Optical material

Abstract

To provide an optical material which is a novel high refractive index polymer material that has excellent moldability and enables producing optical components by molding without going through a dissolution process.SOLUTION: An optical material comprises an iodine-containing polymer containing a repeating unit derived from a triiodophenyl group-containing acrylic monomer (1) represented by the formula: CH2=C(-X1)-C(=O)-Y1-(L1O)p-TIP (in the formula, TIP is a triiodophenyl group, X1 is a hydrogen atom, a methyl group, or a halogen atom, Y1 is -O- or -NH-, L1 is each independently an alkylene group having 1 to 10 carbon atoms, and p is 1 to 5).SELECTED DRAWING: None

Description

[Technical field]

[0001] In particular, the present disclosure relates to optical materials that include iodine-containing polymers for use in high refractive index polymeric materials. [Background technology]

[0002] In recent years, research and development of high refractive index polymer materials has been progressing. Patent Document 1 discloses, as a high refractive index polymer material, an iodine-containing polymer that includes a repeating unit derived from an acrylic monomer containing a triiodophenyl group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2022-131503 A Summary of the Invention [Problem to be solved by the invention]

[0004] Conventionally, optical components are formed by dissolving a highly refractive polymer material in an appropriate solvent and casting the resulting solution on a substrate. However, such a manufacturing method requires the selection of a solvent, the management of the solvent, dissolving, applying, and removing the solvent, which can be industrially disadvantageous due to poor productivity.

[0005] An object of the present disclosure is to provide an optical material that is a novel high refractive index polymer material that has excellent moldability and can be molded to produce optical components without going through a dissolution process. [Means for solving the problem]

[0006] One embodiment of the present disclosure is as follows: [Section 1] formula: CH2=C(-X 1 )-C(=O)-Y 1 -(L 1 O) p-TIP [In the formula, TIP is a triiodophenyl group, X 1 is a hydrogen atom, a methyl group or a halogen atom, Y 1 is -O- or -NH-, L 1 each independently represents an alkylene group having 1 to 10 carbon atoms, p is between 1 and 5.] An optical material comprising an iodine-containing polymer containing a repeating unit derived from a triiodophenyl group-containing acrylic monomer (1) represented by the following formula: [Section 2] L 1 are each independently an alkylene group having 1 to 4 carbon atoms, Item 2. The optical material according to item 1, wherein p is 1 to 3. [Section 3] -Y 1 -(L 1 O) p -but formula: -O-CH2CH2-O- Item 3. The optical material according to item 1 or 2, represented by the formula: [Section 4] Item 4. The optical material according to any one of items 1 to 3, which is for molding. [Section 5] Item 5. The optical material according to any one of items 1 to 4, which is for forming a free-standing film. [Section 6] The iodine-containing polymer is formula: CH2=C(-X 2 )-C(=O)-Y 2 -R [In the formula, TIP is the triiodophenyl group, X 2 is a hydrogen atom, a methyl group or a halogen atom, Y 2 is -O- or -NH-, R is an organic group having 2 to 30 carbon atoms. 6. The optical material according to any one of items 1 to 5, having a repeating unit derived from a triiodophenyl group-free acrylic monomer (2) represented by the following formula: [Section 7] Item 7. The optical material according to item 6, wherein R is an alkylene group or a (poly)oxyalkylene group. [Section 8] 8. The optical material according to any one of items 1 to 7, wherein the content of the repeating unit derived from the monomer (1) in the iodine-containing polymer is 75% by weight or more. [Section 9] Item 9. The optical material according to any one of items 1 to 8, wherein the iodine-containing polymer has a structure derived from a molecular weight control agent. [Section 10] Item 10. An optical component comprising the optical material according to any one of items 1 to 9. [Section 11] Item 11. The optical component according to item 10, which is a molded product of the optical material. [Section 12] Item 12. The optical component according to item 10 or 11, which is a free-standing film. [Section 13] Item 10. A method for producing an optical component, comprising a step of molding the optical material according to any one of items 1 to 9. [Section 14] Item 14. The method for producing an optical component according to item 13, further comprising the steps of: forming a film of an optical material on a substrate by performing the molding process; and separating the film from the substrate. [Section 15] Item 13. An optical article comprising the optical component according to any one of items 10 to 12. Effect of the Invention

