etc. are preferred. Among these, 2-methylpyridine, 3-methylpyridine, and 4-methylpyridine are more preferred, and 3-methylpyridine and 4-methylpyridine are even more preferred. The compound (M2) may or may not have a substituent. The substituent may be an electron-withdrawing group or an electron-donating group. Examples of the electron-withdrawing group include a hydroxyl group, a formyl group, a cyano group, and a nitro group. Examples of the electron-donating group include a hydroxymethylene group.

[0122] The following describes an unsaturated heterocyclic compound (M3) containing an unsaturated five-membered ring having the above-mentioned substituent. This compound is also referred to as compound (M3). Examples of the unsaturated five-membered ring include heterocyclic compounds such as furan and pyrrole. The above-mentioned substituent may be an electron-withdrawing group or an electron-donating group. Examples of electron-withdrawing groups include a hydroxyl group, a formyl group, a cyano group, and a nitro group. Examples of electron-donating groups include a hydroxymethylene group. Examples of the above-mentioned compound (M3) include furfuryl alcohol, furfural, and 1-methylpyrrole.

[0123] The compound (M4) having the above amide group will be explained. This compound is also referred to as compound (M4). Examples of the compound (M4) include N-methyl-2-pyrrolidone, N,N-dimethylpropionamide, N,N-dimethylformamide, dimethylacetamide, and tetramethylurea.

[0124] The compound (M5) having the above imino group will be explained. This compound is also referred to as compound (M4). An example of the compound (M5) is 1,1,3,3-tetramethylguanidine.

[0125] Among the above compounds (M), benzaldehyde, 2-hydroxybenzaldehyde (salicylaldehyde), benzonitrile, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and dimethylacetamide are preferred from the viewpoint that a polymer-containing composition in which the sulfur-containing polymer is uniformly dissolved at a high concentration can be easily obtained even under mild conditions. Furthermore, when the polymer-containing composition of the present invention further contains inorganic particles, benzaldehyde, 2-hydroxybenzaldehyde (salicylaldehyde), benzonitrile, and N-methyl-2-pyrrolidone are preferred from the viewpoint of excellent dissolution and dispersion speed in a mixed system of the sulfur-containing polymer and the inorganic particles.

[0126] <Mixing ratio, etc.> The polymer-containing composition of the present invention contains the sulfur-containing polymer and the compound (M). As will be described in detail later, the polymer-containing composition of the present invention can be suitably used as a coating composition or a molding composition. The form of the sulfur-containing polymer in the polymer-containing composition of the present invention is not particularly limited. For example, the sulfur-containing polymer may be contained alone in a dissolved or dispersed state in the composition, or may be contained in a complex form with other components described later. For example, inorganic particles described later may have a form in which the sulfur-containing polymer is chemically bonded to or adsorbed to a part or all of the surface of the inorganic particles.

[0127] The content of the sulfur-containing polymer in the polymer-containing composition is not particularly limited, but is preferably 1 to 60 mass % and more preferably 2 to 50 mass % relative to 100 mass % of the total amount of the polymer-containing composition.

[0128] The content of the compound (M) in the polymer-containing composition is not particularly limited, but is preferably 0.1 to 99 mass%, more preferably 10 to 90 mass%, and even more preferably 20 to 80 mass%, relative to 100 mass% of the total content of the sulfur-containing polymer and the compound (M).

[0129] The total content of the sulfur-containing polymer and the compound (M) in the polymer-containing composition is not particularly limited, but is preferably 1 to 100% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, relative to 100% by mass of the polymer-containing composition.

[0130] When the polymer-containing composition contains a polymerizable compound (M) as the compound (M), the total content of the sulfur-containing polymer and the polymerizable compound (M) is preferably 5 to 100% by mass, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to 100% by mass of the total amount of the polymer-containing composition.

[0131] When the polymer-containing composition is used, for example, as a coating composition, the total content of the sulfur-containing polymer and the polymerizable compound (M) is preferably 5 to 60% by mass, more preferably 10% by mass or more, and even more preferably 20% by mass or more. On the other hand, the upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less. When the polymer-containing composition is used, for example, as a molding composition, the total content of the sulfur-containing polymer and the polymerizable compound (M) is preferably 80 to 100% by mass, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0132] When the polymer-containing composition of the present invention contains a polymerizable compound (M) as the compound (M), it preferably further contains a polymerization initiator. The polymerization initiator can be appropriately selected from conventionally known thermal polymerization initiators and photopolymerization initiators. For example, preferred polymerization initiators include radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators. 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 compound (M).

[0133] The polymer-containing composition of the present invention may further contain other components. The other components are not particularly limited and can be appropriately selected from known components depending on the purpose and use of the polymer-containing composition. The polymer-containing composition of the present invention may also contain a polymerizable monomer as another component. By including a polymerizable monomer, it is possible to improve the mechanical strength of a film or the like obtained from the polymer-containing composition of the present invention. Here, the polymerizable monomer refers to a polymerizable monomer other than the polymerizable compound (M). In the present invention, the polymerizable compound (M) and the polymerizable monomer are also collectively referred to as polymerizable components. The type of the polymerizable monomer is not particularly limited, and a preferred example is a monomer having an unsaturated double bond.

[0134] Examples of the monomer having an unsaturated double bond include vinyl monomers such as vinyl acetate, vinyl chloride, acrylonitrile, acrylamide, vinyl benzoate, and divinylbenzene; (meth)acrylic monomers such as (meth)acrylic esters, (meth)acrylic acid, and 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol; styrene monomers such as styrene, α-methylstyrene, and chloromethylstyrene; olefin monomers such as ethylene and propylene; diallyl ethers, aryl ethers, and the like. and allyl monomers such as allyl alcohol, allyl phenoxy acetate, 3-allyloxy-1,2-propanediol, allyl n-octyl ether, glycerol α,α'-diallyl ether, and diallyl-2,2'-biphenyldicarboxylate; as well as maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, itaconic acid monobutyl ester, etc. Among these, polyfunctional monomers having a molecular weight of 100 or more are preferred.

[0135] When the polymer-containing composition of the present invention contains the polymerizable monomer, the content of the polymerizable monomer is not particularly limited, but the total content of the polymerizable compound (M) and the polymerizable monomer is preferably 0.1 to 99% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, relative to 100% by mass of the sulfur-containing polymer. When the polymer-containing composition of the present invention contains the polymerizable monomer, it is preferable that the composition further contains a polymerization initiator. As the polymerization initiator, the same polymerization initiators as those described above can be used. The content of the polymerization initiator also conforms to the content relative to the polymerizable compound (M).

[0136] The polymer-containing composition of the present invention may contain inorganic particles as another component. The inclusion of inorganic particles makes it easier to control the refractive index of a film or the like obtained from the polymer-containing composition of the present invention. A polymer-containing composition containing the sulfur-containing polymer, the compound (M), and inorganic particles is also one of preferred embodiments of the polymer-containing composition of the present invention.

