Sulfur-containing polymer, method for producing the same, and sulfur-containing polymer composition

Abstract

The present invention aims to provide a polymer material having a high refractive index and suitable for optical applications. The present invention relates to 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), wherein the polymer has a reactive functional group (in the above general formulas (1), (2), and (3), X 1 、X 2 and X 3 are the same or different and represent a divalent aromatic hydrocarbon group which may or may not have a substituent).

Description

Technical Field

[0001] The present invention relates to a sulfur-containing polymer, a method for producing the same, and a sulfur-containing polymer composition. More specifically, it relates to a sulfur-containing polymer having a high refractive index, a method for producing the same, and a sulfur-containing polymer composition. Background Art

[0002] Known high-refractive-index materials include polycarbonates with aromatic rings and polymer materials with fluorene skeletons. Materials with high Abbe numbers, meaning low light dispersion, are required for refractive-index adjustment materials to improve light extraction efficiency in LEDs and for lens materials in imaging systems. Materials with such high refractive indices and low light dispersion have been developed, including those containing sulfur or halogen molecules and metal oxide nanoparticles.

[0003] Various studies have been conducted on sulfur-containing materials with high refractive index and low light dispersion. For example, Patent Document 1 describes a polymer material having a main chain containing repeating units of a benzene ring in which two hydrogen atoms are substituted with methyl groups and a sulfur atom. The polymer material has a dispersion of 3.0 or higher, resulting in excellent moldability in a solution state.

[0004] In addition, for example, Patent Document 2 describes a polymer material that has excellent moldability in a solution state and can be formed into an optical component with a high refractive index by containing a polymer having repeating units of a benzene ring in which one hydrogen atom is substituted by a methyl group and a sulfur atom in the main chain.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-168790

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2017-52834 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] However, the refractive index of the above-mentioned polymer materials cannot be said to be sufficiently high, and there is room for improvement. In addition, in recent years, there is a demand for polymer materials with high refractive index, which can impart excellent physical properties required for various applications such as optical applications, such as heat resistance, mechanical strength, and adhesion to substrates, and can be used for a wider range of applications.

[0011] In view of the above-mentioned current situation, an object of the present invention is to provide a polymer material having a high refractive index and being suitably used for optical applications and the like.

[0012] Means for solving problems

[0013] The present inventors have conducted extensive research on high-refractive-index materials and have discovered that by creating a sulfur-containing polymer having specific functional groups and a specific structure, a polymer material having a high refractive index suitable for optical applications can be formed. Furthermore, by combining such a sulfur-containing polymer with an inorganic substance to form a sulfur-containing polymer composition, a high-refractive-index material having excellent transparency and further suitable for use as an optical material can be formed, thereby completing the present invention.

[0014] That is, the present invention relates to 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), wherein the polymer has a reactive functional group.

[0015] [Chemistry 1]

[0016]

[0017] [Chemistry 2]

[0018]

[0019] [Chemistry 3]

[0020]

[0021] (In formulas (1), (2) and (3), X 1 、X 2 and X 3 are the same or different and represent a divalent aromatic hydrocarbon group which may or may not have a substituent.

[0022] The sulfur-containing polymer preferably contains, as a repeating unit, at least one structural unit selected from the group consisting of the structural unit (A), the structural unit (B), and the structural unit (C).

[0023] The sulfur-containing polymer preferably has the reactive functional group at the main chain terminal and / or the side chain.

[0024] In the sulfur-containing polymer, the reactive functional group is preferably at least one functional group selected from the group consisting of a carboxyl group, a phosphoric acid group, a phosphonic acid group, a hydroxyl group, and a curable functional group, or a group containing such a functional group.

[0025] In the sulfur-containing polymer, the substituent is preferably a reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group which may have a substituent, or a sulfur-containing substituent.

[0026] In the sulfur-containing polymer, the element content 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 is preferably 0.1 to 1.5.

[0027] The above-mentioned sulfur-containing polymer is preferably used for optical applications.

[0028] The present invention also relates to a sulfur-containing polymer composition, which comprises the above-mentioned sulfur-containing polymer and at least one selected from the group consisting of an inorganic substance, a cross-linking agent and an organic resin.

[0029] The present invention also relates to a cured product of the above-mentioned sulfur-containing polymer.

[0030] The present invention also relates to a cured product of the above-mentioned sulfur-containing polymer composition.

[0031] The present invention also relates to a method for producing a sulfur-containing polymer, which is the method for producing a sulfur-containing polymer described above, characterized by comprising a step of reacting a compound having a polymerizable double bond and a reactive functional group with a sulfur-containing aromatic polymer having a terminal disulfide bond and / or a thiol group.

[0032] Effects of the Invention

[0033] According to the present invention, a high-refractive-index sulfur-containing polymer and a sulfur-containing polymer composition can be provided. The sulfur-containing polymer and the sulfur-containing polymer composition of the present invention can be suitably used in optical applications such as imaging system lens materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a photograph of the hybrid membrane obtained in Example 1.

[0035] Figure 2 are photographs of the nanoparticle dispersions of Example 2 and Comparative Example 1.

[0036] Figure 3 These are photographs of hybrid membranes obtained using the nanoparticle dispersions of Example 2 and Comparative Example 1.

[0037] Figure 4 These are photographs of the hybrid films obtained in Experimental Examples 3-1, 3-4, and 3-5.

[0038] Figure 5 This is a graph showing the measurement data of the refractive index of the hybrid solutions of Experimental Examples 8-1 and 8-4 in Example 7.

[0039] Figure 6 These are photographs of hybrid films obtained in Experimental Examples 8-1 to 8-4 in Example 7.

[0040] Figure 7 It is a figure which shows the XRD spectrum of PPS of Example 9 and P1.

[0041] Figure 8 This is a graph showing the measured data of the transmittance of the P1 film of Example 9.

[0042] Figure 9 This is a diagram showing the measurement data of the refractive index of the P1 film of Example 9.

[0043] Figure 10 It is a figure which shows the XRD spectrum of PPS and P2 of Example 9.

[0044] Figure 11 It is a graph showing the DSC curves of P1 and P2.

[0045] Figure 12 This is a graph showing the measured data of the transmittance of the P2 film of Example 9.

[0046] Figure 13 This is a diagram showing the measurement data of the refractive index of the P2 film of Example 9.

[0047] Figure 14 It is a graph showing the measurement data of the transmittance of OHPPS and Me-OMePPS.

[0048] Figure 15 It is a graph showing the measurement data of the refractive index of OHPPS and Me-OMePPS. DETAILED DESCRIPTION

[0049] The present invention is described in detail below.

[0050] In addition, an embodiment in which two or more preferred embodiments of the present invention described below are combined is also a preferred embodiment of the present invention.

[0051] 1. Sulfur-containing polymers

[0052] The sulfur-containing polymer of the present invention is a 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), and is characterized in that the polymer has a reactive functional group.

[0053] [Chemistry 4]

[0054]

[0055] [Chemistry 5]

[0056]

[0057] [Chemistry 6]

[0058]

[0059] (In formulas (1), (2) and (3), X 1 、X 2 and X 3 are the same or different and represent a divalent aromatic hydrocarbon group which may or may not have a substituent.

[0060] The sulfur-containing polymer of the present invention has a high refractive index due to the structure described above. This is presumably because the sulfur-containing polymer of the present invention has a high refractive index because it contains structural units in which S atoms, which have high atomic refractive index, are directly bonded to aromatic hydrocarbon groups.

[0061] The sulfur-containing polymer of the present invention is characterized in that it has a reactive functional group.

[0062] The reactive functional groups can be appropriately selected according to the purpose and application of the sulfur-containing polymer of the present invention, and examples thereof include acidic functional groups such as carboxyl (-COOH), phosphoric acid (-OPO(OH)3), hydroxyl (-OH), sulfonic acid (-SO3H), sulfuric acid (-OSO3H), phosphonic acid (-PO(OH)3), phosphinate (-PO(OH)-), thiol (mercapto) (-SH); amino, ammonium, imino, amide, imide, maleimide , basic functional groups such as cyano group; curable functional groups such as groups having reactive unsaturated bonds (for example, groups having reactive double bonds, as representative examples, are vinyl, (meth)acryloyl, allyl, methallyl, etc.), groups having reactive ionic bonds (for example, groups having reactive cyclic ether groups, groups having reactive cyclic thioethers, as representative examples, are epoxy groups, oxetane groups, episulfide (thiirane), etc.); nitro groups; nitroso groups; and groups containing these functional groups.

[0063] Examples of the group containing these functional groups include the above-mentioned acidic functional group, basic functional group, curable functional group, nitro group or nitroso group and a hydrocarbon chain or linking group.

[0064] That is, in the present invention, the reactive functional group includes not only the acidic functional group, basic functional group, curable functional group, nitro group, or nitroso group, but also a group including these functional groups and a bonding chain.

[0065] Examples of the linking chain include divalent hydrocarbon groups such as an alkylene group and an arylene group, linking groups such as an ether, an ester, a carbonyl group, and an amide group, and combinations thereof.

[0066] Among the reactive functional groups, for example, acidic functional groups, basic functional groups, or groups containing these functional groups are preferred from the perspective of improving the dispersibility of inorganic substances, and carboxyl groups, phosphoric acid groups, phosphonic acid groups, hydroxyl groups, or groups containing these functional groups are more preferred.

[0067] From the viewpoint of low linear expansion coefficient, a carboxyl group, a phosphoric acid 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.

[0068] From the viewpoint of improving adhesion to the substrate, a carboxyl group, a phosphoric acid group, a phosphonic acid group, or a group containing these functional groups is preferred, and a phosphoric acid group, a phosphonic acid group, or a group containing these functional groups is more preferred.

[0069] From the perspective of improving heat resistance, mechanical strength, and solvent resistance, carboxyl groups, hydroxyl groups, amino groups, maleimide groups, curable functional groups, or groups containing these functional groups are preferred, and carboxyl groups, hydroxyl groups, amino groups, maleimide groups, vinyl groups, (meth)acryloyl groups, allyl groups, methallyl groups, epoxy groups, oxetane groups, or groups containing these functional groups are more preferred.

[0070] Among them, from the perspective of being able to provide excellent physical properties and a higher refractive index, the above-mentioned 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, 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 further preferably a phosphate group, a hydroxyl group, a vinyl group, or a group containing these functional groups.

[0071] Furthermore, from the viewpoint of having a low linear expansion coefficient in addition to a high refractive index and being able to improve adhesion to the substrate, the reactive functional group is more preferably a carboxyl group, a phosphoric acid group, or a group containing these functional groups.

[0072] In order to further increase the refractive index, the sulfur-containing polymer preferably has a substituent that participates in hydrogen bonding in the reactive functional group. Hydrogen bonding increases the density of the polymer and can increase the refractive index.

[0073] Examples of the substituent group that participates in hydrogen bonding include a hydroxyl group, a carboxylic acid group, an amino group, an amide group, an imide group, a cyano group, a nitro group, a nitroso group, and a sulfonic acid group.

[0074] The amount of the substituent participating in hydrogen bonding is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 50 mol% or more, still more preferably 70 mol% or more, and particularly preferably 90 mol% or more, based on the repeating units (monomer structural units) of the sulfur-containing polymer.

[0075] One repeating unit may contain two or more of the above-mentioned substituents participating in hydrogen bonding, and the average amount thereof is preferably 0.1 mol or more, more preferably 0.5 mol or more, even more preferably 1 mol or more, still more preferably 1.5 mol or more, still more preferably 2 mol or more, and particularly preferably 3 mol or more. From the perspective of solubility in solvents and heat resistance, the average amount of the above-mentioned substituents participating in hydrogen bonding is preferably less than 4 mol, more preferably less than 3.5 mol.

[0076] The sulfur-containing polymer may have one or more or two or more of the reactive functional groups.

[0077] The sulfur-containing polymer preferably has the reactive functional group at the main chain terminal and / or side chain. Having the reactive functional group at least at the main chain terminal or side chain allows the polymer to exhibit excellent physical properties in addition to a high refractive index.

[0078] The case where the reactive functional group is present in the side chain includes not only the case where the sulfur-containing polymer has the reactive functional group in the side chain but also the case where the substituent in the structural units (A) to (C) represented by the general formulae (1) to (3) is the reactive functional group.

[0079] The sulfur-containing polymer has at least one structural unit selected from the group consisting of the structural unit (A) represented by the general formula (1), the structural unit (B) represented by the general formula (2), and the structural unit (C) represented by the general formula (3).

[0080] The sulfur-containing polymer includes, as a repeating unit, at least one structural unit selected from the group consisting of the structural unit (A), the structural unit (B), and the structural unit (C).

[0081] The above-mentioned structural units (A), (B) and (C) are preferably contained in a plurality in the sulfur-containing polymer, and more preferably contained as repeating units.

[0082] In the above general formulas (1), (2) and (3), X 1 、X 2 and X 3 The same or different groups represent divalent aromatic hydrocarbon groups which may have a substituent or not.

[0083] Examples of the divalent aromatic hydrocarbon group include phenylene, naphthylene, anthrylene, triphenylene, biphenylene, and phenanthrylene. From the perspective of reducing light dispersion of the sulfur-containing polymer, the divalent aromatic hydrocarbon group is preferably phenylene, naphthylene, anthrylene, biphenylene, or triphenylene, and more preferably phenylene.

[0084] Preferred substituents that the divalent aromatic hydrocarbon group may have (hereinafter also referred to as "substituent A") include reactive functional groups, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aralkyl groups, and sulfur-containing substituents.

[0085] Examples of the reactive functional group in the substituent A include the same groups as those mentioned above.

[0086] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a bromine atom is preferred.

[0087] Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and hexyl. Of these, alkyl groups having 1 to 18 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and methyl groups are still more preferred.

[0088] Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy, cyclohexyloxy, and benzyloxy. Of these, alkoxy groups having 1 to 18 carbon atoms are preferred, alkoxy groups having 1 to 6 carbon atoms are more preferred, and methoxy groups are still more preferred.

[0089] Examples of the aryl group include phenyl, naphthyl, and biphenyl. Phenyl is preferred. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0090] Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, and phenyloctyl. The aralkyl group preferably has 7 to 14 carbon atoms, and more preferably 7 to 9 carbon atoms.

[0091] Examples of the sulfur-containing substituent include thioalkyl and thioaryl groups. Among them, thioalkyl is preferred. The sulfur-containing substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0092] The above-mentioned alkyl group, alkoxy group, aryl group, aralkyl group and sulfur-containing substituent group may have a substituent (hereinafter also referred to as "substituent B").

[0093] Examples of the substituent B include the above-mentioned groups other than the above-mentioned reactive functional groups, such as halogen atoms.

[0094] Among them, from the perspective of being able to further increase the refractive index, the substituent (substituent A) possessed by the above-mentioned divalent aromatic hydrocarbon group is preferably the above-mentioned reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group or sulfur-containing substituent with or without a substituent (substituent B), more preferably the above-mentioned reactive functional group, an alkyl group with or without a substituent (substituent B) or a sulfur-containing substituent, further preferably the above-mentioned reactive functional group, a methyl group or a thioalkyl group, and particularly preferably the above-mentioned reactive functional group and a methyl group.

[0095] The substituents may be one or more. If the substituent is one, the substituent may be one or more. If the substituent is two or more, the substituents may be one or more.

[0096] When the divalent aromatic hydrocarbon group is a phenylene group, the substituent of the phenylene group is preferably a hydroxyl group, a carboxyl group, an amino group, an amide group, an imide group, a cyano group, a nitro group, a nitroso group, or a sulfo group in order to achieve a higher refractive index.

[0097] In order to achieve a higher refractive index, the positions of the substituents in the phenylene group are preferably a combination of the 2nd and 6th positions, the 2nd and 3rd positions, the 2nd and 4th positions, or the 2nd and 5th positions, and more preferably a combination of the 2nd and 6th positions.

[0098] Among them, the phenylene group is particularly preferably a phenylene group having hydroxyl groups at positions 2 and 6. Here, position 1 refers to the position of the carbon of the phenylene group bonded to the sulfur atom in the structural unit.

[0099] From the perspective of achieving both a high refractive index and high transparency, the sulfur-containing polymer preferably further has a substituent capable of imparting amorphous properties to the sulfur-containing polymer as a substituent other than the reactive functional group. More preferably, it has an alkyl group such as a methyl, ethyl, or propyl group, an alkoxy group such as a methoxy or ethoxy group, an aryl group, a sulfur-containing substituent, or a halogen-containing group. A methyl group or a methoxy group is even more preferred. The sulfur-containing polymer may have such a substituent as the substituent A or as the substituent B.

[0100] The number of substituents A possessed by the divalent aromatic hydrocarbon group is not particularly limited, but is preferably as small as possible to further improve the refractive index of the sulfur-containing polymer. Specifically, it is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1.

[0101] The sulfur-containing polymer is preferably composed of the above-mentioned structural unit (A), structural unit (B) or structural unit (C) as a repeating unit. The positions at which these structural units are linked to each other are respectively relative to X 1 、X 2 、X3 The bonding position of -S-, -SO-, and -SO2- can be any one of the ortho, meta, and para positions, or two or more. From the perspective of high refractive index, the para position is preferred, and from the perspective of solubility, the ortho and meta positions are preferred.

[0102] The sulfur-containing polymer may include two or more types of structural units in which the linkage positions of the structural units are different from each other.

[0103] In the above-mentioned sulfur-containing polymer, the amount of the structural units linked at the para position is preferably 10 mol% or more, more preferably 30 mol% or more, relative to 100 mol% of all structural units of the polymer, and is preferably less than 99 mol%, more preferably less than 90 mol%, and even more preferably less than 80 mol%.

[0104] The structural unit (A) represented by the general formula (1) is preferably a structural unit (A-1) represented by the following general formula (1-1).

[0105] [Chemistry 7]

[0106]

[0107] (Where R 1 are the same or different and represent a halogen atom, a reactive functional group, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a sulfur-containing substituent group which may or may not have a substituent. a represents R 1 The number is an integer from 0 to 4.)

[0108] Furthermore, the structural unit (B) represented by the general formula (2) is preferably a structural unit (B-1) represented by the following general formula (2-1).

[0109] [Chemistry 8]

[0110]

[0111] (Where R 2 are the same or different and represent a halogen atom, a reactive functional group, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a sulfur-containing substituent group which may or may not have a substituent. b represents R 2 The number is an integer from 0 to 4.)

[0112] Furthermore, the structural unit (C) represented by the general formula (3) is preferably a structural unit (C-1) represented by the following general formula (3-1).

[0113] [Chemistry 9]

[0114]

[0115] (Where R 3are the same or different and represent a halogen atom, a reactive functional group, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a sulfur-containing substituent group which may or may not have a substituent. c represents R 3 The number is an integer from 0 to 4.)

[0116] As the above R 1 、R 2 and R 3 Preferred examples of the halogen atom, reactive functional group, alkyl group, alkoxy group, aryl group, aralkyl group, and sulfur-containing substituent include the same groups as those mentioned above.

[0117] In addition, as the substituent which these groups may have, preferably there are the same groups as those for the substituent B described above.

[0118] a, b, c represent R 1 、R 2 、R 3 The number of substituents is an integer of 0-4, preferably an integer of 0-2, and more preferably an integer of 1-2.

[0119] The sulfur-containing polymer may be an alternating copolymer of the structural units (A), (B) and (C), a block copolymer or a random copolymer.

[0120] The sulfur-containing polymer may contain one or two or more of the structural units (A), (B) or (C).

[0121] The sulfur-containing polymer may comprise only one of the structural units (A), (B), and (C), two of the structural units, or three of the structural units. These embodiments and their proportions may be appropriately selected depending on the purpose and application of the sulfur-containing polymer.

[0122] For example, from the viewpoint of achieving a higher refractive index, the sulfur-containing polymer preferably contains the structural unit (A), and more preferably contains the structural unit (A) as a main component.

[0123] Furthermore, from the viewpoint of achieving both solubility and a high refractive index, the sulfur-containing polymer preferably contains the structural unit (B), and more preferably contains the structural unit (B) as a main component.

[0124] Furthermore, from the viewpoint of being able to achieve both transparency and a high refractive index, the sulfur-containing polymer preferably contains the structural unit (C), and more preferably contains the structural unit (C) as a main component.

[0125] From the above-mentioned viewpoint, in the sulfur-containing polymer, the content of the structural unit (A) is preferably 1 mol% to 100 mol%, more preferably 10 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%, relative to 100 mol% of all structural units in the polymer, from the viewpoint of high refractive index.

[0126] In this case, the total content of the structural units (B) and (C) is preferably 0 to 99 mol%, more preferably 0 to 90 mol%, and even more preferably 0 to 50 mol%, relative to 100 mol% of all structural units.

[0127] In the sulfur-containing polymer, the content of the structural unit (B) is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and even more preferably 50 to 100 mol%, relative to 100 mol% of all structural units in the polymer, from the perspective of high polarity due to solubility.

[0128] In this case, the total content of the structural units (A) and (C) is preferably 0 to 99 mol%, more preferably 0 to 90 mol%, and even more preferably 0 to 50 mol%, relative to 100 mol% of all structural units.

[0129] In the sulfur-containing polymer, the content of the structural unit (C) is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and even more preferably 50 to 100 mol%, relative to 100 mol% of all structural units in the polymer, from the viewpoint of high transparency.

[0130] In this case, the total content of the structural units (A) and (B) is preferably 0 to 99 mol%, more preferably 0 to 90 mol%, and even more preferably 0 to 50 mol%, relative to 100 mol% of all structural units.

[0131] 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, still more preferably 95 mol% or more, and particularly preferably 100 mol% based on 100 mol% of all the structural units of the polymer.

[0132] The sulfur-containing polymer may have another structural unit (D) in addition to the structural unit (A), structural unit (B), and structural unit (C). The sulfur-containing polymer may further have the structural unit (D) as a repeating unit.

[0133] Examples of the structural unit (D) include structural units having at least the reactive functional group described above.

[0134] Examples of the structural unit (D) include structural units derived from a monomer having a polymerizable double bond and the reactive functional group.

[0135] Examples of the polymerizable double bond include a vinyl group, a (meth)acryloyl group, an allyl group, and a methallyl group. Among them, a (meth)acryloyl group is preferred.

[0136] Examples of the monomer having the 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 phosphate; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate; vinyl ether group-containing (meth)acrylates such as 2-(2-vinyloxyethoxy)ethyl (meth)acrylate; and the like.

