Sulfide bond-containing polymer, method for producing the same, sulfide bond-containing polymer composition, and optical material

Abstract

To provide a polymer which has a high refractive index and high transparency, and can be suitably used for optical applications.SOLUTION: A sulfide bond-containing polymer has a structural unit represented by the general formula (1) in the figure. [In the formula, R1 represents a hydrogen atom, a C1-18 alkyl group which may have a substituent, or an aromatic ring-containing group; R2 represents a divalent aromatic ring-containing group.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a sulfide bond-containing polymer, a production method thereof, a sulfide bond-containing polymer composition, and an optical material. More specifically, the present invention relates to a sulfide bond-containing polymer having a high refractive index and high transparency, a production method thereof, a sulfide bond-containing polymer composition, and an optical material. [Background technology]

[0002] Polydithioacetal is expected to be a high refractive index material. Polydithioacetal can be synthesized from an aldehyde monomer and a dithiol monomer, and various synthesis methods have been reported. For example, Patent Document 1 describes that crosslinkable polydithioacetal can be synthesized from a polyfunctional aldehyde monomer and a dithiol monomer. Also, for example, Non-Patent Document 1 describes a synthesis method using an alkyldithiol as the dithiol monomer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2022 / 178254 [Non-patent literature]

[0004] [Patent Document 1] Yang,Y.et al.Angew.Chem.Int.Ed.2023,62,(26),No.e202303039. Summary of the Invention [Problem to be solved by the invention]

[0005] However, the polymers obtained by conventional methods do not have a high refractive index, and are still insufficient for applications requiring a high refractive index of 1.7 or higher, leaving room for improvement. In addition, the polymers have low transparency and are not sufficient materials for optical applications.

[0006] In view of the above-mentioned current situation, an object of the present invention is to provide a polymer that has a high refractive index and high transparency and can be suitably used for optical applications. [Means for solving the problem]

[0007] The present inventors have conducted extensive research into high refractive index materials and have found that the inclusion of specific structural units containing a dithioacetal skeleton results in a polymer that has a high refractive index and excellent transparency and is suitable for use as an optical material, leading to the completion of the present invention.

[0008] That is, the present invention includes the following aspects. <1> A sulfide bond-containing polymer characterized by having a structural unit represented by the following general formula (1):

[0009] [ka]

[0010] (In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aromatic ring-containing group. 2 represents an aromatic ring-containing group. <2> The above-mentioned polymer having a weight average molecular weight of 1,000 to 10,000,000. <1> 2. The sulfide bond-containing polymer according to claim 1. <3> The glass transition temperature is 30 to 450°C. <1> or <2> 2. The sulfide bond-containing polymer according to claim 1. <4> The above-mentioned amorphous <1> ~ <3> 1. The sulfide bond-containing polymer according to any one of the above items. <5> The above-mentioned sulfide bond-containing polymer is characterized in that when the sulfide bond-containing polymer is formed into a film having a thickness of 2 μm, the visible light transmittance is 70% or more. <1> ~ <4> 1. The sulfide bond-containing polymer according to any one of the above items. <6> A method for producing a sulfide bond-containing polymer, the method comprising a step of polymerizing a monomer component containing an aldehyde compound and a thiol compound, wherein the aldehyde compound comprises a monoaldehyde compound represented by the following general formula (2), and the thiol compound comprises a dithiol compound represented by the following general formula (3) and / or a trithiol compound represented by the following general formula (4): R 1 -CHO (2) (In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aromatic ring-containing group. HS-R 3 -SH (3) (In the formula, R 3 represents a divalent aromatic ring-containing group. R 4 (SH)3(4) (In the formula, R 4 represents a trivalent aromatic ring-containing group. <7> the above <1> ~ <5> 1. A composition containing a sulfide bond-containing polymer, comprising the sulfide bond-containing polymer according to any one of claims 1 to 9, and a component other than the sulfide bond-containing polymer. <8> the above <7> 1. An optical material comprising the sulfide bond-containing polymer composition according to claim 1. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a sulfide bond-containing polymer having a high refractive index and excellent transparency. The sulfide bond-containing polymer of the present invention has a high refractive index and excellent transparency, and therefore can be suitably used as an optical material. [Brief explanation of the drawings]

[0012] [Figure 1]1 shows DSC curves and X-ray diffraction patterns of the polymer (P1) of Example 1 and the polymer (P3) of Example 3. [Figure 2] 1 shows absorbance spectra of the polymer (P1) of Example 1 and the polymer (P3) of Example 3 by ultraviolet-visible spectroscopic analysis. [Figure 3] 1 shows transmittance spectra of the polymer (P1) of Example 1 and the polymer (P3) of Example 3, as determined by ultraviolet-visible spectroscopic analysis. [Figure 4] 1 is a photograph of a thin film formed using the polymer (P1) of Example 1 and the polymer (P3) of Example 3. [Figure 5] 1 shows DSC curves and X-ray diffraction patterns of the polymer (P1) of Example 1 and the polymer (P4) of Example 4. [Figure 6] 1 shows absorbance spectra of the polymer (P1) of Example 1 and the polymer (P4) of Example 4 by ultraviolet-visible spectroscopic analysis. [Figure 7] 1 is a photograph of a thin film formed using the polymer (P1) of Example 1 and the polymer (P4) of Example 4. [Figure 8] 1 shows differential refractive index spectra of the polymer (P1) of Example 1 and the polymer (P4) of Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below. It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0014] 1. Sulfide bond-containing polymers The sulfide bond-containing polymer of the present invention is characterized by having a structural unit represented by the following general formula (1) (hereinafter also referred to as "structural unit (A)").

[0015] [ka]

[0016] (In the formula, R 1represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aromatic ring-containing group. 2 represents an aromatic ring-containing group. The sulfide bond-containing polymer of the present invention has a high refractive index and excellent transparency, which is presumably due to the high sulfur content and the repeating structure containing methine groups.

[0017] R 1 The alkyl group having 1 to 18 carbon atoms represented by the formula (I) may be linear or branched, but is preferably branched since it tends to provide higher transparency. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms, since this tends to increase the refractive index.

[0018] R 1 Examples of the substituent that the alkyl group having 1 to 18 carbon atoms represented by the following formula may have include a halogen atom, an alkoxy group, an aryl group, a sulfur-containing substituent, and a reactive functional group.

[0019] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a bromine atom and an iodine atom are preferred because they have a higher refractive index.

[0020] Examples of the alkoxy group include a methoxy group, an ethoxy group, etc. The number of carbon atoms in the alkoxy group is preferably 1 to 18, and more preferably 1 to 12, since this tends to increase the refractive index.

[0021] Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, etc. The number of carbon atoms in the aryl group is preferably 2 to 50, more preferably 4 to 40, and even more preferably 6 to 30, since this tends to increase the refractive index.

[0022] Examples of the sulfur-containing substituent include an alkylthio group, an arylthio group, a hydrocarbon sulfonyl group, etc. The number of carbon atoms in the sulfur-containing substituent is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, since the refractive index tends to be higher.

[0023] Examples of the alkylthio group include a methylthio group, an ethylthio group, etc. The number of carbon atoms in the alkylthio group is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, since the refractive index tends to be higher.

[0024] Examples of the arylthio group include a phenylthio group, a naphthylthio group, etc. The number of carbon atoms in the arylthio group is preferably 6 to 24, more preferably 6 to 18, and even more preferably 6 to 12, since the refractive index tends to be higher.

[0025] The hydrocarbon sulfonyl group is a group represented by -SO2R (wherein R represents a hydrocarbon group). The hydrocarbon group represented by R is preferably an alkyl group or an aryl group, more preferably an alkyl group from the viewpoint of solubility during the reaction, and more preferably an aryl group from the viewpoint of a high refractive index and heat resistance. In the aryl group, at least one hydrogen atom in the aromatic ring of the aryl group may be substituted with, for example, an alkyl group having 1 to 6 carbon atoms. The hydrocarbon group represented by R preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.

[0026] Examples of the hydrocarbon sulfonyl group include alkylsulfonyl groups such as a methylsulfonyl group, and arylsulfonyl groups such as a phenylsulfonyl group and a p-toluenesulfonyl group. Among these, arylsulfonyl groups are preferred because of their higher heat resistance.

[0027] Examples of the reactive functional group include acidic functional groups such as a carboxyl group (-COOH), a phosphate group (-OPO(OH)), a hydroxyl group (-OH), a sulfo group (-SOH), a sulfate group (-OSOH), a phosphonic acid group (-PO(OH)), a phosphinic acid group (-PO(OH)-), and a thiol group (mercapto group) (-SH); basic functional groups such as an amino group, an ammonium group, an imino group, an amide group, an imide group, a maleimide group, and a cyano group; curable functional groups such as a group having a reactive unsaturated bond (for example, a group having a reactive double bond; representative examples include a vinyl group, a (meth)acryloyl group, an allyl group, and a methallyl group) and a group having a reactive ionic bond (for example, a group having a reactive cyclic ether group or a group having a reactive cyclic thioether; representative examples include an epoxy group, an oxetane group, and an episulfide (thiirane)); a nitro group; a nitroso group; and groups containing these functional groups.

[0028] Examples of the groups containing these functional groups include groups having the above-mentioned acidic functional group, basic functional group, curable functional group, nitro group, or nitroso group and a binding chain. Examples of the binding chain include divalent hydrocarbon groups such as alkylene groups and arylene groups, ether, ester, carbonyl, and amide binding groups, and groups formed from combinations of these.

[0029] Among them, the above R 1 As a substituent that the alkyl group represented by the formula (I) may have, a sulfur-containing substituent, a nitro group, a cyano group, a hydroxyl group, a halogen atom, or an alkoxy group is preferable, a sulfur-containing substituent, a nitro group, a cyano group, or a halogen atom is more preferable, and a sulfur-containing substituent or a halogen atom is even more preferable, in that the refractive index is likely to be high.