[0137] Examples of materials constituting the inorganic particles include metals, inorganic oxides, inorganic nitrides, inorganic carbides, inorganic sulfides, inorganic hydroxides, etc. The inorganic particles may be composed of one of these materials or may contain two or more of these materials.

[0138] Examples of the metal include lithium, sodium, potassium, boron, magnesium, calcium, manganese, strontium, barium, titanium, zirconium, iron, cobalt, nickel, copper, zinc, aluminum, tin, silicon, cesium, and indium.

[0139] The inorganic oxide is preferably a metal oxide containing a metal element. Examples of the metal oxide include single metal oxides consisting of one metal element, composite oxides consisting of two or more metal elements, and solid solution oxides in which a different element is dissolved in the single metal oxide or the composite oxide. The different element may be a metal element or a non-metal element other than oxygen, such as nitrogen or fluorine. Examples of the metal element include the metal elements described above. Examples of the single metal oxide include magnesium oxide, calcium oxide, strontium oxide, barium oxide, titanium oxide, zinc oxide, cerium oxide, silicon oxide, tin oxide, zirconium oxide, aluminum oxide, and indium oxide. Examples of the composite oxide include perovskite-type composite oxides such as barium titanate, barium strontium titanate, strontium titanate, barium zirconium strontium titanate, barium zirconium titanate, and lead zirconate titanate; spinel-type composite oxides such as spinel and lithium titanate; and composite oxides such as aluminum titanate. The solid solution oxides include those in which different metal elements and / or non-metal elements other than oxygen, such as nitrogen and fluorine, are solid-solved in the single metal oxides or composite oxides.

[0140] The inorganic nitride is preferably a metal nitride, for example, boron nitride, carbon nitride, aluminum nitride, etc. The inorganic carbide is preferably a metal carbide, for example, silicon carbide, calcium carbide, titanium carbide, boron carbide, etc. The inorganic sulfide is preferably a metal sulfide, for example, copper sulfide, zinc sulfide, cadmium sulfide, etc. The inorganic hydroxide is preferably a metal hydroxide, for example, aluminum hydroxide, magnesium hydroxide, barium hydroxide, etc.

[0141] Among these, inorganic oxides are preferred as materials for the inorganic particles because they have a wide band gap (transparent to visible light), and metal oxides are more preferred. Among the inorganic particles, oxides containing Ti, Zr, Ce, Zn, In, Al, Si, and Sn as the main metal element are more preferred because they have no or little absorption in the visible light region, making it easier to obtain compositions in which coloring due to the inorganic particles is suppressed. Titanium oxide (TiO2), zirconium oxide (ZrO2), cerium oxide (CeO2), zinc oxide (ZnO), indium oxide (In2O3), aluminum oxide (Al2O3), silicon oxide (SiO2), and tin oxide (SnO2) are particularly preferred.

[0142] Among the above materials, zirconium oxide, titanium oxide, and silicon dioxide are more preferred in terms of ease of controlling the refractive index of the polymer-containing composition and enabling low linear expansion of the composition, and zirconium oxide and titanium oxide are more preferred in terms of improving the refractive index of the polymer-containing composition. Furthermore, perovskite-type complex oxides are preferred in terms of having a high dielectric constant and allowing the polymer-containing composition to be suitably used as a ferroelectric material or piezoelectric material. Boron nitride, aluminum hydroxide, and aluminum titanate are preferred in terms of having a high thermal conductivity and allowing the polymer-containing composition to be suitably used as a heat-dissipating material.

[0143] From the viewpoint of imparting antistatic properties or electrical conductivity to the polymer-containing composition while suppressing coloration due to the addition of inorganic particles, a solid solution oxide in which a different metal element or an additive element such as fluorine is solid-solved in zinc oxide (ZnO), indium oxide (In2O3), or tin oxide (SnO2) is preferred. For example, zinc oxide in which In, Al, or Ga is solid-solved, indium oxide in which Sn or Ti is solid-solved, or tin oxide in which Sb or F is solid-solved are more preferred.

[0144] The shape of the inorganic particles is not particularly limited, and may be any of amorphous, granular, plate-like, columnar, needle-like, etc., but granular is preferred.The inorganic particles may be surface-treated.The surface treatment is not particularly limited as long as it does not affect the effect of the present invention, and may include known methods such as the method of using a silane coupling agent, the method of reacting a compound having a phosphate group, the method of reacting a compound having a carboxylic acid group, etc.

[0145] The average particle size of the inorganic particles is preferably 1 nm or more and 1,000 nm or less. When the average particle size of the inorganic particles is within the above range, light transmittance in the visible light and infrared regions can be improved. The average particle size of the inorganic particles is more preferably 5 nm or more, even more preferably 10 nm or more, and more preferably 100 nm or less, even more preferably 50 nm or less. The average particle size is determined by observing the inorganic particles with an SEM (magnification 1,000 to 100,000 times, preferably 10,000 times), analyzing the obtained image, determining the particle diameters (circular area equivalent diameters) of approximately 10 to 1,000 individual particles (primary particles), and evaluating the 50% particle size based on the number-based particle size distribution. For image analysis, known image analysis software (e.g., Mac-View manufactured by Mountec Co., Ltd.) can be used.

[0146] The content of the inorganic particles is not particularly limited and can be appropriately set depending on the purpose and use of the polymer-containing composition. For example, the content of the inorganic particles is preferably 1 to 2000% by mass relative to 100% by mass of the sulfur-containing polymer. From the viewpoints of easily adjusting the refractive index of a film obtained from the polymer-containing composition of the present invention and easily achieving low linear expansion, the content of the inorganic particles is more preferably 100% by mass or more, and even more preferably 500% by mass or more, relative to 100% by mass of the sulfur-containing polymer. Furthermore, from the viewpoints of the mechanical strength of a film obtained from the polymer-containing composition of the present invention, the content of the inorganic particles is more preferably 1000% by mass or less, and even more preferably 800% by mass or less, relative to 100% by mass of the sulfur-containing polymer.

[0147] A preferred embodiment of the present invention is a polymer-containing composition comprising the sulfur-containing polymer and the compound (M), and further comprising the inorganic particles and the polymerizable monomer.

[0148] The solid content of the polymer-containing composition is preferably 5 to 100% by mass, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to 100% by mass of the total amount of the polymer-containing composition. When the polymer-containing composition is used, for example, as a coating composition, the solid content is preferably 5 to 60% by mass, more preferably 10% by mass or more, and even more preferably 20% by mass or more. On the other hand, the upper limit is more preferably 50% by mass or less, and even more preferably 40% by mass or less. When the polymer-containing composition is used, for example, as a molding composition, the solid content is preferably 80 to 100% by mass, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass.