[0137] The content of the structural unit (D) is preferably 0 to 80 mol%, more preferably 0 to 50 mol%, further preferably 0 to 20 mol%, still more preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%, based on 100 mol% of all structural units in the polymer.

[0138] In the sulfur-containing polymer, the element content ratio (O / S) of oxygen atoms O bonded to the main chain sulfur atoms S to the main chain sulfur atoms S is preferably 0.1 to 1.5. When the element content ratio is within the above range, transparency and refractive index are further improved.

[0139] Specifically, the sulfur atom S in the main chain refers to, for example, the sulfur atom S located in the main chain in the structural unit (A) represented by the general formula (1). Furthermore, the sulfur atom S located in the main chain in the structural unit (B) represented by the general formula (2) refers to the sulfur atom S located in the main chain in the -SO- group. Furthermore, the sulfur atom S located in the main chain in the structural unit (C) represented by the general formula (3) refers to the sulfur atom S located in the main chain in the -SO2- group.

[0140] Regarding the oxygen atom bonded to the sulfur atom S in the above-mentioned main chain, specifically, for example, in the structural unit (B) represented by the above-mentioned general formula (2), it refers to the oxygen atom O of -SO- located in the main chain, and in the structural unit (C) represented by the above-mentioned general formula (3), it refers to the oxygen atom O of -SO2- located in the main chain.

[0141] From the perspective of further improving transparency, the element content ratio (O / S) is more preferably 0.3 or more, and more preferably 0.7 or more. From the perspective of further improving the refractive index, it is more preferably 1.3 or less, and more preferably 1.1 or less.

[0142] The above-mentioned element content ratios can be determined by evaluating and measuring the peak intensities of the 1s orbital (O1s) of oxygen atoms, the 1s orbital (C1s) of carbon atoms, and the 2p orbital (S2p) of sulfur atoms using an X-ray photoelectron spectroscopy device (XPS). Specifically, they can be determined by the method described in the examples below.

[0143] The sulfur-containing polymer preferably has a glass transition temperature (Tg) of 80°C to 250°C. A glass transition temperature within this range facilitates molding. To improve heat resistance, the glass transition temperature is more preferably 90°C or higher, and even more preferably 100°C or higher. To facilitate molding, the glass transition temperature is more preferably 200°C or lower.

[0144] The glass transition temperature can be determined by using a differential scanning calorimeter (DSC) to raise the temperature from room temperature (heating rate 10°C / min) to 250°C in a nitrogen atmosphere, and evaluating the intersection of the baseline and the tangent line at the inflection point from the obtained DSC curve.

[0145] In the sulfur-containing polymer, the SO bond energy is preferably 163 eV to 167 eV. When the SO bond energy is within the above range, the refractive index and transparency can be further improved.

[0146] The SO bond energy can be determined by evaluating the position of the peak top of the 2p 3 / 2 orbital of the sulfur atom measured by an X-ray photoelectron spectroscopy (XPS).

[0147] 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 this range, the polymer is suitable for use as an optical material. To improve mechanical properties, the weight-average molecular weight is more preferably 1,000 or greater, even more preferably 3,000 or greater, and even more preferably 10,000 or greater. To reduce melt viscosity, the weight-average molecular weight is more preferably 1,000,000 or less, even more preferably 100,000 or less.

[0148] The dispersity (weight average molecular weight / number average molecular weight) of the sulfur-containing polymer is preferably 1 to 10. When the dispersity is within this range, molding becomes easier. To further improve moldability, the dispersity is more preferably 5 or less, and even more preferably 3 or less.

[0149] The weight average molecular weight and number average molecular weight can be determined by gel permeation chromatography (GPC), specifically, by the method described in the Examples below. The degree of dispersion can be determined by dividing the weight average molecular weight by the number average molecular weight.

[0150] The sulfur-containing polymer preferably has a refractive index of 1.69 or greater. When the refractive index falls within this range, the polymer can be suitably used in various applications, including optical materials (components), mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and construction materials, molding materials, and coating and adhesive materials. The refractive index is more preferably 1.7 or greater, and even more preferably 1.71 or greater.

[0151] The refractive index can be determined by preparing a 50 nm thick film of the sulfur-containing polymer as a measurement sample and measuring the film using a spectroscopic ellipsometer UVISEL (manufactured by HORIBA Scientific) using Na D line (589 nm).

[0152] The sulfur-containing polymer preferably has an Abbe number of 10 or greater. When the Abbe number is within this range, light dispersion is low, allowing the polymer to be used as an optical material suitable for lenses and the like. The Abbe number is more preferably 15 or greater, even more preferably 18 or greater, and even more preferably 20 or greater. From the perspective of adjusting light dispersion, the Abbe number is preferably 60 or less, and more preferably 55 or less.

[0153] The Abbe number can be determined similarly to the refractive index by forming a film using the sulfur-containing polymer, measuring the refractive index at the D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm) using the spectroscopic ellipsometer, and using the following formula.

[0154] Abbe value (v D )=(n D -1) / (n F -n C )

[0155] Where n D 、n F 、n C These respectively represent the refractive indices at Fraunhofer D-line (589.3 nm), F-line (486.1 nm), and C-line (658.3 nm).

[0156] The sulfur-containing polymer preferably has a visible light transmittance of 70% or more. When the visible light transmittance is within the above range, it can be suitably used as an optical material. The visible light transmittance is more preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more.

[0157] The above-mentioned visible light transmittance is a parallel line transmittance, which can be obtained as follows: using a film of a certain thickness (for example, 1 μm) composed of the above-mentioned sulfur-containing polymer, or standardizing the thickness, using a spectrophotometer (for example, the JASCO UV-Vis-Infrared Spectrophotometer V-700 series), without using an integrating sphere, the range of 400 nm to 700 nm is measured with air as an object, and the lowest value of the transmittance is evaluated.

[0158] The above-mentioned sulfur-containing polymer is preferably amorphous for optical material applications requiring transparency. The crystallinity of the above-mentioned sulfur-containing polymer is preferably less than 80%, more preferably less than 50%, even more preferably less than 30%, particularly preferably less than 10%, and most preferably less than 5%. Furthermore, for applications requiring heat resistance but not requiring transparency, the crystallinity of the above-mentioned sulfur-containing polymer is preferably 1% or more, more preferably 10% or more, even more preferably 30% or more, and particularly preferably 60% or more.

[0159] The above-mentioned crystallinity can be determined by X-ray diffraction (XRD) measurement. The crystallinity can be determined by separating the obtained XRD spectrum into multiple peaks, defining peaks with a half-width of less than 1 as crystalline, and peaks with a half-width of 1 or greater as amorphous. The ratio of the area of ​​the crystalline peak to the total peak area is calculated as the crystallinity.

[0160] The sulfur-containing polymer is preferably thermoplastic. If the sulfur-containing polymer is thermoplastic, it can be formed into a uniform thin film, can be formed into a complex shape with high precision, has good moldability, and can be easily applied to a wide range of applications.

[0161] Furthermore, the above-mentioned sulfur-containing polymer can also be converted into a thermoplastic resin by copolymerization or addition reaction with other monomers using reactive functional groups, particularly curable functional groups.

[0162] When forming the thermoplastic resin, it is preferable to use a compound (monomer) having a substituent that reacts with the reactive functional group of the sulfur-containing polymer. The sulfur-containing polymer may also be used as the monomer.

[0163] As substituents for the above-mentioned monomers, there can be mentioned, for example: ring-opening polymerizable groups such as epoxy groups, oxetane rings, thiirane groups, aziridine groups, etc.; free radical curing groups and / or addition curing groups such as acryloyl groups, methacryloyl groups, allyl groups, vinyl groups, maleimide groups, etc.; addition reactive groups such as hydroxyl groups, thiol groups, hydrosilyl groups, etc.; esterification reactive groups such as carboxylic acid groups, oxazoline groups, hydroxyl groups, thiol groups, amino groups, etc.; carbamate- and thiocarbamate-reactive groups such as isocyanate groups, etc.

[0164] Preferred monomers include compounds having a ring-opening polymerizable group (epoxy, oxetane, thiirane, etc.) that is cured by cationic curing, compounds having an acryloyl and / or methacryloyl group that is cured by free radical curing, and compounds having a vinyl group that is cured by an addition reaction such as hydrosilylation or enethiol reaction.

[0165] For example, a thermoplastic copolymer can be obtained by free radical polymerization of a sulfur-containing polymer having a monofunctional double bond at its terminal end with another monofunctional double bond. Alternatively, a thermoplastic polymer can be obtained by allowing a sulfur-containing polymer having a monofunctional thiol group at its terminal end to undergo an ene-thiol reaction with the double bonds of another polymer.

[0166] <Method for producing sulfur-containing polymer>

[0167] The method for producing the sulfur-containing polymer of the present invention is not particularly limited as long as it is a method capable of producing a polymer having at least the aforementioned reactive functional group and any one of the structural units (A) to (C). Examples include known polymerization methods, such as a method of polymerizing a monomer component containing a sulfur-containing monomer having the aforementioned reactive functional group; a method of introducing the reactive functional group into the polymer by reacting a polymer obtained by polymerizing a monomer component containing a sulfur-containing monomer with a compound having the aforementioned reactive functional group. Among these, a method of introducing the functional group by reacting a compound having the aforementioned reactive functional group with a polymer is preferred from the perspective of efficiently producing the sulfur-containing polymer.

[0168] A preferred method for producing the sulfur-containing polymer of the present invention includes a step of reacting a compound having a polymerizable double bond and a reactive functional group with a sulfur-containing aromatic polymer having a disulfide bond and / or a thiol group at a terminal. This method for producing the sulfur-containing polymer is also one aspect of the present invention.

[0169] As an example of the above-mentioned reaction process, the following method (method a) can be cited: for a sulfur-containing aromatic polymer having a disulfide bond at the terminal, the disulfide bond at the terminal of the sulfur-containing aromatic polymer is cleaved using light or a free radical initiation catalyst, and the compound having the above-mentioned polymerizable double bond and a reactive functional group is reacted with the polymer to bind the above-mentioned compound, thereby introducing the reactive functional group.

[0170] Another method (method b) includes reacting the compound having a polymerizable double bond and a reactive functional group with a sulfur-containing aromatic polymer having a thiol group at a terminal, and bonding the compound via a thiol-ene reaction to introduce a reactive functional group.

[0171] Another method (method c) can be mentioned: a sulfur-containing aromatic polymer having a terminal disulfide bond is reacted with a reducing agent such as sodium borohydride, triphenylphosphine, ferrosoferric oxide, or ferric oxide to form a thiol group (-SH) at the terminal, and then a compound having a polymerizable double bond and a reactive functional group is reacted with the compound to introduce a reactive functional group by bonding the compound via a thiol-ene reaction.

[0172] Another method for producing the above-mentioned sulfur-containing polymer is to introduce a reactive functional group into a sulfur-containing aromatic polymer having a substituent such as a halogen atom (for example, a haloalkyl substituent) by generating a hydroxyl group through a nucleophilic reaction of water (method d).

[0173] In addition, examples of methods for producing the above-mentioned sulfur-containing polymers include: a method of obtaining a polymer from a sulfur-containing monomer containing a substituent having a reactive functional group such as a carboxyl group using the method described below (method e); a method of introducing a reactive functional group by generating a hydroxyl group using a reducing agent such as dimethyl sulfide borane, a borane-tetrahydrofuran complex, or N,N-dimethylaniline borane into the sulfur-containing aromatic polymer having a carboxyl group obtained in the above (method e) (method f); and the like.

[0174] The above-mentioned (method a), (method b), and (method c) are preferable as methods for producing a sulfur-containing polymer having a reactive functional group at a main chain terminal.

[0175] The above-mentioned (method d), (method e), and (method f) are preferable as methods for producing a sulfur-containing polymer having a reactive functional group in a side chain.

[0176] Examples of the polymerizable double bond include a vinyl group, a (meth)acryloyl group, an allyl group, and a methallyl group.

[0177] Examples of the reactive functional group include the reactive functional groups described above.

[0178] The above-mentioned (method a) to (method f) can be appropriately selected according to the type of reactive functional group to be introduced and the above-mentioned compound to be used. In addition, the reaction conditions and the like can also be appropriately selected from known techniques.

[0179] Next, some preferred examples of the method for producing the sulfur-containing polymer of the present invention will be described.

[0180] For example, when producing a sulfur-containing polymer having a carboxyl group, a phosphoric acid group, a phosphonic acid group, or a curable functional group at the terminal, the above (method c) is preferred.

[0181] Specifically, first, a sulfur-containing aromatic polymer having a disulfide bond at a terminal is subjected to cleavage of the disulfide bond (-SS-) using a reducing agent such as sodium borohydride, thereby forming a thiol group at the terminal.

[0182] As the reducing agent, in addition to sodium borohydride, lithium triethylborohydride, triphenylphosphine, Rongalite (sodium formaldehyde sulfoxylate), and the like can also be used.

[0183] The amount of the reducing agent used can be appropriately set depending on the amount of side chains and terminal groups of the sulfur-containing aromatic polymer. For example, it is preferably 1 to 1000 parts by mass, more preferably 5 to 300 parts by mass, and even more preferably 10 to 100 parts by mass, relative to 100 parts by mass of the sulfur-containing aromatic polymer.

[0184] The reaction temperature for forming a thiol group via a disulfide bond is preferably 0 to 200° C., more preferably 10 to 100° C. The reaction time is not particularly limited, but is usually 0.1 to 100 hours, preferably 0.5 to 50 hours, more preferably 1 to 24 hours.

[0185] In the above-mentioned reaction for forming a thiol group, a solvent may be used. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and γ-butyrolactone; ether solvents such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), and tetrahydrofuran (THF); aromatic hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, fluorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and trifluorotoluene; amide solvents such as dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone; and dimethyl sulfoxide (DMSO) and nitromethane.

[0186] Next, a compound having a polymerizable double bond and a carboxyl group, a phosphoric acid group, a phosphonic acid group, or a curable functional group (two or more polymerizable groups) is reacted with the terminal thiol group.

[0187] As the above-mentioned compound having a polymerizable double bond and a carboxyl group, a phosphoric acid group or a phosphonic acid group, any compound having a polymerizable double bond and a carboxyl group, a phosphoric acid group or a phosphonic acid group that can react with a thiol group may be used, and examples thereof include compounds having a vinyl group and a carboxyl group, compounds having a (meth)acryloyl group and a phosphonic acid group, compounds having a (meth)acryloyl group and a carboxyl group, and compounds having a (meth)acryloyl group and a phosphoric acid group.

[0188] Specific examples of the above-mentioned compounds include 4-pentenoic acid, carboxyethyl acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phosphate, and vinylphosphonic acid. Among them, 4-pentenoic acid, carboxyethyl acrylate, 2-acryloyloxyethyl phosphate, and vinylphosphonic acid are preferred because they can be highly refracted and have high reactivity.

[0189] The amount of the compound used can be appropriately set depending on the amount of reactive functional groups to be introduced. For example, it is preferably 0.1 to 1000 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the sulfur-containing aromatic polymer.

[0190] The reaction with the compound having a polymerizable double bond and a carboxyl group, a phosphate group or a phosphonic acid group is also preferably carried out by light irradiation. The light irradiation can be carried out by a known method using a known light source. In addition, the reaction can be carried out using a known polymerization initiator or catalyst, and the type and amount thereof can also be appropriately set.

[0191] Furthermore, for example, when the thiolation step is shortened and a reactive functional group is directly introduced, the above (method a) is preferred.

[0192] In the above (method a), for example, the compound having a polymerizable double bond and a carboxyl group, a phosphoric acid group, or a phosphonic acid group is directly reacted with the sulfur-containing aromatic polymer.

[0193] In the above (method a), the amount of the compound having a polymerizable double bond and a carboxyl group, a phosphoric acid group or a phosphonic acid group can be appropriately set according to the amount of the reactive functional group to be introduced. For example, it is preferably 0.1 to 5000 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the sulfur-containing aromatic polymer.

[0194] In the above-mentioned (method a), the reaction with the above-mentioned compound with polymerizable double bond and carboxyl group is preferably carried out by light irradiation. The above-mentioned light irradiation can be carried out by a known method using a known light source. In addition, the above-mentioned reaction can be carried out using a known initiator or catalyst etc., and its type and amount also can be appropriately set.

[0195] When a sulfur-containing polymer having a thiol group is used, for example, the above-mentioned (method b) is preferred. The reaction of the sulfur-containing polymer having a thiol group with the compound having a polymerizable double bond and a reactive functional group is preferably carried out under the same conditions as the above-mentioned (method c).

[0196] For example, when producing a sulfur-containing polymer having the above-mentioned reactive functional group in a side chain, the above-mentioned (method d) or (method e) is preferred.

[0197] In the above (method d), the sulfur-containing aromatic polymer having a substituent such as a halogen atom can be obtained, for example, by adding N-bromosuccinimide and 2,2'-azobis(isobutyronitrile) to a sulfur-containing polymer having an alkyl substituent in the method for producing a sulfur-containing aromatic polymer described below and reacting them.

[0198] The reaction temperature is not particularly limited, but is preferably 10°C to 200°C, more preferably 50°C to 150°C.

[0199] By adding water to the obtained haloalkyl sulfur-containing aromatic polymer, a sulfur-containing polymer having a hydroxyl group in a side chain can be obtained.

[0200] When producing a sulfur-containing polymer having a carboxyl group in a side chain by the above (method e), the polymer can be obtained by using benzenethiol having a carboxyl group, specifically 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, etc., as the sulfur-containing monomer in the method for producing a sulfur-containing aromatic polymer described below.

[0201] Furthermore, as a method for producing a sulfur-containing polymer having a curable functional group such as a vinyl group in a side chain, for example, the following method can be mentioned: N-bromosuccinimide and 2,2'-azobis(isobutyronitrile) are added to the sulfur-containing polymer having an alkyl substituent as described above, and the reaction is carried out to obtain a sulfur-containing aromatic polymer having a halogen atom (bromine atom) as a substituent, and then triphenylphosphine, an aqueous formaldehyde solution, and potassium tert-butoxide are reacted.

[0202] In addition, as a method for producing a sulfur-containing polymer having a hydroxyl group in a side chain, for example, the following method can be mentioned: in the method for producing a sulfur-containing aromatic polymer described below, a monomer having an alkoxy substituent such as a methoxy group is used to obtain a sulfur-containing aromatic polymer having an alkoxy substituent, and then the obtained polymer is reacted with boron tribromide and water is added.

[0203] In the production method of the present invention, the sulfur-containing aromatic polymer may be produced by polymerization or may be a commercially available product.

[0204] Examples of methods for producing the sulfur-containing aromatic polymer include a method of polymerizing monomer components including a sulfur-containing monomer.

[0205] Preferred examples of the sulfur-containing monomer include disulfide compounds and thiol compounds. Specifically, more preferred examples include diaryl disulfide compounds represented by the following general formula (4) and thioaryl compounds represented by the following general formula (5).

[0206] [Chemistry 10]

[0207] A 1 -SSA 2 (4)

[0208] A 1 -SH (5)

[0209] In the above general formulas (4) and (5), A 1 and A 2 The same or different groups represent monovalent aromatic hydrocarbon groups which may have a substituent or not.

[0210] As A 1 and A 2 The monovalent aromatic hydrocarbon group represented by 1 The divalent aromatic hydrocarbon group shown is a monovalent aromatic hydrocarbon group, and examples thereof include phenyl, naphthyl, anthracenyl, triphenyl, biphenyl, phenanthrenyl, etc. Among them, phenyl, naphthyl, anthracenyl, biphenyl, or triphenyl is preferred, and phenyl is more preferred.

[0211] As A 1 and A 2 The substituents possessed by the monovalent aromatic hydrocarbon group shown in the figure include reactive functional groups, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aralkyl groups, sulfur-containing substituents, etc. Examples of the reactive functional groups, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aralkyl groups, and sulfur-containing substituents include the same groups as those mentioned above.

[0212] The diaryl disulfide compound is preferably a compound represented by the following general formula (4-1).

[0213] The thioaryl compound is preferably a compound represented by the following general formula (5-1).

[0214] [Chemistry 11]

[0215]

[0216] (In formulas (4-1) and (5-1), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 are the same or different and represent a hydrogen atom, a halogen atom, a reactive functional group, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a sulfur-containing substituent group which may or may not have a substituent.

[0217] Examples of the halogen atom, reactive functional group, or alkyl group, alkoxy group, aryl group, aralkyl group or sulfur-containing substituent group which may or may not have a substituent include the following: 1 The groups shown are the same groups.

[0218] Examples of the substituent that these groups may have include the same substituents as those for the substituent B described above, and among these, a halogen atom is preferred.

[0219] The disulfide compound can also be produced by oxidation of a thiol compound. Therefore, in the polymerization step, a thiol compound can be used as a precursor of the disulfide compound. The disulfide compound can be obtained by oxidatively bonding two molecules of the thiol compound.

[0220] The method for oxidizing a thiol compound to obtain a disulfide compound is not particularly limited, and the method can be carried out by a known method such as oxidation using hydrogen peroxide, iodine, or the like.

[0221] The above-mentioned sulfur-containing monomers may be used alone or in combination of two or more.

[0222] The polymerization is preferably oxidative polymerization. The oxidative polymerization is not particularly limited and can be performed using known methods such as methods using quinone compounds or methods using metal compounds such as vanadium compounds. Of these, oxidative polymerization is preferably performed using a quinone oxidant due to its improved transparency. Metal compounds are preferably used due to their reduced usage relative to the monomer components and reduced waste.

[0223] Examples of the quinone-based oxidizing agent include 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 2,3,5,6-tetrachloro-p-benzoquinone (chloranil), 2,3,5,6-tetrabromobenzoquinone (bromoquinone), 2,3,5,6-tetrafluoro-p-benzoquinone, anthraquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dibromo-1,4-naphthoquinone, 2,3-dicyano-1,4-naphthoquinone, 3,4,5,6-tetrachloro-o-benzoquinone (o-chloranil), 3,4,5,6-tetrabromo-o-benzoquinone (o-bromoquinone), and 3,4,5,6-tetrafluorobenzoquinone. DDQ is preferred due to its high oxidizing power and ease of availability. The quinone-based oxidizing agent may be used alone or in combination of two or more.