[0030] Also, the above R 1 As the substituent that the alkyl group represented by the formula (I) may have, a hydrocarbon sulfonyl group is preferred, and an aryl sulfonyl group is more preferred, in terms of further improving the heat resistance of the polymer.

[0031] Above R 1The alkyl group represented by the following formula may have one or more kinds of substituents. The number of substituents on the alkyl group may be one or two or more.

[0032] R 1 The aromatic ring-containing group represented by the formula (I) is not particularly limited as long as it is a group containing an aromatic ring, and may be a group consisting of an aromatic ring, or a group containing an aromatic ring and a bond such as a hydrocarbon chain or -S-. The aromatic ring may be monocyclic or polycyclic, may contain a heteroatom, or may have a substituent.

[0033] Examples of the monocyclic aromatic ring-containing group include monocyclic aromatic hydrocarbon groups such as a phenyl group, and monocyclic aromatic heterocyclic groups. Examples of the monocyclic aromatic heterocyclic group include monovalent groups obtained by removing one hydrogen atom from a monocyclic heteroaromatic compound such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, triazole, thiazole, thiadiazole, tetrazole, etc. Among these, monovalent groups obtained by removing one hydrogen atom from the aromatic ring of the monocyclic heteroaromatic compound are preferred, from the viewpoint that the sulfide bond-containing polymer is likely to have a high refractive index.

[0034] The rings constituting the polycyclic aromatic ring-containing group may be condensed, may be bonded by a single bond, or may be linked in a manner that shares one carbon atom. Furthermore, the rings constituting the polycyclic aromatic ring-containing group only need to contain an aromatic ring, and may be a group consisting of only aromatic rings, or a group consisting of aromatic rings and non-aromatic rings.

[0035] Examples of the polycyclic aromatic ring-containing group include monovalent groups obtained by removing one hydrogen atom from fused ring hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, tetracene, fluorene, and azulene; bonded ring hydrocarbon compounds such as biphenyl and terphenyl; and polycyclic heteroaromatic compounds containing hetero atoms such as carbazole, benzoxazole, purine, benzofuran, isobenzofuran, benzothiophene, benzotriazole, isobenzothiophene, indole, isoindole, benzimidazole, and benzothiazole. From the viewpoint that the sulfide bond-containing polymer is likely to have a high refractive index, monovalent groups obtained by removing one hydrogen atom from the aromatic ring of the fused ring hydrocarbon compounds, bonded ring hydrocarbon compounds, and polycyclic heteroaromatic compounds are preferred.

[0036] The aromatic ring-containing group may have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a sulfur-containing substituent, or a reactive functional group.

[0037] The halogen atom, alkoxy group, aryl group, sulfur-containing substituent, and reactive functional group are the same as those described above in R 1 The substituents are the same as those that may be possessed by the alkyl group represented by the following formula:

[0038] Examples of the alkyl group which may be a substituent on the aromatic ring-containing group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a hexyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8.

[0039] Examples of the aralkyl group that may be a substituent on the aromatic ring-containing group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenyloctyl group, etc. The number of carbon atoms in the aralkyl group is preferably 3 to 50, more preferably 5 to 40, and even more preferably 7 to 30.

[0040] Among them, R 1 is preferably an aromatic ring-containing group, more preferably a phenyl group, naphthyl group, biphenyl group, carbazole group, or fluorene group which may have a substituent, and even more preferably a phenyl group, naphthyl group, or biphenyl group which may have a substituent, in that the refractive index tends to be higher. As the substituent, a halogen atom, an alkoxy group, or a sulfur-containing substituent is preferred in that it provides a higher refractive index and higher transparency, and a hydrocarbon sulfonyl group is more preferred in that it further improves the heat resistance of the polymer.

[0041] R 2 represents an aromatic ring-containing group. 2 Examples of the aromatic ring-containing group represented by the formula (I) include the above-mentioned R 1 or a divalent aromatic ring-containing group obtained by removing one hydrogen atom from an aromatic ring-containing group represented by the above-mentioned R 1 Examples of such a group include a trivalent aromatic ring-containing group obtained by removing two hydrogen atoms from an aromatic ring-containing group represented by the following formula: 1 or a divalent aromatic ring-containing group obtained by removing one hydrogen atom from the aromatic ring of an aromatic ring-containing group represented by the above-mentioned R 1 A trivalent aromatic ring-containing group obtained by removing two hydrogen atoms from the aromatic ring of an aromatic ring-containing group represented by the following formula is preferred.

[0042] R 2 The aromatic ring-containing group represented by the following formula (I) preferably contains a sulfur atom. By containing a sulfur atom, the refractive index of the polymer becomes even higher.

[0043] R 2 Preferred examples of the aromatic ring-containing group represented by the formula (a) below or the aromatic ring-containing group represented by the formula (b) below are given. -R a1 -(SR a2 ) n - (a) (In the formula, R a1 and Ra2 are the same or different and represent a divalent aromatic ring-containing group; and n represents 0 or 1.

[0044] [ka]

[0045] (In the formula, R b1 represents a trivalent aromatic ring-containing group. b2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or a monovalent aromatic ring-containing group. b3 represents a divalent aromatic ring-containing group, and n represents an integer of 0 or 1 or more.

[0046] R in the above general formula (a) a1 and R a2 The divalent aromatic ring-containing group represented by the formula (I) includes the above-mentioned R 1 Examples of such a divalent aromatic ring-containing group include a divalent aromatic ring-containing group obtained by removing one more hydrogen atom from the aromatic ring of a monovalent aromatic ring-containing group represented by the following formula: The divalent aromatic ring-containing group is preferably a divalent aromatic hydrocarbon group which may have a substituent, and more preferably a phenylene group which may have a substituent, in that the refractive index becomes even higher. In the above general formula (a), n is preferably 1, since this results in a higher refractive index.

[0047] In the above general formula (b), R b1 The trivalent aromatic ring-containing group represented by the formula (I) includes the above-mentioned R 1 and trivalent aromatic ring-containing groups obtained by removing two more hydrogen atoms from the aromatic ring of a monovalent aromatic ring-containing group represented by the formula: b1 The trivalent aromatic ring-containing group represented by the formula (I) is preferably a trivalent aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent, and more preferably a trivalent monocyclic aromatic hydrocarbon group or monocyclic aromatic heterocyclic group which may have a substituent. The trivalent aromatic hydrocarbon group or monocyclic aromatic heterocyclic group preferably has 3 to 50 carbon atoms, more preferably 3 to 40 carbon atoms, and even more preferably 3 to 30 carbon atoms.

[0048] In the above general formula (b), R b2 The alkyl group having 1 to 18 carbon atoms and optionally having a substituent represented by the formula (I) is the same as the above-mentioned R 1 Examples of the groups include the same groups represented by the following formula:

[0049] In the above general formula (b), R b2 The monovalent aromatic ring-containing group represented by the formula (I) includes the above-mentioned R 1 Examples of the monovalent aromatic ring-containing group include groups similar to those represented by the following formula: The monovalent aromatic ring-containing group is preferably a monovalent aromatic hydrocarbon group which may have a substituent. The monovalent aromatic hydrocarbon group preferably has 6 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, and even more preferably 6 to 30 carbon atoms.

[0050] In the above general formula (b), R b3 The divalent aromatic ring-containing group represented by the formula (I) includes the above-mentioned R 1 Examples of such divalent aromatic ring-containing groups include divalent aromatic ring-containing groups obtained by removing one more hydrogen atom from the aromatic ring of a monovalent aromatic ring-containing group represented by the following formula: Preferred examples of such divalent aromatic ring-containing groups include aromatic ring-containing groups represented by the following general formula (a) or divalent aromatic hydrocarbon groups or aromatic heterocyclic groups which may have a substituent. The divalent aromatic hydrocarbon group or aromatic heterocyclic group preferably has 3 to 50 carbon atoms, more preferably 3 to 40 carbon atoms, and even more preferably 3 to 30 carbon atoms.

[0051] In the above general formula (b), n is preferably an integer of 0 to 10,000, and more preferably an integer of 0 to 1,000.

[0052] Among them, R 2 is preferably an aromatic ring-containing group represented by the above general formula (a), since this tends to further increase the refractive index.

[0053] The sulfide bond-containing polymer may have one or more types of the structural unit (A). The content of the structural unit (A) in the sulfide bond-containing polymer is preferably 1 to 100 mol %, more preferably 10 to 100 mol %, even more preferably 30 to 100 mol %, and particularly preferably 50 to 100 mol %, relative to 100 mol % of all structural units in the polymer.

[0054] The sulfide bond-containing polymer is a polymer having the structural unit (A) as a repeating unit, but may also contain a structural unit (B) other than the structural unit (A). Examples of the structural unit (B) include phenylene, biphenylene, fluorene, and triazine.

[0055] The sulfide bond-containing polymer may have at least one thiol group (-SH) at its terminal, but the thiol group (-SH) present at the terminal of the sulfide bond-containing polymer is preferably blocked in order to improve the thermal stability of the polymer. Examples of methods for blocking the thiol group include acylation (e.g., acetylation, benzoylation, pivaloylation, etc.), alkylation, tritylation, benzylation, silylation, and acetalization. Among these, acylation is preferred in terms of ease of reaction, and acetylation is more preferred. For example, when a thiol group (-SH) is acetylated, the terminal structure becomes -S-CO-CH3.

[0056] The acetylation method is not particularly limited, and examples thereof include known methods such as a method in which the sulfide bond-containing polymer having a thiol terminal is reacted with acetic anhydride in the presence of a basic compound to acetylate the thiol terminal. Examples of the basic compound include triethylamine, N,N-diisopropylethylamine, and pyridine. Specific acetylation methods will be described later in the section on the production method of a sulfide bond-containing polymer.

[0057] The weight-average molecular weight of the sulfide bond-containing polymer is preferably 1,000 to 10,000,000, more preferably 2,500 to 10,000,000, and even more preferably 10,000 to 10,000,000, in terms of increasing the glass transition temperature (Tg). The weight-average molecular weight can be determined by measurement using gel permeation chromatography (GPC) in polystyrene equivalent, and specifically, can be determined by the method described in the examples below.