[0007] The optical material according to the present disclosure has excellent moldability and exhibits a high refractive index. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Optical materials> The optical material in the present disclosure is a material that is a raw material for various optical components, and is particularly used in optical components that utilize its high refractive index. The optical material in the present disclosure contains an iodine-containing polymer described below.

[0009] [Iodine-containing polymer] The iodine-containing polymer in the present disclosure contains a repeating unit derived from a triiodophenyl group-containing acrylic monomer (1).

[0010] [Characteristics of iodine-containing polymers] The iodine-containing polymer of the present disclosure has excellent moldability. The term "excellent moldability" means, for example, that the polymer exhibits plasticity and viscosity suitable for molding and can be formed into a predetermined shape. The molding process may be a thermoforming process, or the polymer may be molded in a softened state by heating. Examples of the molding process include compression molding, extrusion molding, and injection molding. Conventional iodine-containing polymers have problems such as not exhibiting sufficient moldability and softening properties, and are not suitable for molding.

[0011] In addition, the iodine-containing polymer of the present disclosure can be treated as a self-supporting film after molding. A self-supporting film is one that does not have a base material or substrate and can maintain its shape by itself. Conventional iodine-containing polymers do not have sufficient moldability, and even if they are made into a film, they are difficult to separate from the base material due to poor flexibility and mechanical strength of the polymer, and cannot be a self-supporting film.

[0012] Furthermore, the optical material of the present disclosure may be excellent not only in refractive index and moldability, but also in solubility, film-forming properties, and / or heat resistance.

[0013] (Refractive index of iodine-containing polymer) The refractive index of the iodine-containing polymer in the present disclosure may be 1.65 or more, 1.70 or more, 1.72 or more, 1.76 or more, 1.78 or more, 1.80 or more, or 1.82 or more, preferably 1.72 or more, and more preferably 1.78 or more.

[0014] (Heat resistance of iodine-containing polymers) The heat resistance temperature of the iodine-containing polymer in the present disclosure (the temperature at which a 5% weight loss is observed when the temperature is increased at a rate of 10°C / min in a nitrogen gas atmosphere) may be 250°C or higher, 260°C or higher, 270°C or higher, 280°C or higher, 290°C or higher, 300°C or higher, 310°C or higher, or 320°C or higher, preferably 260°C or higher, and more preferably 280°C or higher.

[0015] (Molecular weight of iodine-containing polymer) The weight average molecular weight of the iodine-containing polymer in the present disclosure may be 10000 or more, 25000 or more, 50000 or more, 75000 or more, 100000 or more, 150000 or more, 200000 or more, 250000 or more, or 300000 or more, preferably 50000 or more, more preferably 75000 or more. The number average molecular weight of the iodine-containing polymer in the present disclosure may be 3000000 or less, 2000000 or less, 1000000 or less, 500000 or less, 250000 or less, 150000 or less, or 100000. The molecular weight in the above range, particularly the above lower limit or more, is suitable for the molding processability and refractive index of the iodine-containing polymer. The weight average molecular weight may be a polystyrene-equivalent molecular weight.

[0016] The dispersion index (Mw / Mn) of the iodine-containing polymer in the present disclosure may be 1.5 or more, 2 or more, 3 or more, or 4 or more. The dispersion index (Mw / Mn) of the iodine-containing polymer in the present disclosure may be 7.5 or less, 5 or less, 4 or less, or 3 or less.

[0017] [Structure of iodine-containing polymer] The iodine-containing polymer may be linear or branched, but is preferably linear.