[0149] The solid content includes not only nonvolatile components such as the sulfur-containing polymer and inorganic particles, but also volatile polymerizable components such as the polymerizable compound (M) and polymerizable monomers, which can be polymerized to form a film or molding material. Therefore, the solid content refers to the total content of the various solid components, i.e., the total content (total content) of the sulfur-containing polymer, inorganic particles, polymerizable compound (M), polymerizable monomer, and other components contained in the polymer-containing composition. For example, if the polymer-containing composition does not contain polymerizable components such as inorganic particles, polymerizable compound (M), or polymerizable monomers, the solid content refers to the content of the sulfur-containing polymer. Alternatively, if the polymer-containing composition further contains inorganic particles but does not contain polymerizable components such as the polymerizable compound (M) and polymerizable monomers, the solid content refers to the total content of the sulfur-containing polymer and inorganic particles.

[0150] In addition to the sulfur-containing polymer, compound (M), inorganic particles, and polymerizable monomers described above, the polymer-containing composition may contain, for example, pigments, dyes, antioxidants, UV absorbers, resins, reactive diluents, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, adhesion improvers such as coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, defoaming agents, leveling agents, wetting and dispersing agents, anti-settling agents, thickeners and anti-sagging agents, color-flux inhibitors, emulsifiers, slip and scratch inhibitors, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic assistants), and solvents. These components may be used alone or in combination of two or more. These components may be appropriately selected from known components and used. The amounts of these components may be appropriately determined.

[0151] When the polymer-containing composition is used for an optical material, it may contain other components as appropriate depending on the intended use of the optical material. Specific examples of the other components include ultraviolet absorbers, IR cutters, reactive diluents, pigments, detergents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, and antifoaming agents.

[0152] The polymer-containing composition preferably has a glass transition temperature (Tg) of 80 to 250°C. When the glass transition temperature is in the above range, molding can be easily performed. From the viewpoint of increasing heat resistance, the glass transition temperature is more preferably 90°C or higher, and even more preferably 100°C or higher, and from the viewpoint of facilitating molding, it is more preferably 200°C or lower. The glass transition temperature can be determined by the same method as the method for measuring the glass transition temperature of the sulfur-containing polymer described above.

[0153] The polymer-containing composition preferably has a refractive index of 1.69 or more. When the refractive index is within the above range, it can be suitably used as an optical material, etc. The refractive index is more preferably 1.70 or more, and even more preferably 1.71 or more. The refractive index can be determined by the same method as the method for measuring the refractive index of the sulfur-containing polymer described above.

[0154] The polymer-containing composition preferably has an Abbe number of 10 or more. When the Abbe number is within the above range, light dispersion is small and the composition can be an optical material suitable for lenses. The Abbe number is more preferably 15 or more, even more preferably 18 or more, and even more preferably 20 or more. From the viewpoint of adjusting light dispersion, the Abbe number is more preferably 60 or less, and even more preferably 55 or less. The Abbe number can be determined by the same method as the method for measuring the Abbe number of the sulfur-containing polymer described above.

[0155] The polymer-containing composition preferably has excellent transparency to visible light. For example, when the polymer-containing composition is filled in a cell with an optical path length of 1 cm, the haze value is preferably 20% or less. More preferably, it is 10% or less, and even more preferably, it is 5% or less. The haze value can be measured at 25°C using a commercially available turbidity meter. For example, a commercially available turbidity meter such as the HAZE METER NDH 5000 manufactured by Nippon Denshoku Industries Co., Ltd. can be used.

[0156] The polymer-containing composition preferably has excellent visible light transmittance. For example, when the polymer-containing composition is filled in a cell with an optical path length of 1 cm, the total light transmittance is preferably 70% or more. The total light transmittance is more preferably 80% or more, and even more preferably 85% or more. The total light transmittance can be determined by measuring the haze value using the same device under the same conditions.

[0157] The method for producing the polymer-containing composition is not particularly limited. For example, the composition can be prepared by mixing and stirring the sulfur-containing polymer, compound (M), and, if necessary, other components such as inorganic particles. When producing a polymer-containing composition containing inorganic particles, a method can be used in which a composite containing the sulfur-containing polymer and inorganic particles is prepared and then mixed with compound (M). Examples of the composite include a mixed powder in which inorganic particles and a sulfur-containing polymer are physically mixed, and a composite powder in which a sulfur-containing polymer is bonded to part or all of the surface of inorganic particles via chemical bonding or the like.

[0158] The mixing and stirring can be carried out by known means such as a bead mill, roll mill, ball mill, jet mill, kneader, blender, etc. The temperature during mixing and stirring is not particularly limited and may be selected as appropriate, but is preferably 10 to 200°C, more preferably 20 to 100°C, and even more preferably 50°C or less. The stirring time is not particularly limited, but is preferably 0.01 to 10 hours, more preferably 0.1 to 2 hours, and even more preferably 0.5 to 1 hour.

[0159] 2. Processing with polymer-containing compositions The polymer-containing composition of the present invention can be suitably used as a coating composition or a molding composition. A method for producing a film when the polymer-containing composition of the present invention is used as a coating composition will be described in detail. A method for producing a film using the polymer-containing composition of the present invention is also one of the preferred embodiments of the present invention. When used as the coating composition, the sulfur-containing polymer, the content of compound (M), the solid content, etc. are as described above.

[0160] The coating method is not particularly limited, and conventionally known methods can be used. Among these, spin coating, bar coating, squeegee coating, inkjet coating, etc. are preferred. The coating thickness is not particularly limited, and may be appropriately selected depending on the intended use of the resulting film. 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 0.1 to 1000 μm. The coating thickness is more preferably 0.5 to 100 μm, and even more preferably 1 to 10 μm.

[0161] It is preferable to heat and / or irradiate the applied film (coating film). When a non-polymerizable compound (M) is used as the compound (M), the compound contained in the coating film can be evaporated and removed by heating. When a polymerizable compound (M) is used as the compound (M), the polymerization reaction of the polymerizable compound (M) contained in the coating film can be promoted by heating or irradiating with active energy rays.

[0162] When heating is performed, the heating temperature is not particularly limited, but is preferably 50 to 400° C., more preferably 100 to 300° C. The heating time is not particularly limited, but is preferably 0.01 to 10 hours, more preferably 0.1 to 2 hours.

[0163] 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 is preferably 0.001 to 100 J / cm 2 2 It is preferable to irradiate so that the radiation dose is in the range of 0.01 to 50 J / cm.2 , and more preferably 0.05 to 10 J / cm 2 As the light source, various mercury lamps and the like can be used, but an ultra-high pressure mercury lamp or a metal halide lamp is preferred.

[0164] The substrate to be coated is not particularly limited, but 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).

[0165] A film can be produced from the polymer-containing composition of the present invention by the above-mentioned method. The film preferably has excellent transparency to visible light. For example, the haze value when formed on a glass substrate is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. The haze value can be measured at 25°C using a commercially available turbidity meter. For example, a commercially available turbidity meter such as the HAZE METER NDH 5000 manufactured by Nippon Denshoku Industries Co., Ltd. can be used.