[0058] From the viewpoint of excellent heat resistance and moldability in optical materials, the glass transition temperature (Tg) of the sulfide bond-containing polymer is preferably 30 to 450° C., more preferably 60 to 400° C., and even more preferably 70 to 350° C. The glass transition temperature can be determined by a method in which a differential scanning calorimeter (DSC) is used to obtain a DSC curve by heating from room temperature to 500° C. (heating rate: 20° C. / min) in a nitrogen gas atmosphere, and the DSC curve is evaluated by determining the intersection point between the baseline and the tangent at the inflection point.

[0059] The sulfide bond-containing polymer is preferably amorphous. Being amorphous improves transparency. Whether the sulfide bond-containing polymer is amorphous or not can be confirmed by powder X-ray diffraction measurement. Specifically, when an X-ray diffraction pattern obtained by powder X-ray diffraction measurement (2θ=10 to 60 degrees) is measured, it is judged whether a diffraction line representing a crystalline peak can be confirmed. If no crystalline peak can be confirmed, it can be determined that the polymer is amorphous.

[0060] The sulfide bond-containing polymer preferably has a visible light transmittance of 70% or more when made into a film having a thickness of 2 μm and made of the sulfide bond-containing polymer. The visible light transmittance of the sulfide bond-containing polymer can be determined by preparing a 2 μm thick film made of the sulfide bond-containing polymer and measuring the transmittance of light with a wavelength of 400 nm using a spectrophotometer (for example, a JASCO V-700 series ultraviolet-visible-infrared spectrophotometer). The transmittance is a parallel beam transmittance. If the measurement sample does not contain a substrate (a 2 μm thick film only), air is used as the blank; if the sample contains a substrate, the substrate is used as the blank, and the transmittance of a 2 μm thick film made of a sulfide bond-containing polymer can be determined. The film thickness can be measured using a film thickness meter. The visible light transmittance is more preferably 80% or more, and even more preferably 85% or more.

[0061] The refractive index of the sulfide bond-containing polymer is preferably 1.60 or more. When the refractive index is in the above range, the polymer can be suitably used for a wide variety of applications, including optical materials (members). The refractive index is more preferably 1.65 or more, and even more preferably 1.70 or more. The refractive index can be determined by forming a film having a thickness of 50 nm using the polymer as a measurement sample and measuring the film using a spectroscopic ellipsometer UVISEL (manufactured by HORIBA Scientific) with Na D line (589 nm).

[0062] The Abbe number of the sulfide bond-containing polymer is preferably 10 or more. When the Abbe number is within the above range, the light dispersion is small and the polymer can be used as an optical material (member) suitable for lenses. The Abbe number is more preferably 13 or more, and even more preferably 15 or more. The Abbe number can be calculated by forming a film using the polymer in the same manner as in measuring the refractive index, measuring the refractive index at D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm) using the spectroscopic ellipsometer, and then using the following calculation formula. Abbe number (vD) = (nD-1) / (nF-nC) In the formula, nD, nF, and nC represent the refractive indices at the Fraunhofer D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm), respectively.

[0063] 2. Method for producing sulfide bond-containing polymer The method for producing the sulfide bond-containing polymer is not particularly limited as long as it is a method that can produce the above-mentioned polymer. However, examples of methods that can efficiently produce a polymer include a method that includes a step of polymerizing monomer components containing an aldehyde compound and a thiol compound, wherein the aldehyde compound includes a monoaldehyde compound represented by the following general formula (2), and the thiol compound includes a dithiol compound represented by the following general formula (3) and / or a trithiol compound represented by the following general formula (4). R 1 -CHO (2) (In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aromatic ring-containing group. HS-R 3 -SH (3) (In the formula, R 3 represents a divalent aromatic ring-containing group. R 4 (SH)3(4) (In the formula, R 4 represents a trivalent aromatic ring-containing group.

[0064] Such a method for producing a sulfide bond-containing polymer, which comprises a step of polymerizing a monomer component containing an aldehyde compound and a thiol compound, wherein the aldehyde compound comprises a monoaldehyde compound represented by the general formula (2) above, and the thiol compound comprises a dithiol compound represented by the general formula (3) above and / or a trithiol compound represented by the general formula (4) above, also constitutes one aspect of the present invention.

[0065] The above production method includes a step of polymerizing a monomer component containing an aldehyde compound and a thiol compound. The aldehyde compound includes a monoaldehyde compound represented by the general formula (2). 1 represents R in the structural unit represented by the general formula (1) above. 1 The aldehyde compound may contain two or more kinds of monoaldehyde compounds.

[0066] The aldehyde compound may further include a dialdehyde compound and a trialdehyde compound in addition to the monoaldehyde compound. The dialdehyde compound may be, for example, a compound represented by the general formula (2) R 1 Examples include compounds in which two aldehyde groups (-CHO) are attached to The trialdehyde compound may be, for example, a compound represented by the general formula (2) R 1 An example is a compound with three aldehyde groups attached to it.

[0067] The content of the monoaldehyde compound in the aldehyde compound is preferably 10 mol% or more, more preferably 50 mol% or more, even more preferably 80 mol% or more, and particularly preferably 95 mol% or more, relative to 100 mol% of the aldehyde compound.

[0068] The thiol compound includes a dithiol compound represented by the general formula (3) and / or a trithiol compound represented by the general formula (4). 3 The divalent aromatic ring-containing group represented by the formula (1) is R 2 Examples of the divalent aromatic ring-containing group include the same as the divalent aromatic ring-containing group represented by the following formula:

[0069] Examples of the dithiol compound represented by the general formula (3) include 4,4'-thiobisbenzenethiol, 1,4-benzenedithiol, 1,3-benzenedithiol, 4,4'-biphenyldithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 1,5-naphthalenedithiol, 1,6-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol, 6-(methylthio)- Examples thereof include 1,3,5-triazine-2,4-dithiol, 6-(benzylthio)-1,3,5-triazine-2,4-dithiol, 6-phenylamino-1,3,5-triazine-2,4-dithiol, 6-(methyl(phenyl)amino)-1,3,5-triazine-2,4-dithiol, 6-(diphenylamino)-1,3,5-triazine-2,4-dithiol, 6-phenyl-1,3,5-triazine-2,4-dithiol, and 6-methoxy-1,3,5-triazine-2,4-dithiol.

[0070] R in the above general formula (4) 4 The trivalent aromatic ring-containing group represented by the formula (1) is R 2 Examples of the trivalent aromatic ring-containing group include the same as the trivalent aromatic ring-containing group represented by the following formula:

[0071] Examples of the trithiol compound represented by the general formula (4) include 1,3,5-benzenetrithiol, 1,3,5-triazine-2,4,6-thiol, 1,3,6-naphthalenedithiol, 1,4,6-naphthalenedithiol, and 1,3,7-naphthalenedithiol.

[0072] The thiol compound may further include a monothiol compound in addition to the dithiol compound and trithiol compound. The monothiol compound is, for example, R in general formula (3) representing the dithiol compound. 3 Examples include compounds with one thiol group (-SH) attached to the .

[0073] Among the thiol compounds, the total content of the dithiol compounds and trithiol compounds is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 85 mol% or more, and particularly preferably 100 mol%, relative to 100 mol% of the thiol compounds.

[0074] The total content of the aldehyde compound and the thiol compound in the monomer component is preferably 30 mol % or more, more preferably 50 to 100 mol %, and even more preferably 85 to 100 mol %, based on 100 mol % of the total monomer component.

[0075] The molar ratio of the aldehyde groups in the aldehyde compound to the thiol groups in the thiol compound is preferably 40 / 60 to 25 / 75, and more preferably 35 / 65 to 25 / 75, since this tends to increase the refractive index.

[0076] The content ratio (molar ratio) of the aldehyde compound to the dithiol compound is preferably 70 / 30 to 30 / 70, more preferably 65 / 35 to 35 / 65, and even more preferably 60 / 40 to 40 / 60, since this tends to increase the refractive index.

[0077] The content ratio (molar ratio) of the monoaldehyde compound to the dithiol compound is preferably 70 / 30 to 30 / 70, more preferably 65 / 35 to 35 / 65, and even more preferably 60 / 40 to 40 / 60, since this tends to increase the refractive index.

[0078] The above-mentioned monomer component may further contain a compound capable of forming the above-mentioned structural unit (B).

[0079] The polymerization method is not particularly limited, and examples thereof include a method in which the monomer components are reacted by heating in the presence of a solvent and a catalyst.

[0080] Examples of the solvent include alcohol-based solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and γ-butyrolactone; ether-based solvents such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), and tetrahydrofuran (THF); aromatic hydrocarbon-based solvents such as toluene and xylene; halogenated hydrocarbon-based solvents such as chlorobenzene, fluorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and benzotrifluoride; amide-based solvents such as dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone; dimethyl sulfoxide (DMSO), nitromethane, and the like. The solvents may be used alone or in combination. Among these, halogenated hydrocarbon-based solvents are preferred.

[0081] The catalyst is preferably an acid catalyst, and examples thereof include inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid, oxalic acid, benzoic acid, phosphonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonic acid, 10-camphorsulfonic acid, and p-toluenesulfonic acid. The solvents may be used alone or in combination of two or more. Among these, p-toluenesulfonic acid is preferred.

[0082] In the above reaction, in addition to the above-mentioned solvent and catalyst, other additives that are usually used may be used.

[0083] The above reaction may be carried out in air or in an inert gas atmosphere.

[0084] The reaction temperature is not particularly limited, but is preferably −20 to 250° C., more preferably 0 to 200° C., and even more preferably 5 to 150° C., in that the polymerization rate is fast and side reactions are unlikely to occur. The reaction time is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.5 to 50 hours, and even more preferably 1 to 25 hours, in terms of excellent productivity.

[0085] The above production method may include steps other than the polymerization step, such as a step of reacting a polymer with a sulfonating agent and a reducing substance, an oxidation step, an end-capping step, and a purification step.

