Polymers, compositions, coatings, molded articles, and optical components

Abstract

To provide a novel polymer exhibiting high refraction. 【Solution means】 A polymer containing a structure represented by the following general formula (1). TIFF2026048231000013.tif33153 (In the above general formula (1), R 1 represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted cycloalkyl group, R 2 and R 3 each independently represent a substituted or unsubstituted arylene group, or a substituted or unsubstituted cycloalkylene group, X represents a sulfur atom, a sulfone group, or -Si(R 4 )(R 5 )-, R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, a polyether group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms, and n represents an integer of 1 or more.)

Description

Technical Field

[0001] The present invention relates to polymers, compositions, coating materials, molded articles, and optical components.

Background Art

[0002] Polymers having a high refractive index can be used, for example, as materials constituting optical components such as optical lenses. Examples of polymers having a high refractive index include the polymers described in Non-Patent Document 1.

[0003] Non-Patent Document 1 discloses a polymer represented by the following general formula.

[0004]

Chemical Formula

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

[0008] 1. A polymer containing a structure represented by the following general formula (1). [Chemical formula] (In the general formula (1), R represents a substituted or unsubstituted aryl group or a substituted or unsubstituted cycloalkyl group, R 2 and R 3 each independently represent a substituted or unsubstituted arylene group or a substituted or unsubstituted cycloalkylene group, X represents a sulfur atom, a sulfone group, or -Si(R 4 )(R 5 )-, R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, a polyether group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. n represents an integer of 1 or more.) 2. The polymer according to 1., wherein in the general formula (1), R 1 represents a substituted or unsubstituted aryl group, and R 2 and R 3 each independently represent a substituted or unsubstituted arylene group. 3. The polymer according to 2., containing a structure represented by the following general formula (2). [Chemical formula] (In the general formula (2), R 6 to R 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, a polyether group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. X is a sulfur atom, a sulfone group, or -Si(R 4 )(R 5 )- indicates, R 4 and R 5 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group. n represents an integer greater than or equal to 1. 4. In the above general formula (1), R 4 and R 5 The polymer according to any one of 1 to 3, wherein each independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group. 5. In the general formula (2) above, R 6 ~R 18 The polymer according to 3. or 4., wherein each independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group. 6. In the general formula (2) above, R 4 and R 5 The polymer according to any one of 3. to 5., wherein each independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group. 7. A polymer according to any of 1. to 6., wherein the 5% weight loss temperature (Td5) is 180°C or higher. 8. A polymer according to any of 1. to 7., having a glass transition temperature (Tg) of 35°C or higher. 9. A polymer according to any of 1. to 8., having a weight-average molecular weight (Mw) of 700 or more. 10. A polymer according to any of 1 to 9, wherein the refractive index (nD) obtained by measuring the coating film obtained by the following <film-forming method> using the following <measurement method> is 1.60 or greater. <Film forming method> 0.1 g of the polymer is dissolved in 1.9 g of THF, and the solution is filtered through a syringe filter with a pore size of 0.45 μm to obtain the solution. The obtained solution is dropped onto a silicon wafer, and a spin coater is used to rotate it at 200 rpm for 5 seconds, then at 2000 rpm for 30 seconds to obtain a coating film. <Measurement method> The refractive index (nD) of the obtained coating film is measured using a spectroscopic ellipsometer. The dielectric function of the coating film is modeled using the Cauchy model and the Lorentz model, with an analysis range of 250-950 nm, and the analysis variables are film thickness [nm] and B [μm]. 2 ], f, E0[eV], Γ[eV], N inf Let's assume that. 11. A polymer described in any of 1. to 10., used in optical components. 12. A composition comprising the polymer described in any of items 1 to 11. 13. A coating material comprising a polymer described in any of items 1 to 11, and a solvent. 14. A molded article containing the polymer described in any of items 1 to 11. 15. Optical components including the molded body described in 14. 16. An optical lens, as described in 15. [Effects of the Invention]

[0009] According to the present invention, a novel polymer exhibiting high refractive index can be provided. [Modes for carrying out the invention]

[0010] In this embodiment, unless otherwise specified, "A~B" indicating a numerical range means A or greater and B or less.