[0224] The amount of the quinone-based oxidizing agent added is preferably 0.1 mol to 3 mol, more preferably 0.8 mol to 1.5 mol, and even more preferably 0.9 mol to 1.1 mol, relative to 1 mol of the sulfur-containing monomer used.

[0225] When using the above-mentioned quinone-based oxidizing agent, an acid may be further added. When the above-mentioned quinone-based oxidizing agent acts, the quinone-based compound becomes a dianion of hydroquinone. When an acid is added, the dianion can be stabilized and the oxidizing power can be maintained.

[0226] The acid is not particularly limited, and examples thereof include sulfuric acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, and perfluorobutyric acid. Among these, trifluoroacetic acid is preferred from the perspective of increasing acidity. The acids may be used alone or in combination of two or more.

[0227] The amount of the acid added is preferably 10 mol to 1000 mol, more preferably 50 mol to 500 mol, and even more preferably 80 mol to 120 mol, based on 100 mol of the total amount of the quinone-based oxidizing agent added.

[0228] The reaction temperature is not particularly limited as long as it is a temperature at which polymerization can proceed. From the perspective of facilitating the oxidative polymerization, the reaction temperature is preferably 0 to 200°C, more preferably 10°C or higher, and even more preferably 15°C or higher. From the perspective of suppressing side reactions, the reaction temperature is more preferably 180°C or lower, and even more preferably 150°C or lower.

[0229] The reaction time is not particularly limited, but is usually 0.1 to 100 hours, preferably 1 to 80 hours, more preferably 5 to 50 hours, and even more preferably 10 to 24 hours.

[0230] A solvent may be used in the polymerization reaction. Preferred solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, nitrobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, N-methylpyrrolidone, tetrahydrofuran, and ethyl acetate.

[0231] In the above-mentioned polymerization reaction, monomer components including a sulfur-containing monomer may be added successively during the polymerization reaction.

[0232] Alternatively, the polymerization may be performed in multiple stages, for example, by oxidatively polymerizing the thiol compound to obtain a disulfide compound, and then oxidatively polymerizing the obtained disulfide compound.

[0233] The method for producing the above-mentioned sulfur-containing polymer may include a step of oxidizing the polymer into which the above-mentioned reactive functional groups have been introduced in the above-mentioned step using an oxidizing agent. In the oxidation step, -S- in the main chain is oxidized to -SO- or -SO2-, thereby obtaining a sulfur-containing polymer having the above-mentioned structural units (B) and / or (C).

[0234] The oxidizing agent is not particularly limited, and a known oxidizing agent can be used. Among them, peroxide or chloric acid is preferably used because it can moderately oxidize the sulfide group (-S-) located on the main chain to form a sulfoxide (sulfinyl) group (-SO-).

[0235] Examples of the peroxide include m-chloroperbenzoic acid, hydrogen peroxide, ammonium persulfate, sodium persulfate, peracetic acid, and t-butyl hydroperoxide.

[0236] Among them, the oxidizing agent is preferably a peroxide, more preferably m-chloroperbenzoic acid or hydrogen peroxide, from the perspective of being soluble in the same solvent as the sulfur-containing polymer. From the perspective of not using water that causes polymer precipitation and suppressing oxidation to form sulfonyl groups due to excess oxidizing agent, the oxidizing agent is further preferably m-chloroperbenzoic acid.

[0237] When hydrogen peroxide is used as the peroxidizing agent, it is preferred to suppress the amount of water and use a phase transfer catalyst such as trifluoroacetone from the viewpoint of suppressing the precipitation of the polymer.

[0238] The above-mentioned oxidizing agents may be used alone or in combination of two or more.

[0239] The amount of the oxidizing agent added is not particularly limited as long as it is an amount that allows the desired oxidation reaction of the sulfur atoms to proceed. Generally, it is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, and even more preferably 0.8 to 1.5 mol per 1 mol of sulfur atoms in the sulfur-containing polymer.

[0240] The reaction temperature of the above-mentioned oxidation reaction is not particularly limited as long as it is a temperature at which the desired oxidation reaction can proceed. From the perspective of facilitating the above-mentioned oxidation reaction, it is preferably 0 to 200°C, more preferably 10°C or higher, and even more preferably 15°C or higher. From the perspective of suppressing side reactions, it is more preferably 180°C or lower, and even more preferably 150°C or lower.

[0241] The reaction time is not particularly limited, but is usually 0.1 to 100 hours, preferably 1 to 80 hours, more preferably 5 to 50 hours, and even more preferably 10 to 24 hours.

[0242] When oxidizing to -SO2-, the reaction can be carried out at a longer time than the above-mentioned reaction temperature. The amount of the oxidizing agent added is not particularly limited as long as it allows the desired oxidation reaction of the sulfur atoms to proceed. Generally, the amount is preferably 1.5 to 100 mol, more preferably 2 to 50 mol, and even more preferably 2 to 10 mol per 1 mol of sulfur atoms in the sulfur-containing polymer.

[0243] A solvent may be used in the oxidation reaction. Preferred examples of the solvent include the same solvents as those used in the polymerization step.

[0244] The polymer obtained by the above-mentioned oxidation step may contain residual acid, etc., so it is preferably washed. The washing method is not particularly limited, and methods using water, acid, alkali, etc. can be used. In addition, to remove unreacted products, the polymer can be passed through a filter or washed with a solvent. The above-mentioned solvent is not particularly limited, and the same solvent as the reaction solvent can be used.

[0245] The above-mentioned method for producing a sulfur-containing polymer may include other steps in addition to the above-mentioned steps. Examples of such other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, and a purification step. These steps can be carried out by known methods.

[0246] 2. Sulfur-containing polymer composition

[0247] The sulfur-containing polymer of the present invention can be combined with other components to form a sulfur-containing polymer composition. The other components are not particularly limited and can be appropriately selected from known components depending on the purpose and application of the sulfur-containing polymer composition.

[0248] The content of the sulfur-containing polymer in the sulfur-containing polymer composition can be appropriately set depending on the application and purpose of the sulfur-containing polymer composition. It is preferably 10% to 100% by mass based on 100% by mass of the total solids content of the sulfur-containing polymer composition. From the perspective of further improving transmittance and refractive index, it is more preferably 20% by mass or greater, and even more preferably 50% by mass or greater. From the perspective of maintaining a low viscosity of the sulfur-containing polymer composition, the content is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 85% by mass or less, particularly preferably 80% by mass or less, and most preferably 60% by mass or less.

[0249] As the specific example of above-mentioned other components, the compositions such as the close fitting improving agent such as inorganic matter, cross-linking agent, curing catalyst, curing agent, organic resin, pigment, dye, antioxidant, ultraviolet light absorber, IR cut-off agent, reactive diluent, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization initiator, polymerization inhibitor, filler, coupling agent, heat stabilizer, antibacterial / mildewproof agent, flame retardant, matting agent, defoamer, leveling agent, wetting / dispersant, anti-settling agent, thickener, anti-sagging agent, anti-floating color agent, emulsifier, anti-skid / anti-scratch agent, anti-skinning agent, desiccant, antifouling agent, antistatic agent, conductive agent (static auxiliary agent), solvent can be enumerated.These compositions can only use 1 kind, also can use in combination more than 2 kinds.These compositions can be suitably selected to use from known thing.In addition, their compounding amount can suitably set.

[0250] The sulfur-containing polymer composition preferably comprises the sulfur-containing polymer and at least one selected from the group consisting of an inorganic substance, a cross-linking agent, and an organic resin.

[0251] For example, when an inorganic substance is combined with the above-mentioned sulfur-containing polymer, the characteristics of the added inorganic substance can be imparted, and since the dispersibility is excellent, the transparency of the composition can be significantly improved.

[0252] Examples of the inorganic substance include metals, inorganic oxides, inorganic nitrides, inorganic carbides, inorganic sulfides, and inorganic hydroxides. These inorganic substances may be used alone or in combination of two or more.

[0253] The above-mentioned inorganic substance preferably contains a metal.

[0254] Examples of the above-mentioned metals include lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), manganese (Mn), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), tin (Sn), and silicon (Si).

[0255] As the above-mentioned inorganic oxide, a metal oxide containing a metal element is preferred. As the above-mentioned metal oxide, a single metal oxide composed of one metal element, an oxide composed of two or more metal elements, i.e., a composite oxide, and a solid solution oxide in which a different element is solid-dissolved in the above-mentioned single metal oxide or the above-mentioned composite oxide. The above-mentioned different element may be a metal element, or may be a non-metallic element other than oxygen, such as nitrogen or fluorine. As the metal element, the above-mentioned metal elements may be mentioned.

[0256] 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.

[0257] Examples of the composite oxides 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.

[0258] Examples of the solid solution oxide include those in which a different metal element and / or a non-metallic element other than oxygen, such as nitrogen or fluorine, is solid-dissolved in the above-mentioned single metal oxide or composite oxide.

[0259] As the inorganic nitride, metal nitride is preferable, and examples thereof include boron nitride, carbon nitride, and aluminum nitride.

[0260] As the inorganic carbide, metal carbide is preferable, and examples thereof include silicon carbide, calcium carbide, titanium carbide, and boron carbide.

[0261] As the inorganic sulfide, metal sulfide is preferable, and examples thereof include copper sulfide, zinc sulfide, and cadmium sulfide.

[0262] As the inorganic hydroxide, metal hydroxides are preferred, and examples thereof include aluminum hydroxide, magnesium hydroxide, and barium hydroxide.

[0263] Among them, from the viewpoint of wide band gap (visible light transparency), the inorganic substance is preferably an inorganic oxide, and more preferably a metal oxide.

[0264] In addition, among the above-mentioned inorganic substances, oxides with Ti, Zr, Ce, Zn, In, Al, Si, and Sn as main components of metal elements are further preferred, and 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, from the perspective of having no absorption or little absorption in the visible light region, thereby suppressing coloration caused by inorganic substances and making it easy to obtain colorless and transparent compositions.

[0265] Among the above-mentioned inorganic substances, zirconium oxide, titanium oxide, and silicon dioxide are more preferred from the perspective of further improving the transparency of the sulfur-containing polymer composition and achieving low linear expansion of the composition. Zirconium oxide and titanium oxide are more preferred from the perspective of increasing the refractive index of the sulfur-containing polymer composition. Furthermore, perovskite-type composite oxides are preferred from the perspective of having a high dielectric constant, making the sulfur-containing polymer composition suitable for use as a ferroelectric or piezoelectric material. Boron nitride, aluminum hydroxide, and aluminum titanate are preferred from the perspective of having a high thermal conductivity, making the sulfur-containing polymer composition suitable for use as a heat dissipation material.

[0266] From the perspective of suppressing coloration caused by the addition of inorganic substances to the above-mentioned sulfur-containing polymer composition while imparting antistatic properties or conductivity, preferred are solid solution oxides in which a different metal element or an added element such as fluorine is solid-dissolved in zinc oxide (ZnO), indium oxide (In2O3) or tin oxide (SnO2). For example, zinc oxide in which In, Al or Ga is solid-dissolved, indium oxide in which Sn or Ti is solid-dissolved, and tin oxide in which Sb or F is solid-dissolved are more preferred.

[0267] The shape of the inorganic substance is not particularly limited and may be any of amorphous, granular, plate-like, fibrous, etc., but is preferably granular.

[0268] The inorganic substance may be surface treated. The surface treatment is not particularly limited as long as it does not affect the effects of the present invention, and examples thereof include methods using a silane coupling agent, a method of reacting a compound having a phosphate group, a method of reacting a compound having a carboxylic acid group, and other known methods.

[0269] The average particle size of the inorganic material is preferably between 1 nm and 1000 nm. When the average particle size of the inorganic material falls within the above range, the transmittance in the visible light region and the infrared region can be improved. To reduce the amount of organic resin, the average particle size of the inorganic material is more preferably 5 nm or more, and even more preferably 10 nm or more. Furthermore, the average particle size of the inorganic material is more preferably 100 nm or less, even more preferably 50 nm or less, and even more preferably less than 30 nm.

[0270] In order to achieve the closest packing of the inorganic substances, two or more inorganic substances having different particle sizes may be used.

[0271] The average particle size is determined by observing the inorganic material using a SEM (magnification of 1,000 to 100,000 times, preferably 10,000 times), analyzing the resulting image, and determining the particle size (circle area equivalent diameter) of approximately 10 to 1,000 individual particles (primary particles). The 50% particle size of the number-based particle size distribution is then evaluated. For image analysis, known image analysis software (e.g., Mac-View manufactured by Mountech) can be used.

[0272] The content of the aforementioned inorganic substance is not particularly limited and can be appropriately set depending on the purpose and application of the sulfur-containing polymer composition. For example, to further improve transparency and achieve low linear expansion, the content of the aforementioned inorganic substance is preferably 10 parts by mass or greater, more preferably 30 parts by mass or greater, even more preferably 50 parts by mass or greater, particularly preferably 70 parts by mass or greater, and most preferably 80 parts by mass or greater, relative to 100 parts by mass of the sulfur-containing polymer. Furthermore, to reduce the melt viscosity during production of a resin molded article, the content of the aforementioned inorganic substance is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less, relative to 100 parts by mass of the sulfur-containing polymer.

[0273] The cross-linking agent is not particularly limited, but preferably includes a curable organic compound having a curable functional group that can react with the reactive functional group of the sulfur-containing polymer.

[0274] The curable functional group is a functional group that undergoes a curing reaction by heat or light (a group that causes the polymer composition to undergo a curing reaction).

[0275] Examples of the curable functional groups include: ring-opening polymerizable groups such as epoxy groups, oxetane rings, thiirane groups, and aziridine groups; free radical curable groups and / or addition curable groups such as acryloyl groups, methacryloyl groups, allyl groups, vinyl groups, and maleimide groups; addition reactive groups such as hydroxyl groups, thiol groups, and hydrosilyl groups; esterification reactive groups such as carboxylic acid groups, oxazoline groups, hydroxyl groups, thiol groups, and amino groups; and carbamate- and thiocarbamate-reactive groups such as isocyanate groups.

[0276] As above-mentioned curable organic compound, preferably there is the compound of the ring-opening polymerizable group (epoxy group, oxetane, thiirane etc.) solidified by cationic curing, there is the compound of the acryloyl group and / or methacryloyl group solidified by free radical curing, there is the compound of the vinyl solidified by addition reactions such as hydrosilylation or ene-thiol reaction.If these compounds are used, then the time until one-step curing is short, productivity is good, and the heat resistance (resistance to thermal decomposition, heat-resistant coloration) of the obtained cured product is excellent.Wherein, the shrinkage ratio during one-step curing is low, it is easy to give the aspect of shape in the moulding of the mould utilizing nanoimprint etc., resin mould etc., more preferably there is the compound of the ring-opening polymerizable group solidified by cationic curing, there is the compound of the thiol group carrying out ene-thiol reaction.As the above-mentioned compound with ring-opening polymerizable group, as long as it is the compound comprising more than 1 ring-opening polymerizable group in 1 molecule, preferably with the compound, i.e. multifunctional compound, having more than 2 ring-opening polymerizable groups in total as essential component. This further improves the curing reactivity and provides a resin composition having excellent curability and curing speed, and thus a cured molded article can be obtained in a shorter time.

[0277] When the reactive functional group of the sulfur-containing polymer is a group having a reactive unsaturated bond, the cross-linking agent used is preferably a cross-linking agent having a thiol group or a cross-linking agent having a reactive double bond.

[0278] When the reactive functional group of the sulfur-containing polymer is a group having a reactive ionic bond, the crosslinking agent used is preferably a crosslinking agent having a thiol group, a crosslinking agent having a reactive ionic bond, or a crosslinking agent having an amine.

[0279] When the reactive functional group of the sulfur-containing polymer is a hydroxyl group, the crosslinking agent used is preferably a crosslinking agent having a reactive double bond, a crosslinking agent having a reactive ionic bond, or a crosslinking agent having an isocyanate group.

[0280] When the reactive functional group of the sulfur-containing polymer is a thiol group, the cross-linking agent used is preferably a cross-linking agent having a reactive double bond, a cross-linking agent having a reactive ionic bond, or a cross-linking agent having an isocyanate group.

[0281] Examples of the crosslinking agent having a thiol group include aliphatic polythiol compounds such as methanedithiol, 1,2-ethanedithiol, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, and tris(mercaptoethylthio)methane; and 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3- ,4-toluenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol and other aromatic polythiol compounds; 2-methylamino-4,6-dithio-s-triazine, 3,4-thiophenedithiol, 2,5-dimercaptothiadiazole, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane and other heterocyclic polythiol compounds, etc.

[0282] Examples of the cross-linking agent having a reactive double bond include compounds having an acryloyl group, a methacryloyl group, an allyl group, or a vinyl group. Specific examples include aromatic vinyl monomers such as divinylbenzene; aromatic allyl monomers such as diallyl phthalate and diallylphenylphosphonate; vinyl ester monomers such as polyvinyl acetate; (meth)acrylic monomers such as (di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, adamantyl (meth)acrylate, fluorene (meth)acrylate, and tris[2-(meth)acryloyloxyethyl]triazine; and triallyl cyanurate.

[0283] Examples of the cross-linking agent having a reactive ionic bond include compounds having an epoxy group, compounds having an oxetane ring, and episulfide compounds.

[0284] Examples of the compound having an epoxy group include aromatic epoxy compounds such as bisphenol A epoxy compounds, bisphenol F epoxy compounds, fluorene epoxy compounds, and aromatic epoxy compounds having a bromine substituent; aliphatic epoxy compounds such as epoxy compounds obtained by a condensation reaction of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG600) and epihalohydrin; alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, and bis(3,4-epoxycyclohexyl)adipate; and hydrogenated epoxy compounds such as hydrogenated bisphenol A epoxy compounds, hydrogenated bisphenol S epoxy compounds, and hydrogenated bisphenol F epoxy compounds.

[0285] Examples of the compound having an oxetane ring include aliphatic oxetane compounds such as 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane and dipentaerythritol tetra(3-ethyl-3-oxetanylmethyl)ether; and aromatic oxetane compounds such as phenol novolac oxetane, dioxetane compounds having a biphenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL(R) OXBP), dioxetane compounds having a phenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL(R) OXTP), and dioxetane compounds having a fluorene skeleton.

[0286] Examples of the episulfide compounds include aliphatic episulfide compounds such as bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, and 1,3-bis(2,3-epithiopropylthio)cyclohexane; aromatic episulfide compounds such as 1,2-bis(2,3-epithiopropylthio)benzene and 1,3-bis(2,3-epithiopropylthio)benzene; and sulfur-containing episulfide compounds such as 3-mercaptopropylenesulfide and 4-mercaptobutylenesulfide.

[0287] Examples of the cross-linking agent having an isocyanate group include aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine triisocyanate, and xylylene diisocyanate; alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and 4,9-bis(isocyanatomethyl)tricyclodecane; and aromatic polyisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate, and phenylene diisocyanate. compounds; heterocyclic polyisocyanate compounds such as 4,5-bis(isocyanatomethyl)-1,3-dithiophene; aliphatic polyisocyanate compounds such as bis(isothiocyanatoethyl) disulfide; alicyclic polyisocyanate compounds such as 3,9-bis(isothiocyanatomethyl)tricyclodecane and 4,8-bis(isothiocyanatomethyl)tricyclodecane; aromatic polyisocyanate compounds such as toluene diisocyanate; sulfur-containing heterocyclic polyisocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-bis(isothiocyanatomethyl)thiophene, etc.

[0288] The content of the crosslinking agent is preferably 0.1 to 1000 parts by mass, more preferably 1 to 500 parts by mass, further preferably 5 to 100 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of the sulfur-containing polymer.

[0289] In order to promote the reaction between the reactive functional groups of the sulfur-containing polymer and the crosslinking agent, a curing catalyst and a curing agent may be contained in combination, and these can be appropriately selected according to the reaction.

[0290] As above-mentioned curing catalyst and curing agent, for example, when carrying out heat curing, reaction by heating, can enumerate heat latent cation curing catalyst, photolatent cation curing catalyst, heat latent free radical curing catalyst, photolatent free radical curing catalyst, acid anhydride system curing agent, phenolic curing agent or amine curing agent etc.Wherein, preferably use heat latent cation curing catalyst, heat latent free radical curing catalyst.In order to reduce the shrinkage of solidified material, particularly preferably use heat latent cation curing catalyst.In addition, when reacting by active energy ray irradiation, preferably use curing agent, photolatent cation curing catalyst, photolatent free radical curing catalyst.In order to reduce the shrinkage of solidified material, particularly preferably use photolatent cation curing catalyst.These curing catalysts, curing agent can be used in combination one or more than two kinds.

[0291] As the above-mentioned thermolatent cationic curing catalyst and photolatent cationic curing catalyst, onium salts and boron compounds (boron complexes) are preferred.

[0292] Preferred examples of the thermolatent radical curing catalyst include organic peroxides such as cumene hydroperoxide and azo compounds such as 2,2'-azobis(isobutyronitrile).

[0293] Preferred examples of the photolatent free radical curing catalyst include: acetophenones such as acetophenone and diethoxyacetophenone; benzoins such as benzoin and benzoin methyl ether; benzophenones such as benzophenone and methyl o-benzoylbenzoate; thioxanthones such as 2-isopropylthioxanthone; xanthones; anthraquinones such as 2-methylanthraquinone; and acylphosphine oxides.

[0294] The content of the curing catalyst is preferably 0.01% by mass to 10% by mass relative to 100% by mass of the sulfur-containing polymer composition.

[0295] In the curing by irradiation with active energy rays, it is preferred to use a photosensitizer in addition to the above-mentioned photolatent curing catalyst.

[0296] Preferred examples of the photosensitizer include amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, (2-dimethylamino)ethyl benzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate.

[0297] The amount of the photosensitizer blended is preferably 0.1% by mass to 20% by mass relative to 100% by mass of the sulfur-containing polymer composition.

[0298] Examples of the curing agent include commonly used curing agents such as acid anhydride-based, phenol-based, and amine-based curing agents.

[0299] Examples of the acid anhydride curing agent include anhydrides of aliphatic carboxylic acids such as tetrahydrophthalic anhydride and polydodecanedioic anhydride; and aromatic carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic anhydride.

[0300] When using the above-mentioned acid anhydride-based, phenol-based, or amine-based curing agent, it is preferred to use a curing accelerator in combination.