[0086] (Step of reacting sulfonating agent and reducing substance) If the above production method further comprises a step of reacting the polymer with a sulfonating agent and a reducing substance, a mercapto group can be introduced into the polymer. By reacting the polymer with a sulfonating agent and a reducing substance, a sulfonyl group is introduced by the sulfonating agent, and the sulfonyl group is reduced to a thiol group by the action of the reducing substance, which is thought to be the mechanism by which the reaction proceeds.

[0087] Examples of the sulfonating agent and reducing substance include the sulfonating agents and reducing substances described in paragraphs

[0096] and

[0097] of WO 2022 / 270533. In addition, for the method of reacting the above polymer with a sulfonating agent and a reducing substance, for example, the method described in paragraphs

[0099] to

[0102] of WO 2022 / 270533 can be referenced.

[0088] (oxidation process) The oxidation step is a step of oxidizing the polymer obtained in the polymerization step. When the production method of the present invention further includes the oxidation step, sulfur atoms in sulfide groups (-S-) in the main chain of the polymer are oxidized to form "-SO-" or "-SO2-", which makes it possible to control the refractive index, solubility, etc. of the polymer.

[0089] For the oxidizing agent used in the oxidation step and the method for oxidizing the polymer, for example, the methods described in paragraphs

[0108] to

[0115] of WO 2022 / 270533 can be referenced.

[0090] (Terminal sealing process) The end-capping step is a step of capping the thiol groups (-SH) at the ends of the polymer. Capping the thiol groups at the ends of the polymer improves thermal stability. Therefore, the above-mentioned production method preferably includes the end-capping step. Examples of methods for terminal blocking include acylation (e.g., acetylation, benzoylation, pivaloylation, etc.), alkylation, tritylation, benzylation, silylation, and acetalization of a thiol group. Among these, acylation is preferred in terms of ease of reaction, and acetylation is more preferred.

[0091] The acetylation is not particularly limited and may be carried out by a known method, for example, a method in which acetic anhydride is added to a sulfide bond-containing polymer having a terminal thiol group in the presence of the above-mentioned basic compound to cause a reaction.

[0092] The amount of acetic anhydride added in the acetylation reaction may be at least an equimolar amount relative to the terminal thiol group.

[0093] The amount of the basic compound added is preferably at least an equimolar amount relative to the amount of acetic anhydride.

[0094] The reaction temperature is not particularly limited and is usually 0 to 100°C, preferably 10 to 60°C, and more preferably 20 to 50°C. The reaction time is not particularly limited, and is usually 10 minutes to 6 hours, preferably 10 minutes to 3 hours, and more preferably 10 minutes to 1 hour.

[0095] (purification process) When the production method of the present invention further comprises a purification step, the amount of catalyst residues and the like contained in the polymer solution can be reduced, and as a result, the heat resistance and the like of the polymer can be improved. As the purification method, a conventionally known purification method can be used. For example, it is preferable to use a reprecipitation method. The reprecipitation method is not particularly limited, but examples thereof include a method in which a polymer solution is dropped into a poor solvent such as methanol to precipitate the polymer, which is then filtered to obtain a precipitate, and the obtained precipitate is washed with water or a lower alcohol such as methanol.

[0096] In the purification step, a method using a conventionally known adsorbent such as activated carbon can be used to remove components derived from the oxidizing agent used in the oxidation step and impurity components derived from the polymerization step. It is also preferable to use the reprecipitation method and the method using an adsorbent in combination.

[0097] The timing of carrying out the purification step is not particularly limited, and the purification step may be carried out before or after the oxidation step. That is, the polymer obtained after the purification step may be subjected to the oxidation step, or the purification step may be carried out on a composition containing the polymer obtained in the oxidation step. In particular, when the production method includes the oxidation step, it is preferable to carry out the purification step on a composition containing the polymer obtained after both the polymerization step and the oxidation step, since this allows the production of a sulfide bond-containing polymer with fewer impurities derived from the raw materials used in each step.

[0098] Furthermore, when the production method includes the step of reacting a sulfide bond-containing polymer with the sulfonating agent and the reducing substance and the purification step, the purification step may be performed before or after the step of reacting a sulfide bond-containing polymer with the sulfonating agent and the reducing substance, but it is preferable to perform the purification step after the step, since this allows the sulfide bond-containing polymer to have fewer impurities derived from the raw materials used in each step to be obtained.

[0099] When the production method includes the step of reacting the sulfonating agent and the reducing substance with the sulfide bond-containing polymer and the oxidation step, either of these steps may be carried out first, but it is preferable to carry out the oxidation step first from the viewpoint of suppressing side reactions.

[0100] The method for producing the sulfide bond-containing polymer may further include other steps in addition to the steps described above. Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a solvent substitution step, a dissolution step, etc. These steps can be carried out by known methods.

[0101] 3. Sulfide bond-containing polymer composition The sulfide bond-containing polymer of the present invention can be combined with other components to form a sulfide bond-containing polymer composition. The other components are not particularly limited and may be appropriately selected from known components depending on the purpose and use of the sulfide bond-containing polymer composition. Such a sulfide bond-containing polymer composition comprising the above-mentioned sulfide bond-containing polymer and other components other than the sulfide bond-containing polymer also constitutes one aspect of the present invention.

[0102] The content of the sulfide bond-containing polymer is preferably 1 to 99% by mass, more preferably 3 to 90% by mass, and even more preferably 5 to 80% by mass, based on 100% by mass of the total solid content of the sulfide bond-containing polymer composition. The total solid content refers to the total amount of components excluding volatile components such as solvents.

[0103] (1) Composition containing inorganic particles The sulfide bond-containing polymer composition preferably contains inorganic particles. By containing inorganic particles, it becomes easier to control various physical properties of the composition of the present invention, such as optical properties such as refractive index, dielectric properties, and thermal conductivity. An inorganic particle-containing composition containing the sulfide bond-containing polymer and inorganic particles is one preferred embodiment of the composition of the present invention.

[0104] Examples of materials constituting the inorganic particles include metals, inorganic oxides, inorganic nitrides, inorganic carbides, inorganic sulfides, inorganic hydroxides, etc. The inorganic particles may be composed of one of these materials or may contain two or more of these materials.

[0105] Examples of the metal include lithium, sodium, potassium, boron, magnesium, calcium, manganese, strontium, barium, titanium, zirconium, iron, cobalt, nickel, copper, zinc, aluminum, tin, silicon, cesium, and indium.

[0106] The inorganic oxide is preferably a metal oxide containing a metal element, such as a single metal oxide made of one metal element, a composite oxide made of two or more metal elements, or a solid solution oxide in which a different element is dissolved in the single metal oxide or the composite oxide.

[0107] The different element may be a metal element or a non-metal element other than oxygen, such as nitrogen or fluorine. Examples of the metal element include the metal elements described above.

[0108] 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.

[0109] 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.

[0110] The solid solution oxides include those in which different metal elements and / or non-metal elements other than oxygen, such as nitrogen and fluorine, are solid-solved in the single metal oxides or composite oxides.

[0111] The inorganic nitride is preferably a metal nitride, and examples thereof include boron nitride, carbon nitride, and aluminum nitride.

[0112] The inorganic carbide is preferably a metal carbide, such as silicon carbide, calcium carbide, titanium carbide, or boron carbide.

[0113] The inorganic sulfide is preferably a metal sulfide, such as copper sulfide, zinc sulfide, or cadmium sulfide.

[0114] The inorganic hydroxide is preferably a metal hydroxide, such as aluminum hydroxide, magnesium hydroxide, or barium hydroxide.

[0115] Among the above, inorganic oxides are preferred as materials constituting the inorganic particles because they have a wide band gap (transparent to visible light), and metal oxides are more preferred. Furthermore, among the inorganic particles, oxides containing Ti, Zr, Ce, Zn, In, Al, Si, and Sn as the main metal element are more preferred because they have no or little absorption in the visible light region, making it easier to obtain compositions in which coloring due to the inorganic particles is suppressed. Titanium oxide (TiO2), zirconium oxide (ZrO2), cerium oxide (CeO2), zinc oxide (ZnO), indium oxide (In2O3), aluminum oxide (Al2O3), silicon oxide (SiO2), and tin oxide (SnO2) are particularly preferred.

[0116] Among the materials constituting the inorganic particles, zirconium oxide, titanium oxide, and silicon oxide are more preferred in terms of ease of controlling the refractive index of the composition of the present invention and of enabling the composition of the present invention to have a low linear expansion, and zirconium oxide and titanium oxide are more preferred in terms of improving the refractive index of the composition of the present invention. Furthermore, perovskite-type complex oxides are preferred in terms of their high dielectric constant and ease of imparting ferroelectric properties, piezoelectric properties, and the like to the composition of the present invention. Boron nitride, aluminum hydroxide, and aluminum titanate are preferred in terms of their high thermal conductivity and ease of improving the heat dissipation properties of the composition of the present invention.

[0117] From the viewpoint of imparting antistatic properties or electrical conductivity to the composition of the present invention while suppressing coloration due to the addition of inorganic particles, the inorganic particles are preferably solid solution oxides in which a different metal element or an additive element such as fluorine is solid-solved in zinc oxide (ZnO), indium oxide (In2O3), or tin oxide (SnO2). For example, zinc oxide in which In, Al, or Ga is solid-solved, indium oxide in which Sn or Ti is solid-solved, or tin oxide in which Sb or F is solid-solved are more preferred.

[0118] The shape of the inorganic particles is not particularly limited, and may be any of amorphous, granular, plate-like, columnar, needle-like, etc., but granular is preferred. The inorganic particles may be surface-treated. The surface treatment is not particularly limited as long as it does not affect the effects of the present invention, and known methods include a method using a silane coupling agent, a method of reacting a compound having a phosphate group, and a method of reacting a compound having a carboxylic acid group. The granular shape refers to a uniform shape with an aspect ratio of 2 or less.