[0011] In this embodiment, "having substituents" of an alkyl group, unless otherwise specified, means that hydrogen atoms present in its structure are substituted by substituents. The position of the substituents and the number of substituents are not particularly limited. Note that if the substituent has carbon atoms, the number of carbon atoms in the substituent is not included in the total number of carbon atoms of the substituted group. For example, an ethyl group having a phenyl group as a substituent is considered an alkyl group with 2 carbon atoms.

[0012] Furthermore, the various monomers in this embodiment may be derived from fossil raw materials, from biological sources such as biomass, or from mixtures thereof.

[0013] 1. Polymer The processing method of this embodiment will be described below.

[0014] The polymer of this embodiment includes a structure represented by the following general formula (1).

[0015] [ka]

[0016] In general formula (1), R 1 R represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted cycloalkyl group. 2 and R 3 Each of these independently represents a substituted or unsubstituted arylene group, or a substituted or unsubstituted cycloalkylene group, where X is a sulfur atom, a sulfone group, or -Si(R 4 )(R 5 )- indicates R 4 and R 5 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group, where n is an integer of 1 or more.

[0017] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 1 R represents a substituted or unsubstituted aryl group. 2 and R 3 Preferably, each of these groups independently represents a substituted or unsubstituted arylene group.

[0018] From the viewpoint of further improving the refractive index of the polymer of this embodiment, it is preferable that the polymer of this embodiment includes a structure represented by the following general formula (2).

[0019] [ka]

[0020] In general formula (2), R 6 ~R 18 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group, where X is a sulfur atom, a sulfone group, or -Si(R 4 )(R 5 )- indicates R 4 and R 5 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group, where n is an integer of 1 or more.

[0021] [General formula (1)] The general formula (1) will be explained below.

[0022] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 1 It is preferable that the group represents a substituted or unsubstituted aryl group, more preferably a substituted or unsubstituted phenyl group, and even more preferably an unsubstituted phenyl group.

[0023] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 2 and R 3 Each of these groups independently preferably represents a substituted or unsubstituted arylene group, more preferably a substituted or unsubstituted phenylene group, even more preferably a substituted or unsubstituted p-phenylene group, and even more preferably an unsubstituted p-phenylene group.

[0024] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), X is a sulfur atom or -Si(R 4 )(R 5 It is preferable to show )- and more preferable to show a sulfur atom.

[0025] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 4 and R 5 Each of these elements independently preferably represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl halide having 1 to 20 carbon atoms, and more preferably represents an alkyl group having 1 to 20 carbon atoms or an alkyl halide having 1 to 20 carbon atoms.

[0026] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 4 and R 5 Each of these elements independently more preferably represents an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, and more preferably represents an alkyl group having 1 to 20 carbon atoms.

[0027] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 4 and R 5Each of these groups independently more preferably represents an alkyl group having 1 to 8 carbon atoms or a halogenated alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or a halogenated alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or a halogenated alkyl group having 1 carbon atom, and more preferably a methyl group.

[0028] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 4 and R 5 Preferably, each independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group; more preferably, it represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, or a nonpolymerizable C1-C20 halogenated alkyl group; and even more preferably, it represents a nonpolymerizable C1-C20 alkyl group, or a nonpolymerizable C1-C20 halogenated alkyl group.

[0029] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 4 and R 5 Each of these elements independently more preferably represents a nonpolymerizable C1-C20 alkyl group or a nonpolymerizable C1-C20 fluoroalkyl group, and more preferably represents a nonpolymerizable C1-C20 alkyl group.