[0301] Examples of the curing accelerator include acid salts of organic bases and aromatic compounds having tertiary nitrogen. Examples of the acid salts of organic bases include organic onium salts such as organic phosphonium salts and organic ammonium salts, and acid salts of organic bases having tertiary nitrogen.

[0302] Examples of the organic phosphonium salt include phosphonium bromides having four phenyl rings, such as tetraphenylphosphonium bromide and triphenylphosphine-toluene bromide.

[0303] Examples of the organic ammonium salt include tetra(C1-C8)alkylammonium bromides such as tetraoctylammonium bromide, tetrabutylammonium bromide, and tetraethylammonium bromide.

[0304] Examples of the acid salt of the organic base having a tertiary nitrogen include organic acid salts of an alicyclic base having a tertiary nitrogen in the ring and organic acid salts of various imidazoles.

[0305] The above-mentioned curing accelerators may be used alone or in combination of two or more.

[0306] The amount of the curing accelerator used is preferably 0.01% by mass to 5% by mass, more preferably 0.03% by mass to 3% by mass, relative to 100% by mass of the sulfur-containing polymer composition.

[0307] The organic resin is not particularly limited as long as it is an organic resin other than the above-mentioned sulfur-containing polymer. Conventionally known polymer materials can be used, and examples thereof include polyolefins such as polyethylene, polypropylene, and cyclic polyolefins; vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, and polyvinyl alcohol; (meth)acrylic resins; polyurethanes; fluororesins such as polytetrafluoroethylene; ABS resins; AS resins; polyamides; polyacetals; polycarbonates; modified polyphenylene ethers; polyesters such as polyethylene terephthalate and polybutylene terephthalate; amorphous polyarylates; liquid crystal polymers; polyetheretherketones; polyimides; silicone resins; polyamideimides; cellulose polymers; epoxy resins; urea resins; melamine resins; phenolic resins; urethane resins; unsaturated polyester resins; diallyl phthalate resins; alkyd resins; and fluorene-containing resins. Among these, polystyrene, polycarbonates, fluorene-containing resins, and cyclic polyolefins are preferred.

[0308] When the organic resin is included, the content of the organic resin is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on 100% by mass of the total solids content of the sulfur-containing polymer composition, from the perspective of further improving the refractive index. Furthermore, from the perspective of improving curability and heat resistance, the content of the organic resin is preferably less than 90% by mass, more preferably less than 80% by mass, and even more preferably less than 70% by mass, based on 100% by mass of the total solids content of the sulfur-containing polymer composition.

[0309] The sulfur-containing polymer composition preferably has a glass transition temperature (Tg) of 80°C to 250°C. When the glass transition temperature is within this range, molding and processing can be easily performed. To improve heat resistance, the glass transition temperature is more preferably 90°C or higher, and even more preferably 100°C or higher. To facilitate molding and processing, the glass transition temperature is more preferably 200°C or lower.

[0310] 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.

[0311] The refractive index of the sulfur-containing polymer composition is preferably 1.69 or greater. When the refractive index is within the above range, the composition can be suitably used as an optical material, etc. The refractive index is more preferably 1.70 or greater, and even more preferably 1.71 or greater.

[0312] The refractive index can be determined by the same method as the method for measuring the refractive index of the sulfur-containing polymer.

[0313] The sulfur-containing polymer composition preferably has an Abbe number of 10 or greater. When the Abbe number is within this range, light dispersion is low, making it suitable as an optical material for lenses. The Abbe number is more preferably 15 or greater, even more preferably 18 or greater, and even more preferably 20 or greater. From the perspective of adjusting light dispersion properties, the Abbe number is more preferably 60 or less, and even more preferably 55 or less.

[0314] The Abbe number can be determined by the same method as the method for measuring the Abbe number of the sulfur-containing polymer.

[0315] The sulfur-containing polymer composition preferably has a visible light transmittance of 70% or greater. When the visible light transmittance is within the above range, the composition can be suitably used in optical materials. The visible light transmittance is more preferably 80% or greater, further preferably 85% or greater, and even more preferably 88% or greater.

[0316] The visible light transmittance is a parallel line transmittance, and can be determined by the same method as the method for measuring the visible light transmittance of the sulfur-containing polymer.

[0317] The density of the sulfur-containing polymer composition is preferably 1.1 g / cm2 when the inorganic substance is not included, from the viewpoint of further increasing the refractive index. 3 More preferably, 1.3 g / cm 3 More preferably, 1.4 g / cm 3 More preferably, 1.6 g / cm 3 More than, particularly preferably 1.8 g / cm 3 On the other hand, from the perspective of lightness, the density of the sulfur-containing polymer composition is preferably less than 3.0 g / cm 3 , more preferably less than 2.5g / cm 3 , more preferably less than 2.0g / cm 3 .

[0318] The method for producing the sulfur-containing polymer composition is not particularly limited. The sulfur-containing polymer can be obtained by mixing the sulfur-containing polymer with the inorganic substance and, if necessary, other components. The mixing can be performed using known means such as a bead mill, a roll mill, a ball mill, a jet mill, a kneader, and a mixer.

[0319] The sulfur-containing polymer composition is preferably thermoplastic. Because it contains the sulfur-containing polymer, the sulfur-containing polymer composition has a high refractive index and possesses essential properties such as heat resistance. A thermoplastic sulfur-containing polymer composition exhibits excellent moldability and is readily applicable to various applications requiring these properties.

[0320] The curing method for the sulfur-containing polymer and the sulfur-containing polymer composition is not particularly limited and can be performed by heating, irradiation with active energy rays, or a combination thereof. The curing method can be appropriately selected depending on the reactive functional groups of the sulfur-containing polymer and the purpose and application of the sulfur-containing polymer composition.

[0321] The heating method is not particularly limited, and examples thereof include a method of heating at 40°C to 400°C for 30 seconds to 48 hours, preferably at 50°C to 300°C for 10 minutes to 30 hours, and more preferably at 120°C to 260°C for 30 minutes to 3 hours.

[0322] The active energy rays are not particularly limited, and known active energy rays such as electron beams, ultraviolet rays, and visible light can be used. The amount of active energy rays used is not particularly limited and can be appropriately set according to the purpose and application of the sulfur-containing polymer and the sulfur-containing polymer composition.

[0323] Cured products obtained by curing the above-mentioned sulfur-containing polymers and sulfur-containing polymer compositions have high refractive indices and various properties based on the reactive functional groups possessed by the above-mentioned sulfur-containing polymers, and can be suitably used in optical applications and the like.

[0324] The cured product of the above-mentioned sulfur-containing polymer is also one aspect of the present invention. In addition, the cured product of the above-mentioned sulfur-containing polymer composition is also one aspect of the present invention.

[0325] 3. Purpose

[0326] The sulfur-containing polymers and sulfur-containing polymer compositions of the present invention are used for various applications, both optical and non-optical, and are preferably used for optical applications. Specifically, they are used in various applications, such as imaging lenses, optical materials (components), mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and construction materials, molding materials, and coating and adhesive materials. Among them, they are particularly suitable for use in optical materials, optical device components, and display device components. Specific examples of such applications include eyeglass lenses, camera lenses for (digital) cameras, mobile phone cameras, and car cameras, beam converging lenses, light diffusing lenses, and other lenses, LED sealing materials, optical adhesives, optical bonding materials, light transmission bonding materials, optical filters, diffraction gratings, diffraction optical elements, prisms, light guide elements, watch glasses, transparent glass or glass covers for display devices, and the like; optical device applications such as optical sensors (optical sensors (CMOS sensors, TOF sensors, etc.)), optical switches, LEDs, Micro LEDs, light emitting elements, optical waveguides, combiners, demultiplexers, circuit breakers, optical splitters, and optical fiber adhesives; substrates for display elements such as LCDs, organic ELs, and PDPs, substrates for color filters, substrates for touch panels, and the like. Applications include: display devices such as display backlights, display screen protective films, display screen backlights, light guide plates, anti-reflection films, anti-fog films, and light extraction enhancers for LED and organic EL.

[0327] Furthermore, the sulfur-containing polymer and sulfur-containing polymer composition of the present invention are also excellent in heat resistance and can therefore be suitably used in heat-resistant materials, ferroelectric materials, heat dissipating materials, separators for battery materials, filters such as gas separation membranes and liquid separation membranes, and the like.

[0328] Furthermore, the sulfur-containing polymers and sulfur-containing polymer compositions of the present invention have a wide range of non-absorption in the visible and infrared regions, making them suitable for use as optical materials in the visible and infrared regions. Furthermore, due to their excellent heat resistance, they can also be used in battery components such as electrode materials and electrolyte materials for fuel cells and lithium batteries. Furthermore, they can also be used as insulating materials and antenna materials utilizing low dielectric properties.

[0329] The sulfur-containing polymers and sulfur-containing polymer compositions of the present invention are suitable for use as molding materials. Examples of molding methods include known methods such as injection molding, T-die molding, inflation molding, imprint molding, and nanoimprint molding using molds or resin molds. Molding into a desired shape can also be achieved by methods such as casting and coating. The aforementioned shapes are not particularly limited, and examples thereof include various known shapes such as lenses, sheets, and films.

[0330] Furthermore, the sulfur-containing polymers and sulfur-containing polymer compositions of the present invention can be suitably used in processing using conventionally known etching processes such as plasma etching and conventionally known processes using resists with poor solubility. Furthermore, they can also be suitably used in coating processes such as spin coating, bar coating, doctor blade coating, and inkjet coating.

[0331] The sulfur-containing polymer composition of the present invention is preferably a thermoplastic resin composition from the viewpoint of good processability, and is preferably a curable resin composition from the viewpoint of low viscosity and good conformability to a small mold or resin mold during molding.

[0332] As described above, the sulfur-containing polymer and the sulfur-containing polymer composition of the present invention have a high refractive index and can have various properties according to the purpose. Therefore, they can be suitably used in a wide range of applications including optical applications.

[0333] Example

[0334] The present invention will be further described in detail with reference to the following examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0335] In the examples, each evaluation was performed by the following methods.

[0336] <Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn), Dispersity (Mw / Mn)>

[0337] The weight average molecular weight and number average molecular weight of the polymer were determined by gel permeation chromatography (GPC) under the following conditions. The degree of dispersion was calculated by dividing the weight average molecular weight by the number average molecular weight.

[0338] Device: SHIMAZU, CBM-20A

[0339] Detector: Differential refractive index detector (RI) (SHIMAZU, SPD-20MA) and UV-visible infrared spectrophotometer (SHIMAZU, SPD-20MA)

[0340] Column: TOSOH, TSKgel SuperHM-N

[0341] Column temperature: 40°C

[0342] Flow rate: 0.3 ml / min

[0343] Calibration curve: polystyrene standards

[0344] Eluent: chloroform

[0345] < 1 H-NMR,13 C-NMR, DOSY-NMR

[0346] The obtained polymer was subjected to the following conditions: 1 H-NMR, 13 C-NMR and DOSY-NMR determination.

[0347] Equipment: Nuclear magnetic resonance equipment manufactured by Agilent Technologies (600 MHz)

[0348] Determination solvent: deuterated chloroform

[0349] Sample preparation: Several mg to several tens of mg of the obtained polymer are dissolved in a measurement solvent.

[0350] <ir>

[0351] IR measurement was performed under the following conditions.

[0352] Apparatus: Fourier transform infrared spectrophotometer (FT / IR-6100) manufactured by JASCO

[0353] Sample preparation: About 2 mg of sample was mixed with about 300 mg of dry potassium bromide (KBr), and the mixture was ground with a mortar and pestle and shaped.

[0354] <Refractive index (n D )>

[0355] The resulting film was measured using a spectroscopic ellipsometer, UVISEL, manufactured by HORIBA Scientific, to measure the phase difference of polarized light before and after incident and the reflection deflection angle ratio. The incident light wavelength (450 nm) and incident angle (75°) were set to pre-set values, and the complex refractive index was calculated. The refractive index from 190 to 2000 nm was calculated, and the refractive index at a wavelength of 589.3 nm was also determined.

[0356] If no description is given regarding the membrane formation method, 30 mg of a sulfur-containing polymer or a sulfur-containing polymer composition was dissolved in 1,1,2,2-tetrachloroethane (1 ml), the solution was passed through a membrane filter with a pore size of 0.2 μm, and 0.4 ml of the solution that passed through the filter was dropwise applied to a glass substrate (2 cm × 2 cm) to obtain a membrane with a thickness of approximately 50 nm, which was then measured.

[0357] <Abbe value (v D )>

[0358] The refractive index of the obtained film was measured using a spectroscopic ellipsometer UVISEL manufactured by HORIBA Scientific using the D line (589.3 nm), the F line (486.1 nm), and the C line (656.3 nm), and the Abbe number (v) was calculated using the following calculation formula (A). D ).

[0359] Abbe value (v D )=(n D -1) / (n F -n C )(A)

[0360] Where n D 、n F 、n C These represent the refractive indices at Fraunhofer D-line (589.3 nm), F-line (486.1 nm), and C-line (656.3 nm), respectively.

[0361] Unless otherwise specified regarding the film forming method, a film having a thickness of 50 nm was obtained by the same method as the above-mentioned refractive index measurement, and the refractive index was measured.

[0362] <Glass transition temperature (Tg)>

[0363] A differential scanning calorimeter manufactured by Seiko Instruments Inc. was used, using α-alumina as a reference, and the temperature was raised from room temperature to 250°C at a heating rate of 10°C / min. The glass transition temperature was determined by evaluating the intersection of the baseline and the tangent line at the inflection point from the obtained DSC curve.

[0364] <Element Content Ratio O / S Ratio>

[0365] 0.25 ml of the polymer solution was spin-coated onto a silicon wafer, and the resulting film sample was used to measure the peak intensity of the sulfur atom's 2p orbital and the peak intensity of the oxygen atom's 1s orbital using a JEOL photoelectron spectrometer (JPS-9010TR, XPS instrument, light source: Mg, X-ray output: 400 W). The integrated ratio was calculated to calculate the elemental content ratio (O / S ratio) of oxygen atoms bonded to sulfur atoms in the polymer's main chain relative to the sulfur atoms in the main chain. The peak intensity of the carbon atom's 1s orbital was also measured as needed, and the O / S ratio was calculated taking this into account.

[0366] For the measurement method and the position of the bond energy, etc., refer to Handbook of X-ray Photoelectron Spectroscopy (JEOL, published in March 1991).

[0367] <Key Energy>

[0368] 0.25 ml of the polymer solution was spin-coated on a silicon wafer, and the resulting film sample was used to measure the bond energy based on the peak position of the 2p3 / 2 orbital of the sulfur atom using a JEOL photoelectron spectrometer (JPS-9010TR, XPS apparatus).

[0369] <Thin Film Transmittance (T%)>

[0370] The transmittance of the resulting films was measured using a spectrophotometer (V-700 series UV-Vis-Infrared Spectrophotometer, manufactured by JASCO Corporation). To evaluate visible light transmittance, the transmittance at 400 nm and the average transmittance from 400 to 700 nm were compared. Note that in Examples 7, 9, 10, and 11, a glass substrate was used as a control; in all other examples, air was used as a control sample.

[0371] If the film formation method is not described, a solution containing approximately 5% of the polymer was prepared using an organic solvent capable of dissolving the polymer. The resulting solution was spin-coated at approximately 500 rpm for 60 seconds onto a glass substrate that absorbs little visible light and dried at 100°C for 10 minutes to form a thin film (1 μm thick). The drop-coated film showed the transmittance at the measured film thickness.

[0372] Example 1

[0373] <Sulfur-containing polymer 1>

[0374] (Synthesis of Methoxy-Substituted Polyphenylene Sulfide Resin (OMePPS))

[0375] Chloroform (300 mL) and 2-methoxybenzenethiol (28.0 g, 0.2 mol) were added to a 1000 mL conical beaker. A methanol solution (300 mL) containing iodine (25.4 g, 0.1 mol) was further added, and the mixture was stirred at room temperature for 1 hour. An aqueous sodium thiosulfate solution was then added to remove the iodine, and the solvent was distilled off. The reaction mixture was dispersed in diethyl ether and washed with an aqueous hydrochloric acid solution (3% by mass), an aqueous sodium hydroxide solution (5% by mass), and pure water, in that order. The mixture was then dehydrated, the solvent removed, and vacuum dried to obtain bis(2-methoxyphenyl) disulfide.

[0376] In a 50 mL three-necked flask, the obtained bis(2-methoxyphenyl) disulfide (5.568 g, 20 mmol) was added to a dichloromethane solution (20 mL) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 1 M) and trifluoroacetic acid (1 M), and stirred at room temperature for 20 hours to carry out oxidative polymerization. After removing the by-products in the polymerization solution with a glass filter, the polymerization solution was added dropwise to hydrochloric acid-acidic methanol to precipitate the generated polymer, which was filtered with a glass filter and recovered in the form of a powder. Thereafter, it was washed with potassium hydroxide aqueous solution (0.1 M), pure water, and methanol in sequence, and vacuum dried to synthesize methoxy-substituted polyphenylene sulfide resin (OMePPS). The molecular weight was Mw = 4200, and the dispersity was 1.7. The glass transition temperature Tg was 118°C, the 5% weight loss temperature Td5% was 317°C, and the molar absorption coefficient ε was 6.2×10 2 L / (mol·cm), a refractive index of 1.73, and an Abbe number of 22. OMePPS is amorphous and soluble in chloroform, tetrahydrofuran, N,N'-dimethylacetamide, and N,N'-dimethylformamide, so it can be made into a transparent film by drop coating.

[0377] (Synthesis of Thiol-Terminated Methoxy-Substituted Polyphenylene Sulfide Resin (SH-OMePPS))

[0378] The above OMePPS (2.0 g) was added to a 100 mL three-necked flask and dissolved in tetrahydrofuran (THF, 40 mL). Sodium borohydride (2 g, excess) was then added, and methanol (1 mL) was added dropwise with stirring. The mixture was then heated at reflux for 20 hours at 65°C. After the reaction was completed, the mixture was purified by precipitation in hydrochloric acid-containing methanol (600 mL, containing 5 vol% hydrochloric acid), filtered using a glass filter, and washed with methanol and water. Then, the mixture was dried in vacuum overnight (25°C, 12 hours) to obtain a thiol-terminated methoxy-substituted polyphenylene sulfide resin (SH-OMePPS) (yield 81%, terminal thiol concentration 100%).

[0379] (Synthesis of Carboxyl-Terminated Methoxy-Substituted Polyphenylene Sulfide Resin (COOH-OMePPS))

[0380] The above-mentioned SH-OMePPS (1.3 g, -SH group concentration 0.6 mmol, 1 eq) was added to a 10 mL eggplant-shaped flask and dissolved in dimethylformamide (DMF, 3 mL). 4-Pentenoic acid (600 mg, 6 mmol, 10 eq) and 2,2-dimethoxy-2-phenylacetophenone (DMPA, 31 mg, 0.12 mmol, 0.2 eq) were then added. After five cycles of freeze degassing (Ar gas), the mixture was irradiated with UV light for 4 hours at room temperature to carry out a thiol-ene reaction (Hg lamp, hv = 365 nm). After the reaction, the solution was diluted with DMF (10 mL) and then purified by precipitation in hydrochloric acid-containing methanol (300 mL, containing 5 vol% hydrochloric acid). The solution was filtered using a glass filter, washed with methanol and water, and dried in vacuum overnight (25°C, 12 hours) to obtain a carboxyl-terminated methoxy-substituted polyphenylene sulfide resin (COOH-OMePPS) (sulfur-containing polymer 1) (yield 88%, terminal carboxylic acid concentration 90%).

[0381] By infrared spectrophotometry (IR), only SH-OMePPS showed a peak at 2560 cm -1 The absorption of SH stretching vibration was observed, and only COOH-MePPS was at 1740 cm -1 C═O stretching vibration was confirmed. Neutralization titration revealed that the rate of introduction of carboxylic acid into COOH-MePPS was 89%.

[0382] The chemical reaction formula for synthesizing COOH-OMePPS from OMePPS is shown below. Table 1 shows various physical properties of the obtained polymers.

[0383] [Chemistry 12]

[0384]

[0385] [Table 1]

[0386] polymer <![CDATA[Mn(x10 3 )]]> <![CDATA[Mw(x10 3 )]]> Mw / Mn <![CDATA[n D ]]> <![CDATA[v D ]]> OMePPS 2.5 4.2 1.7 1.73 22 SH-OMePPS 2 3.2 1.7 1.73 22 COOH-OMePPS 2.1 4.3 2.0 1.72 21

[0387] From Table 1, it was confirmed that the sulfur-containing polymer COOH-OMePPS having a carboxyl group is a high-refractive-index material having a refractive index of 1.7 or more.

[0388] <Preparation of Titanium Oxide Hybrid Film of Sulfur-Containing Polymer 1 by Sol-Gel Method>

[0389] The above-mentioned COOH-OMePPS (0.0274 g) was added to a 10 mL sample vial and dissolved in dimethylacetamide (1.5 mL). Hydrochloric acid (37% by mass, 25 μL) was then added and stirred at room temperature for 30 minutes. A solution prepared by pre-dissolving tetrabutyl orthotitanate (50 μL) in 1-butanol (100 μL) in a glove box was added dropwise to the stirred polymer solution and allowed to react for an additional 30 minutes. After the reaction, impurities were removed using a membrane filter, and the reaction solution was diluted with dimethylacetamide to a solute concentration of 60 mg / mL or 15 mg / mL to prepare a hybrid solution (sulfur-containing polymer composition).

[0390] A hybrid solution (solute concentration 60 mg / mL solution) was dropped onto a silicon wafer and spin-coated at 2000 rpm for 20 seconds. The solution was then heat-treated at 0.08 MPa and 60°C for 4 hours and at 0.08 MPa and 150°C for 3 hours to obtain a hybrid film (thickness 0.13 μm).

[0391] Separately, a hybrid solution (solute concentration 15 mg / mL solution, 400 μL) was dropped onto a glass substrate and heat treated at 0.08 MPa and 60°C for 4 hours and at 0.08 MPa and 150°C for 3 hours to obtain a hybrid film (thickness 5.5 μm).

[0392] By IR measurement, at 3400 cm -1 The absorption of -OH groups originating from the TiO2 domain surface was observed at 610 cm -1 The absorption of Ti-O-Ti stretching vibration was observed, thereby confirming the formation of TiO2.