[0119] The inorganic particles preferably have an average particle size of 1 nm or more and 1,000 nm or less. When the average particle size of the inorganic particles is within the above range, light transmittance in the visible light region and the infrared region can be improved. The inorganic particles preferably have an average particle size of 5 nm or more, more preferably 10 nm or more, and more preferably 100 nm or less, and even more preferably 50 nm or less. The average particle size of the inorganic particles is preferably in the range of 1 to 1000 nm, more preferably 5 to 100 nm, and even more preferably 10 to 50 nm.

[0120] The average particle size is determined by observing the inorganic particles with a SEM (magnification 1,000 to 100,000 times, preferably 10,000 times), analyzing the resulting image to determine the particle diameters (circular area equivalent diameters) of approximately 10 to 1,000 individual particles (primary particles), and evaluating the 50% particle size based on the number-based particle size distribution. For the image analysis, known image analysis software (e.g., Mac-View manufactured by Mountech Co., Ltd.) can be used.

[0121] The content of the inorganic particles is not particularly limited and can be appropriately set depending on the intended use and application of the inorganic particle-containing composition. For example, the content of the inorganic particles is preferably 1 to 2000% by mass relative to 100% by mass of the sulfide bond-containing polymer contained in the inorganic particle-containing composition. From the viewpoint of easily adjusting the refractive index of the inorganic particle-containing composition and films and cured products obtained from the composition, and from the viewpoint of easily achieving low linear expansion, the content of the inorganic particles is more preferably 100% by mass or more, and even more preferably 500% by mass or more, relative to 100% by mass of the sulfide bond-containing polymer contained in the inorganic particle-containing composition.

[0122] Furthermore, from the viewpoint of the mechanical strength of the inorganic particle-containing composition and the film or cured product obtained from the composition, the content of the inorganic particles is more preferably 1000% by mass or less, and even more preferably 800% by mass or less, relative to 100% by mass of the sulfide bond-containing polymer contained in the inorganic particle-containing composition.

[0123] The content of the inorganic particles is more preferably in the range of 100 to 1000% by mass, and even more preferably 500 to 800% by mass, relative to 100% by mass of the sulfide bond-containing polymer contained in the inorganic particle-containing composition.

[0124] The inorganic particle-containing composition of the present invention may further contain a polymerizable monomer and / or a solvent, and an inorganic particle-containing composition containing these components is also one of the preferred embodiments of the composition of the present invention.

[0125] Specific examples of the polymerizable monomer will be explained in the section (3) Polymerizable composition below, and specific examples of the solvent will be explained in the section (2) Solvent-containing composition below.

[0126] (2) Solvent-containing composition The composition of the present invention preferably contains a solvent. By containing a solvent, processability such as thin film formability can be imparted to the composition of the present invention. A solvent-containing composition containing the above-mentioned sulfide bond-containing polymer and a solvent is also one of preferred embodiments of the composition of the present invention.

[0127] The solvent is not particularly limited, and examples thereof include halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, and 1,3-dichlorobenzene; and non-halogenated solvents such as nitromethane, nitrobenzene, benzonitrile, N-methylpyrrolidone, dimethylethyleneurea, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate, benzyl acetate, benzyl alcohol, cyclopentyl methyl ether, cyclohexanone, cyclopentanone, cycloheptanone, toluene, xylene, propylene glycol monomethyl ethyl ether acetate, methyl ethyl ketone, and sulfolane. One or more of these solvents may be used. Of these, non-halogen solvents are preferred, and it is particularly preferred that the solvent contains at least one solvent selected from the group consisting of cyclohexanone, cyclopentanone, propylene glycol monomethyl ethyl ether acetate, methyl ethyl ketone, toluene, xylene, tetrahydrofuran, N-methylpyrrolidone, and the like.

[0128] The content of the solvent in the solvent-containing composition is not particularly limited, but the content of the solvent is preferably 10 to 20,000 mass%, more preferably 100 to 10,000 mass%, and even more preferably 50 to 5,000 mass%, relative to 100 mass% of the sulfide bond-containing polymer contained in the solvent-containing composition.

[0129] The solvent-containing composition may further contain a polymerizable monomer and / or the inorganic particles, etc., and a solvent-containing composition containing these components is also one of the preferred embodiments of the composition of the present invention.

[0130] (3) Polymerizable composition The composition of the present invention can be used as either a thermoplastic composition or a polymerizable composition, but is preferably used as a polymerizable composition. To be used as a polymerizable composition, the composition of the present invention preferably contains a polymerizable monomer. By including a polymerizable monomer, it is possible to impart curability to the composition of the present invention, thereby improving the mechanical strength, heat resistance, etc. of films obtained from the composition. A polymerizable composition containing the sulfide bond-containing polymer and a polymerizable monomer is also one preferred embodiment of the composition of the present invention.

[0131] The polymerizable monomer is preferably a compound having, in the molecule, one or more groups capable of reacting with the reactive functional group possessed by the sulfide bond-containing polymer. The two or more groups capable of reacting with the reactive functional group possessed by the polymerizable monomer may be the same or different.

[0132] The polymerizable monomer is not particularly limited as long as it is a monomer having a polymerizable functional group, and examples thereof include a compound having an ethylenically unsaturated group, a compound having two or more ring-opening polymerizable groups in the molecule, a compound containing two or more isocyanate groups in the molecule, and a compound containing two or more oxazoline groups in the molecule.

[0133] The compound having an ethylenically unsaturated group is not particularly limited, and examples thereof include compounds having a radical curable group and / or an addition curable group such as an acrylic group, a methacrylic group, an acrylamide group, a methacrylamide group, an allyl group, or a vinyl group or a maleimide group. Specific examples thereof include aromatic vinyl monomers such as divinylbenzene; aromatic allyl monomers such as diallyl phthalate and diallylbenzene phosphonate; (meth)acrylamide monomers such as N-benzyl(meth)acrylamide and 4-acryloylmorpholine; vinyl ester monomers such as vinyl acetate; vinyl thioethers such as bis(4-vinylthiophenyl) sulfide and phenyl vinyl sulfide;(Di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, benzyl (meth)acrylate, 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, (9H-fluorene-9,9-diyl)bis(4,1-phenylene)di(meth)acrylate di(meth)acrylates having a fluorene skeleton such as tris[2-(meth)acryloyloxyethyl]triazinebenzyl(meth)acrylate, phenoxyethyl(meth)acrylate, (1-naphthyl)methyl(meth)acrylate, 2-naphthalene(meth)acrylic acid, (decahydro-1,4:5,8-dimethanonaphthalen)-2-yl(meth)acrylate, 4-phenylbenzyl(meth)acrylate, biphenylmethyl such as 2-phenylbenzyl(meth)acrylate Bisphenol A (meth)acrylate, bisphenol A-(EO)-(meth)acrylate, bisphenol S (meth)acrylate, bisphenol S-(EO)-(meth)acrylate Examples of the (meth)acrylic monomers include sulfur-containing (meth)acrylates such as bis(4-methacryloylthiophenyl)sulfide, 1H,1H,2H,2H-heptafluorodecyl (meth)acrylate, and (meth)acrylates having an adamantyl skeleton; triallyl cyanurate; glycidyl (meth)acrylate; and 3,4-epoxycyclohexylmethyl methacrylate.

[0134] The compound having two or more ring-opening polymerizable groups in the molecule is not particularly limited, and examples thereof include compounds having ring-opening polymerizable groups such as an epoxy group, an oxetane group, an ethylene sulfide group, and an aziridine group. Specific examples thereof include aromatic epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene-based epoxy compounds, and aromatic epoxy compounds having a bromo substituent; aliphatic epoxy compounds such as those obtained by a condensation reaction of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol (PEG600) with epihalohydrin; alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epsilon-caprolactone-modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, and bis-(3,4-epoxycyclohexyl)adipate; hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, and hydrogenated bisphenol F type epoxy compounds. hydrogenated epoxy compounds such as epoxide compounds, aliphatic oxetane compounds such as 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane and dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether; phenol novolak oxetane, dioxetane compounds having a biphenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) OXBP), dioxetane compounds having a phenyl skeleton (manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) OXTP), dioxetane compounds having a fluorene skeleton, aromatic oxetane compounds such as tungstate compounds; aliphatic episulfide compounds such as bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) disulfide, and 1,3-bis(2,3-epithiopropylthio)cyclohexane; aromatic episulfide compounds such as 1,2-bis(2,3-epithiopropylthio)benzene and 1,3-bis(2,3-epithiopropylthio)benzene; and mercapto group-containing epithio compounds such as 3-mercaptopropylene sulfide and 4-mercaptobutene sulfide.

[0135] The compound containing two or more isocyanate groups in the molecule is not particularly limited, and examples thereof include aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine triisocyanate, and xylylene diisocyanate; alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and 4,9-bis(isocyanatomethyl)tricyclodecane; and aromatic polyisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenylsulfide-4,4-diisocyanate, and phenylene diisocyanate. Examples of suitable polyisothiocyanate compounds include cyanate compounds; heterocyclic polyisothiocyanate compounds such as 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane; aliphatic polyisothiocyanate compounds such as bis(isothiocyanatoethyl) disulfide; alicyclic polyisothiocyanate compounds such as 3,9-bis(isothiocyanatomethyl)tricyclodecane and 4,8-bis(isothiocyanatomethyl)tricyclodecane; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate; and sulfur-containing heterocyclic polyisothiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-bis(isothiocyanatomethyl)thiophene.

[0136] Examples of compounds containing two or more oxazoline groups in the molecule include 2,2'-(1,3-phenylene)bis-(2-oxazoline) and oxazoline group-containing polymers such as EPOCROS (registered trademark) manufactured by Nippon Shokubai.

[0137] The polymerizable monomer is preferably a compound having an ethylenically unsaturated group, more preferably a compound having a (meth)acrylic group, and even more preferably a (meth)acrylic monomer having an aromatic group.

[0138] The content of the polymerizable monomer in the polymerizable composition is not particularly limited, but the content of the polymerizable monomer is preferably 0.1 to 99% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, relative to 100% by mass of the sulfide bond-containing polymer in the polymerizable composition.