[0030] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), R 4 and R 5Each of these independently preferably represents a nonpolymerizable C1-C8 alkyl group or a nonpolymerizable C1-C8 halogenated alkyl group, a nonpolymerizable C1-C4 alkyl group or a nonpolymerizable C1-C4 halogenated alkyl group, a nonpolymerizable C1-C3 alkyl group or a nonpolymerizable C1-C3 halogenated alkyl group, a methyl group or a nonpolymerizable C1 halogenated alkyl group, and a methyl group.

[0031] In this embodiment, polymerizability refers to the property of being able to react and bond with other polymerizable functional groups, as described later. Examples of polymerizable functional groups include carbon-carbon double bonds such as vinyl groups and epoxy groups. In this embodiment, a non-polymerizable functional group refers to a functional group other than a polymerizable functional group.

[0032] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (1), n ​​is preferably an integer between 1 and 500, more preferably an integer between 1 and 100, even more preferably an integer between 2 and 50, even more preferably an integer between 2 and 30, and even more preferably an integer between 3 and 20.

[0033] The content of the structure represented by general formula (1) in the polymer of this embodiment is preferably 60% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, even more preferably 95% to 100% by mass, even more preferably 98% to 100% by mass, and even more preferably 99% to 100% by mass, when the total amount of the polymer of this embodiment is 100% by mass, from the viewpoint of further improving the refractive index of the polymer of this embodiment.

[0034] [General formula (2)] The general formula (2) will be explained below.

[0035] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 6 ~R 18 Each of these elements independently preferably represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl halide having 1 to 20 carbon atoms, more preferably a hydrogen atom or a halogen atom, and even more preferably a hydrogen atom.

[0036] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 6 ~R 18 Each of these preferably independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group; more preferably a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, or a nonpolymerizable C1-C20 halogenated alkyl group; even more preferably a hydrogen atom or a halogen atom; and still more preferably a hydrogen atom.

[0037] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), X is a sulfur atom or -Si(R 4 )(R 5 It is preferable to show )- and more preferable to show a sulfur atom.

[0038] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 4 and R 5 Each of these elements independently preferably represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl halide having 1 to 20 carbon atoms, and more preferably represents an alkyl group having 1 to 20 carbon atoms or an alkyl halide having 1 to 20 carbon atoms.

[0039] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 4 and R 5 Each of these elements independently more preferably represents an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, and more preferably represents an alkyl group having 1 to 20 carbon atoms.

[0040] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 4 and R 5 Each of these groups independently more preferably represents an alkyl group having 1 to 8 carbon atoms or a halogenated alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or a halogenated alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or a halogenated alkyl group having 1 carbon atom, and more preferably a methyl group.

[0041] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 4 and R 5 Preferably, each independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group; more preferably, it represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, or a nonpolymerizable C1-C20 halogenated alkyl group; and even more preferably, it represents a nonpolymerizable C1-C20 alkyl group, or a nonpolymerizable C1-C20 halogenated alkyl group.

[0042] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 4 and R 5Each of these elements independently more preferably represents a nonpolymerizable C1-C20 alkyl group or a nonpolymerizable C1-C20 fluoroalkyl group, and more preferably represents a nonpolymerizable C1-C20 alkyl group.

[0043] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), R 4 and R 5 Each of these independently preferably represents a nonpolymerizable C1-C8 alkyl group or a nonpolymerizable C1-C8 halogenated alkyl group, a nonpolymerizable C1-C4 alkyl group or a nonpolymerizable C1-C4 halogenated alkyl group, a nonpolymerizable C1-C3 alkyl group or a nonpolymerizable C1-C3 halogenated alkyl group, a methyl group or a nonpolymerizable C1 halogenated alkyl group, and a methyl group.

[0044] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in general formula (2), n is preferably an integer between 1 and 500, more preferably an integer between 1 and 100, even more preferably an integer between 2 and 50, even more preferably an integer between 2 and 30, and even more preferably an integer between 3 and 20.