[0018] ((1) Triiodophenyl group-containing acrylic monomer) The iodine-containing polymer has a repeating unit derived from a triiodophenyl group-containing acrylic monomer (1). Conventionally, iodine-containing polymers have a problem in that their moldability is insufficient. The present inventors unexpectedly discovered that by selecting a triiodophenyl group-containing acrylic monomer (1) among iodine-containing monomers, it is possible to solve these problems while having a high refractive index.

[0019] The monomer (1) in the present disclosure is formula: CH2=C(-X 1 )-C(=O)-Y 1 -(L 1 O) p -TIP [In the formula, TIP is a triiodophenyl group, X 1 is a hydrogen atom, a methyl group or a halogen atom, Y 1 is -O- or -NH-, L 1 each independently represents an alkylene group having 1 to 10 carbon atoms, p is between 1 and 5.] It may be expressed as:

[0020] TIP is a triiodophenyl group, which may be a 2,3,5-triiodophenyl group or a 2,4,6-triiodophenyl group, and is preferably a 2,4,6-triiodophenyl group.

[0021] X 1 is preferably a hydrogen atom or a methyl group.

[0022] Y 1 is preferably -O-.

[0023] L 1 may have 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more carbon atoms, and may have 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less, for example, 4 or less.

[0024] p may be 1 or more, 2 or more, 3 or more, or 4; and may be 5 or less, 4 or less, 3 or less, 2 or less, or 1, for example, 3 or less.

[0025] -(L 1 O) p -L 1 Specific examples of O- include: -CH2CH2O- -CH2CH(CH3)O- -CH2CH(C2H5)O- -CH2C(CH3)2O- -CH2CH2CH2CH2O- etc.

[0026] ((2) Triiodophenyl group-free acrylic monomers) The iodine-containing polymer may contain a repeating unit derived from a non-triiodophenyl group-containing acrylic monomer (2).

[0027] The triiodophenyl group-free acrylic monomer (2) does not have a triiodophenyl group. The triiodophenyl group-free acrylic monomer (2) may not have an iodophenyl group, and may not have an iodine atom.

[0028] The monomer (2) in the present disclosure is formula: CH2=C(-X 2 )-C(=O)-Y 2 -R [In the formula, X 2 is a hydrogen atom, a methyl group or a halogen atom, Y 2 is -O- or -NH- R is a hydrogen atom, a hydroxyl group, or an organic group having 1 to 30 carbon atoms.] It may be expressed as:

[0029] X 2 is preferably a hydrogen atom or a methyl group.

[0030] Y 2 is preferably -O-.

[0031] R may be an aliphatic or aromatic group, preferably an aliphatic group, in particular an alkyl group or a (poly)oxyalkylene group.

[0032] When R is an alkyl group, R may have 1 or more, 2 or more, 3 or more, 5 or more, or 10 or more carbon atoms, and may have 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less carbon atoms.

[0033] When R is a (poly)oxyalkylene group, the number of oxygen atoms in R may be 1 or more, 2 or more, or 3 or more, and may be 25 or less, 7 or less, or 5 or less.

[0034] When R is a (poly)oxyalkylene group, R is a group of the formula: -(R 1 O) q -R 2 [In the formula, R 1 are each independently an alkylene group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and q is 1 or more and 100 or less.] It may be expressed as:

[0035] R 1 may have 1 or more, 2 or more, 3 or more, or 5 or more carbon atoms, and may have 10 or less, 7 or less, 5 or less, or 3 or less carbon atoms.

[0036] q may be 1 or more, 3 or more, 5 or more, 10 or more, 25 or more, or 50 or more; and may be 100 or less, 80 or less, 60 or less, 40 or less, 20 or less, 10 or less, or 5 or less.

[0037] -(R 1 O) q -R 1 Specific examples of O- include: -CH2CH2O- -CH2CH(CH3)O- -CH2CH(C2H5)O- -CH2C(CH3)2O- -CH2CH2CH2CH2O- etc.