[0393] Table 2 shows various physical properties of the COOH-OMePPS hybrid solutions having different TiO2 contents (Experimental Examples 1-1 to 1-4). The refractive index and Abbe number were measured for the hybrid films formed on silicon wafers.

[0394] in addition, Figure 1 The figures show hybrid films produced on glass substrates using sulfur-containing polymer compositions having different mixing ratios of the sulfur-containing polymer and TiO 2 . Figure 1 In the figure, (a) represents the cases where the solid content mass ratio of (COOH-OMePPS / TiO2) is (100 / 0), (90 / 10), (70 / 30), and (50 / 50) from the left, and (b) represents the case where the mass ratio of (OMePPS / TiO2) is (80 / 20).

[0395] [Table 2]

[0396]

[0397] As shown in Table 2, the n of COOH-OMePPS hybrid membrane with 50 mass% TiO2 is D =1.85, and Tg was 136° C. This confirmed that the polymer composition containing COOH-OMePPS and a metal oxide had a high refractive index and was excellent in transparency and heat resistance.

[0398] In addition, by Figure 1 It was confirmed that COOH-OMePPS (a) containing reactive functional groups maintained transparency and a high refractive index even with the addition of 50% TiO2. On the other hand, OMePPS (b) containing no reactive functional groups became cloudy when 20% TiO2 was added. This indicates that the introduction of carboxyl groups contributes to improved transparency.

[0399] Example 2

[0400] <Sulfur-containing polymer 2>

[0401] (Synthesis of Methyl-Substituted Polyphenylene Sulfide Resin (Methyl-Substituted PPS))

[0402] In Example 1, methyl-substituted polyphenylene sulfide resin (MePPS) was obtained by the same method as above (Synthesis of OMePPS), except that bis(3-methylphenyl)disulfide was obtained by using m-toluenethiol instead of 2-methoxybenzenethiol and this was used to synthesize the polymer.

[0403] (Synthesis of Methyl-Substituted PPS Containing Carboxyl Group)

[0404] The obtained methyl-substituted PPS and acrylic acid monomer (2-carboxyethyl acrylate) were mixed at a mass ratio of 5 / 1 or 3 / 1, degassed, and irradiated with light (wavelength: 230 nm to 320 nm, illuminance: 30 mW / cm 2 ), and purified by precipitation in acidic methanol to obtain a methyl-substituted PPS having a polycarboxylic acid terminal (methyl-substituted PPS containing a carboxyl group) (sulfur-containing polymer 2) as a white powder. The synthesis reaction formula of methyl-substituted PPS containing a carboxyl group is shown below. In the formula, (1) represents methyl-substituted PPS, and (4) represents methyl-substituted PPS containing a carboxyl group.

[0405] pass 1 The incorporation rate was calculated by H-NMR, and the formation of a copolymer was confirmed by observing peaks derived from methyl-substituted PPS and acrylic acid at the same diffusion coefficient using DOSY-NMR. Table 3 shows various physical properties of MePPS and the resulting carboxyl-containing methyl-substituted PPS (Experimental Examples 2-1 to 2-3). The refractive index of the resulting polymer decreased with the incorporation of acrylic acid units, but remained high at 1.7 or higher.

[0406] [Chemistry 13]

[0407]

[0408] [Table 3]

[0409]

[0410] <Preparation of Nanoparticle Dispersion of Carboxyl-Containing Methyl-Substituted PPS>

[0411] To 1 mL (30 mg / mL) of the obtained toluene solution of the carboxyl-containing methyl-substituted PPS was mixed 20 μL of a methyl ethyl ketone solution (ZP-153, 70% by mass, manufactured by Nippon Shokubai Co., Ltd.) in which zirconium oxide nanoparticles were dispersed, to obtain a nanoparticle dispersion (sulfur-containing polymer composition).

[0412] The obtained dispersion was spin-coated on a silicon wafer or drop-coated on a glass substrate to form a film (film thickness of about 0.1 μm).

[0413] Visual observation confirmed that the fine particles were dispersed in the obtained nanoparticle dispersion and thin film. The refractive index of the nanoparticle dispersion was 1.73.

[0414] Comparative Example 1

[0415] A nanoparticle dispersion was obtained in the same manner as in Example 2 except that the above-mentioned methyl-substituted PPS was used instead of the carboxyl group-containing methyl-substituted PPS in the preparation of the nanoparticle dispersion, and a film was formed using the obtained dispersion (Comparative Example 1).

[0416] Figure 2 is a photograph of the nanoparticle dispersion obtained above, Figure 3 This is a photograph of a hybrid membrane obtained using the above nanoparticle dispersion. Figure 2 and Figure 3 Among them, (a) is a nanoparticle dispersion containing carboxyl-containing methyl-substituted PPS of Example 2 or a hybrid membrane obtained using the same, and (b) is a nanoparticle dispersion containing methyl-substituted PPS of Comparative Example 1 or a hybrid membrane obtained using the same.

[0417] These results show that the sulfur-containing polymer compositions of Examples have a higher refractive index and are more transparent than the sulfur-containing polymer compositions of Comparative Examples. Furthermore, it is shown that the inclusion of nanoparticles reduces linear expansion.

[0418] Example 3

[0419] (Surface modification of zirconia nanoparticles)

[0420] Referring to S. Kawaguchi et al., Macromolecules, 2017, 50, 9713-9725, a 100 mL flask was charged with p-toluic acid (0.15 g, 23% relative to the nanoparticles), methanol (15 mL), toluene (0.5 mL), and an aqueous dispersion of zirconium oxide (ZrO2) nanoparticles (manufactured by ITEC, average particle size 4 nm, 30% by mass) (1.8 g, 0.54 g of nanoparticles) and stirred at room temperature for 2 hours. A methanol-toluene mixed solution (methanol / toluene volume ratio = 7 / 3) (approximately 20 mL) was added, and the solvent was removed using an evaporator to a total of approximately 5 mL. The methanol-toluene mixed solution was then added again and the solvent was removed again. This operation was repeated approximately six times while varying the methanol volume ratio from 70% to 100%. Acetone was added to the resulting surface-modified zirconium oxide nanoparticles, and the supernatant was removed to remove unreacted components, yielding surface-modified zirconium oxide nanoparticles.

[0421] By IR determination, the 1690 cm-1 -1 The decrease of the peak near 1550 cm-1 derived from the carboxylate group -1 、1450cm -1 , 1100cm from Zr-OC- -1 The upward movement of the peak confirmed the surface modification of the zirconium oxide nanoparticles by p-toluic acid.

[0422] The modification ratios WF and M were calculated using a thermogravimetric differential thermal analyzer (TG-DTA, manufactured by Rigaku Corporation, TG8120). The modification ratio was 18% by mass. Furthermore, dynamic light scattering (DLS, manufactured by Malvern, Zetasaizer Nano ZS) indicated that the surface-modified zirconium oxide nanoparticles aggregated in toluene to a size of about 6 (average particle size: 3 nm).

[0423] (Optical properties of hybrid films)

[0424] The surface modified zirconium oxide nanoparticles obtained above were added to toluene in various amounts and dispersed using a homogenizer for about 5 minutes to obtain a toluene dispersion of zirconium oxide nanoparticles. The carboxyl-containing methyl-substituted PPS (30 mg / ml) obtained in Example 2 was added to the obtained dispersion according to the mixing ratio shown in Table 4 and mixed. The obtained mixed solution (sulfur-containing polymer composition) was drop-coated on a glass substrate to form a film (thickness 3 μm) to produce a hybrid film. According to spectroscopic ellipsometry and UV-vis measurements, the ZrO2 content was 16.4% (ZrO2 / 1), showing good optical properties (n D =1.73, v D =23, %T=84%).

[0425] Comparative Example 2

[0426] In Example 3, a dispersion was prepared to produce a hybrid membrane in the same manner as in Example 3 except that the methyl-substituted PPS of Comparative Example 1 was used instead of the carboxyl group-containing methyl-substituted PPS.

[0427] Various physical property values ​​of the hybrid membranes obtained in Example 3 and Comparative Example 2 are shown in Table 4. In Table 4, Experimental Examples 3-1 to 3-4 are hybrid membranes of Example 3, and Experimental Example 3-5 is a hybrid membrane of Comparative Example 2.

[0428] [Table 4]

[0429]

[0430] In Table 4, polymer 2 represents a methyl-substituted PPS containing a carboxyl group (Mw = 2.8 × 10 4 , acrylic acid monomer unit / (MePPS unit+acrylic acid monomer unit)=0.18), polymer 1 represents methyl-substituted PPS.

[0431] In the evaluation of dispersibility, "∘" indicates "dispersed" and "×" indicates "turbid".

[0432] Refractive index (n D ) (calculated value) According to the Lorenz-Lorenz effective medium theory (n DZrO2 =2.13,n D聚合物 =1.70,n D修饰体 =1.52,ρ ZrO2 =5.68g / cm 3 , ρ 聚合物 =1.28g / cm 3 , ρ 修饰体 =1.06g / cm 3 ).

[0433] The film thickness was measured using a stylus height difference meter (P-6, manufactured by KLA Tencor) from the uneven shape of a sample after a portion of the surface was cut away.

[0434] in addition, Figure 4 ] The photographs of the hybrid films of Experimental Examples 3-1, 3-4, and 3-5 are shown in FIG.

[0435] Table 4 shows that the thin film formed from the dispersion containing carboxyl group-containing methyl-substituted PPS and surface-modified zirconium oxide nanoparticles has excellent dispersibility, a high refractive index, and excellent transparency.

[0436] Example 4

[0437] <Sulfur-containing polymer 3>

[0438] (Synthesis of Monomers)

[0439] Chloroform (300 mL) and m-toluene mercaptan (24.8 g, 0.2 mol) were added to a 1000 mL conical beaker, and a methanol solution (300 mL) containing iodine (25.4 g, 0.1 mol) was further added, and the mixture was stirred at room temperature for 1 hour. An aqueous sodium thiosulfate solution was then added to remove the iodine, and the solvent was removed by distillation. The reaction solution was dispersed in diethyl ether, and the solution was separated and washed in the order of aqueous hydrochloric acid solution (3% by mass), aqueous sodium hydroxide solution (5% by mass), and pure water. Bis(3-methylphenyl) disulfide was recovered by dehydration, solvent removal, and vacuum drying. The yield was 80%. By 1 H-NMR, 13 The structure was confirmed by C-NMR and FAB-MS.

[0440] [Bis(3-methylphenyl)disulfide]

[0441] 1 H-NMR (CD2Cl2, 500MHz, ppm): δ = 7.30 (s, 2H, Ph-H), 7.28 (d, 2H, Ph-H), 7.16 (t, 2H, Ph-H), 7.01 (d, 2H, Ph-H), 2.78 (s, 6H, methyl-H)

[0442] 13 C-NMR (CD2Cl2, ppm): δ=139.5,137.1,129.2,128.4,128.3,124.9,21.4

[0443] Mass: m / z 245.7(found),246.4(calcd).

[0444] [Chemistry 14]

[0445]

[0446] (Synthesis of Polymers)

[0447] In a 50 mL three-necked flask, diphenyl disulfide (3.64 g, 16.67 mmol) and bis(3-methylphenyl) disulfide (0.821 g, 3.33 mmol) obtained in the above (Synthesis of Monomers) were added to a dichloromethane solution (20 mL) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 1 M) and trifluoroacetic acid (1 M). The mixture was stirred at room temperature for 20 hours to carry out oxidative polymerization. After removing byproducts from the polymerization solution using a glass filter, the polymerization solution was added dropwise to hydrochloric acid-acidified methanol to precipitate the generated polymer. The precipitate was filtered using a glass filter and recovered as a powder. The solution was then washed with potassium hydroxide aqueous solution (0.1 M), pure water, and methanol in that order and vacuum dried to obtain polymer A having a repeating unit represented by the following formula (A).

[0448] use 1 H-NMR, 13 Polymer A was identified by C-NMR. The weight-average molecular weight (Mw) of the resulting polymer A was 2700 and its Mn was 1300. Its glass transition temperature was 73°C and its refractive index was 1.79. XPS analysis revealed that the elemental ratio (O / S) of oxygen atoms bonded to the sulfur atoms in the main chain of polymer A to the sulfur atoms in the main chain was 0.04 (0.04 / 1). The SO bond energy was 162-164 eV. In other words, 100% of the S was sulfide. The yield of polymer A was 72%. x in formula (A) is 0.833.

[0449] [Polymer A]

[0450] 1 H-NMR (CD2Cl2, 500MHz, ppm): δ = 7.23 (m, 23H, Ph-H), 2.25 (s, 3H, methyl-H)

[0451] 13 C-NMR (CD2Cl2, ppm): δ=141.2,136.5,134.1,131.1,127.9,127.4,20.7

[0452] [Chemistry 15]

[0453]

[0454] (Synthesis of Thiol-Terminated PPS)

[0455] 8.92 g of polymer A was weighed and dissolved in tetrahydrofuran (THF, 79.3 mL). 0.6 g of sodium borohydride was then added, and 16 mL of methanol was added dropwise with stirring. The mixture was then stirred at 25°C for 18 hours. After the reaction, the mixture was purified by precipitation in hydrochloric acid-containing methanol (1600 mL, containing 5 vol% hydrochloric acid), filtered using a glass filter, and washed with methanol and water. The mixture was then vacuum dried overnight (25°C, 12 hours) to obtain a thiol-terminated methyl-substituted polyphenylene sulfide resin (SH-MePPS) (yield 68%, terminal thiol concentration 100%).

[0456] (Synthesis of Phosphoric Acid-Terminated Methyl-Substituted PPS (P-MePPS))

[0457] 6.1 g (53.9 mmol of monomer units) of the SH-MePPS obtained above was weighed and dissolved in 53.9 mL of THF. 0.82 g (21.6 mmol) of sodium borohydride and 19 g (10.7 mmol) of 2-acryloyloxyethyl phosphate were then added. 1.6 mL of methanol was then added dropwise with stirring, and the mixture was stirred at 25°C for 18 hours. The resulting solution was purified by precipitation in hydrochloric acid-containing methanol (1100 mL, containing 5 vol% hydrochloric acid). The solution was filtered through a glass filter, washed with methanol and water, and dried under vacuum overnight (25°C for 12 hours) to obtain 5.7 g of phosphate-terminated methyl-substituted PPS (P-MePPS) (94% yield, with one phosphate group introduced per 19.2 monomer units of the terminal phosphate group). NMR and GPC revealed a 60% phosphate introduction rate into the thiol groups.

[0458] (Synthesis of Phosphoric Acid-Terminated Methyl-Substituted PPS Oxide (P-MePPSO))

[0459] The P-MePPS (5.7 g, 50.7 mmol) obtained above was added to 203 mL of a chloroform solution of m-chloroperbenzoic acid (mCPBA, 0.25 M) and stirred at room temperature for 20 hours to oxidize it. The reaction solution was then added dropwise to hydrochloric acid-containing methanol, centrifuged, and vacuum-dried to obtain a polymer P-MePPSO (sulfur-containing polymer 3). The yield was 95%. The structure of the obtained polymer is shown in FIG. 1 Identification was performed by H-NMR, IR, and XPS. The element content ratio (O / S) of the oxygen atoms bonded to the sulfur atoms in the main chain to the sulfur atoms in the main chain was 1.

[0460] (Preparation of a composite composition of phosphoric acid-terminated methyl-substituted PPS oxide (P-MePPSO) and ZrO2 particles)

[0461] P-MePPSO was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) to a concentration of 5% by mass (solute mass / solution mass). Separately, P-MePPSO and a methyl ethyl ketone solution (ZP-153 manufactured by Nippon Shokubai, Ltd., solids content 70%) containing dispersed zirconium oxide (ZrO2) nanoparticles were dissolved in HFIP to a solids content of 2.5% by mass (solute mass / solution mass).

[0462] These solutions were applied to a glass slide using a spin coater (500 rpm × 60 s, film thickness approximately 1 μm), dried by heating at 260°C for 10 minutes, and the transmittance was evaluated. Furthermore, each solution was diluted 10-fold by adding HFIP, and then applied to a silicon wafer using a spin coater (1000 rpm × 60 s, film thickness 10-900 nm). The films were dried by heating at 260°C for 10 minutes, and the refractive index was evaluated. The results are shown in Table 5.

[0463] Comparative Example 3

[0464] A zirconium oxide nanoparticle dispersion was prepared in the same manner as in Example 4, except that polymer A-1, in which the main chain of polymer A was oxidized, was used instead of P-MePPSO. Films were formed and their transmittance and refractive index were evaluated. The results are shown in Table 5. The following describes the method for preparing polymer A-1.

[0465] (Preparation of Polymer A-1)

[0466] In a 50 mL eggplant-shaped flask, the polymer A (0.302 g) obtained above was added to 10 mL of a chloroform solution of meta-chloroperbenzoic acid (mCPBA, 0.25 M) and stirred at room temperature for 20 hours for oxidation. Then, the reaction solution was added dropwise to hydrochloric acid-acid methanol, centrifuged and vacuum-dried to obtain a polymer A-1 having a repeating unit represented by the following formula (A-1). The yield was 97%. Using 1 The structure of the resulting polymer was identified by H-NMR, IR, and XPS. The elemental content ratio (O / S) of oxygen atoms bonded to sulfur atoms in the main chain of the polymer was 0.92 (0.92 / 1). Regarding SO bond energy, peaks were observed at 165 eV and 163 eV. Peak separation allowed the peaks to be separated into those at 164-168 eV (sulfoxide) and 162-168 eV (sulfide). The peak areas for sulfoxide and sulfide were 47.8 to 4.4, respectively.

[0467] In formula (A-1), x is 0.08 and y is 0.92.

[0468] [Polymer A-1]

[0469] 1 H-NMR (CD2Cl2, 500MHz, ppm): δ = 7.55 (m, 23H, Ph-H), 2.34 (s, 3H, methyl-H)

[0470] IR(cm -1 ): 1045 (νS=O)

[0471] [Chemistry 16]

[0472]

[0473] [Table 5]

[0474]

[0475] Table 5 confirms that P-MePPSO has a high refractive index of over 1.7 and a high transmittance of over 87%. Furthermore, it was confirmed that the transmittance and refractive index of P-MePPSO were further improved when combined with ZrO2 compared to the polymer alone. This indicates that even at high temperatures of 260°C, ZrO2 aggregation is suppressed, resulting in a highly heat-resistant, high-refractive-index, transparent material suitable for polymer injection molding. On the other hand, the transmittance of Polymer A-1 in Comparative Example 3 was reduced when combined with ZrO2.

[0476] Example 5

[0477] <Sulfur-containing polymer 4>

[0478] (Synthesis of Thiol-Terminated PPS-2)

[0479] 20 g (0.18 mol) of polymer A used in Example 4 above was weighed and dissolved in tetrahydrofuran (THF, 200 mL). Then, 4.8 g of triphenylphosphine was added and stirred at 35°C for 18 hours. After the reaction, the mixture was purified by precipitation in hydrochloric acid-containing methanol (2000 mL, containing 5 vol% hydrochloric acid), filtered using a glass filter, and washed with methanol and water. The mixture was then vacuum-dried overnight (25°C, 12 hours) to obtain a thiol-terminated methyl-substituted polyphenylene sulfide resin (SH-MePPS-2) (yield 91%, terminal thiol concentration 100%).

[0480] (Synthesis of Carboxyl-Terminated Methyl-Substituted PPS (COOH-MePPS))

[0481] Weigh 1 g of the above-mentioned SH-MePPS-2, dissolve it in 10 mL of THF and 0.5 mL of water, then add 0.28 g of 2-carboxyethyl acrylate and 0.76 g of potassium carbonate, and stir at 25°C for 18 hours. In the solution after the reaction, hydrochloric acid-acidic methanol (100 mL, containing 5 vol% hydrochloric acid) is used for precipitation and purification. After filtering with a glass filter, washing with methanol and water, and vacuum drying overnight (25°C, 12 hours), 0.8 g of carboxyl-terminated methyl-substituted PPS (COOH-MePPS) is obtained (yield 81%, one carboxylic acid group is introduced into the terminal carboxylic acid for every 22.3 monomer units). According to 1 H-NMR and GPC showed that the carboxylic acid introduction rate of the thiol group was 52%.

[0482] (Synthesis of Carboxyl-Terminated Methyl-Substituted Oxide PPS (COOH-MePPSO))

[0483] 0.8 g of the COOH-MePPS obtained above was added to 28.5 mL of a chloroform solution of m-chloroperbenzoic acid (mCPBA, 0.25 M) and stirred at 25°C for 20 hours for oxidation. The reaction solution was then added dropwise to hydrochloric acid-containing methanol, centrifuged, and vacuum-dried to obtain a polymer COOH-MePPSO (sulfur-containing polymer 4). The yield was 85%. 1 The structure of the obtained polymer was identified by H-NMR, IR, and XPS. The element content ratio (O / S) of the polymer of oxygen atoms bonded to sulfur atoms in the main chain to the sulfur atoms in the main chain was 0.97.

[0484] (Preparation of a Composite Composition of Carboxyl-Terminated Methyl-Substituted Oxide PPS (COOH-MePPSO) and ZrO2 Particles)

[0485] The COOH-MePPSO and a methyl ethyl ketone solution containing dispersed zirconium oxide nanoparticles (ZP-153, manufactured by Nippon Shokubai, solid content 70% by mass) were dissolved in HFIP so that the solid content of each solution was 2.5% by mass (solute mass / solution mass) to prepare a composite composition (sulfur-containing polymer composition).

[0486] Separately, a composition was prepared by dissolving the aforementioned COOH-MePPSO in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) so that the COOH-MePPSO content was 5% by mass (solute mass / solution mass).

[0487] Each of the above compositions was applied onto a slide glass using a spin coater (500 rpm×60 s, film thickness of approximately 1 μm), and dried by heating at 260° C. for 10 minutes to form a film, and the transmittance was evaluated.

[0488] HFIP was further added to each composition to dilute it 10-fold, and the mixture was applied on a silicon wafer using a spin coater (1000 rpm×60 s, film thickness 10-900 nm). The film was dried by heating at 260° C. for 10 minutes, and the refractive index was evaluated.

[0489] Furthermore, comparisons were made with the polymer A-1 and the composite composition of the polymer A-1 and the zirconium oxide nanoparticle dispersion of Comparative Example 3. The results are shown in Table 6.