[0045] The content of the structure represented by general formula (2) in the polymer of this embodiment is preferably 60% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, even more preferably 95% to 100% by mass, even more preferably 98% to 100% by mass, and even more preferably 99% to 100% by mass, when the total amount of the polymer of this embodiment is 100% by mass, from the viewpoint of further improving the refractive index of the polymer of this embodiment.

[0046] From the viewpoint of further improving the refractive index of the polymer of this embodiment, it is preferable that the polymer of this embodiment contains one or more chemical structures selected from the chemical structures represented by the following formula (11) and the chemical structures represented by the following formula (12).

[0047] [ka]

[0048] In equation (11), n ​​represents an integer greater than or equal to 1.

[0049] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in formula (11), n ​​is preferably an integer between 1 and 500, more preferably an integer between 1 and 100, even more preferably an integer between 2 and 50, even more preferably an integer between 2 and 30, and even more preferably an integer between 3 and 20.

[0050] [ka]

[0051] In equation (12), n represents an integer greater than or equal to 1.

[0052] From the viewpoint of further improving the refractive index of the polymer of this embodiment, in formula (12), n is preferably an integer between 1 and 500, more preferably an integer between 1 and 100, even more preferably an integer between 2 and 50, even more preferably an integer between 2 and 30, and even more preferably an integer between 3 and 20.

[0053] The 5% weight loss temperature (Td5) of the polymer in this embodiment is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 210°C or higher, even more preferably 220°C or higher, even more preferably 230°C or higher, and even more preferably 235°C or higher, from the viewpoint of improving the heat resistance of the resulting molded articles and optical components. The upper limit of the 5% weight loss temperature (Td5) of the polymer in this embodiment is not particularly limited, but for example it may be 500°C or lower, 400°C or lower, 300°C or lower, or 270°C or lower.

[0054] The glass transition temperature (Tg) of the polymer in this embodiment is preferably 35°C to 250°C, more preferably 40°C to 200°C, even more preferably 45°C to 150°C, even more preferably 50°C to 120°C, even more preferably 55°C to 100°C, and even more preferably 60°C to 90°C, from the viewpoint of improving the balance between the heat resistance and moldability of the resulting molded articles and optical components.

[0055] The number-average molecular weight (Mn) of the polymer in this embodiment is preferably 500 to 20000, more preferably 800 to 15000, even more preferably 1000 to 10000, even more preferably 1200 to 8000, and even more preferably 1500 to 5000.

[0056] The weight-average molecular weight (Mw) of the polymer in this embodiment is preferably 700 to 25000, more preferably 1000 to 20000, even more preferably 1200 to 15000, even more preferably 1500 to 10000, and even more preferably 2000 to 7000.

[0057] The degree of dispersion (Mn / Mw) of the polymer in this embodiment is preferably 1.00 to 5.00, more preferably 1.00 to 4.00, even more preferably 1.00 to 3.00, even more preferably 1.00 to 2.00, and even more preferably 1.10 to 1.80.

[0058] The refractive index (nD) obtained by measuring the coating film obtained by the following <film formation method> using the following <measurement method> is preferably 1.60 or higher, more preferably 1.62 or higher, even more preferably 1.64 or higher, even more preferably 1.65 or higher, and even more preferably 1.67 or higher. The upper limit of the refractive index (nD) is not particularly limited, but for example it may be 2.00 or less, 1.90 or less, 1.85 or less, 1.80 or less, or 1.78 or less. <Film forming method> 0.1 g of the polymer of this embodiment is dissolved in 1.9 g of THF, and the solution is filtered through a syringe filter with a pore size of 0.45 μm to obtain the solution. The obtained solution is dropped onto a silicon wafer, and a spin coater is used to rotate it at 200 rpm for 5 seconds, then at 2000 rpm for 30 seconds to obtain a coating film. <Measurement method> The refractive index (nD) of the obtained coating film is measured using a spectroscopic ellipsometer. The dielectric function of the coating film is modeled using the Cauchy model and the Lorentz model, with an analysis range of 250-950 nm, and the analysis variables are film thickness [nm] and B [μm]. 2 ], f, E0[eV], Γ[eV], N inf Let's assume that.