[0038] R 2 When R is an alkyl group, 2 may have 1 or more, 2 or more, 3 or more, or 5 or more carbon atoms, and may have 10 or less, 7 or less, 5 or less, or 3 or less carbon atoms.

[0039] (Sulfur-containing structure) The iodine-containing polymer in the present disclosure may have a sulfur atom. The refractive index of the iodine-containing polymer may be improved by having a sulfur atom. The sulfur atom may be present in the main chain or in a side chain, and is preferably present in the main chain.

[0040] (Structure derived from molecular weight control agent) The iodine-containing polymer in the present disclosure may have a structure derived from a molecular weight control agent. The molecular weight control agent is an additive that can control the molecular weight range by suppressing polymerization, and is typically a chain transfer agent. The molecular weight control agent is preferably an aromatic compound. By being aromatic, the refractive index of the iodine-containing polymer can be improved. Examples of the molecular weight control agent include various chain transfer agents, RAFT agents, NMP agents, ATRP agents, and TERP agents, and sulfur-containing chain transfer agents such as thiol-type chain transfer agents and RAFT agents are preferred.

[0041] The thiol type chain transfer agent may be a monothiol compound, a dithiol compound, a trithiol compound, or a polythiol compound having tetrathiol or more, but is preferably a monothiol compound or a dithiol compound. The thiol type chain transfer agent may be a thiol compound having a sulfur atom in addition to a thiol group. The thiol compound may be a molecule consisting of only carbon, hydrogen, and sulfur.

[0042] Specific examples of thiol-type chain transfer agents include aliphatic monothiol compounds such as methanethiol, ethanethiol, propanethiol, butanethiol, and cyclohexanethiol;

[0043] Methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercapto-1-propanol(2-mercaptoacetate), 2,3-dimercapto-1-propanol(3-mercaptopropionate), diethylene glycol bis( aliphatic polythiol compounds such as bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl)ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), and tetrakis(mercaptomethyl)methane;

[0044] Bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropyl)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, bis(1,3-Dimercapto-2-propyl) sulfide, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl ethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-Mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), thioglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), 4,4'-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester) Aliphatic thiols containing a sulfur atom in addition to a mercapto group, such as dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4'-dithiodibutyric acid bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid bis(2,3-dimercaptopropyl ester), and dithiodipropionic acid (2,3-dimercaptopropyl ester);

[0045] Aromatic monothiol compounds such as benzenethiol, o-methyl-α-toluenethiol, o-toluenethiol, m-toluenethiol, p-toluenethiol, 1-naphthalenethiol, and 2-naphthalenethiol;

[0046] 1,2-Dimercaptobenzene, 1,3-Dimercaptobenzene, 1,4-Dimercaptobenzene, 1,2-Bis(mercaptomethyl)benzene, 1,3-Bis(mercaptomethyl)benzene, 1,4-Bis(mercaptomethyl)benzene, 1,2-Bis(mercaptoethyl)benzene, 1,3-Bis(mercaptoethyl)benzene, 1,4-Bis(mercaptoethyl)benzene, 1,2,3-Trimercaptobenzene, 1,2,4-Trimercaptobenzene, 1,3,5-Trimercaptobenzene, 1,2,3-Tris(mercaptomethyl)benzene, 1,2, aromatic polythiols such as 4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane;