[0166] A film using the polymer-containing composition preferably has an excellent simple average value (average transmittance) of parallel ray transmittance for each wavelength in a required wavelength range, for example, in the range of 400 to 1000 nm. For example, the parallel ray transmittance of a film formed on a glass substrate is preferably 70% or more. The parallel ray transmittance is more preferably 80% or more, and even more preferably 85% or more. The parallel ray transmittance can be determined, for example, by measurement at 25°C using a UV-3600 device manufactured by Shimadzu Corporation.

[0167] A method for producing a molding material when the polymer-containing composition of the present invention is used as a molding composition will be described in detail. A method for producing a molding material using the polymer-containing composition of the present invention is also one of preferred embodiments of the present invention. When used as the molding composition, the sulfur-containing polymer, the content of compound (M), the solid content, etc. are as described above.

[0168] Examples of molding methods include conventionally known methods such as injection molding, T-die molding, inflation molding, imprint molding, nanoimprint molding, and other molding methods using a mold or resin mold, and casting.

[0169] In the above molding method, it is also preferable to heat and / or irradiate with active energy rays for the purpose of promoting polymerization of the polymerizable component contained in the polymer-containing composition. The heating temperature and time when heating may be appropriately selected depending on the molding method employed. The same applies to the preferred embodiments and conditions for irradiating with active energy rays. By the above method, a material molded into a desired shape, such as a lens, sheet, or film, can be obtained.

[0170] 3.Applications The polymer-containing composition of the present invention and films, molding materials, etc. obtained from the polymer-containing composition of the present invention are suitably used for optical materials, optical device members, display device members, etc. Specific examples of such applications include optical applications such as eyeglass lenses, imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and in-vehicle cameras, light beam focusing lenses, light diffusing lenses, and other 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 glass and cover glass for display devices; optical device applications such as photosensors (optical sensors (CMOS sensors, TOF sensors, etc.)), photoswitches, LEDs, micro LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, disconnectors, optical splitters, and optical fiber adhesives; and display device applications such as substrates for display elements such as LCDs, organic electroluminescent (EL) displays, and PDPs, color filter substrates, 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, organic electroluminescent (EL) displays, etc.

[0171] Among these, imaging lenses, filters, diffraction gratings, diffractive optical elements, prisms, light guides, LEDs, micro LEDs, light-emitting elements, color filters, and touch panels are more preferred. Furthermore, the sulfur-containing polymer obtained by the production method of the present invention is likely to generally have a wide range of no absorption in the visible and infrared regions. Such polymers are also suitable for use as optical materials in the visible and infrared regions.

[0172] The uses of the polymer-containing composition of the present invention and the films and molding materials obtained therefrom are not limited to optical applications. They are also used in a variety of applications, including mechanical component materials, electrical and electronic component materials, automotive component materials, civil engineering and construction materials, molding materials, and coating materials and adhesive materials. For example, films and molding materials obtained from the polymer-containing composition of the present invention tend to have excellent heat resistance and can be used as heat-resistant materials, ferroelectric materials, heat-dissipating materials, separators for battery materials, filters such as gas separation membranes and liquid separation membranes, battery components such as electrode materials for fuel cells and Li batteries, and electrolyte materials. They can also be suitably used as insulating materials and antenna materials, taking advantage of their low dielectric properties. [Example]

[0173] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." The polymers obtained in each production example and the polymers used in each example and comparative example were evaluated according to the following methods.

[0174] <Measurement of heavy metal content> Measurements were performed using an ICP-8100 optical emission spectrometer (Shimadzu Corporation) under appropriate plasma conditions (radio frequency output 1.4 kW, coolant gas 20.0 L / min, plasma gas 1.40 L / min, carrier gas 0.60 L / min, plasma light source). The amount of heavy metals (iron) in the polymer was evaluated based on a calibration curve, and the amount of heavy metals (ppm) relative to the polymer was calculated. Measurement samples were diluted with a solvent to a polymer concentration of 0.1 to 10% by mass. N-methylpyrrolidone was used as the solvent for polymers with unoxidized main chains, and dimethylformamide was used for polymers with an oxidation rate of 90% or more.

[0175] <Weight average molecular weight (Mw)> The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC) under the following conditions. Equipment 1: SHIMAZU, CBM-20A. Device 2: Agilent Technologies 1260 Infinity. Detector: Differential refractive index detector (RI) (SHIMAZU, SPD - 20MA), and ultraviolet - visible - infrared spectrophotometer (SHIMAZU, SPD - 20MA). Column: TOSOH, TSKgel SuperHM - N. Column temperature: 40 °C. Flow rate: 0.3 ml / min. Calibration curve: Polystyrene Standards. Eluent: Chloroform, tetrahydrofuran.

[0176] <MALDI (Matrix - Assisted Laser Desorption / Ionization Time - of - Flight Mass Spectrometry)> For the obtained polymer, MALDI measurement was carried out under the following conditions. Device: Time - of - flight mass spectrometer (Bruker AutoflexIII). Sample preparation: Approximately 2 mg of the measurement sample was dissolved in 1.0 g of tetrahydrofuran. As a matrix agent, 20 mg of 2,5 - dihydroxybenzoic acid and as an ionizing agent, 2.0 mg of sodium iodide were dissolved. The adjusted solution was applied to the measurement target plate and dried at room temperature for about 100 minutes.

[0177] < 1 <1H - NMR> For the obtained polymer, 1 1H - NMR measurement was carried out under the following conditions. Device: Nuclear magnetic resonance apparatus (400 MHz) manufactured by JEOL Ltd. Measurement solvent: Deuterated dichloromethane, deuterated chloroform. Sample preparation: Several mg to several tens of mg of the obtained polymer was dissolved in the measurement solvent.

[0178] <ir> For the obtained polymer, IR measurement was carried out under the following conditions. Apparatus: Fourier transform infrared spectrophotometer (FT / IR-6100) manufactured by JASCO Corporation. Sample preparation: Approximately 2 mg of the sample was diluted with approximately 300 mg of dry potassium bromide (KBr). The mixture was ground with a mortar and pestle and molded. <000083​​​​​​​​​​​​​​​​​​​​​​​​​​Equipment: Hitachi High-Tech TM3000, SwiftED3000.

[0183] The compositions obtained in the examples and comparative examples were evaluated as follows. <Transparency> Transparency was determined by haze evaluation. A portion of each composition obtained in each Example and Comparative Example was taken and used as a sample to measure haze. Haze was measured using the following equipment, with the sample (composition) filled in a cell with an optical path length of 1 cm. The sample temperature during measurement was 25°C. Equipment: HAZE METER NDH 5000, manufactured by Nippon Denshoku Industries Co., Ltd. The transparency was evaluated based on the haze value obtained, and the evaluation criteria were as follows: Good: Haze is 10% or less. ×: Haze is more than 10%.

[0184] <Precipitate> The presence and amount of precipitate was determined visually. A portion of each composition obtained in each Example and Comparative Example was collected in a colorless, transparent screw tube and allowed to stand at room temperature for 1 hour, after which the presence and amount of precipitate was visually confirmed.