[0059] Since the polymer of this embodiment exhibits high refractive index, it can be suitably used in optical components.

[0060] 2. Composition The composition of this embodiment will be described below.

[0061] The composition of this embodiment includes the polymerization of this embodiment.

[0062] The content of the polymer of this embodiment in the composition of this embodiment can be arbitrarily set in terms of compatibility with any component described later, as long as it does not hinder the objective of the present invention.

[0063] The composition of this embodiment has high refractive index due to the inclusion of the polymer of this embodiment, and therefore can be suitably used in optical components.

[0064] The composition of this embodiment may contain any component as long as it does not impair the purpose of the present invention. For example, the composition of this embodiment may contain one or more selected from the group consisting of epoxy resins, curable acrylic resins, diallyl phthalate resins, unsaturated polyester resins, styrene resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyamide resins, polyurethane resins, polythiourethane resins, cycloolefin copolymers, and (meth)acrylic resins.

[0065] The composition of this embodiment may contain any component as long as it does not impair the purpose of the present invention. For example, the composition of this embodiment may contain one or more selected from the group consisting of stabilizers, antioxidants, ultraviolet absorbers, hydrochloric acid absorbers, metal deactivators, surfactants, antistatic agents, antifogging agents, lubricants, nucleating agents, plasticizers, and flame retardants.

[0066] 3. Coating material The coating material of this embodiment will be described below.

[0067] The coating material of this embodiment comprises the polymer of this embodiment and a solvent.

[0068] The coating material of this embodiment may contain any component as long as it does not impair the objective of the present invention. The optional components listed as optional components of the composition of this embodiment can be used.

[0069] The solvent contained in the coating material of this embodiment is not particularly limited as long as it does not impair solubility or affinity for the polymer of this embodiment and any of the above components, for example: saturated hydrocarbons such as heptane, hexane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decahydronaphthalene; aromatic hydrocarbons such as toluene, benzene, xylene, mesitylene, and pseudocumene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; acetone, methyl isobutyl ketone, methyl ethyl ketone, and phenyl It comprises one or more selected from the group consisting of ketone solvents such as anthanone, hexanone, cyclohexanone, isophorone, and acetophenone; cellsolves such as methyl cellsolve and ethyl cellsolve; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene, and preferably one or more selected from the group consisting of heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, and pseudocumene.

[0070] In this embodiment, the method for preparing the coating material can be any method, but for example, it includes a step of mixing the polymer of this embodiment with the optional components mentioned above as needed and with a solvent. There are no restrictions on the order in which the components are mixed, and it can be done in any way, such as all at once or in stages. There are also no restrictions on the apparatus used to prepare the coating material, and it can be carried out using any batch or continuous apparatus capable of stirring and mixing. The temperature when preparing the coating material can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. Alternatively, the reaction solution obtained when the polymer of this embodiment is obtained may be used as the solvent, and a coating material may be prepared by dissolving any components or solvents in it.

[0071] 4. Molded body The molded body of this embodiment will be described below.

[0072] The molded article of this embodiment includes the polymer of this embodiment.

[0073] The content of the polymer of this embodiment in the molded article of this embodiment can be arbitrarily set from the viewpoint of compatibility with any of the aforementioned components, as long as it does not hinder the objective of the present invention.

[0074] 5. Optical components The molded body of this embodiment will be described below.

[0075] The optical component of this embodiment includes the molded body of this embodiment.

[0076] The optical components of this embodiment are one or more selected from the group consisting of, for example, optical lenses such as lenses for various sensors, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, camera lenses, light guide plates, lenses for head-mounted displays, plastic eyeglass lenses, goggles, eyeglass lenses for vision correction, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, lenticular lenses, and contact lenses; encapsulating materials for light-emitting diodes (LEDs); optical adhesives used for joining optical waveguides and wafer-level optical components (WLOs); optical adhesives; anti-reflective coatings used for optical lenses and transparent coatings used for liquid crystal display device components (substrates, light guide plates, films, sheets, etc.); transparent sheets or films that are attached to car windshields, motorcycle helmets, etc.; and transparent substrates used in electronic devices, and are preferably optical lenses.