[0047] 1,2-bis(mercaptomethylenethio)benzene, 1,3-bis(mercaptomethylenethio)benzene, 1,4-bis(mercaptomethylenethio)benzene, 1,2-bis(mercaptoethylenethio)benzene, 1,3-bis(mercaptoethylenethio)benzene, 1,4-bis(mercaptoethylenethio)benzene, 1,2-bis(mercaptopropylenethio)benzene, 1,3-bis(mercaptopropylenethio)benzene, 1,4-bis(mercaptopropylenethio)benzene, 1,2-bis(mercaptoethylenethiomethylene)benzene, 1,3 -Bis(mercaptoethylenethiomethylene)benzene, 1,4-bis(mercaptoethylenethiomethylene)benzene, 1,2-bis(mercaptopropylenethiomethylene)benzene, 1,3-bis(mercaptopropylenethiomethylene)benzene, 1,4-bis(mercaptopropylenethiomethylene)benzene, bis(4-mercaptophenyl)sulfide, bis(3-mercaptophenyl)sulfide, 4,4'-oxybisbenzenethiol, 4,4'-biphenyldithiol, 1,2-bis(mercaptomethyleneoxy)benzene, 1,3-bis(methyl) 1,4-bis(mercaptomethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis(mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxymethylene)benzene, 1,3-bis(mercaptoethyleneoxymethylene)benzene, 1,4-bis(mercaptoethyleneoxymethylene)benzene, 1,2-bis(mercaptopropyleneoxymethylene)benzene, 1,3-bis(mercaptopropyleneoxymethylene)benzene, aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups, such as 1,4-bis(mercaptopropyleneoxymethylene)benzene, 1,4-bis(mercaptopropyleneoxymethylene)benzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, and 1,3,5-tris(mercaptoethylthio)benzene;

[0048] Heterocyclic compounds containing a sulfur atom in addition to a mercapto group, such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole;

[0049] 2-Mercaptoethanol, 3-Mercapto-1,2-propanediol, Glycerin di(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, Pentaerythritol tris(3-mercaptopropanediol) Examples of the mercapto group include compounds containing a hydroxy group in addition to a mercapto group, such as pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), dipentaerythritol pentakis(3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, and 1-hydroxyethylthio-3-mercaptoethylthiobenzene, as well as derivatives thereof. These may be used alone or in combination of two or more.

[0050] Specific examples of RAFT agents include dithioesters such as 2-cyano-2-propyl benzodithioate and 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid; trithiocarbonates such as 2-cyano-2-propyl dodecyl trithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid and cyanomethyl dodecyl trithiocarbonate; dithiocarbamates such as cyanomethyl methyl(phenyl)carbamodithioate; and disulfides such as bis(thiobenzoyl) disulfide and bis(dodecylsulfanylthiocarbonyl) disulfide. These may be used alone or in combination of two or more.

[0051] (Structures derived from other sources) The iodine-containing polymer of the present disclosure may have a structure derived from other raw materials in addition to the above. Specific examples of other raw materials include styrene monomers such as styrene, p-methylstyrene, α-methylstyrene, halogenated styrene, vinyl benzoic acid, 4-vinylbenzenesulfonic acid, 4-vinylbenzenesulfonic acid ester, and 4-vinylbenzenesulfonic acid amide; amide group-containing vinyl monomers such as (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide; methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, and 2-methyl(meth)acrylate; -ethylhexyl, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, Nt-butylaminoethyl (meth)acrylate, polyethylene glycol (meth)acrylate, and other (meth)acrylate and (meth)acrylamide monomers; nitrile group-containing vinyl monomers such as (meth)acrylonitrile; and other monomers such as vinyl halide, vinylidene halide, and vinyl acetate. These may be used alone or in combination of two or more.

[0052] [Composition of iodine-containing polymer] The content of the repeating unit derived from the monomer (1) in the iodine-containing polymer may be 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, or 95% by weight or more, and is preferably 70% by weight or more. The content of the repeating unit derived from the monomer (1) in the iodine-containing polymer may be 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or more, or 45% by weight or less. From the viewpoint of improving the refractive index, the larger the amount of the monomer (1), the more preferable.