[0185] The evaluation of the films obtained in each example and comparative example is as follows. <Light transmittance of films, etc.> The light transmittance of the film was measured using the following device (spectrophotometer). Equipment: Shimadzu UV-3600 The transmittance at wavelengths of 400 to 1000 nm was measured, and the average transmittance at wavelengths of 400 to 1000 nm was calculated. The light transmittance of the film was determined based on this average transmittance. Air was used as a control sample. The measured transmittance was a parallel beam transmittance. The criteria for judgment are as follows: ◯: Average transmittance is 80% or more. △: The average transmittance is 60% or more and less than 80%. ×: The average transmittance is less than 60%. The glass substrate on which the film was formed was also measured in the same manner and judged according to the same evaluation criteria.

[0186] (Monomer synthesis) [Synthesis Example 1] A 500 mL three-neck flask was charged with water (98 mL), o-toluenethiol (2-methylbenzenethiol) (18.2 g, 0.147 mol), and tetrabutylammonium iodide (54.3 mg, 0.147 mmol). 30% aqueous hydrogen peroxide (15.2 mL, 0.147 mol) was added dropwise at 1 mL / min, and the mixture was stirred at 60°C for 2 hours. The mixture was cooled to room temperature, and the supernatant (aqueous layer) was removed. An aqueous sodium thiosulfate solution was then added, and the mixture was stirred at room temperature for 2 hours. The supernatant (aqueous layer) was then removed. The reaction solid was filtered, washed with purified water and then methanol, and vacuum dried to recover bis(2-methylphenyl)disulfide. The yield was 98%. 1 H-NMR, 13 C-NMR and FAB-MS confirmed that the product was bis(2-methylphenyl) disulfide (2,2'-dimethyldiphenyl disulfide).

[0187] [Synthesis Example 2] A synthesis reaction was carried out under the same conditions as in Synthesis Example 1, except that the raw material in Synthesis Example 1 was changed to p-toluenethiol (4-methylbenzenethiol) instead of o-toluenethiol, and bis(4-methylphenyl) disulfide was obtained in a yield of 98%. 1 H-NMR, 13 C-NMR and FAB-MS confirmed that the product was bis(4-methylphenyl) disulfide (4,4'-dimethyldiphenyl disulfide).

[0188] (Synthesis of sulfide-containing polymers) [Manufacturing Example 1] Diphenyl disulfide (131.00 g, 0.6 mol), bis(2-methylphenyl) disulfide (36.01 g, 0.15 mol) obtained in Synthesis Example 1 above, iron(III) chloride (6.05 g, 37.30 mmol), (+)-CSA (1.73 g, 7.46 mmol), and NaSO (1.78 g, 7.46 mmol) were added to a 500 mL three-neck flask, and the reaction solution was heated to 160 °C while air bubbling (100 mL / min) and stirred for 40 hours to carry out oxidative polymerization. After cooling to room temperature, a black solid polymer (Ps1) was obtained in 92% yield. The structure of the resulting polymer (Ps1) is as follows: 1 Identification was carried out using H-NMR, GPC, ICP, XPS, and MALDI. 1 H-NMR (CD2Cl2, 400 MHz, ppm): δ = 7.18 (m, 23H), 2.25 (m, 3H). The weight-average molecular weight (Mw) was 2400. ICP analysis revealed an iron content of 21500 ppm. XPS analysis revealed a peak at 160.3-164.9 eV. Peak separation revealed peaks at 160.3-164.9 eV (sulfide) and 163.5-164.9 eV (disulfide). The peak area ratio of sulfide to disulfide was 93:7. MALDI analysis also revealed repeating peaks at m / z 107.98 and m / z 122.04, confirming that the polymer contained -CH4S- and -CH3(CH3)S- as components (A).

[0189] [Manufacturing Example 2] The polymerization reaction was carried out under the same conditions as in Production Example 1, except that the monomer in Production Example 1 was changed from bis(2-methylphenyl) disulfide to bis(4-methylphenyl) disulfide obtained in Synthesis Example 2 above, and the reaction time was changed to 60 hours, thereby obtaining a polymer (Ps2) in a yield of 94%. The structure of the obtained polymer (Ps2) is as follows: 1 Identification was carried out using H-NMR, GPC, ICP, XPS, and MALDI. 1 H-NMR (CD2Cl2, 400 MHz, ppm): δ = 7.20 (m, 23H), 2.25 (m, 3H), weight-average molecular weight 3040. ICP analysis revealed an iron content of 22,500 ppm. XPS analysis revealed a peak at 160.1-164.8 eV. Peak separation revealed peaks at 160.1-164.8 eV (sulfide) and 163.5-164.8 eV (disulfide). The peak area ratio of sulfide to disulfide was 95:5. MALDI analysis also revealed repeating peaks at m / z 107.95 and m / z 122.02, confirming that the polymer contained -CH4S- and -CH3(CH3)S- as components (A).

[0190] [Manufacturing Example 3] To a 100 ml recovery flask, 1.1 g of the polymer (Ps1) obtained in Production Example 1 and 10 mL of THF (tetrahydrofuran, 1.0 M) were added as a solvent. After stirring for 10 minutes, 0.5 mL of pure water was added and the mixture was stirred for 5 minutes. Next, while the recovery flask was cooled on an ice bath, 0.987 g of NaClO·5H2O was added, followed by gradual addition of 0.5 mL of concentrated hydrochloric acid. After stirring for 2 hours, 0.131 g of zinc powder was added and the mixture was stirred at room temperature for 16 hours. After the reaction was completed, 40 mL of methanol was gradually added to the reaction solution to precipitate the product. The precipitate in the reaction solution was filtered using a Kiriyama filter and washed with methanol and pure water. The resulting powder was then dried in a vacuum at room temperature to obtain the polymer (Po1) powder. The structure of the resulting polymer (Po1) is as follows: 1 Identification was carried out using H-NMR, XPS, ICP, and IR. 1 H-NMR (CD2Cl2,400MHz,ppm):δ=7.19(m,7H)δ=7.56(m,12H),2.35(m,3H), 2570cm from IR -1 A peak derived from mercapto was observed around this area, confirming that the terminal structure was -SH.

[0191] [Manufacturing Example 4] To a 100 ml recovery flask, 1.1 g of the polymer (Ps2) obtained in Production Example 2 and THF (1.0 M, 10 mL) as a solvent were added, and after stirring for 10 minutes, 1.0 mL of pure water (THF:water = 10:1) was added and stirred for 5 minutes. Next, while the recovery flask was ice-cooled in an ice bath, TCCA (0.369 g) was added, and after stirring for 2 hours, zinc powder (0.131 g) was added and stirred at room temperature for 16 hours. After the reaction was completed, the product was precipitated by gradually adding methanol (40 mL) to the reaction solution. The precipitate in the reaction solution was filtered using a Kiriyama filter and washed with methanol and pure water. The obtained powder was then vacuum-dried at room temperature to obtain polymer (Po2) powder. The structure of the obtained polymer (Po2) is as follows: 1 Identification was carried out using H-NMR, XPS, ICP, IR, and elemental analysis. 1 H-NMR (CD2Cl2,400MHz,ppm):δ=7.19(m,9H)δ=7.56(m,14H),2.35(m,3H), 2570cm from IR -1 A peak derived from mercapto was observed around this area, and elemental analysis confirmed that the chlorine atom content in the polymer was below the detection limit and that the terminal structure was -SH.