[0077] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0078] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0079] The bis(4-bromophenyl) sulfide, ditosylphenylbismuth, and bis(4-bromophenyl)dimethylsilane used in the following examples were synthesized by the methods described in CrystEngComm, 2013, 15, 9429-9436, Organometallics, 2020, 39, 778-782, and Trans.Mat.Res.Soc.Japan, 2012, 37, 459-462, respectively.

[0080] [Example 1] Poly(4-thiophenyl)(4-phenyl)phenylbismuth (hereinafter sometimes referred to as the polymer of Example 1) was synthesized by the following procedure. Under a nitrogen atmosphere, 306 mg (12.60 mmol) of magnesium (manufactured by Kanto Chemical Co., Ltd.) was added to 20 mL of tetrahydrofuran (hereinafter sometimes referred to as THF), and then a few drops of 1,2-dibromoethane (manufactured by Fujifilm Wako Co., Ltd.) were added, and the mixture was stirred for 10 minutes. 2.06 g (6.00 mmol) of bis(4-bromophenyl) sulfide was added and the mixture was stirred overnight at 80°C. 60 mL of THF was added, the reaction system was cooled to -20°C, 3.72 g (5.94 mmol) of ditosylphenylbismuth was added, and the mixture was stirred for a further 2 hours. A sodium bicarbonate solution was added, and insoluble matter was removed by Celite filtration. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was removed by evaporation. The obtained solid was dissolved in 20 mL of THF and filtered through a membrane filter with a pore size of 0.45 μm. The filtrate was reprecipitation using 1000 mL of a mixed solvent of hexane:ethyl acetate = 7:3 (v / v), and the precipitate was filtered off to obtain 0.645 g of the polymer from Example 1 as a white solid. The reaction yield was 23%.

[0081] The number-average molecular weight (Mn) of the polymer in Example 1, measured by the method described below, was 2100, the weight-average molecular weight (Mw) was 2500, and the degree of dispersion (Mw / Mn) was 1.19.

[0082] The polymer of Example 1 was measured by the following method. 1 The H-NMR data is as follows: 1 H-NMR(400MHz,CDCl3)δ:7.85-7.18(m,13H),0.65-0.31(m,6H)ppm

[0083] The polymer of Example 1 obtained by the following method 1 From the 1H-NMR chart and mass spectrum, it was confirmed that the polymer of Example 1 contains the chemical structure represented by the following formula (11).

[0084] [ka]

[0085] [Example 2] Poly((4-dimethylsilyl)phenyl)(4-phenyl)phenylbismuth (hereinafter sometimes referred to as the polymer of Example 2) was synthesized by the following procedure. Under a nitrogen atmosphere, 911 mg (37.50 mmol) of magnesium (manufactured by Kanto Chemical Co., Ltd.) was added to 50 mL of THF, a few drops of 1,2-dibromoethane (manufactured by Fujifilm Wako Co., Ltd.) were added, and the mixture was stirred for 10 minutes. 5.55 g (15.00 mmol) of bis(4-bromophenyl)dimethylsilane was added and the mixture was stirred overnight at 80°C. 150 mL of THF was added, the reaction system was cooled to -20°C, 9.42 g (14.99 mmol) of ditosylphenylbismuth was added, and the mixture was stirred for a further 2 hours. A sodium bicarbonate solution was added, and insoluble matter was removed by Celite filtration. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was removed by evaporation. The obtained solid was dissolved in 40 mL of THF and filtered through a membrane filter with a pore size of 0.45 μm. The filtrate was reprecipitation using 2000 mL of a mixed solvent of hexane:ethyl acetate = 4:1 (v / v), and the precipitate was filtered off to obtain 2.409 g of the polymer from Example 2 as a white solid. The reaction yield was 32%.