[0053] The content of the repeating unit derived from the monomer (2) in the iodine-containing polymer may be 2.0% by weight or more, 4.0% by weight or more, 6.0% by weight or more, 8.0% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more. The content of the repeating unit derived from the monomer (2) in the iodine-containing polymer may be 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, or 7.5% by weight or less. The presence of the repeating unit derived from the monomer (2) makes it possible to form a high molecular weight polymer, and the density of the synthesized polymer increases, thereby increasing the refractive index. It may also be preferable from the viewpoint of moldability.

[0054] The content of the structure derived from the molecular weight control agent in the iodine-containing polymer may be 1.0% by weight or more, 3.0% by weight or more, 5.0% by weight or more, or 10% by weight or more, and preferably 3% by weight or more. The content of the structure derived from the molecular weight control agent in the iodine-containing polymer may be 50% by weight or less, 40% by weight or less, 30% by weight or less, or 25% by weight or less, and preferably 40% by weight or less.

[0055] The content of the structure derived from other raw materials in the iodine-containing polymer may be 1.0% by weight or more, 3.0% by weight or more, 5.0% by weight or more, or 10% by weight or more. The content of the structure derived from other raw materials in the iodine-containing polymer may be 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0056] The iodine content in the iodine-containing polymer may be 10% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, or 45% by weight or more, and is preferably 30% by weight or more. The iodine content in the iodine-containing polymer may be 55% by weight or less, 50% by weight or less, or 45% by weight or less.

[0057] The sulfur content in the iodine-containing polymer may be 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, 4.0% by weight or more, 5.0% by weight or more, or 7.5% by weight or more, and is preferably 2.0% by weight or more. The sulfur content in the iodine-containing polymer may be 30% by weight or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less, and is preferably 10% by weight or less.

[0058] The content of the repeating unit derived from the monomer (1) may be 2.0 molar parts or more, 3.0 molar parts or more, 5.0 molar parts or more, 10 molar parts or more, 15 molar parts or more, or 20 molar parts or more, preferably 3 molar parts or more, relative to 1 molar part of the structure derived from the molecular weight regulator in the iodine-containing polymer. The content of the repeating unit derived from the monomer (1) may be 50 molar parts or less, 45 molar parts or less, 40 molar parts or less, 35 molar parts or less, 30 molar parts or less, or 25 molar parts or less, preferably 40 molar parts or less, relative to 1 molar part of the structure derived from the molecular weight regulator.

[0059] The content of the repeating unit derived from the monomer (2) may be 0.2 molar parts or more, 0.3 molar parts or more, 0.5 molar parts or more, 1.0 molar parts or more, 1.5 molar parts or more, or 2 molar parts or more, preferably 0.3 molar parts or more, relative to 1 molar part of the structure derived from the molecular weight regulator in the iodine-containing polymer. The content of the repeating unit derived from the monomer (1) may be 5.0 molar parts or less, 4.5 molar parts or less, 4.0 molar parts or less, 3.5 molar parts or less, 3.0 molar parts or less, or 2.5 molar parts or less, preferably 4.0 molar parts or less, relative to 1 molar part of the structure derived from the molecular weight regulator.

[0060] The content of the repeating unit derived from the monomer (2) may be 0.01 molar parts or more, 0.02 molar parts or more, 0.03 molar parts or more, 0.05 molar parts or more, 0.1 molar parts or more, 0.15 molar parts or more, or 0.2 molar parts or more, preferably 0.03 molar parts or more, for example 0.1 molar parts or more, relative to 1 molar part of the repeating unit derived from the monomer (1) in the iodine-containing polymer. The amount of the monomer (2) used may be 0.5 molar parts or less, 0.45 molar parts or less, 0.4 molar parts or less, 0.35 molar parts or less, 0.3 molar parts or less, 0.25 molar parts or less, 0.15 molar parts or less, or 0.10 molar parts or less, preferably 0.4 molar parts or less, relative to 1 molar part of the monomer (1).

[0061] By containing each component in the above range, the iodine-containing polymer can have a high refractive index and moldability, while also exhibiting a good balance of excellent solubility, film-forming ability, heat resistance and transparency.