[0192] [Manufacturing Example 5] A 100 ml recovery flask was charged with 4.0 g of the polymer (Po1) obtained in Production Example 3, 12 g of THF as a solvent, and 8 g of NMP (N-methylpyrrolidone). After stirring for 10 minutes, 64 g of ZrO2-dispersed toluene (particle size 20 nm, pure ZrO2 content 16% by mass) was added and stirred at 25°C for 2 hours. Next, 120 mL of hexane was added dropwise, and the mixture was stirred at 25°C for 1 hour and then allowed to stand for 0.5 hours. After filtration, the residue was washed with a mixture of hexane and acetone at 50 wt%. The obtained powder was then vacuum dried at room temperature to obtain a composite (Po-Zr1) powder. The structure of the obtained composite (Po-Zr1) is as follows: 1 The identification was carried out using H-NMR, XPS, ICP, IR, elemental analysis, and SEM-EDS analysis. 1 H-NMR (CD2Cl2, 400 MHz, ppm) showed almost no organic matter other than Po1, estimated to be less than 5 wt%. SEM-EDS analysis confirmed that the composition ratio (mass ratio) of Po1:ZrO2 was 20 mass%:80 mass%.

[0193] [Manufacturing Example 6] A 100 ml recovery flask was charged with 4.0 g of the polymer (Po2) obtained in Production Example 4, 12 g of THF as a solvent, and 8 g of NMP (N-methylpyrrolidone). After stirring for 10 minutes, 64 g of ZrO2-dispersed toluene (particle size 20 nm, pure ZrO2 content 16 mass%) was added and stirred at 25°C for 2 hours. Next, 120 mL of hexane was added dropwise, and the mixture was stirred at 25°C for 1 hour and then allowed to stand for 0.5 hours. After filtration, the residue was washed with a mixture of hexane and acetone at 50 wt%. The obtained powder was then vacuum dried at room temperature to obtain a composite (Po-Zr2) powder. The structure of the obtained composite (Po-Zr2) is as follows: 1 The identification was carried out using H-NMR, XPS, ICP, IR, elemental analysis, and SEM-EDS analysis. 1 H-NMR (CD2Cl2, 400 MHz, ppm) showed almost no organic matter other than Po1, estimated to be less than 5 wt%. SEM-EDS analysis confirmed that the composition ratio (mass ratio) of Po2:ZrO2 was 20 mass%:80 mass%.

[0194] [Example 1-1] 15 parts of the polymer (Ps2) powder obtained in Production Example 2 and 85 parts of benzonitrile were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (1-1). The evaluation results of composition (1-1) are shown in Table 1.

[0195] [Comparative Example 1-1] A composition (c1-1) was obtained in the same manner as in Example 1-1, except that 95 parts of acetone was used instead of 85 parts of benzonitrile. The evaluation results of the composition (c1-1) are shown in Table 1.

[0196] [Examples 1-2 to 1-9, Comparative Examples 1-2 to 1-8] Compositions (1-2) to (1-9) according to each example and compositions (c1-2) to (c1-8) according to each comparative example were obtained in the same manner as in Example 1-1, except that in Example 1-1, 85 parts of benzonitrile were replaced with the compounds shown in Table 1, the compounds and polymer (Ps2) powder were charged in the amounts shown in Table 1, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 1. The evaluation results of each composition obtained in each example and comparative example are shown in Table 1.

[0197] [Example 2-1] 15 parts of the polymer (Po2) powder obtained in Production Example 4 and 85 parts of benzonitrile were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (2-1). The evaluation results of composition (2-1) are shown in Table 2.

[0198] [Comparative Example 2-1] Composition (c2-1) was obtained in the same manner as in Example 2-1, except that 95 parts of acetone was used instead of 85 parts of benzonitrile. The evaluation results of composition (c2-1) are shown in Table 2.

[0199] [Examples 2-2 to 2-14, Comparative Examples 2-2 to 2-8] Compositions (2-2) to (2-14) according to each example and compositions (c2-2) to (c2-8) according to each comparative example were obtained in the same manner as in Example 2-1, except that in Example 2-1, 85 parts of benzonitrile were replaced with the compounds shown in Table 1, the compounds and polymer (Po2) powder were charged in the amounts shown in Table 1, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 2. The evaluation results of each composition obtained in each example and comparative example are shown in Table 2.

[0200] [Example 3-1] 15 parts of the composite (Po-Zr1) powder obtained in Production Example 5 and 85 parts of benzonitrile were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (3-1). The evaluation results for composition (3-1) are shown in Table 3.

[0201] [Comparative Example 3-1] Composition (c3-1) was obtained in the same manner as in Example 3-1, except that 95 parts of acetone was used instead of 85 parts of benzonitrile. The evaluation results of composition (c3-1) are shown in Table 3.

[0202] [Examples 3-2 to 3-22, Comparative Examples 3-2 to 3-8] Compositions (3-2) to (3-22) according to each example and compositions (c3-2) to (c3-8) according to each comparative example were obtained in the same manner as in Example 3-1, except that in Example 3-1, 85 parts of benzonitrile were replaced with the compounds shown in Table 3, the compounds and composite (Po-Zr1) powder were charged in the amounts shown in Table 3, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 3. The evaluation results of each composition obtained in each example and comparative example are shown in Table 3.

[0203] [Example 4-1] 15 parts of the composite (Po-Zr2) powder obtained in Production Example 6 and 85 parts of benzonitrile were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (4-1). The evaluation results for composition (4-1) are shown in Table 4.

[0204] [Comparative Example 4-1] A composition (c4-1) was obtained in the same manner as in Example 4-1, except that 95 parts of acetone was used instead of 85 parts of benzonitrile. The evaluation results of the composition (c4-1) are shown in Table 4.

[0205] [Examples 4-2 to 4-20, Comparative Examples 4-2 to 4-8] Compositions (4-2) to (4-20) according to each example and compositions (c4-2) to (c4-8) according to each comparative example were obtained in the same manner as in Example 4-1, except that in Example 4-1, 85 parts of benzonitrile were replaced with the compounds shown in Table 4, the compounds and composite (Po-Zr2) powder were charged in the amounts shown in Table 4, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 4. Table 4 shows the evaluation results of each composition obtained in each example and comparative example.