[0490] [Table 6]

[0491]

[0492] Table 6 confirms that the carboxyl-terminated methyl-substituted oxidized PPS exhibits a high refractive index of over 1.7 and a high transmittance of over 86%. Furthermore, it was confirmed that the carboxyl-terminated methyl-substituted oxidized PPS exhibited further improvements in both transmittance and refractive index when combined with ZrO2 compared to the polymer alone. Furthermore, it was found that ZrO2 aggregation was suppressed even at temperatures of 260°C, resulting in a highly heat-resistant, high-refractive-index, transparent material suitable for polymer injection molding.

[0493] Example 6

[0494] <Sulfur-containing polymer 5>

[0495] (Synthesis of Vinyl-Terminated Methyl-Substituted PPS (V-MePPS))

[0496] Weigh 1 g of the above-mentioned SH-MePPS-2, dissolve it in 20 mL of THF and 1 mL of water, then add 0.34 g of VEEA (registered trademark) (manufactured by Nippon Shokubai, CAS86273-46-3) and 0.76 g of potassium carbonate, and stir at 25°C for 18 hours. After the reaction, the solution was purified by precipitation in hydrochloric acid-acidic methanol (200 mL, containing 5 vol% hydrochloric acid), filtered out with a glass filter, washed with methanol and water, and vacuum dried overnight (25°C, 12 hours) to obtain 0.9 g of vinyl-terminated methyl-substituted PPS (V-MePPS) (sulfur-containing polymer 5) (yield 94%, one vinyl group was introduced into the terminal vinyl group for every 55.2 monomer units). According to NMR and GPC, the vinyl introduction rate of the thiol group was 21%. Refractive index (n D ) is 1.73.

[0497] Example 7

[0498] <Sulfur-containing polymer 6>

[0499] (Synthesis of Bromine-Containing Polymer B)

[0500] Poly(2,6-dimethyl-1,4-phenylene sulfide) (PMPS) was synthesized by the same method as in Example 1 (Synthesis of OMePPS) except that 2,6-dimethylthiophenol was used instead of 2-methoxybenzenethiol and bis(2,6-methylphenyl)disulfide was used instead of bis(2-methoxyphenyl)disulfide.

[0501] The above PMPS (2.7242 g, repeating unit 20 mmol, 20 mmol) was added to a 300 mL three-necked flask and dissolved in chlorobenzene (100 mL).

[0502] Next, NBS (N-bromosuccinimide, 3.5998 g, 20 mmol, 1 eq. in PMPS) and AIBN (2,2'-azobisisobutyronitrile, 98.526 mg, 0.6 mmol, 0.03 eq. in PMPS) were added, and nitrogen was passed (bubbled) at room temperature for 30 minutes. The temperature was then raised to 80°C and refluxed for 5 hours under a nitrogen atmosphere. After the reaction was completed, a precipitate derived from NBS appeared when the mixture was cooled in an ice bath, so it was filtered off. The recovered filtrate was then concentrated using an evaporator and then added dropwise to hydrochloric acid-containing methanol (MeOH 800 mL / HCl aq. 5 vol%) for precipitation purification. The precipitate was recovered by centrifugation and dried under reduced pressure to obtain polymer B (yield: 89%) as a light yellow powder.

[0503] (Oxidation reaction of polymer backbone)

[0504] Polymer B (0.98481 g, 5.0 mmol, 0.25 M) was added to a 50 mL flask and dissolved in chloroform (20 mL). Next, 1 equivalent of m-chloroperbenzoic acid (mCPBA) was added, and the mixture was allowed to react for 20 hours at room temperature under atmospheric pressure. After the reaction, chloroform was added to the reaction solution to disperse the precipitate, which was then added dropwise to a solution of hydrochloric acid in methanol (600 mL of MeOH / 5 vol% aq. HCl) for precipitation and purification. The precipitate was recovered by centrifugation and dried under reduced pressure to obtain Polymer B-1 as a white powder (yield: 77%, calculated assuming a 100% reaction rate of mCPBA).

[0505] (Synthesis of Hydroxyl-Containing Polymer B-1-1)

[0506] Polymer B-1 (0.42003 g, 2.0 mmol, 0.2 M) was added to a 50 mL flask and dissolved in NMP (N-methyl-2-pyrrolidone, 10 mL). H₂O (1 mL, 10 vol% in NMP) was then added, and the mixture was heated under reflux at 100°C for 90 hours. After the reaction was completed, the reaction solution was added dropwise to hydrochloric acid-methanol (500 mL of MeOH / 5 vol% of HCl aq.) for precipitation and purification. The precipitate was recovered by centrifugation and dried under reduced pressure to obtain polymer B-1-1 (sulfur-containing polymer 6) as a light brown to off-white powder (yield: 78%, calculated assuming 100% replacement of bromine groups with hydroxyl groups).

[0507] The SO and SO2 contents of each polymer were determined by IR; the OH, Br, and CH3 contents were determined by 1 It was determined by H-NMR measurement.

[0508] In addition, the glass transition temperature (Tg) and the refractive index (n) at the Fraunhofer D line (589.3 nm) of each polymer were analyzed. D ), Abbe value (v D ) and evaluated using the above method. The results are shown in Table 7.

[0509] [Table 7]

[0510]

[0511] Experimental Examples 8-1 to 8-4

[0512] (Hybridization of hydroxyl-containing polymer B-1-1 and TiO2)

[0513] In a 10 mL sample vial, polymer B-1-1 (20 mg, 0.03 M) was dissolved in DMAc (dimethylacetamide, 4 mL). Hydrochloric acid ([HCl] / [Ti] = 2) was then added and stirred for 30 minutes. Subsequently, a butanol solution of tetrabutyl orthotitanate (1.47 M Ti solution) was added to polymer B-1-1 at the mass composition shown in Table 8, and the mixture was stirred for a further 30 minutes to prepare a hybrid solution (sulfur-containing polymer composition).

[0514] The obtained hybrid solution was deposited on a glass substrate or on a silicon wafer by spin coating to the thickness shown in Table 8, and then dried under reduced pressure at 60°C for 2 hours and at 150°C for 1 hour to prepare a hybrid film. The absorbance at 400 nm and the refractive index (n) at Fraunhofer D line (589.3 nm) of the obtained hybrid film were evaluated by the above-mentioned method. D ), Abbe value (v D ). The results are shown in Table 8.

[0515] in addition, Figure 5 Graphs showing the measured data of the refractive index of the sulfur-containing polymer compositions of Experimental Examples 8-1 and 8-4 in Example 7 are shown in FIG. In the graph, the solid line represents Experimental Example 8-1, and the dotted line represents Experimental Example 8-4.

[0516] in addition, Figure 6 ] Figures 2 and 3 show photographs of hybrid films obtained in Experimental Examples 8-1 to 8-4 in Example 7.

[0517] [Table 8]

[0518]

[0519] From Table 8, it was confirmed that the sulfur-containing polymer composition comprising the sulfur-containing polymer of the Examples and the metal oxide had a high refractive index and high transparency.

[0520] Example 8

[0521] <Sulfur-containing polymer 7>

[0522] (Synthesis of Bromine-Substituted PPS)

[0523] In a 100 mL two-necked flask, poly(2,6-dimethyl-1,4-phenylene sulfide) (PMPS) (1.5 g, repeating unit 11.0 mmol, 1 eq) was dissolved in chlorobenzene (55 mL). N-bromosuccinimide (NBS) (0.55 eq or 0.28 eq) and AIBN (0.016 eq or 0.008 eq) were then added, and the mixture was heated under reflux at 135°C for 4 hours. After the reaction, the precipitated succinimide was filtered, and the filtrate was purified by precipitation in hydrochloric acid-containing methanol (1000 mL, containing 5 vol% hydrochloric acid), filtered using a glass filter, washed with methanol and water, and vacuum dried to obtain bromine-substituted PPS.

[0524] (Synthesis of Vinyl-Substituted PPS)

[0525] Bromine-substituted PPS (0.5 g, 1 eq) at various introduction ratios was added to a 100 mL flask. THF was added to dissolve the polymer at a concentration of 0.1 M, and triphenylphosphine (4 eq relative to benzyl bromide) was added. The mixture was then heated under reflux at 70°C for 24 hours. After the reaction, the solution was cooled, and a 37% formaldehyde aqueous solution (32 eq relative to benzyl bromide) was added. The mixture was stirred for 10 minutes, followed by the addition of potassium tert-butoxide (4.2 eq relative to benzyl bromide), and the reaction was continued at room temperature for 1 hour. After the reaction, the mixture was purified by precipitation in hydrochloric acid-containing methanol (500 mL, containing 5 vol% hydrochloric acid), washed with methanol and water, and vacuum dried to obtain vinyl-substituted PPS (sulfur-containing polymer 7). The synthesis reaction formula for vinyl-substituted PPS is shown below.

[0526] [Chemistry 17]

[0527]

[0528] Table 9 shows the introduction ratios (x, y) and glass transition temperatures (Tg) of the various structural units in the resulting polymers. Polymer 5 in Table 9 represents polymer (5) in the above reaction formula, and polymer 6 represents polymer (6) in the above reaction formula. The introduction ratios x and y are the values ​​of x and y in the above reaction formula (6).

[0529] Table 10 shows the obtained polymer 6. 1 H-NMR measurement results and various molecular weights.

[0530] [Table 9]

[0531]

[0532] [Table 10]

[0533]

[0534] according to 1 In H-NMR, a peak derived from a methylene group was observed at 4.6 ppm in (5) of the above reaction formula, and in (6), the peak derived from a methylene group decreased, while peaks derived from a vinyl group newly appeared at 7.2 ppm, 5.4 ppm, and 5.2 ppm, thereby confirming the structure.

[0535] According to IR, in (5) at 1210 cm -1 The absorption of C-Br stretching vibration was observed. The intensity of C-Br stretching vibration in (6) decreased. -1 The absorption of the out-of-plane CH vibration of the vinyl group was newly observed, confirming the progress of the reaction.

[0536] According to DSC, the glass transition temperature increased to a maximum of 201°C after bromination and vinylation.

[0537] The obtained sulfur-containing polymer has a refractive index of 1.7 or higher and a Tg of 200° C. or higher, indicating that it is reactive.

[0538] Example 9

[0539] <Sulfur-containing polymer 8>

[0540] (Synthesis of Bis(2,6-dimethoxyphenyl) Disulfide)

[0541] Magnesium (1.16 g, 48 mmol) was added to a 100 mL two-necked flask and dispersed in THF (20 mL). Two drops of 1,2-dibromoethane were added, and after nitrogen substitution, a THF solution of 1,3-dimethoxy-2-bromobenzene (8.68 g, 40 mmol / 10 mL) was added dropwise. The mixture was allowed to react under reflux for 2 hours. After cooling to 0°C, sulfur (0.70 g, 22 mmol) was added and the reaction continued at room temperature for a further 3 hours. The mixture was quenched with dilute hydrochloric acid (10 vol%, 50 mL) and extracted with chloroform (150 mL). The solvent was removed using an evaporator to obtain crude 3,5-dimethoxybenzenethiol.

[0542] The crude 3,5-dimethoxybenzenethiol product was further dissolved in chloroform, and an iodine-methanol solution (0.5 mM, 15 mL) was added dropwise and allowed to react for 1 hour. Unreacted iodine was reacted with a 15% sodium thiosulfate aqueous solution, and the solvent was removed by evaporation. Purification by separation (chloroform) and recrystallization (chloroform / methanol = 1:10) yielded bis(2,6-dimethoxyphenyl) disulfide (2,6-DMDPS) as an off-white solid (yield 63%).

[0543] By FAB-MS (338.44 (m / z)), 1 H-NMR(7.22ppm(t,J=8.5Hz,2H),6.50ppm(d,J=9.0Hz,4H),3.69ppm(s,12H,Me)), 13 The structure was identified by C-NMR (161.2 ppm, 130.9 ppm, 113.0 ppm, 103.8 ppm, 56.0 ppm). The melting point determined by DSC was 205°C. The synthesis reaction formula is shown below.

[0544] [Chemistry 18]

[0545]

[0546] (Synthesis of dimethoxy-substituted PPS by oxidative polymerization)

[0547] The above-mentioned 2,6-DMDPS (0.17 g, 0.5 mmol) was added to a 10 mL flask and dissolved in 1,2-dichloroethane (1 mL, DCE). Trifluoroacetic acid (TFA) (7.5 μL, 0.1 M) was then added, along with DDQ (0.11 g, 1 eq per 2,6-DMDPS) as an oxidizing agent, and the mixture was allowed to react at room temperature. After the reaction, DCE (2 mL) was added to disperse the product, which was then filtered through a glass filter. The filtrate was added dropwise to hydrochloric acid-containing ethanol (5 vol%, 300 mL) for precipitation and purification, and recovered through a glass filter. The product was washed with potassium hydroxide aqueous solution (5 wt%), pure water, and methanol, and dried under reduced pressure to yield dimethoxy-substituted PPS (sulfur-containing polymer 8) as a white powder (yield 72%, Mn 3300, Mw 4100, Mw / Mn = 1.2).

[0548] By IR measurement, the meta-substituted form of thioether (870 cm -1 ), para-substituted form (910cm -1 ), absorption of the out-of-plane angle vibration of each aromatic ring CH. 1 The ratio of each substitution was calculated by H-NMR measurement. The results showed that (meta-substitution): (para-substitution): (branched structure) = x: y: z = 0.34: 0.55: 0.11. 13 C. 13 C-DEPTNMR, the corresponding peaks are also consistent.

[0549] The reaction formula of the oxidative polymerization of 2,6-DMDPS and the chemical formula of the obtained dimethoxy-substituted PPS (P1) are shown below.

[0550] [Chemistry 19]

[0551]

[0552] The X-ray diffraction (XRD) spectrum of dimethoxy-substituted PPS (P1) showed no crystalline peaks derived from PPS, indicating amorphous properties. Furthermore, the 5% weight loss temperature based on thermogravimetric analysis (TGA) was 334°C, and the glass transition temperature based on DSC was 116°C.

[0553] Dimethoxy-substituted PPS (P1) was dissolved in 1,1,2,2-tetrachloroethane at a concentration of 30 mg / mL, drop-coated on a glass substrate, and dried under reduced pressure at 40°C for 4 hours to form a film. The film thickness was 5.2 μm, and the transmittance of the film at 400 nm was 82%. Separately, a DMF solution (concentration: 30 mg / mL) of dimethoxy-substituted PPS (P1) was spin-coated on a silicon wafer to form a film. The refractive index and Abbe number were measured. D =1.74, v D =16.

[0554] Figure 7 3 and 4 show the XRD spectra of polyphenylene sulfide resin (PPS) and dimethoxy-substituted PPS (P1) films.

[0555] in addition, Figure 8 The transmittance measurement data of the dimethoxy-substituted PPS (P1) film based on UV-vis measurement are shown in FIG. Figure 9 Measured data of the refractive index of the dimethoxy-substituted PPS film (P1) are shown in FIG.

[0556] (Synthesis of Dihydroxy-Substituted PPS)

[0557] The dimethoxy-substituted PPS (P1) obtained above (0.2 g, in 2.4 mmol-OMe) was added to a 50 mL flask and dissolved in dichloromethane (DCM) (10 mL) under an argon atmosphere in a glove box. Cool to 0°C, add 1 M boron tribromide dichloromethane solution (6 mL) with a syringe, react at 0°C for 30 minutes, and react at room temperature for 20 hours. Quench with water and remove the solvent with an evaporator. Redissolve in methanol and precipitate and purify in water. The precipitate was recovered using a glass filter and dried under reduced pressure to obtain dihydroxy-substituted PPS (P2) (sulfur-containing polymer 8) (yield 77%). The reaction formula is shown below.

[0558] [Chemistry 20]

[0559]

[0560] Depend on 1 H-NMR measurement confirmed the introduction of hydroxyl groups by demethylation, and the calculated introduction rate was 94%. 1 In H-NMR measurement, the peak of hydroxyl group disappeared, indicating that it has proton exchangeability. In IR measurement of dihydroxy substituted PPS (P2), the absorption of OH stretching vibration related to hydrogen bonding was observed (3400 cm -1 ), which also confirmed the progress of the reaction.

[0561] XRD analysis of dihydroxy-substituted PPS (P2) revealed no peaks attributable to PPS crystallinity, indicating that it maintains amorphous properties even after demethylation. The glass transition temperature of dihydroxy-substituted PPS (P2) is 140°C, significantly higher than that of dimethoxy-substituted PPS (P1) due to the introduction of hydrogen bonds.

[0562] Figure 10 3 and 4 show the XRD spectra of polyphenylene sulfide resin (PPS) and dihydroxy-substituted PPS (P2). Figure 11 The DSC curves of dimethoxy-substituted PPS (P1) and dihydroxy-substituted PPS (P2) are shown in FIG. That is, P1 is PPS before demethylation, and P2 is PPS after demethylation.

[0563] Separately, a dihydroxy-substituted PPS (P2) was dissolved in DMF at a concentration of 15 mg / mL and drop-coated on a glass substrate. The film was then dried under reduced pressure at 40°C for 4 hours to form a film. The film thickness was 2.5 μm, and the transmittance at 400 nm was 90%. Separately, a DMF solution (concentration: 30 mg / mL) of dihydroxy-substituted PPS (P2) was spin-coated on a silicon wafer to form a film. The refractive index and Abbe number were measured. D =1.85, v D =16.

[0564] Figure 12 The transmittance measurement data of the hydroxyl-substituted PPS (P2) film based on UV-vis measurement are shown in FIG. Figure 13 Measured data of the refractive index of the hydroxyl-substituted PPS (P2) film are shown in FIG.

[0565] The true densities of dimethoxy-substituted PPS (P1) and hydroxyl-substituted PPS (P2) were measured using a dry automatic density meter (AccuPycII 1340, manufactured by Shimadzu Corporation) and were 1.42 g / cm 3 , 1.87g / cm 3 This suggests that the intermolecular hydrogen bonds formed by the substitution of hydroxyl groups in the side chains of PPS (P2) by hydroxyl groups increase the interaction between the main chains, and that the high density and low molecular volume contribute to the improvement of the refractive index.

[0566] Example 10

[0567] The toughness imparted by cross-linking of vinyl-substituted PPS

[0568] Three types of vinyl-substituted PPS (P3) were synthesized by the same method as in Example 8 using poly(3-methyl-1,4-phenylene sulfide) instead of poly(2,6-dimethyl-1,4-phenylene sulfide).

[0569] Each vinyl-substituted PPS (P3) was dissolved in 1,1,2,2-tetrachloroethane, filtered through a membrane, and then m-phenylenedithiol was added and stirred to prepare a sulfur-containing polymer composition. Specifically, the concentration of P3 was adjusted to 100 mg / mL, and 0.5 equivalents of m-phenylenedithiol were added relative to the vinyl group. 1.5 mL of the sulfur-containing polymer composition was dropwise added to a 1 cm x 5 cm Teflon (registered trademark) plate and heated at 50°C for 12 hours, 100°C for 2 hours, 120°C for 12 hours, and 150°C for 3 hours to obtain a crosslinked film P3-BDTH (crosslinked product). The chemical formula representing the crosslinking reaction is shown below. Table 11 shows the vinyl (CH=CH2) content and Br content of each vinyl-substituted PPS used, as well as the results of thermal physical properties and dynamic viscoelasticity measurements of the resulting crosslinked product.

[0570] In Table 11, CH=CH2 (mol%) and Br (mol%) are 1 Tg was determined by H-NMR. a) Determine by DSC measurement. b) , G', G", and tanδ were determined by dynamic viscoelasticity measurement (DMA).

[0571] [Chemistry 21]

[0572]

[0573] [Table 11]

[0574]

[0575] As can be seen from Table 11, the prepared cross-linked bodies 1, 2, and 3 are all bendable and soft.

[0576] Furthermore, these crosslinked bodies were subjected to dynamic viscoelasticity measurement. As a result, the storage modulus of the crosslinked body 2 showed a maximum value of G′=1.90 GPa.

[0577] Example 11

[0578] <Sulfur-containing polymer 9>

[0579] (Synthesis of Methyl-Terminated Methoxy-Substituted PPS (Me-OMePPS))

[0580] In a 100 mL two-necked flask, 0.6 g of methoxy-substituted PPS (OMePPS) (Mn = 2500, disulfide concentration 0.24 mmol) was dissolved in THF (8.1 mL). The mixture was cooled to 0°C, and iodomethane (299 μL, 4.8 mmol, 20 eq) was added with stirring. Once the solution became homogeneous, a solution of sodium borohydride (182 mg, 4.8 mmol, 20 eq) dispersed in water (0.9 mL) was added dropwise. After foaming, the mixture was warmed to room temperature and reacted for 3 hours. The resulting solution was purified by precipitation in methanol (300 mL), recovered on a glass filter, washed with methanol and water, and dried under reduced pressure to yield methyl-terminated methoxy-substituted PPS (Me-OMePPS) (0.47 g, 79% yield) as a white powder (GPC (THF, polystyrene standard): Mn = 2100, Mw / Mn = 1.8).

[0581] according to 1 H-NMR showed that a new peak derived from the terminal methyl group appeared near 2.4 to 2.1 ppm, and the number average molecular weight Mn calculated from the integral ratio of the peak derived from the methoxy group (4 to 3.3 ppm) to the peak derived from the terminal methyl group was 2100. The calculation used Mn = 138.2 (repeating unit molecular weight) × AOMe (integral value of the peak derived from the methoxy group) / AMe (integral value of the peak derived from the terminal methyl group). 1 By H-DOSY-NMR, peaks derived from methoxy and methyl groups were observed at the same diffusion coefficient, confirming the addition of a methyl group to the main chain terminal.

[0582] [Chemistry 22]

[0583]

[0584] (Synthesis of Hydroxyl-Substituted PPS (OHPPS))

[0585] 0.3g of the above-mentioned Me-OMePPS was added to a 100mL flask, moved into a glove box, and dissolved in dichloromethane (9.1mL). The flask was sealed and moved out, cooled to 0°C, and 1M boron tribromide dichloromethane solution (5.42mL, 5.42mmol) was added with a syringe, stirred at 0°C for 30 minutes, then warmed to room temperature and further stirred for 20 hours. After the reaction was completed, pure water (12mL) was slowly added dropwise while cooling the flask with an ice bath, thereby quenching the reaction and removing the solvent with an evaporator. The remaining product was redissolved in DMF (10mL) and purified by precipitation in 1M hydrochloric acid (300mL) to obtain a white precipitate. After recovering with a glass filter and washing with water, vacuum drying was performed until the recovered solid was completely dry. The product was redissolved in acetone (20 mL) and then reprecipitated and purified in 1 M hydrochloric acid (200 mL) (twice in total). After recovery using a glass filter, washing with water, and vacuum drying, hydroxy-substituted PPS (OHPPS) (sulfur-containing polymer 9) (0.21 g, yield 79%) was obtained as a white powder (Mn (calculated by NMR) = 2000).