[0139] The polymerizable composition preferably further contains a polymerization initiator. The polymerization initiator is not particularly limited, and may be appropriately selected from conventionally known thermal polymerization initiators and photopolymerization initiators, such as aminobenzoate initiators, acetophenone initiators, benzoin initiators, benzophenone initiators, acylphosphine oxide initiators, oxime ester initiators, and cationic initiators. The polymerization initiator may be commercially available, and examples thereof include aminobenzoate-based initiators such as "Esacure A198," "Omnipol ASA," "Omnirad EDB," and "Omnirad EHA" manufactured by IGM Resins, and "GENOPOL AB-1" and "GENOPOL AB-2" manufactured by Rahn AG; acetophenone-based initiators such as "Omnirad 1173," "Omnirad 127," "Esacure KIP 150," "Esacure KIP 160," and "Omnirad 184" manufactured by IGM Resins; acylphosphine oxide-based initiators such as "Omnirad TPO," "Omnirad TPO-L," and "Omnirad 819" manufactured by IGM Resins; and Omnirad 1312, Omnirad 1314, and Omnirad 1315 manufactured by IGM Resins. Examples of initiators include oxime ester initiators such as "Omnicat 1316" manufactured by IGM Resins, and cationic initiators such as "Omnicat 250" and "Omnicat 432" manufactured by IGM Resins.

[0140] The content of the polymerization initiator is not particularly limited, but is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass, relative to 100% by mass of the polymerizable monomer.

[0141] The polymerizable composition may contain a photosensitizer. The photosensitizer is not particularly limited, and a conventionally known photosensitizer can be appropriately selected and used, for example, thioxanthone-based photosensitizers such as "Omnirad ITX," "Omnirad DETX," and "Omnirad DETX," manufactured by IGM Resins, and coumarin-based photosensitizers such as "Esacure 3644."

[0142] The content of the photosensitizer is not particularly limited, but is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass, relative to 100% by mass of the polymerizable monomer.

[0143] The polymerizable composition may contain an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and a conventionally known ultraviolet absorber may be appropriately selected and used. Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479, and benzotriazole-based ultraviolet absorbers such as TINUVIN 326, TINUVIN 360, TINUVIN 900, TINUVIN 928, and TINUVIN 1130, both manufactured by BASF.

[0144] The polymerizable composition may contain a light stabilizer. The light stabilizer is not particularly limited, and a conventionally known light stabilizer can be appropriately selected and used, for example, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77, ADK STAB LA-81, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-402XP, ADK STAB LA-502XP (all manufactured by ADEKA Corporation), TINUVIN 11 Examples of such an agent include 1FDL, Tinuvin 123, Tinuvin 144 (bis(1,2,2,6,6-pentamethyl-4-piperidyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butylmalonate), Tinuvin 292 (a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate), and Tinuvin 5100 (all manufactured by BASF).

[0145] The polymerizable composition may further contain the inorganic particles, a solvent, etc. A preferred embodiment of the composition of the present invention is one in which the polymerizable composition further contains the inorganic particles and / or a solvent. Preferred examples of the solvent include the same solvents as those used in the solvent-containing composition.

[0146] The method for curing the polymerizable composition is not particularly limited, and can be any conventionally known method such as a heating method (thermal curing) or a method using active energy rays. In the case of a heating method, the heating temperature is not particularly limited, but is preferably 50 to 400°C, and more preferably 100 to 300°C. The heating time is not particularly limited, but is preferably 0.01 to 10 hours, and more preferably 0.1 to 2 hours.

[0147] In the method using active energy rays, ultraviolet rays or electron beams are preferred as the active energy rays, and ultraviolet rays are more preferred. When ultraviolet rays are used, the amount of ultraviolet rays to be irradiated (cumulative exposure amount) is not particularly limited, but is preferably 0.001 to 100 J / cm 2 2It is preferable to irradiate so that the radiation dose is in the range of 0.01 to 50 J / cm. 2 , and more preferably 0.05 to 10 J / cm 2 As the light source, various mercury lamps and the like can be used, but ultra-high pressure mercury lamps and metal halide lamps are preferred. By these curing methods, a cured product of the polymerizable composition can be obtained.

[0148] The present invention also includes a cured product obtained from the polymerizable composition. As described above, the composition of the present invention can take various preferred embodiments depending on the other components.

[0149] (4) Coating composition, molding composition The composition of the present invention can also be suitably used as a coating composition or a molding composition. As the coating composition, various preferred embodiments of the composition of the present invention described above can be used. For example, it is preferable to use the solvent-containing composition, and it is more preferable to use a solvent-containing composition containing a polymerizable monomer, as it is easier to obtain a film made of a cured product. As the coating composition, it is even more preferable to use a solvent-containing composition containing the polymerizable monomer and the inorganic particles. As the coating composition, the polymerizable composition is more preferable.

[0150] The method for applying the coating composition is not particularly limited, and any conventionally known method can be used, among which spin coating, bar coating, squeegee coating, inkjet coating, etc. are preferred.

[0151] The coating thickness is not particularly limited and may be appropriately selected depending on the intended use of the resulting film. For example, when used as an optical material, it is preferable to adjust the coating thickness so that the resulting film has a thickness of 0.1 to 1000 μm. The coating thickness is more preferably 0.5 to 100 μm, and even more preferably 1 to 10 μm.

[0152] It is preferable to heat and / or irradiate with active energy rays the film (coating film) coated with the composition of the present invention. By heating, the solvent contained in the coating film can be evaporated and removed. When the coating composition contains the polymerizable monomer, by heating or irradiating with active energy rays, the crosslinking reaction between the polymerizable monomer contained in the coating film and the sulfide bond-containing polymer can be promoted, and a film made of a cured product can be obtained.

[0153] When a film (coating film) coated with the composition of the present invention is heated, the heating temperature is not particularly limited, but is preferably 50 to 400° C., and more preferably 100 to 300° C. The heating time is not particularly limited, but is preferably 0.01 to 10 hours, and more preferably 0.1 to 2 hours.

[0154] The active energy rays are preferably ultraviolet rays or electron beams, and more preferably ultraviolet rays. When ultraviolet rays are irradiated, the amount of ultraviolet rays (cumulative exposure amount) is not particularly limited, but is preferably 0.001 to 100 J / cm 2 2 It is preferable to irradiate so that the radiation dose is in the range of 0.01 to 50 J / cm. 2 , and more preferably 0.05 to 10 J / cm 2 is. As the light source, various mercury lamps and the like can be used, but an ultra-high pressure mercury lamp or a metal halide lamp is preferred.

[0155] The substrate to which the composition of the present invention is applied is not particularly limited, but examples thereof include light-transmitting substrates such as glass plates, quartz plates, organic resin films, organic resin molded products, and films, sheets, and plates having a transparent inorganic oxide layer on the surface thereof; light-receiving substrates such as Si semiconductor substrates and compound semiconductor substrates such as InGaAs; and light-emitting substrates such as LEDs, organic ELs, and laser diodes (semiconductor lasers).

[0156] When the composition of the present invention is used as a molding composition, the compositions of the various preferred embodiments described above can be used. Among them, it is preferable to use the polymerizable composition or the inorganic particle-containing composition, and it is more preferable to use a polymerizable composition that further contains inorganic particles.

[0157] Examples of the molding method include conventionally known methods, such as injection molding, T-die molding, inflation molding, imprint molding, nanoimprint molding, and other molding methods using a mold or resin mold, and casting.

[0158] When a polymerizable composition is used as the molding composition, it is preferable to heat and / or irradiate with active energy rays after molding, for example, in these molding methods, for the purpose of promoting the crosslinking reaction. The heating temperature and time when heating may be appropriately selected depending on the molding method employed. The same applies to preferred embodiments and conditions for irradiating with active energy rays. By the above method, a material molded into a desired shape, such as a lens, sheet, or film, can be obtained.

[0159] The composition of the present invention can also be used as a thermoplastic material. In this case, the molding method is not particularly limited, and includes methods generally known as thermoplastic resin processing methods, such as injection molding, extrusion molding, T-die molding, and inflation molding. It may also be molded into a desired shape by a casting method, coating method, or the like. The shape is not particularly limited, and includes various known shapes such as lenses, sheets, and films.

[0160] In addition to the sulfide bond-containing polymer, inorganic particles, solvent, polymerizable monomer, etc., the composition of the present invention may contain, for example, pigments, dyes, antioxidants, UV absorbers, resins, reactive diluents, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, adhesion improvers such as coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, defoaming agents, leveling agents, wetting and dispersing agents, anti-settling agents, thickeners and anti-sagging agents, color-flux inhibitors, emulsifiers, slip and scratch prevention agents, anti-skinning agents, drying agents, antifouling agents, antistatic agents, conductive agents (electrostatic assistants), etc. These components may be used alone or in combination of two or more. These components can be appropriately selected from known components and used, and the amounts of these components can be appropriately set.

[0161] When the composition of the present invention is used for an optical material, it may contain other components as appropriate depending on the intended use of the optical material. Specific examples of the other components include ultraviolet absorbers, IR cutters, reactive diluents, pigments, detergents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, and antifoaming agents.

[0162] 4.Applications The sulfide bond-containing polymer and the sulfide bond-containing polymer composition of the present invention are suitably used as optical materials, materials for optical devices, materials for display devices, and the like. Specific examples of such applications include optical materials such as eyeglass lenses, imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and in-vehicle cameras, light beam focusing lenses, light diffusing lenses, and other lenses; LED encapsulants, optical adhesives, optical pressure-sensitive adhesives, optical transmission bonding materials, filters, diffraction gratings, diffractive optical elements, prisms, light guides, watch glasses, and transparent glass and cover glass for display devices; optical device materials such as photosensors (optical sensors (CMOS sensors, TOF sensors, etc.)), photoswitches, LEDs, micro LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, disconnectors, optical splitters, and optical fiber adhesives; and display device materials such as substrates for display elements such as LCDs, organic electroluminescent (EL) displays, and PDPs, color filter substrates, touch panel substrates, index matching materials used in touch panels, etc., display protective films, display backlights, light guide plates, anti-reflection films, anti-fogging films, and light extraction enhancers for LEDs, organic electroluminescent (EL) displays, etc.