[0062] [Method for producing iodine-containing polymer] In the method for producing the iodine-containing polymer of the present disclosure, the iodine-containing polymer can be obtained by a step of polymerizing the above-mentioned monomers as raw materials. The method for producing an iodine-containing polymer according to the present disclosure includes the steps of: Polymerizing the monomer in the presence of a molecular weight control agent By polymerizing the monomer in the presence of a molecular weight control agent, it becomes easy to control the molecular weight within the above-mentioned range.

[0063] The amount of the raw material used can be appropriately changed so that the above-mentioned iodine-containing polymer can be obtained. The amount of the monomer (1) used can be 2.0 molar parts or more, 3.0 molar parts or more, 5.0 molar parts or more, 10 molar parts or more, 15 molar parts or more, or 20 molar parts or more, preferably 3 molar parts or more, for example 10 molar parts or more, relative to 1 molar part of the molecular weight control agent. The amount of the monomer (1) used can be 50 molar parts or less, 45 molar parts or less, 40 molar parts or less, 35 molar parts or less, 30 molar parts or less, or 25 molar parts or less, preferably 40 molar parts or less, relative to 1 molar part of the molecular weight control agent. For example, by increasing the amount of the molecular weight control agent, polymerization can be suppressed, and it is possible to suppress the increase in molecular weight.

[0064] The amount of the monomer (2) used may be 0.2 molar parts or more, 0.3 molar parts or more, 0.5 molar parts or more, 1.0 molar parts or more, 1.5 molar parts or more, or 2 molar parts or more, preferably 0.3 molar parts or more, for example 1 molar part or more, relative to 1 molar part of the molecular weight control agent. The amount of the monomer (2) used may be 5.0 molar parts or less, 4.5 molar parts or less, 4.0 molar parts or less, 3.5 molar parts or less, 3.0 molar parts or less, or 2.5 molar parts or less, preferably 4.0 molar parts or less, relative to 1 molar part of the molecular weight control agent. For example, by increasing the amount of the molecular weight control agent, polymerization can be suppressed, and it is possible to suppress the increase in molecular weight.

[0065] The amount of monomer (2) used may be 0.01 molar parts or more, 0.02 molar parts or more, 0.03 molar parts or more, 0.05 molar parts or more, 0.1 molar parts or more, 0.15 molar parts or more, or 0.2 molar parts or more, preferably 0.03 molar parts or more, for example 0.1 molar parts or more, relative to 1 molar part of monomer (1). The amount of monomer (2) used may be 0.5 molar parts or less, 0.45 molar parts or less, 0.4 molar parts or less, 0.35 molar parts or less, 0.3 molar parts or less, 0.25 molar parts or less, 0.15 molar parts or less, or 0.10 molar parts or less, preferably 0.4 molar parts or less, relative to 1 molar part of monomer (1). The presence of monomer (2) can improve film-forming properties.

[0066] In the present disclosure, the polymerization method is not particularly limited, and can be performed by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., but is preferably solution polymerization. Also, a known polymerization method such as radical polymerization, anionic polymerization, cationic polymerization, etc. can be selected, but is preferably radical polymerization. An appropriate polymerization method can be selected depending on the type of monomer, polymerization temperature, etc.

[0067] In the present disclosure, an appropriate polymerization initiator can be selected and used depending on the type of monomer, polymerization temperature, etc. Examples of polymerization initiators include azo-based initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,2-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis(2-amidinopropane)dihydrochloride; and peroxide-based initiators such as benzoyl peroxide, di-t-butyl hydroperoxide, t-butyl hydroperoxide, cumyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, dicumyl peroxide, ethyl 3,3-di(t-amylperoxy)butyrate, potassium sulfate, and ammonium persulfate. These may be used alone or in combination of two or more kinds.