[0586] exist 1 In H-NMR, the peak derived from the methoxy group (4-3.3 ppm) disappeared after demethylation, and a broad peak derived from the hydroxyl group was newly observed at 11-9.5 ppm, confirming the progress of the reaction. Since the integration ratio of the peaks derived from the hydroxyl group and the peaks derived from the aromatic ring was 1:1, the introduction rate of the hydroxyl group was calculated to be 100%. The OH stretching vibration (3400 cm-1) after the reaction was observed by IR. -1 ) absorption, COC stretching vibration (1200cm -1 ) disappears, thus supporting the reaction. In addition, the absorption derived from the CH stretching vibration of the methyl group (3000-2800 cm -1 ) is greatly attenuated after the reaction, originating from the Ar-H stretching vibration of the aromatic ring (3070 cm -1 ), CH out-of-plane angular vibration (920~800cm -1 ) absorption was also observed after the reaction, thus also supporting the structure.

[0587] According to the XRD spectra of Me-OMePPS and OHPPS, no crystallinity peaks were observed even after demethylation. The average distance between aromatic rings calculated by Bragg's equation is And OHPPS is (CuKα ray: using In DSC, the glass transition temperature of Me-OMePPS is 119°C, while that of OHPPS increases to 125°C, suggesting that the interaction between the molecular chains is enhanced through intermolecular hydrogen bonding.

[0588] [Chemistry 23]

[0589]

[0590] Hydroxyl-substituted PPS (OHPPS) was dissolved in DMF at a concentration of 15 mg / mL and drop-coated on a glass substrate. The film was then dried under reduced pressure at 50°C for 12 hours and then at room temperature for another 12 hours to form a colorless, transparent film with a thickness of 4.5 μm. Separately, methyl-terminated methoxy-substituted PPS (Me-OMePPS) was dissolved in N,N-dimethylacetamide (DMAc) at a concentration of 15 mg / mL and drop-coated on a glass substrate. The film was then dried under reduced pressure at 50°C for 12 hours and then at room temperature for another 12 hours to form a colorless, transparent film with a thickness of 2.8 μm. The transmittance of each of the two films, calculated as a thickness of 1 μm, was determined. Figure 14 The measured data of the transmittance of these films are shown in FIG. Figure 14 As shown, the transmittance of OHPPS was 97%, which was higher than the transmittance of Me-OMePPS of 93%.

[0591] Separately, OHPPS (60 mg) was dissolved in DMF (1 mL), added dropwise to a silicon wafer, and spun at 2000 rpm for 30 seconds using a spin coater to form a film. The obtained sample was dried under reduced pressure at 50°C for 12 hours and at room temperature for 12 hours to obtain a uniform thin film. Me-OMePPS (30 mg) was dissolved in 1,1,2,2-tetrachloroethane (1 mL), added dropwise to a silicon wafer, and spun at 500 rpm for 45 seconds and at 1500 rpm for 50 seconds using a spin coater to form a film. The obtained sample was dried under reduced pressure at 50°C for 12 hours and then at room temperature for 12 hours to obtain a uniform thin film. The refractive index (D line) and Abbe number of the obtained film were measured. Figure 15 The measurement data of the refractive index are shown in Table 12. The measurement results are shown in Table 12.

[0592] From Table 12, it was confirmed that OHPPS having a hydroxyl group had a higher refractive index and a smaller Abbe number than Me-OMePPS.

[0593] The true densities of Me-OMePPS and OHPPS were measured using a dry automatic density meter (AccuPycII 1340, manufactured by Shimadzu Corporation). The measurement results are shown in Table 12. As shown in Table 12, the true density of OHPPS is higher than that of Me-OMePPS. This is because the interaction between the main chains is enhanced by intermolecular hydrogen bonds formed by the hydroxyl groups in the OHPPS side chains, and it is believed that the higher density and lower molecular volume contribute to the improvement in refractive index.

[0594] [Table 12]

[0595] < / ir>

Claims

1. A sulfur-containing polymer comprising 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), wherein: The total content ratio of the structural unit (A), the structural unit (B), and the structural unit (C) is 80 mol% or more relative to 100 mol% of all the structural units of the sulfur-containing polymer, The sulfur-containing polymer comprises the structural unit (B), wherein the content ratio of the structural unit (B) is 1 mol% to 100 mol% relative to 100 mol% of all structural units of the sulfur-containing polymer, and the total content ratio of the structural unit (A) and the structural unit (C) is 0 to 99 mol% relative to 100 mol% of all structural units of the sulfur-containing polymer. The sulfur-containing polymer has reactive functional groups, The reactive functional group is an acidic functional group, a basic functional group or a group containing these functional groups, The acidic functional group is at least one selected from the group consisting of a phosphoric acid group, a sulfuric acid group, a phosphonic acid group, a phosphinic acid group and a thiol group, The basic functional group is at least one selected from the group consisting of an ammonium group, an imino group and a maleimide group, [Chemistry 1] [Chemistry 2] [Chemistry 3] In formulas (1), (2) and (3), X 1 、X 2 and X 3 The same or different groups represent phenylene, naphthylene, anthracene, biphenylene or triphenylene groups which may have a substituent or not.

2. The sulfur-containing polymer according to claim 1, wherein The sulfur-containing polymer includes, as a repeating unit, at least one structural unit selected from the group consisting of the structural unit (A), the structural unit (B), and the structural unit (C).

3. The sulfur-containing polymer according to claim 1, wherein The sulfur-containing polymer has the reactive functional group at the main chain terminal and / or the side chain.

4. The sulfur-containing polymer according to claim 1, wherein The reactive functional group is a phosphoric acid group, a phosphonic acid group, or a group containing these functional groups.

5. The sulfur-containing polymer according to claim 1, wherein The reactive functional group is a maleimide group or a group containing the functional group.

6. The sulfur-containing polymer according to claim 1, wherein The reactive functional group is at least one functional group selected from the group consisting of a phosphoric acid group and a phosphonic acid group, or a group containing the functional group.

7. The sulfur-containing polymer according to claim 1, wherein The reactive functional group is a phosphate group or a group containing the same.

8. The sulfur-containing polymer according to claim 1, wherein The X 1 、X 2 and X 3 It is a phenylene group which may have a substituent.

9. The sulfur-containing polymer according to claim 1, wherein The substituent of the phenylene group, naphthylene group, anthracene group, biphenylene group or triphenylene group is the reactive functional group, a halogen atom, or an alkyl group, alkoxy group, aryl group, aralkyl group or a sulfur-containing substituent which may have a substituent.

10. The sulfur-containing polymer according to claim 1, wherein The substituent of the phenylene group, naphthylene group, anthracene group, biphenylene group or triphenylene group is the reactive functional group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a sulfur-containing substituent.

11. The sulfur-containing polymer according to claim 9, wherein The halogen atom is a bromine atom.

12. The sulfur-containing polymer according to claim 9, wherein The alkyl group is an alkyl group having 1 to 18 carbon atoms.

13. The sulfur-containing polymer according to claim 9, wherein The alkyl group is an alkyl group having 1 to 6 carbon atoms.

14. The sulfur-containing polymer according to claim 9, wherein The alkyl group is methyl.

15. The sulfur-containing polymer according to claim 9, wherein The alkoxy group is an alkoxy group having 1 to 18 carbon atoms.

16. The sulfur-containing polymer according to claim 9, wherein The alkoxy group is an alkoxy group having 1 to 6 carbon atoms.

17. The sulfur-containing polymer according to claim 9, wherein The alkoxy group is a methoxy group.

18. The sulfur-containing polymer according to claim 9, wherein The aryl group is a phenyl group.

19. The sulfur-containing polymer according to claim 9, wherein The aryl group has 6 to 30 carbon atoms.

20. The sulfur-containing polymer according to claim 9, wherein The aryl group has 6 to 18 carbon atoms.

21. The sulfur-containing polymer according to claim 9, wherein The aryl group has 6 to 12 carbon atoms.

22. The sulfur-containing polymer according to claim 9, wherein The aralkyl group has 7 to 14 carbon atoms.

23. The sulfur-containing polymer according to claim 9, wherein The aralkyl group has 7 to 9 carbon atoms.

24. The sulfur-containing polymer according to claim 9, wherein The sulfur-containing substituent is a thioalkyl group.

25. The sulfur-containing polymer according to claim 9, wherein The sulfur-containing substituent has 1 to 8 carbon atoms.

26. The sulfur-containing polymer according to claim 9, wherein The sulfur-containing substituent has 1 to 6 carbon atoms.

27. The sulfur-containing polymer according to claim 9, wherein The sulfur-containing substituent has 1 to 4 carbon atoms.

28. The sulfur-containing polymer according to claim 1, wherein The substituent of the phenylene group, naphthylene group, anthracene group, biphenylene group or triphenylene group is the reactive functional group, or an alkyl group or a sulfur-containing substituent group which may have a substituent.

29. The sulfur-containing polymer according to claim 1, wherein The substituent of the phenylene group, naphthylene group, anthracene group, biphenylene group, or triphenylene group is the reactive functional group, a methyl group, or a thioalkyl group.

30. The sulfur-containing polymer of claim 1, wherein The substituent of the phenylene group, naphthylene group, anthracene group, biphenylene group, or triphenylene group is the reactive functional group or a methyl group.

31. The sulfur-containing polymer of claim 1, wherein The substituent of the phenylene group is an amide group, an imide group, a cyano group, a nitroso group or a sulfo group.

32. The sulfur-containing polymer of claim 1, wherein The positions of the substituents in the phenylene group are a combination of the 2-position and the 6-position, a combination of the 2-position and the 4-position, or a combination of the 2-position and the 5-position.

33. The sulfur-containing polymer of claim 1, wherein The positions of the substituents in the phenylene group are a combination of the 2-position and the 6-position.

34. The sulfur-containing polymer of claim 1, wherein The phenylene group is a phenylene group having hydroxyl groups at the 2-position and the 6-position.

35. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer further has a substituent capable of imparting amorphous properties to the sulfur-containing polymer in addition to the reactive functional group.

36. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer further has an alkyl group, an alkoxy group, an aryl group, a sulfur-containing substituent group, or a halogen-containing group in addition to the reactive functional group.

37. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer further has a methyl group or a methoxy group in addition to the reactive functional group.

38. The sulfur-containing polymer of claim 1, wherein The number of substituents possessed by the phenylene group, naphthylene group, anthracene group, biphenylene group or triphenylene group is 1 to 6.

39. The sulfur-containing polymer of claim 1, wherein The number of substituents possessed by the phenylene group, naphthylene group, anthracene group, biphenylene group or triphenylene group is 1 to 3.

40. The sulfur-containing polymer of claim 1, wherein The number of substituents possessed by the phenylene group, naphthylene group, anthracene group, biphenylene group, or triphenylene group is 1.

41. The sulfur-containing polymer of claim 1, wherein The connection positions of the structural units are respectively relative to X 1 、X 2 、X 3 The bonding position of -S-, -SO- or -SO2- is para.

42. The sulfur-containing polymer of claim 1, wherein The connection positions of the structural units are respectively relative to X 1 、X 2 、X 3 The bonding position of -S-, -SO- or -SO2- is ortho or meta.

43. The sulfur-containing polymer of claim 41, wherein The amount of the structural units linked at the para position is 10 mol% or more relative to 100 mol% of all the structural units of the sulfur-containing polymer.

44. The sulfur-containing polymer of claim 41, wherein The amount of the structural units linked at the para position is 30 mol% or more relative to 100 mol% of all the structural units of the sulfur-containing polymer.

45. The sulfur-containing polymer of claim 41, wherein The amount of the structural units linked at the para position is less than 99 mol % relative to 100 mol % of all structural units of the sulfur-containing polymer.

46. ​​The sulfur-containing polymer of claim 41, wherein The amount of the structural units linked at the para position is less than 90 mol % relative to 100 mol % of all structural units of the sulfur-containing polymer.

47. The sulfur-containing polymer of claim 41, wherein The amount of the structural units linked at the para position is less than 80 mol % relative to 100 mol % of all structural units of the sulfur-containing polymer.

48. The sulfur-containing polymer of claim 1, wherein The structural unit (A) is a structural unit (A-1) represented by the following general formula (1-1), Where R 1 are the same or different and represent a halogen atom, the reactive functional group, or an alkyl group, alkoxy group, aryl group, aralkyl group or sulfur-containing substituent group which may or may not have a substituent; a represents R 1 The number is an integer from 0 to 4.

49. The sulfur-containing polymer of claim 48, wherein In the general formula (1-1), a is an integer of 0-2.

50. The sulfur-containing polymer of claim 48, wherein In the general formula (1-1), a is an integer of 1 to 2.

51. The sulfur-containing polymer of claim 1, wherein The structural unit (B) is a structural unit (B-1) represented by the following general formula (2-1), Where R 2 are the same or different and represent a halogen atom, the reactive functional group, or an alkyl group, alkoxy group, aryl group, aralkyl group or sulfur-containing substituent group which may or may not have a substituent; b represents R 2 The number is an integer from 0 to 4.

52. The sulfur-containing polymer of claim 51, wherein In the general formula (2-1), b is an integer of 0-2.

53. The sulfur-containing polymer of claim 51, wherein In the general formula (2-1), b is an integer of 1 to 2.

54. The sulfur-containing polymer of claim 1, wherein The structural unit (C) is a structural unit (C-1) represented by the following general formula (3-1), Where R 3 are the same or different and represent a halogen atom, the reactive functional group, or an alkyl group, alkoxy group, aryl group, aralkyl group or sulfur-containing substituent group which may or may not have a substituent; c represents R 3 The number is an integer from 0 to 4.

55. The sulfur-containing polymer of claim 54, wherein In the general formula (3-1), c is an integer of 0 to 2.

56. The sulfur-containing polymer of claim 54, wherein In the general formula (3-1), c is an integer of 1 to 2.

57. The sulfur-containing polymer of claim 1, wherein Contains the structural unit (A).

58. The sulfur-containing polymer of claim 1, wherein Contains the structural unit (C).

59. The sulfur-containing polymer of claim 1, wherein The content ratio of the structural unit (B) is 10 mol% to 100 mol% based on 100 mol% of all the structural units of the sulfur-containing polymer.

60. The sulfur-containing polymer of claim 1, wherein The content ratio of the structural unit (B) is 50 mol% to 100 mol% based on 100 mol% of all the structural units of the sulfur-containing polymer.

61. The sulfur-containing polymer of claim 1, wherein The total content of the structural unit (A) and the structural unit (C) is 0 to 90 mol% relative to 100 mol% of all the structural units of the sulfur-containing polymer.

62. The sulfur-containing polymer of claim 1, wherein The total content of the structural unit (A) and the structural unit (C) is 0 to 50 mol% relative to 100 mol% of all the structural units of the sulfur-containing polymer.

63. The sulfur-containing polymer of claim 1, wherein The total content ratio of the structural unit (A), the structural unit (B), and the structural unit (C) is 90 mol% or more relative to 100 mol% of all the structural units of the sulfur-containing polymer.

64. The sulfur-containing polymer of claim 1, wherein The total content ratio of the structural unit (A), the structural unit (B), and the structural unit (C) is 95 mol% or more relative to 100 mol% of all the structural units of the sulfur-containing polymer.

65. The sulfur-containing polymer of claim 1, wherein The total content ratio of the structural unit (A), the structural unit (B), and the structural unit (C) is 100 mol% relative to 100 mol% of all the structural units of the sulfur-containing polymer.

66. The sulfur-containing polymer of claim 1, wherein It further contains another structural unit (D) other than the structural unit (A), the structural unit (B) and the structural unit (C).

67. The sulfur-containing polymer of claim 66, wherein The content of the structural unit (D) is 0 to 20 mol% relative to 100 mol% of all the structural units of the sulfur-containing polymer.

68. The sulfur-containing polymer of claim 66, wherein The content of the structural unit (D) is 0 to 10 mol% relative to 100 mol% of all the structural units of the sulfur-containing polymer.

69. The sulfur-containing polymer of claim 66, wherein The content of the structural unit (D) is 0 to 5 mol% relative to 100 mol% of all the structural units of the sulfur-containing polymer.

70. The sulfur-containing polymer of claim 1, wherein The element content ratio O / S of the oxygen atom O bonded to the sulfur atom S in the main chain and the sulfur atom S in the main chain is 0.1 to 1.

5.

71. The sulfur-containing polymer of claim 1, wherein The element content 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 is 0.3 or more.

72. The sulfur-containing polymer of claim 1, wherein The element content 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 is 0.7 or more.

73. The sulfur-containing polymer of claim 1, wherein The element content 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 is 1.3 or less.

74. The sulfur-containing polymer of claim 1, wherein The element content 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 is 1.1 or less.

75. The sulfur-containing polymer of claim 1, wherein The glass transition temperature is 80℃~250℃.

76. The sulfur-containing polymer of claim 1, wherein The glass transition temperature is 90°C or higher.

77. The sulfur-containing polymer of claim 1, wherein The glass transition temperature is 100°C or higher.

78. The sulfur-containing polymer of claim 1, wherein The glass transition temperature is 200°C or lower.

79. The sulfur-containing polymer of claim 1, wherein The bond energy of SO is 163eV~167eV.

80. The sulfur-containing polymer of claim 1, wherein The weight average molecular weight is 500 to 10,000,000.

81. The sulfur-containing polymer of claim 1, wherein The weight average molecular weight is 1,000 or more.

82. The sulfur-containing polymer of claim 1, wherein The weight average molecular weight is 3,000 or more.

83. The sulfur-containing polymer of claim 1, wherein The weight average molecular weight is 10,000 or more.

84. The sulfur-containing polymer of claim 1, wherein The weight average molecular weight is 1,000,000 or less.

85. The sulfur-containing polymer of claim 1, wherein The weight average molecular weight is 100,000 or less.

86. The sulfur-containing polymer of claim 1, wherein The dispersion degree is 1 to 10.

87. The sulfur-containing polymer of claim 1, wherein The dispersion degree is 5 or less.

88. The sulfur-containing polymer of claim 1, wherein The dispersion degree is 3 or less.

89. The sulfur-containing polymer of claim 1, wherein The refractive index is 1.69 or higher.

90. The sulfur-containing polymer of claim 1, wherein The refractive index is 1.7 or more.

91. The sulfur-containing polymer of claim 1, wherein The refractive index is 1.71 or higher.

92. The sulfur-containing polymer of claim 1, wherein The Abbe number is 10 or more.

93. The sulfur-containing polymer of claim 1, wherein The Abbe number is 15 or more.

94. The sulfur-containing polymer of claim 1, wherein The Abbe number is 18 or more.

95. The sulfur-containing polymer of claim 1, wherein The Abbe number is 20 or more.

96. The sulfur-containing polymer of claim 1, wherein The Abbe number is less than 60.

97. The sulfur-containing polymer of claim 1, wherein The Abbe number is 55 or less.

98. The sulfur-containing polymer of claim 1, wherein Visible light transmittance is over 70%.

99. The sulfur-containing polymer of claim 1, wherein Visible light transmittance is over 80%.

100. The sulfur-containing polymer of claim 1, wherein Visible light transmittance is over 85%.

101. The sulfur-containing polymer of claim 1, wherein Visible light transmittance is over 88%.

102. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer is amorphous.

103. The sulfur-containing polymer of claim 1, wherein The crystallinity is less than 80%.

104. The sulfur-containing polymer of claim 1, wherein The crystallinity is less than 50%.

105. The sulfur-containing polymer of claim 1, wherein The crystallinity is less than 30%.

106. The sulfur-containing polymer of claim 1, wherein The crystallinity is less than 10%.

107. The sulfur-containing polymer of claim 1, wherein The crystallinity is less than 5%.

108. The sulfur-containing polymer of claim 1, wherein The crystallinity is 1% or more.

109. The sulfur-containing polymer of claim 1, wherein The crystallinity is 10% or more.

110. The sulfur-containing polymer of claim 1, wherein The crystallinity is 30% or more.

111. The sulfur-containing polymer of claim 1, wherein The crystallinity is 60% or more.

112. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer is thermoplastic.

113. The sulfur-containing polymer of claim 1, wherein in, The sulfur-containing polymer is used for optical applications.

114. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer is used for at least one selected from the group consisting of lenses, sealing materials for LEDs, optical adhesives, optical bonding materials, bonding materials for light transmission, filters, diffraction gratings, diffraction optical elements, prisms, light guide elements, watch glasses, and cover glasses for display devices.

115. The sulfur-containing polymer of claim 114, wherein The lens is at least one selected from the group consisting of eyeglass lenses, imaging lenses for cameras, beam converging lenses, and light diffusing lenses.

116. The sulfur-containing polymer of claim 115, wherein The camera imaging lens is at least one selected from the group consisting of a digital camera imaging lens, a mobile phone camera imaging lens, and a vehicle-mounted camera imaging lens.

117. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer is used for optical materials, optical device components, display device components, heat-resistant materials, ferroelectric materials, heat dissipation materials, separators of battery materials, gas separation membrane filters, liquid separation membrane filters, electrode materials, battery components, insulating materials, antenna materials or molding materials.

118. The sulfur-containing polymer of claim 1, wherein The sulfur-containing polymer is used for etching processing, resist processing or coating.

119. A sulfur-containing polymer composition, characterized in that The method comprises the sulfur-containing polymer according to claim 1 and an inorganic substance.

120. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 10% by mass to 100% by mass based on 100% by mass of the total solid content of the sulfur-containing polymer composition.

121. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 20% by mass or more in 100% by mass of the total solid content of the sulfur-containing polymer composition.

122. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 50% by mass or more in 100% by mass of the total solid content of the sulfur-containing polymer composition.

123. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 99% by mass or less in 100% by mass of the total solid content of the sulfur-containing polymer composition.

124. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 95% by mass or less in 100% by mass of the total solid content of the sulfur-containing polymer composition.

125. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 85% by mass or less in 100% by mass of the total solid content of the sulfur-containing polymer composition.

126. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 80% by mass or less in 100% by mass of the total solid content of the sulfur-containing polymer composition.

127. The sulfur-containing polymer composition of claim 119, wherein: The content of the sulfur-containing polymer is 60% by mass or less in 100% by mass of the total solid content of the sulfur-containing polymer composition.

128. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is a metal, an inorganic oxide, an inorganic nitride, an inorganic carbide, an inorganic sulfide or an inorganic hydroxide.

129. The sulfur-containing polymer composition of claim 128, wherein The inorganic oxide is a metal oxide containing a metal element.

130. The sulfur-containing polymer composition of claim 128, wherein: The inorganic nitride is a metal nitride.

131. The sulfur-containing polymer composition of claim 128, wherein The inorganic carbide is a metal carbide.

132. The sulfur-containing polymer composition of claim 128, wherein: The inorganic sulfide is a metal sulfide.

133. The sulfur-containing polymer composition of claim 128, wherein: The inorganic hydroxide is a metal hydroxide.

134. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is an inorganic oxide.

135. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is an oxide whose main component is Ti, Zr, Ce, Zn, In, Al, Si or Sn as a metal element.

136. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is titanium oxide, zirconium oxide, cerium oxide, zinc oxide, indium oxide, aluminum oxide, silicon oxide or tin oxide.

137. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is zirconium oxide, titanium oxide or silicon dioxide.

138. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is zirconium oxide or titanium oxide.

139. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is boron nitride, aluminum hydroxide or aluminum titanate.

140. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is a solid solution oxide in which a different metal element or fluorine as an additive element is solid-dissolved in zinc oxide, indium oxide, or tin oxide.

141. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is zinc oxide containing In, Al or Ga in a solid solution, indium oxide containing Sn or Ti in a solid solution, or tin oxide containing Sb or F in a solid solution.

142. The sulfur-containing polymer composition of claim 119, wherein: The inorganic substance is in the form of particles.

143. The sulfur-containing polymer composition of claim 119, wherein: The average particle size of the inorganic substance is greater than or equal to 1 nm and less than or equal to 1000 nm.

144. The sulfur-containing polymer composition of claim 119, wherein: The average particle size of the inorganic substance is greater than 5 nm.

145. The sulfur-containing polymer composition of claim 119, wherein: The average particle size of the inorganic substance is greater than 10 nm.

146. The sulfur-containing polymer composition of claim 119, wherein: The average particle size of the inorganic substance is less than 100 nm.

147. The sulfur-containing polymer composition of claim 119, wherein: The average particle size of the inorganic substance is 50 nm or less.

148. The sulfur-containing polymer composition of claim 119, wherein: The average particle size of the inorganic substance is less than 30 nm.

149. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 10 parts by mass or more relative to 100 parts by mass of the sulfur-containing polymer.

150. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 30 parts by mass or more relative to 100 parts by mass of the sulfur-containing polymer.

151. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 50 parts by mass or more relative to 100 parts by mass of the sulfur-containing polymer.

152. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 70 parts by mass or more relative to 100 parts by mass of the sulfur-containing polymer.

153. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 80 parts by mass or more relative to 100 parts by mass of the sulfur-containing polymer.

154. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 90 parts by mass or less relative to 100 parts by mass of the sulfur-containing polymer.

155. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 80 parts by mass or less relative to 100 parts by mass of the sulfur-containing polymer.

156. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 70 parts by mass or less relative to 100 parts by mass of the sulfur-containing polymer.

157. The sulfur-containing polymer composition of claim 119, wherein: The content of the inorganic substance is 50 parts by mass or less relative to 100 parts by mass of the sulfur-containing polymer.

158. The sulfur-containing polymer composition of claim 119, wherein: The reactive functional group of the sulfur-containing polymer is a thiol group.

159. The sulfur-containing polymer composition of claim 119, wherein: It further contains a curing catalyst or a curing agent.

160. The sulfur-containing polymer composition of claim 159, wherein: The curing catalyst is a thermolatent cationic curing catalyst or a thermolatent free radical curing catalyst.

161. The sulfur-containing polymer composition of claim 159, wherein: The curing catalyst is a thermolatent cationic curing catalyst.

162. The sulfur-containing polymer composition of claim 159, wherein: The curing catalyst is a photolatent cationic curing catalyst or a photolatent free radical curing catalyst.

163. The sulfur-containing polymer composition of claim 159, wherein: The curing catalyst is a photolatent cationic curing catalyst.

164. The sulfur-containing polymer composition of claim 159, wherein: The curing catalyst is an onium salt or a boron compound.

165. The sulfur-containing polymer composition of claim 160, wherein: The thermolatent free radical curing catalyst is an organic peroxide or an azo compound.

166. The sulfur-containing polymer composition of claim 162, wherein: The photolatent free radical curing catalyst is acetophenone, benzoin, benzophenone, thioxanthone, xanthone, anthraquinone or acylphosphine oxide.

167. The sulfur-containing polymer composition of claim 159, wherein: The content of the curing catalyst is 0.01% by mass to 10% by mass relative to 100% by mass of the sulfur-containing polymer composition.

168. The sulfur-containing polymer composition of claim 159, wherein: The curing agent is an anhydride-based, phenol-based or amine-based curing agent.

169. The sulfur-containing polymer composition of claim 119, wherein: It further contains a photosensitizer.

170. The sulfur-containing polymer composition of claim 169, wherein The photosensitizer is an amine.

171. The sulfur-containing polymer composition of claim 169, wherein The amount of the photosensitizer blended is 0.1% by mass to 20% by mass relative to 100% by mass of the sulfur-containing polymer composition.

172. The sulfur-containing polymer composition of claim 119, wherein: It further contains a curing accelerator.

173. The sulfur-containing polymer composition of claim 172, wherein: The amount of the curing accelerator used is 0.01% by mass to 5% by mass relative to 100% by mass of the sulfur-containing polymer composition.

174. The sulfur-containing polymer composition of claim 172, wherein: The amount of the curing accelerator used is 0.03% by mass to 3% by mass relative to 100% by mass of the sulfur-containing polymer composition.

175. The sulfur-containing polymer composition of claim 119, wherein: The glass transition temperature Tg is 80°C to 250°C.

176. The sulfur-containing polymer composition of claim 119, wherein: The glass transition temperature Tg is 90°C or higher.

177. The sulfur-containing polymer composition of claim 119, wherein: The glass transition temperature Tg is 100° C. or higher.

178. The sulfur-containing polymer composition of claim 119, wherein: The glass transition temperature Tg is 200°C or lower.

179. The sulfur-containing polymer composition of claim 119, wherein: The refractive index is 1.69 or higher.

180. The sulfur-containing polymer composition of claim 119, wherein: The refractive index is 1.70 or more.

181. The sulfur-containing polymer composition of claim 119, wherein: The refractive index is 1.71 or higher.

182. The sulfur-containing polymer composition of claim 119, wherein: The Abbe number is 10 or more.

183. The sulfur-containing polymer composition of claim 119, wherein: The Abbe number is 15 or more.

184. The sulfur-containing polymer composition of claim 119, wherein: The Abbe number is 18 or more.

185. The sulfur-containing polymer composition of claim 119, wherein: The Abbe number is 20 or more.

186. The sulfur-containing polymer composition of claim 119, wherein: The Abbe number is less than 60.

187. The sulfur-containing polymer composition of claim 119, wherein: The Abbe number is 55 or less.

188. The sulfur-containing polymer composition of claim 119, wherein: Visible light transmittance is over 70%.

189. The sulfur-containing polymer composition of claim 119, wherein Visible light transmittance is over 80%.

190. The sulfur-containing polymer composition of claim 119, wherein: Visible light transmittance is over 85%.

191. The sulfur-containing polymer composition of claim 119, wherein Visible light transmittance is over 88%.

192. The sulfur-containing polymer composition of claim 119, wherein: Density is 1.1g / cm 3 above.

193. The sulfur-containing polymer composition of claim 119, wherein: Density is 1.3g / cm 3 above.

194. The sulfur-containing polymer composition of claim 119, wherein Density is 1.4g / cm 3 above.

195. The sulfur-containing polymer composition of claim 119, wherein: Density is 1.6g / cm 3 above.

196. The sulfur-containing polymer composition of claim 119, wherein Density is 1.8g / cm 3 above.

197. The sulfur-containing polymer composition of claim 119, wherein Density less than 3.0g / cm 3 .

198. The sulfur-containing polymer composition of claim 119, wherein Density less than 2.5g / cm 3 .

199. The sulfur-containing polymer composition of claim 119, wherein Density less than 2.0g / cm 3 .

200. The sulfur-containing polymer composition of claim 119, wherein: The sulfur-containing polymer composition is thermoplastic.

201. A cured product of the sulfur-containing polymer according to claim 1.

202. The cured product according to claim 201, wherein The cured product is used for optical applications.

203. A cured product of the sulfur-containing polymer composition of claim 119.

204. The cured product according to claim 203, wherein The cured product is used for optical applications.

205. The sulfur-containing polymer composition of claim 119, wherein: The sulfur-containing polymer composition is used for at least one selected from the group consisting of lenses, sealing materials for LEDs, optical adhesives, optical bonding materials, bonding materials for light transmission, optical filters, diffraction gratings, diffractive optical elements, prisms, light guide elements, watch glasses, and cover glasses for display devices.

206. The sulfur-containing polymer composition of claim 205, wherein The lens is at least one selected from the group consisting of eyeglass lenses, imaging lenses for cameras, beam converging lenses, and light diffusing lenses.

207. The sulfur-containing polymer composition of claim 206, wherein The camera imaging lens is at least one selected from the group consisting of a digital camera imaging lens, a mobile phone camera imaging lens, and a vehicle-mounted camera imaging lens.

208. The sulfur-containing polymer composition of claim 119, wherein: The sulfur-containing polymer composition is used for optical materials, optical device components, display device components, heat-resistant materials, ferroelectric materials, heat dissipation materials, separators of battery materials, gas separation membrane filters, liquid separation membrane filters, electrode materials, battery components, insulating materials, antenna materials or molding materials.

209. The sulfur-containing polymer composition of claim 119, wherein The sulfur-containing polymer composition is used for etching processing, resist processing or coating.

210. The sulfur-containing polymer composition of claim 119, wherein: The sulfur-containing polymer composition is a curable resin composition.

211. A method for producing a sulfur-containing polymer, which is the method for producing a sulfur-containing polymer according to claim 1, characterized in that: include: a reaction step of reacting a compound having a polymerizable double bond and a reactive functional group with a sulfur-containing aromatic polymer having a disulfide bond and / or a thiol group at a terminal; and an oxidation step of oxidizing the polymer into which the reactive functional group is introduced using an oxidizing agent, The reactive functional group is an acidic functional group, a basic functional group or a group containing these functional groups, The acidic functional group is at least one selected from the group consisting of a phosphoric acid group, a sulfuric acid group, a phosphonic acid group, a phosphinic acid group and a thiol group, The basic functional group is at least one selected from the group consisting of an ammonium group, an imino group and a maleimide group, The sulfur-containing aromatic polymer is obtained by polymerizing monomer components including sulfur-containing monomers. The sulfur-containing monomer is a disulfide compound or a thiol compound, The disulfide compound is a diaryl disulfide compound represented by the following general formula (4): A 1 -S-S-A 2 (4) Where A 1 and A 2 The same or different, representing phenyl, naphthyl, anthracenyl, biphenyl or triphenyl with or without substituents, The thiol compound is a thioaryl compound represented by the following general formula (5): THE 1 -SH(5) Where A 1 The same or different groups represent phenyl, naphthyl, anthracenyl, biphenyl or triphenyl groups which may have a substituent.

212. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction step comprises the following steps: cleaving the terminal disulfide bond of a sulfur-containing aromatic polymer having a disulfide bond at the terminal of the sulfur-containing aromatic polymer using light or a free radical initiator catalyst, and reacting the compound having a polymerizable double bond and a reactive functional group with the sulfur-containing aromatic polymer.

213. The method for producing a sulfur-containing polymer according to claim 211, wherein The compound having a polymerizable double bond and a reactive functional group is a compound having a polymerizable double bond and a phosphoric acid group or a phosphonic acid group.

214. The method for producing a sulfur-containing polymer according to claim 213, wherein The compound having a polymerizable double bond and a phosphoric acid group or a phosphonic acid group is used in an amount of 0.1 to 5000 parts by mass based on 100 parts by mass of the sulfur-containing aromatic polymer.

215. The method for producing a sulfur-containing polymer according to claim 213, wherein The compound having a polymerizable double bond and a phosphoric acid group or a phosphonic acid group is used in an amount of 1 to 100 parts by mass based on 100 parts by mass of the sulfur-containing aromatic polymer.

216. The method for producing a sulfur-containing polymer according to claim 213, wherein The compound having a polymerizable double bond and a phosphoric acid group or a phosphonic acid group is used in an amount of 1 to 20 parts by mass based on 100 parts by mass of the sulfur-containing aromatic polymer.

217. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction process is carried out by light irradiation.

218. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction step is a step of reacting the compound having a polymerizable double bond and a reactive functional group with the sulfur-containing aromatic polymer having a thiol group at the terminal, thereby bonding the compounds through a thiol-ene reaction.

219. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction step comprises reacting a reducing agent with the sulfur-containing aromatic polymer having a terminal disulfide bond to form a thiol group at the terminal, and then reacting the compound having a polymerizable double bond and a reactive functional group to bond the compound via a thiol-ene reaction.

220. The method for producing a sulfur-containing polymer according to claim 211, wherein The sulfur-containing polymer has a reactive functional group at the end of the main chain.

221. The method for producing a sulfur-containing polymer according to claim 211, wherein The sulfur-containing polymer has a phosphoric acid group or a phosphonic acid group at the terminal.

222. The method for producing a sulfur-containing polymer according to claim 219, wherein The reducing agent is used in an amount of 1 to 1000 parts by mass relative to 100 parts by mass of the sulfur-containing aromatic polymer.

223. The method for producing a sulfur-containing polymer according to claim 219, wherein The reducing agent is used in an amount of 5 to 300 parts by mass relative to 100 parts by mass of the sulfur-containing aromatic polymer.

224. The method for producing a sulfur-containing polymer according to claim 219, wherein The reducing agent is used in an amount of 10 to 100 parts by mass relative to 100 parts by mass of the sulfur-containing aromatic polymer.

225. The method for producing a sulfur-containing polymer according to claim 219, wherein The reaction temperature for forming the thiol group is 0°C to 200°C.

226. The method for producing a sulfur-containing polymer according to claim 219, wherein The reaction temperature for forming the thiol group is 10°C to 100°C.

227. The method for producing a sulfur-containing polymer according to claim 219, wherein The reaction time for forming the thiol group is 0.1 to 100 hours.

228. The method for producing a sulfur-containing polymer according to claim 219, wherein The reaction time for forming the thiol group is 0.5 to 50 hours.

229. The method for producing a sulfur-containing polymer according to claim 219, wherein The reaction time for forming the thiol group is 1 to 24 hours.

230. The method for producing a sulfur-containing polymer according to claim 211, wherein The compound having a polymerizable double bond and a reactive functional group is 2-acryloyloxyethyl phosphate or vinylphosphonic acid.

231. The method for producing a sulfur-containing polymer according to claim 211, wherein The amount of the compound having a polymerizable double bond and a reactive functional group used is 0.1 to 1000 parts by mass based on 100 parts by mass of the sulfur-containing aromatic polymer.

232. The method for producing a sulfur-containing polymer according to claim 211, wherein The amount of the compound having a polymerizable double bond and a reactive functional group used is 1 to 20 parts by mass based on 100 parts by mass of the sulfur-containing aromatic polymer.

233. The method for producing a sulfur-containing polymer according to claim 211, wherein The amount of the compound having a polymerizable double bond and a reactive functional group used is 1 to 10 parts by mass based on 100 parts by mass of the sulfur-containing aromatic polymer.

234. A method for producing a sulfur-containing polymer, which is a method for producing the sulfur-containing polymer according to claim 1, characterized in that: The invention comprises obtaining a polymer from a sulfur-containing monomer having a substituent having a reactive functional group, The reactive functional group is an acidic functional group, a basic functional group or a group containing these functional groups, The acidic functional group is at least one selected from the group consisting of a phosphoric acid group, a sulfuric acid group, a phosphonic acid group, a phosphinic acid group and a thiol group, The basic functional group is at least one selected from the group consisting of an ammonium group, an imino group, and a maleimide group.

235. The method for producing a sulfur-containing polymer according to claim 234, wherein The sulfur-containing polymer has the reactive functional group at a side chain.

236. The method for producing a sulfur-containing polymer according to claim 211, wherein The monovalent aromatic hydrocarbon group in the general formula (4) is a phenyl group.

237. The method for producing a sulfur-containing polymer according to claim 211, wherein The diaryl disulfide compound is a compound represented by the following general formula (4-1): Where R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 The same or different groups represent a hydrogen atom, a halogen atom, a reactive functional group, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent group which may be substituted.

238. The method for producing a sulfur-containing polymer according to claim 211, wherein The thiol compound is a compound represented by the following general formula (5-1): Where R 4 、R 5 、R 6 and R 7 The same or different groups represent a hydrogen atom, a halogen atom, a reactive functional group, or an alkyl group, an alkoxy group, an aryl group, an aralkyl group, or a sulfur-containing substituent group which may be substituted.

239. The method for producing a sulfur-containing polymer according to claim 211, wherein The polymerization is oxidative polymerization.

240. The method for producing a sulfur-containing polymer according to claim 239, wherein The oxidative polymerization is performed using a quinone-based oxidizing agent.

241. The method for producing a sulfur-containing polymer according to claim 240, wherein The quinone oxidant is 2,3-dichloro-5,6-dicyano-p-benzoquinone.

242. The method for producing a sulfur-containing polymer according to claim 240, wherein The amount of the quinone-based oxidant added is 0.1 mol to 3 mol relative to 1 mol of the sulfur-containing monomer.

243. The method for producing a sulfur-containing polymer according to claim 240, wherein The amount of the quinone-based oxidant added is 0.8 mol to 1.5 mol relative to 1 mol of the sulfur-containing monomer.

244. The method for producing a sulfur-containing polymer according to claim 240, wherein The amount of the quinone-based oxidant added is 0.9 mol to 1.1 mol relative to 1 mol of the sulfur-containing monomer.

245. The method for producing a sulfur-containing polymer according to claim 240, wherein The oxidative polymerization further employs an acid.

246. The method for producing a sulfur-containing polymer according to claim 245, wherein The acid is trifluoroacetic acid.

247. The method for producing a sulfur-containing polymer according to claim 245, wherein The amount of the acid added is 10 mol to 1000 mol relative to 100 mol of the total amount of the quinone-based oxidizing agent.

248. The method for producing a sulfur-containing polymer according to claim 245, wherein The amount of the acid added is 50 mol to 500 mol relative to 100 mol of the total amount of the quinone-based oxidizing agent.

249. The method for producing a sulfur-containing polymer according to claim 245, wherein The amount of the acid added is 80 mol to 120 mol relative to 100 mol of the total amount of the quinone-based oxidizing agent.

250. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction temperature of the oxidative polymerization is 0°C to 200°C.

251. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction temperature of the oxidative polymerization is above 10°C.

252. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction temperature of the oxidative polymerization is above 15°C.

253. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction temperature of the oxidative polymerization is below 180°C.

254. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction temperature of the oxidative polymerization is below 150°C.

255. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction time of the oxidative polymerization is 0.1 hour to 100 hours.

256. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction time of the oxidative polymerization is 1 hour to 80 hours.

257. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction time of the oxidative polymerization is 5 to 50 hours.

258. The method for producing a sulfur-containing polymer according to claim 239, wherein The reaction time of the oxidative polymerization is 10 hours to 24 hours.

259. The method for producing a sulfur-containing polymer according to claim 211, wherein The oxidizing agent is peroxide or chloric acid.

260. The method for producing a sulfur-containing polymer according to claim 211, wherein The oxidizing agent is a peroxide.

261. The method for producing a sulfur-containing polymer according to claim 211, wherein The oxidant is m-chloroperbenzoic acid or hydrogen peroxide.

262. The method for producing a sulfur-containing polymer according to claim 211, wherein The oxidant is m-chloroperbenzoic acid.

263. The method for producing a sulfur-containing polymer according to claim 259, wherein The amount of the oxidizing agent added is 0.1 mol to 10 mol relative to 1 mol of sulfur atoms in the polymer.

264. The method for producing a sulfur-containing polymer according to claim 259, wherein The amount of the oxidizing agent added is 0.5 mol to 5 mol relative to 1 mol of sulfur atoms in the polymer.

265. The method for producing a sulfur-containing polymer according to claim 259, wherein The amount of the oxidizing agent added is 0.8 mol to 1.5 mol relative to 1 mol of sulfur atoms in the polymer.

266. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction temperature of the oxidation process is 0°C to 200°C.

267. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction temperature of the oxidation step is 10° C. or higher.

268. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction temperature of the oxidation step is 15° C. or higher.

269. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction temperature of the oxidation step is 180° C. or lower.

270. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction temperature of the oxidation step is 150° C. or lower.

271. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction time of the oxidation step is 0.1 hour to 100 hours.

272. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction time of the oxidation step is 1 hour to 80 hours.

273. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction time of the oxidation step is 5 to 50 hours.

274. The method for producing a sulfur-containing polymer according to claim 211, wherein The reaction time of the oxidation step is 10 hours to 24 hours.

275. The method for producing a sulfur-containing polymer according to claim 211, wherein The amount of the oxidizing agent added is 1.5 mol to 100 mol relative to 1 mol of sulfur atoms in the sulfur-containing polymer.

276. The method for producing a sulfur-containing polymer according to claim 211, wherein The amount of the oxidizing agent added is 2 mol to 50 mol relative to 1 mol of sulfur atoms in the sulfur-containing polymer.

277. The method for producing a sulfur-containing polymer according to claim 211, wherein The amount of the oxidizing agent added is 2 mol to 10 mol relative to 1 mol of sulfur atoms in the sulfur-containing polymer.

278. The method for producing a sulfur-containing polymer according to claim 211, wherein The polymer obtained in the oxidation step is washed.

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