[0163] Among these, imaging lenses, filters, diffraction gratings, diffractive optical elements, prisms, light guides, LEDs, micro LEDs, light-emitting elements, color filters, and touch panels are more preferable.

[0164] The sulfide bond-containing polymer and sulfide bond-containing polymer composition of the present invention can also be suitably used as molding materials. The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, the T-die method, inflation method, and other methods generally known as thermoplastic resin processing methods. Furthermore, the polymer may be molded into a desired shape by a casting method, coating method, or other method. The shape is not particularly limited, and examples thereof include various known shapes such as lenses, sheets, and films.

[0165] As described above, the sulfide bond-containing polymer and sulfide bond-containing polymer composition of the present invention have a high refractive index and excellent transparency. Therefore, they can be suitably used in a wide range of applications, including optical applications. An optical material comprising the sulfide bond-containing polymer or sulfide bond-containing polymer composition of the present invention also constitutes one aspect of the present invention. [Example]

[0166] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0167] In the examples, each evaluation was carried out by the following methods. <Weight average molecular weight (Mw), number average molecular weight (Mn)> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were determined by gel permeation chromatography (GPC) under the following conditions. Device 1: Shimadzu CBM-20A. Apparatus 2: Agilent Technologies 1260 Infinity. Detector: Refractive index detector (RI) (Shimadzu Corporation, SPD-20MA) and ultraviolet-visible-infrared spectrophotometer (Shimadzu Corporation, SPD-20MA). Column: TSKgel SuperHM-N, manufactured by Tosoh Corporation. Column temperature: 40°C. Flow rate: 0.3ml / min. Calibration curve: Polystyrene Standards. Eluent: chloroform.

[0168] <Refractive index> To prepare a measurement sample, the obtained polymer powder was mixed with 1,1,2,2-tetrachloroethylene and dissolved. The resulting 30 mg / ml solution was dropped onto a silicon wafer and spin-coated using a program consisting of a slope of 3 seconds, 800 rpm for 10 seconds, a slope of 3 seconds, 2000 rpm for 20 seconds, and a slope of 3 seconds. The wafer was then dried under reduced pressure overnight to prepare a measurement sample consisting of a thin film with a thickness of 50 nm. The measurement sample was measured using a spectroscopic ellipsometer UVISEL (manufactured by HORIBA Scientific) with NaD radiation (589.3 nm).

[0169] <Abbe number> Using the same measurement sample as in the refractive index evaluation method above, the refractive index was measured at D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm) using the spectroscopic ellipsometer, and calculated using the following formula. Abbe number (vD) = (nD-1) / (nF-nC) In the formula, nD, nF, and nC represent the refractive indices at the Fraunhofer D line (589.3 nm), F line (486.1 nm), and C line (656.3 nm), respectively.

[0170] <Visible light transmittance> (Sample preparation) The polymers obtained in the examples and comparative examples were each dissolved in chloroform to a concentration of 10% by mass to prepare a solution. The resulting solution was spin-coated at approximately 200 rpm for 60 seconds onto a glass substrate (S1111, manufactured by Matsunami Glass Industry Co., Ltd.) that has almost no absorption in visible light, and dried at 100°C for 10 minutes to form a thin film (2 μm thick), thereby obtaining a substrate on which the thin film was formed. (Measurement 1: Thin film transmittance) The transmittance of the substrate on which the thin film was formed was measured using a spectrophotometer (V-700 series ultraviolet-visible-infrared spectrophotometer manufactured by JASCO Corporation) at a wavelength of 400 nm, with the substrate as a blank, and the obtained value was taken as the visible light transmittance of the thin film. The film thickness of the thin film was measured using a film thickness meter.

[0171] <1 H-NMR The obtained polymer was subjected to the following conditions: 1 H-NMR measurements were carried out. Apparatus: Nuclear magnetic resonance spectrometer (500 MHz) manufactured by JEOL Ltd. Measurement solvent: deuterated dichloromethane, deuterated chloroform. Sample preparation: Several mg to several tens of mg of the obtained polymer was dissolved in a measurement solvent.

[0172] < 13 C-NMR The obtained polymer was subjected to the following conditions: 13 C-NMR measurements were performed. Apparatus: Nuclear magnetic resonance spectrometer (125 MHz) manufactured by JEOL Ltd. Measurement solvent: deuterated chloroform. Sample preparation: Several tens to several hundreds of mg of the obtained polymer was dissolved in a measurement solvent.

[0173] <ir> For the obtained polymer, IR measurement was carried out under the following conditions. Apparatus: Fourier transform infrared spectrophotometer (FT / IR-6100) manufactured by JASCO. Sample preparation: Approximately 2 mg of the sample was diluted with approximately 300 mg of dry potassium bromide (KBr). The mixture was ground with a mortar and pestle and molded.

[0174] <Glass transition temperature> Using a differential scanning calorimeter (DSC), TA Instruments Q200 (manufactured by TA Instruments), in a nitrogen gas atmosphere, heating from room temperature to 500 °C at a heating rate of 20 °C / min, it was determined by the method of evaluating from the intersection of the baseline and the tangent line at the inflection point of the obtained DSC curve.

[0175] <X-ray diffraction (XRD)> Rigaku RINT-Ultima III 2Θ, 10~60deg Measured with an X-ray source, Cu (CuKα ray, wavelength 1.54 Å).

[0176] <Absorbance> Using a spectrophotometer (UV-visible-infrared spectrophotometer V-700 series manufactured by JASCO Corporation), a sample solution (concentration: 0.1 mM, solvent: chloroform) was placed in a quartz cell (optical path length 1 cm), and the absorbance at wavelengths of 200~800 nm was measured.

[0177] (Example 1) 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), benzaldehyde (1.06 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10.00 mmol), chloroform (10.00 mL, 1.00 M), and molecular sieves 4Å (2.00 g) were added to a 100 mL recovery flask and stirred at 50°C for 24 hours. After the reaction was completed, triethylamine (1.01 g) was added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P1). The yield was 86%. The structure of the resulting sulfide bond-containing polymer (P1) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P1) were measured using the above-mentioned evaluation methods. The results are shown in Table 1.

[0178] Example 2 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), benzaldehyde (1.06 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10.00 mmol), chloroform (20.00 mL, 0.50 M), and molecular sieves 4Å (2.00 g) were added to a 100 mL recovery flask and stirred at 50°C for 24 hours. After the reaction was completed, triethylamine (1.01 g) was added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P2). The yield was 81%. The structure of the resulting sulfide bond-containing polymer (P2) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P2) were measured using the methods described above. The results are shown in Table 1.

[0179] Example 3 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), 4-bromobenzaldehyde (1.85 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10.00 mmol), chloroform (10.00 mL, 1.00 M), and molecular sieves 4Å (2.00 g) were added to a 100 mL recovery flask and stirred at 50°C for 24 hours. After the reaction was completed, triethylamine (1.01 g) was added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P3). The yield was 81%. The structure of the resulting sulfide bond-containing polymer (P3) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P3) were measured using the methods described above. The results are shown in Table 1.

[0180] [ka]

[0181] Example 4 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), 4-methoxybenzaldehyde (1.36 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10.00 mmol), chloroform (5.00 mL, 1.00 M), and molecular sieves 4Å (2.00 g) were added to a 100 mL recovery flask and stirred at 50°C for 24 hours. After the reaction was completed, triethylamine (1.01 g) was added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P4). The yield was 52%. The structure of the resulting sulfide bond-containing polymer (P4) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P4) were measured using the methods described above. The results are shown in Table 1.

[0182] Example 5 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), 4-methoxybenzaldehyde (1.36 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10.00 mmol), chloroform (10.00 mL, 1.00 M), and molecular sieves 4Å (2.00 g) were added to a 100 mL recovery flask and stirred at 50°C for 24 hours. After the reaction was completed, triethylamine (1.01 g) was added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P5). The yield was 75%. The structure of the resulting sulfide bond-containing polymer (P5) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P5) were measured using the methods described above. The results are shown in Table 1.

[0183] [ka]

[0184] Example 6 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), benzaldehyde (1.06 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (0.20 g, 1.05 mmol), and benzyl acetate (7.50 mL, 1.33 M) were added to a 50 mL recovery flask and stirred at 50°C for 22 hours. After the reaction was completed, N-methylpyrrolidone (2.00 g) and triethylamine (0.10 g) were added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P6). The yield was 85%. The structure of the resulting sulfide bond-containing polymer (P6) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P6) were measured using the methods described above. The results are shown in Table 1.

[0185] Example 7 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), benzaldehyde (1.06 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (0.20 g, 1.05 mmol), and propylene glycol monomethyl ether acetate (PGMEA) (7.50 mL, 1.33 M) were added to a 50 mL recovery flask and stirred at 50 °C for 15 hours. After completion of the reaction, N-methylpyrrolidone (2.00 g) and triethylamine (0.10 g) were added, and the resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P7). The yield was 90%. The structure of the resulting sulfide bond-containing polymer (P7) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P7) were measured using the methods described above. The results are shown in Table 1.