[0086] The number-average molecular weight (Mn) of the polymer in Example 2, measured by the method described below, was 2800, the weight-average molecular weight (Mw) was 4800, and the degree of dispersion (Mw / Mn) was 1.71.

[0087] The polymer of Example 2 was measured by the following method. 1 The H-NMR data is as follows: 1 H-NMR(400MHz,CDCl3)δ:7.85-7.46(m,6H),7.46-7.10(m,7H)ppm

[0088] The polymer of Example 2 obtained by the following method 1 From the 1H-NMR chart and mass spectrum, it was confirmed that the polymer of Example 2 contains the chemical structure represented by the following formula (12).

[0089] [ka]

[0090] [Number-average molecular weight (Mn) and weight-average molecular weight (Mw)] The measurement conditions are as follows: Measurement device: Optical dispersion detector (Malvern Panalytic Corporation, model name: OMNISEC Reveal) Solvent: THF Sample concentration: 10-20 g / l-solvent Measurement temperature: 40℃

[0091] [ 1 [H-NMR] The measurement conditions are as follows: Measurement device: 400-MR type nuclear magnetic resonance spectrometer (Varian Corporation) Solvent: CDCl3 Sample concentration: 10 g / l-solvent Pulse repetition time: 5 seconds Total number of times: 16 Measurement temperature: 23℃

[0092] [Mass spectrometry (MS)] Each polymer was subjected to mass spectrometry using the FD method to obtain mass spectra.

[0093] [Refractive index (nD)] The refractive index (nD) was obtained by measuring the coating film obtained by the following <film formation method> using the following <measurement method>. The results are shown in Table 1. <Film forming method> 0.1 g of the polymer obtained by the above method was dissolved in 1.9 g of THF, and the solution was obtained by filtering through a syringe filter with a pore size of 0.45 μm. The obtained solution was dropped onto a silicon wafer and, using a spin coater, rotated at 200 rpm for 5 seconds, then at 2000 rpm for 30 seconds to obtain a coating film. The film thickness of the coating film in Example 1 was 301.0 nm, and the film thickness of the coating film in Example 2 was 372.1 nm. <Method> The refractive index (nD) of the obtained coating film was measured using a GES5-E spectroscopic ellipsometer (manufactured by Nippon Semilab Co., Ltd.). The dielectric function of the coating film was modeled using the Cauchy model and the Lorentz model, with an analysis range of 250-950 nm. The analytical variables were film thickness [nm] and B [μm]. 2 ], f, E0[eV], Γ[eV], N inf That's what I decided.

[0094] [5% weight loss temperature (Td5)] From the thermogravimetric curve obtained under the following conditions, the temperature at which the sample weight decreased by 5% relative to the initial sample weight was read and defined as the 5% weight loss temperature (Td5). The results are shown in Table 1. Measuring device: TG / DTA6200 (manufactured by Seiko Instruments Corporation) Atmosphere: Under a nitrogen atmosphere Temperature conditions: The temperature was raised from room temperature to 500°C at a rate of 10°C / minute.

[0095] [Glass transition temperature (Tg)] The glass transition temperature (Tg) was determined from the endothermic curve obtained under the following conditions. The results are shown in Table 1. Measuring device: DSC6200 (manufactured by Seiko Instruments Corporation) Atmosphere: Under a nitrogen atmosphere Temperature conditions: First, the temperature was raised from room temperature to 150°C at a rate of 5°C / min and held for 5 minutes. Then, the temperature was lowered to 0°C at a rate of 5°C / min and held for 5 minutes. Then, the temperature was raised to 150°C at a rate of 5°C / min.