[0206] [Example 5-1] 50 parts of the polymer (Po2) powder obtained in Production Example 4 and 50 parts of eugenol were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (5-1). The evaluation results of composition (5-1) are shown in Table 5.

[0207] [Comparative Example 5-1] Composition (c5-1) was obtained in the same manner as in Example 5-1, except that 95 parts of dipentaerythritol hexaacrylate was used instead of 50 parts of eugenol. The evaluation results of composition (c5-1) are shown in Table 5.

[0208] [Examples 5-2 to 5-6, Comparative Examples 5-2 to 5-8] Compositions (5-2) to (5-6) according to each example and compositions (c5-2) to (c5-8) according to each comparative example were obtained in the same manner as in Example 5-1, except that in Example 5-1, 50 parts of eugenol were replaced with the compounds shown in Table 5, the compounds and polymer (Po2) powder were charged in the amounts shown in Table 5, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 5. Table 5 shows the evaluation results of each composition obtained in each example and comparative example.

[0209] The CAS numbers of the compounds used in Examples 5-1 to 5-6 and Comparative Examples 5-1 to 5-8 are shown below. The same applies to the compounds used in Examples 6-1 to 6-6, 7-1 to 7-6, etc. : Eugenol (CAS No.: 97-53-0), Isoeugenol (CAS No.: 97-54-1), 2-Allylphenol (CAS No.: 1745-81-9), Dipentaerythritol Hexaacrylate (CAS No.: 29570-58-9), Glycerol Dimethacrylate (CAS No.: 1830-78-0), Glycidyl Methacrylate (CAS No.: 106-91-2), 1-(Acryloyloxy)-3-(Methacryloyloxy)-2-Propanol (CAS No.: 1709-71-3).

[0210] [Example 6-1] 50 parts of the composite (Po-Zr1) powder obtained in Production Example 5 and 50 parts of eugenol were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (6-1). The evaluation results of composition (6-1) are shown in Table 6.

[0211] [Comparative Example 6-1] Composition (c6-1) was obtained in the same manner as in Example 6-1, except that 95 parts of dipentaerythritol hexaacrylate was used instead of 50 parts of eugenol. The evaluation results of composition (c6-1) are shown in Table 6.

[0212] [Examples 6-2 to 6-6, Comparative Examples 6-2 to 6-8] Compositions (6-2) to (6-6) according to each example and compositions (c6-2) to (c6-8) according to each comparative example were obtained in the same manner as in Example 6-1, except that in Example 6-1, 50 parts of eugenol were replaced with the compounds shown in Table 6, the compounds and composite (Po-Zr1) powder were charged in the amounts shown in Table 6, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 6. The evaluation results of each composition obtained in each example and comparative example are shown in Table 6.

[0213] [Example 7-1] 50 parts of the composite (Po-Zr2) powder obtained in Production Example 6 and 50 parts of eugenol were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (7-1). The evaluation results for composition (7-1) are shown in Table 7.

[0214] [Comparative Example 7-1] Composition (c7-1) was obtained in the same manner as in Example 7-1, except that 95 parts of dipentaerythritol hexaacrylate was used instead of 50 parts of eugenol. The evaluation results of composition (c7-1) are shown in Table 7.

[0215] [Examples 7-2 to 7-6, Comparative Examples 7-2 to 7-8] Compositions (7-2) to (7-6) according to each example and compositions (c7-2) to (c7-8) according to each comparative example were obtained in the same manner as in Example 7-1, except that in Example 7-1, 50 parts of eugenol were replaced with the compounds shown in Table 7, the compounds and composite (Po-Zr2) powder were charged in the amounts shown in Table 7, and the temperature of the composition during stirring was set to the temperature (preparation temperature) shown in Table 7. Table 7 shows the evaluation results of each composition obtained in each example and comparative example.

[0216] [Example 8-1] <Preparation of Composition> 30 parts of the polymer (Po2) powder obtained in Production Example 4 and 70 parts of salicylaldehyde were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (8-1). The evaluation results of composition (8-1) are shown in Table 8. <Membrane preparation> The composition (8-1) was used as the coating composition (8-1). The coating composition (8-1) was spin-coated onto a glass substrate (S9111 manufactured by Matsunami Glass Industrial Co., Ltd.) at room temperature under conditions such that the film thickness would be 1 μm, forming a coating film on the glass substrate, which was then dried by heating at 250°C for 10 minutes to obtain a glass substrate (8-1) on which a film had been formed. The film thickness was approximately 1 μm. The evaluation results for the light transmittance of the glass substrate (8-1) on which a film had been formed are shown in Table 8.

[0217] Among Examples 8-1 to 8-9 and Examples 9-1 to 9-11, some of the examples used polymerizable monomers c1), c2), and c3) as shown in Tables 8 and 9, and the specific examples are as follows. Polymerizable monomer c1: glycerol α,α'-diallyl ether (CAS number: 17018-07-4). Polymerizable monomer c2: 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol. Polymerizable monomer C3: Diallyl-2,2'-biphenyldicarboxylate (CAS number: 51256-00-9).

[0218] [Example 8-2] <Preparation of Composition> Composition (8-2) was obtained in the same manner as in Example 8-1, except that in <Preparation of composition> in Example 8-1, various compounds shown in Table 8 were used instead of 70 parts of salicylaldehyde, and various compounds and polymer (Po2) powder were mixed in the amounts shown in Table 8. The evaluation results of composition (8-2) are shown in Table 8. <Membrane preparation> Irgacure 184 was added as a photopolymerization initiator to the composition (8-2) so that the amount was 0.5% by mass relative to the solid content (polymer (Po2)), to obtain a coating composition (8-2). The obtained coating composition (8-2) was spin-coated onto a glass substrate (S9111 manufactured by Matsunami Glass Industry Co., Ltd.) at room temperature under conditions such that the thickness of the film was 1 μm, forming a coating film on the glass substrate. The coating film was then irradiated with ultraviolet light (irradiation wavelength 365 nm, 10 J / cm). 2 ) and then heated and dried at 250°C for 10 minutes to obtain a glass substrate (8-2) on which a film was formed. The thickness of the film was approximately 1 µm. The evaluation results for the light transmittance of the glass substrate (8-2) on which a film was formed are shown in Table 8.

[0219] [Examples 8-3 to 8-7] <Preparation of Composition> Compositions (8-3) to (8-7) were obtained in the same manner as in Example 8-1, except that in the <Preparation of Compositions> in Example 8-1, various compounds shown in Table 8 were used instead of 70 parts of salicylaldehyde, and various compounds and polymer (Po2) powder were mixed in the amounts shown in Table 8. The evaluation results of these compositions are shown in Table 8. <Membrane preparation> Coating compositions (8-3) to (8-7) were obtained in the same manner as in Example 8-2 <Preparation of film>, except that compositions (8-3) to (8-7) were used instead of composition (8-2), and glass substrates (8-3) to (8-7) on which films were formed were obtained in the same manner, except that each coating composition was used instead of coating composition (8-1). In all examples, the film thickness was approximately 1 μm. Table 8 shows the evaluation results for the light transmittance of the glass substrates (8-3) to (8-7) on which films were formed.