[0186] Example 8 A 50 mL recovery flask was charged with 4,4'-thiobisbenzenethiol (2.50 g, 10.00 mmol), benzaldehyde (0.98 g, 9.25 mmol), terephthalaldehyde (0.05 g, 0.37 mmol), p-toluenesulfonic acid monohydrate (0.20 g, 1.05 mmol), and propylene glycol monomethyl ether acetate (PGMEA) (7.50 mL, 1.33 M) and stirred at 50 °C for 15 h. After completion of the reaction, N-methylpyrrolidone (2.00 g) and triethylamine (0.10 g) were added. The resulting reaction solution was added dropwise to 100 mL of methanol solution to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer powder (P8). The yield was 95%. The structure of the obtained sulfide bond-containing polymer (P8) is: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the resulting sulfide bond-containing polymer powder (P8) were measured using the methods described above. The results are shown in Table 1. (P8)

[0187] [ka]

[0188] Example 9 4,4'-thiobisbenzenethiol (0.63 g, 2.5 mmol), 4-(methylsulfonyl)benzaldehyde (0.92 g, 5 mmol), p-toluenesulfonic acid monohydrate (48 mg, 0.25 mmol), and chloroform (12.5 mL) were added to a 20 mL recovery flask and stirred at 50°C for 3 hours. After the reaction was completed, triethylamine (2 mL) was added, diluted with chloroform, and added dropwise to methanol (50 mL) to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer (P9). The yield was 88%. The structure of the sulfide bond-containing polymer (P9) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the sulfide bond-containing polymer (P9) were measured by the above-mentioned evaluation methods. The results are shown in Table 1. The glass transition temperature of the sulfide bond-containing polymer (P9) was measured by the above-mentioned evaluation methods and was found to be 136°C. (P9)

[0189] [ka]

[0190] Example 10 4,4'-thiobisbenzenethiol (0.63 g, 2.5 mmol), 4-(methylthio)benzaldehyde (0.33 mL, 2.5 mmol), p-toluenesulfonic acid monohydrate (48 mg, 0.25 mmol), and chloroform (12.5 mL) were added to a 20 mL recovery flask and stirred at 50°C for 3 hours. After the reaction was completed, triethylamine (2 mL) was added, diluted with chloroform, and added dropwise to methanol (50 mL) to precipitate the product. The precipitate was filtered and washed with methanol and pure water. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer (P10). The yield was 95%. The structure of the sulfide bond-containing polymer (P10) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the sulfide bond-containing polymer (P10) were measured by the above-mentioned evaluation methods. The results are shown in Table 1. The glass transition temperature of the sulfide bond-containing polymer (P10) was measured by the above-mentioned evaluation methods and was found to be 84°C. (P10)

[0191] [ka]

[0192] Example 11 1,4-Benzenedithiol (0.36 g, 2.5 mmol), 4-(methylsulfonyl)benzaldehyde (0.46 g, 2.5 mmol), p-toluenesulfonic acid monohydrate (48 mg, 0.25 mmol), and chloroform (12.5 mL) were added to a 10 mL recovery flask and stirred at 50°C for 7 hours. After the reaction was completed, triethylamine (0.05 mL, 0.36 mmol) was added, diluted with chloroform, and added dropwise to methanol (50 mL) to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer (P11). The yield was 92%. The structure of the sulfide bond-containing polymer (P11) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the sulfide bond-containing polymer (P11) were measured by the above-mentioned evaluation methods. The results are shown in Table 1. The glass transition temperature of the sulfide bond-containing polymer (P11) was measured by the above-mentioned evaluation methods and was found to be 152°C. (P11)

[0193] [ka]

[0194] Example 12 1,4-Benzenedithiol (0.36 g, 2.5 mmol), 4-(methylthio)benzaldehyde (0.33 mL, 2.5 mmol), p-toluenesulfonic acid monohydrate (48 mg, 0.25 mmol), and chloroform (2.5 mL) were added to a 10 mL recovery flask and stirred at 50°C for 6 hours. After the reaction was completed, triethylamine (0.05 mL, 0.36 mmol) was added, diluted with chloroform, and added dropwise to methanol (50 mL) to precipitate the product. The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer (P12). The yield was 94%. The structure of the sulfide bond-containing polymer (P12) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the sulfide bond-containing polymer (P12) were measured by the above-mentioned evaluation methods. The results are shown in Table 1. The glass transition temperature of the sulfide bond-containing polymer (P12) was measured by the above-mentioned evaluation methods and was found to be 87°C. (P12)

[0195] [ka]

[0196] Example 13 4,4'-thiobisbenzenethiol (1.00 g, 4.0 mmol), benzaldehyde (6.36 g, 60 mmol), and p-toluenesulfonic acid monohydrate (76 mg, 0.40 mmol) were added to a 100 mL test tube and stirred at 50°C for 6 hours. After the reaction was completed, triethylamine (0.27 mL, 2.0 mmol) and acetic anhydride (0.10 mL, 1.0 mmol) were added, and the mixture was diluted with tetrahydrofuran. The product was precipitated by adding dropwise to methanol (300 mL). The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer (P13). The yield was 85%. The structure of the sulfide bond-containing polymer (P13) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the sulfide bond-containing polymer (P13) were measured using the methods described above. The results are shown in Table 1. (P13)

[0197] [ka]

[0198] Example 14 4,4'-thiobisbenzenethiol (1.00 g, 4.0 mmol), 1-naphthaldehyde (9.36 g, 60 mmol), and p-toluenesulfonic acid monohydrate (76 mg, 0.40 mmol) were added to a 100 mL test tube and stirred at 50°C for 6 hours. After the reaction was completed, triethylamine (0.27 mL, 2.0 mmol) and acetic anhydride (0.10 mL, 1.0 mmol) were added, and the mixture was diluted with tetrahydrofuran. The product was precipitated by adding dropwise to methanol (300 mL). The precipitate was filtered and washed with methanol. The resulting powder was then vacuum dried at room temperature to obtain a white sulfide bond-containing polymer (P14). The yield was 80%. The structure of the sulfide bond-containing polymer (P14) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index, Abbe number, and visible light transmittance of the sulfide bond-containing polymer (P14) were measured using the methods described above. The results are shown in Table 1. (P14)

[0199] [ka]

[0200] (Comparative Example 1) 1,8-octanedithiol (1.78 g, 10.00 mmol), benzaldehyde (1.06 g, 10.00 mmol), p-toluenesulfonic acid monohydrate (1.90 g, 10.00 mmol), chloroform (10.00 mL, 1.00 M), and molecular sieves 4Å (2.00 g) were added to a 100 mL recovery flask and stirred at 50°C for 24 hours. After the reaction was completed, triethylamine (1.01 g) was added, and 100 mL each of chloroform and water were added to the resulting reaction solution for separation and washing. The chloroform solution was then recovered and concentrated, followed by vacuum drying at room temperature to obtain polymer (P1c). The yield was 72%. The structure of the resulting polymer (P1c) is as follows: 1 H-NMR, 13 The polymer was identified by various analyses such as H-NMR, GPC, and IR. Furthermore, the refractive index and visible light transmittance of the obtained polymer powder (P1c) were measured using the evaluation methods described above. The results are shown in Table 1.

[0201] [Table 1]

[0202] FIG. 1 shows the DSC curves and X-ray diffraction patterns of the polymers obtained in Examples 1 and 3. The glass transition temperature (Tg) of Example 1 (P1) was 76°C, and the Tg of Example 3 (P3) was 94°C. FIG. 2 shows the absorbance spectra of the polymers obtained in Examples 1 and 3 by UV-visible spectroscopy. FIG. 3 shows the transmittance spectra of the polymers obtained in Examples 1 and 3 by UV-visible spectroscopy. FIG. 4 shows photographs of thin films formed using the polymers of Examples 1 and 3. The thin films were formed by spin-coating a solution of the obtained polymer in a solvent onto a glass substrate. FIG. 5 shows the DSC curves and X-ray diffraction patterns of the polymers obtained in Examples 1 and 4. FIG. 6 shows the absorbance spectra of the polymers obtained in Examples 1 and 4 by UV-visible spectroscopy. The Tg of Example 4 (P4) was 74°C. FIG. 7 shows photographs of thin films formed using the polymers obtained in Examples 1 and 4. FIG. 8 shows the differential refractive index spectra of the polymers obtained in Examples 1 and 4.

[0203] 1 and 5, the polymers of the examples were confirmed to be amorphous, since no sharp crystalline peaks were observed. Furthermore, FIGS. 2, 3, 6, and 8 confirmed that the polymers of the examples had excellent transparency and very high visible light transmittance. Furthermore, Table 1 shows that the polymers of the examples had high refractive indices of 1.7 or more, and Comparative Example 1 confirmed that the polymer (P1c) obtained using an aliphatic dithiol as the dithiol compound had a refractive index of 1.6 or less. Thus, the polymers of the examples were confirmed to have high refractive indices and excellent transparency. Furthermore, a comparison between Examples 9 and 10 and Examples 11 and 12 confirmed that when a polymer has a methylsulfonyl group in the side chain, the glass transition temperature of the polymer increases.< / ir>

Claims

1. A sulfide bond-containing polymer characterized by having a structural unit represented by the following general formula (1): 【Chemical 1】 (In the formula, R １ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aromatic ring-containing group. ２ represents an aromatic ring-containing group.

2. 2. The sulfide bond-containing polymer according to claim 1, wherein the weight average molecular weight is 1,000 to 10,000,000.

3. 2. The sulfide bond-containing polymer according to claim 1, wherein the glass transition temperature is 30 to 450°C.

4. 2. The sulfide bond-containing polymer according to claim 1, which is amorphous.

5. 2. The sulfide bond-containing polymer according to claim 1, wherein the sulfide bond-containing polymer has a visible light transmittance of 70% or more when formed into a film having a thickness of 2 μm.

6. A method for producing a sulfide bond-containing polymer, comprising: The production method includes a step of polymerizing a monomer component including an aldehyde compound and a thiol compound, The aldehyde compound includes a monoaldehyde compound represented by the following general formula (2): The thiol compound includes a dithiol compound represented by the following general formula (3) and / or a trithiol compound represented by the following general formula (4):

1. A method for producing a sulfide bond-containing polymer, comprising: R １ -CHO (22) (In the formula, R １ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms which may have a substituent, or an aromatic ring-containing group. HS-R ３ -SH (3) (In the formula, R ３ represents a divalent aromatic ring-containing group. R ４ (ShH) ３ (4) (In the formula, R ４ represents a trivalent aromatic ring-containing group.

7. A sulfide bond-containing polymer composition comprising the sulfide bond-containing polymer according to claim 1 and a component other than the sulfide bond-containing polymer.

8. An optical material comprising the sulfide bond-containing polymer composition according to claim 7.

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