[0096] [Light transmittance at a wavelength of 400 nm] The light transmittance at a wavelength of 400 nm was obtained by measuring the coating film obtained by the following <film formation method> using the following <measurement method>. The results are shown in Table 1. <Film forming method> 0.0040 g of the polymer obtained by the above method was dissolved in 2.0 g of THF, and the solution was obtained by filtering through a syringe filter with a pore size of 0.20 μm. The obtained solution was dropped onto quartz glass, and a spin coater was used to rotate it at 200 rpm for 5 seconds, then at 2000 rpm for 30 seconds to obtain a coating film. <Measurement method> The transmittance of the obtained coating film was measured by transmission using a UV-Vis-Near-Infrared Spectrophotometer U-3600plus (manufactured by Shimadzu Corporation).

[0097] [Table 1]

Claims

1. A polymer containing a structure represented by the following general formula (1). 【Chemistry 1】 (In the above general formula (1), R １ This represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted cycloalkyl group. R ２ and R ３ Each of these independently represents a substituted or unsubstituted arylene group, or a substituted or unsubstituted cycloalkylene group. X is a sulfur atom, a sulfone group, or -Si(R ４ ) (Caution ５ ) - indicates, R ４ and R ５ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group. n represents an integer greater than or equal to 1.

2. In the general formula (1), R １ represents a substituted or unsubstituted aryl group, and R ２ and R ３ each independently represent a substituted or unsubstituted arylene group. The polymer according to claim 1.

3. The polymer according to claim 2, comprising a structure represented by the following general formula (2). 【Chemistry 2】 (In the above general formula (2), R ６ ~R １８ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group. X is a sulfur atom, a sulfone group, or -Si(R ４ ) (Caution ５ ) - indicates, R ４ and R ５ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aralkyl group, a C1-C20 polyether group, or a C1-C20 halogenated alkyl group. n represents an integer greater than or equal to 1.

4. In the above general formula (1), R ４ and R ５ The polymer according to any one of claims 1 to 3, wherein each independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group.

5. In the above general formula (2), R ６ ~R １８ The polymer according to claim 3, wherein each of these independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group.

6. In the above general formula (2), R ４ and R ５ The polymer according to claim 3, wherein each of these independently represents a hydrogen atom, a halogen atom, a nonpolymerizable C1-C20 alkyl group, a nonpolymerizable C6-C20 aryl group, a nonpolymerizable C6-C20 aralkyl group, a nonpolymerizable C1-C20 polyether group, or a nonpolymerizable C1-C20 halogenated alkyl group.

7. 5% weight loss temperature (Td ５ The polymer according to any one of claims 1 to 3, wherein the temperature is 180°C or higher.

8. The polymer according to any one of claims 1 to 3, wherein the glass transition temperature (Tg) is 35°C or higher.

9. The polymer according to any one of claims 1 to 3, wherein the weight-average molecular weight (Mw) is 700 or more.

10. The polymer according to any one of claims 1 to 3, wherein the refractive index (nD) obtained by measuring the coating film obtained by the following <film-forming method> using the following <measurement method> is 1.60 or greater. <Film forming method> 0.1 g of the polymer is dissolved in 1.9 g of THF, and the solution is filtered through a syringe filter with a pore size of 0.45 μm to obtain the solution. The obtained solution is dropped onto a silicon wafer, and a spin coater is used to rotate it at 200 rpm for 5 seconds, then at 2000 rpm for 30 seconds to obtain a coating film. <Measurement method> The refractive index (nD) of the obtained coating film is measured using a spectroscopic ellipsometer. The dielectric function of the coating film is modeled using the Cauchy model and the Lorentz model, with an analysis range of 250–950 nm, and the analytical variables are film thickness [nm] and B [μm]. ２ ], f, E ０ [eV], Γ [eV], N ｉｎｆ Let's assume that.

11. A polymer according to any one of claims 1 to 3, used in optical components.

12. A composition comprising the polymer according to any one of claims 1 to 3.

13. A coating material comprising a polymer according to any one of claims 1 to 3 and a solvent.

14. A molded article comprising the polymer according to any one of claims 1 to 3.

15. An optical component comprising the molded body described in claim 14.

16. The optical component according to claim 15, which is an optical lens.

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