[0220] [Examples 8-8 to 8-9] <Preparation of Composition> Compositions (8-8) and (8-9) were obtained in the same manner as in Example 8-1, except that in the <Preparation of Compositions> in Example 8-1, various compounds shown in Table 8 were used instead of 70 parts of salicylaldehyde, and various compounds and polymer (Po2) powder were mixed in the amounts shown in Table 8. The evaluation results of these compositions are shown in Table 8. <Membrane preparation> Coating compositions (8-8) and (8-9) were obtained in the same manner as in <Preparation of Film> in Example 8-2, except that compositions (8-8) and (8-9), respectively, were used instead of composition (8-2). Glass substrates (8-8) and (8-9) on which films were formed were obtained in the same manner, except that each coating composition was used instead of coating composition (8-1) and coating was performed by the squeegee method instead of the spin coating method. In all Examples, the film thickness was approximately 1 μm. The evaluation results for the light transmittance of the glass substrates (8-8) and (8-9) on which films were formed are shown in Table 8.

[0221] [Example 9-1] <Preparation of Composition> 30 parts of the composite (Po-Zr2) powder obtained in Production Example 6 and 70 parts of salicylaldehyde were mixed at room temperature and stirred with a stirrer at room temperature for 10 minutes to obtain composition (9-1). The evaluation results are shown in Table 9. <Membrane preparation> Next, in Example 8-1, the procedure for <Preparation of Film> was repeated except that composition (9-1) was used instead of composition (8-1), to obtain a coating composition (9-1), which was then used to prepare a glass substrate (9-1) on which a film was formed. The thickness of the obtained film was approximately 1 μm. The evaluation results for the light transmittance of the glass substrate (9-1) on which a film was formed are shown in Table 9.

[0222] [Examples 9-2 to 9-9] <Preparation of Composition> Compositions (9-2) to (9-9) were obtained in the same manner as in Example 9-1, except that in the <Preparation of Compositions> in Example 9-1, various compounds shown in Table 9 were used instead of 70 parts of salicylaldehyde, and various compounds and composite (Po-Zr2) powder were mixed in the amounts shown in Table 9. The evaluation results of each composition are shown in Table 9. <Membrane preparation> Coating compositions (9-2) to (9-9) were prepared in the same manner as in <Preparation of film> in Example 8-2, except that compositions (9-2) to (9-9) were used instead of composition (8-2). Glass substrates (9-2) to (9-9) on which films were formed were obtained in the same manner, except that each coating composition was used instead of coating composition (8-2). In all examples, the thickness of the film was approximately 1 μm. Table 9 shows the evaluation results for the light transmittance of glass substrates (9-2) to (9-9) on which films were formed.

[0223] [Examples 9-10 to 9-11] <Preparation of Composition> Compositions (9-10) and (9-11) were obtained in the same manner as in Example 9-1, except that in the <Preparation of Compositions> in Example 9-1, various compounds shown in Table 9 were used instead of 70 parts of salicylaldehyde, and various compounds and composite (Po-Zr2) powder were mixed in the amounts shown in Table 9. The evaluation results of these compositions are shown in Table 9. <Membrane preparation> Coating compositions (9-10) and (9-11) were obtained in the same manner as in Example 8-2 <Preparation of film>, except that compositions (9-10) and (9-11), respectively, were used instead of composition (8-2). Glass substrates (9-10) and (9-11) on which films were formed were obtained in the same manner, except that each coating composition was used instead of coating composition (8-2) and coating was performed by the squeegee method instead of the spin coating method. In all examples, the film thickness was approximately 1 μm. Table 9 shows the evaluation results for the light transmittance of the glass substrates (9-10) and (9-11) on which films were formed.

[0224] The refractive index of the film obtained in Example 9-1 was 1.88 (589 nm), the refractive index of the film obtained in Example 9-5 was 1.86 (589 nm), and the refractive index of the film obtained in Example 9-7 was 1.82 (589 nm).

[0225] [Table 1]

[0226] [Table 2]

[0227] [Table 3]

[0228] [Table 4]

[0229] [Table 5]

[0230] [Table 6]

[0231] [Table 7]

[0232] [Table 8]

[0233] [Table 9]

[0234] As shown in the examples above, the polymer-containing composition of the present invention contains a specific compound, which allows the sulfur-containing polymer to be uniformly dissolved or dispersed, making it possible to form a transparent film. Furthermore, since compositions with excellent transparency were obtained even in examples containing inorganic particles, it can be said that the polymer-containing composition of the present invention contains inorganic particles in a uniformly dispersed state, even when inorganic particles are included. Therefore, the polymer-containing composition of the present invention can be said to be a composition useful for producing transparent, high-refractive-index films, for example, reflecting the high refractive index of the sulfur-containing polymer. Furthermore, even when inorganic particles are included, it can be said to be a composition useful for producing films or molding materials that reflect the functions of the inorganic particles. For example, in the above examples, it was shown that using zirconia particles as inorganic particles resulted in extremely high, transparent films with a refractive index of 1.8 or more.< / ir>

Claims

1. a polymer-containing composition comprising a sulfur-containing polymer and a compound (M), wherein the compound (M) is a polymerizable compound having a polymerizable group, the polymerizable compound being a benzene-based aromatic compound (M1) having an electron-withdrawing group as a substituent, an unsaturated heterocyclic compound (M2) containing an unsaturated 6-membered ring having an electron-withdrawing group as a substituent, or an unsaturated heterocyclic compound (M3) containing an unsaturated 5-membered ring having an electron-withdrawing group as a substituent, wherein the electron-withdrawing group is a hydroxyl group; the sulfur-containing polymer comprises at least one structural unit selected from the group consisting of a structural unit (A-1) represented by the following general formula (1-1), a structural unit (B-1) represented by the following general formula (2-1), and a structural unit (C-1) represented by the following general formula (3-1); and the total content of the structural units (A-1), (B-1), and (C-1) is 80 mol % or more, relative to 100 mol % of all structural units of the sulfur-containing polymer; 【Chemical Formula 1】 (In the formula, R １ are the same or different and represent a reactive functional group, a halogen atom, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent, each of which may have a substituent. １ represents the number of digits, and is an integer from 0 to 4.) 【Chemistry 2】 (In the formula, R ２ are the same or different and represent a reactive functional group, a halogen atom, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent, each of which may have a substituent. ２ represents the number of digits, and is an integer from 0 to 4.) 【Chemistry 3】 (In the formula, R ３ are the same or different and represent a reactive functional group, a halogen atom, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent, each of which may have a substituent. ３ represents the number of digits, and is an integer from 0 to 4.)

2. The polymer-containing composition of claim 1 further comprising inorganic particles.

3. A method for producing a membrane, comprising using the polymer-containing composition according to claim 1 or 2.

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