[0068] When the polymerization is carried out by solution polymerization, a suitable solvent is selected in consideration of the solubility of the monomer and the radical initiator, the polymerization temperature, etc., and the polymerization can be carried out in the solvent. Examples of the solvent include DMF, N-methyl-2-pyrrolidone, acetone, THF, benzene, toluene, ethylbenzene, xylene, chlorobenzene, methyl ethyl ketone, ethyl lactate, isopropyl alcohol, etc. These may be used alone or in combination of two or more kinds.

[0069] The polymerization temperature may be any temperature at which the polymerization initiator decomposes and polymerization begins, and may be, for example, 0°C or higher, 20°C or higher, 40°C or higher, 60°C or higher, or 70°C or higher, and is preferably 40°C or higher, and may be 100°C or lower, 90°C or lower, 80°C or lower, or 70°C or lower.

[0070] The optimal polymerization time can be determined depending on the selected monomer, polymerization initiator, polymerization temperature, etc., and may be, for example, 1 hour or more, 5 hours or more, 10 hours or more, 15 hours or more, or 20 hours or more, and may be 72 hours or less, 60 hours or less, 48 ​​hours or less, 36 hours or less, or 24 hours or less.

[0071] The amount of the polymerization initiator used may vary depending on the type of monomer and the type of initiator, but may be, for example, 0.1 mol% or more, 1 mol% or more, 3 mol% or more, 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, or 25 mol% or more, and may be 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less, based on the total amount of the monomers used.

[0072] The amount of the polymerization solvent used is not particularly limited, but may be in a range such that the raw material concentration is 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, and 50% by weight or less, 40% by weight or less, 30% by weight or less, or 20% by weight or less.

[0073] <Optical components and their manufacturing methods> The optical part includes an optical material containing the above-mentioned iodine-containing polymer. Examples of the optical part include a coating, a film, a sheet, a prism, a lens, a fiber, and the like. Since the optical material of the present disclosure has excellent moldability, the optical part may be produced by molding (e.g., thermoforming) the optical material. That is, the optical part may be a molded product of the optical material.

[0074] The optical component according to the present disclosure can be handled as a free-standing film after molding, because the iodine-containing polymer has excellent flexibility and mechanical strength and can be easily separated from the substrate.

[0075] The manufacturing method of the optical component in the present disclosure may include a step of molding the optical material. The molding may be performed using various molding devices such as compression molding, extrusion molding, and injection molding. The molding temperature is not particularly limited as long as it is a molding process, and may be a temperature equal to or higher than the temperature at which the optical material softens under normal pressure and equal to or lower than the decomposition temperature. The molding temperature may be, for example, 120°C or higher, 140°C or higher, 160°C or higher, 180°C or higher, or 200°C or higher, and may be 300°C or lower, 275°C or lower, 250°C or lower, 225°C or lower, 200°C or lower, or 175°C or lower.

[0076] The method for producing an optical component according to the present disclosure may include a step of forming a film of an optical material on a substrate by the above-mentioned molding process, and separating the film from the substrate. The method for separation is not particularly limited, and examples thereof include a method of physically gripping and peeling off a part of the film or the substrate, and a method of separating the film from the substrate using a sharp tool such as a blade.

[0077] It is also possible to form an optical component by dissolving an optical material in a solvent, applying the material to a substrate, and then drying the solvent. When applying the optical material to a substrate, the material may be used as a solution containing a solvent that dissolves the iodine-containing polymer. The type of solvent is not particularly limited as long as it dissolves the iodine-containing polymer, and for example, organic solvents such as THF, chloroform, DMF, and DMSO can be used. The concentration of the iodine-containing polymer in the liquid may be 0.01 wt% or more, 0.1 wt% or more, 0.5 wt% or more, or 1 wt% or more, and may be 5 wt% or less, 3 wt% or less, 1.5 wt% or less, or 0.5 wt% or less. A coating or the like may be obtained by applying a solution containing an iodine polymer to a substrate and removing the solvent as necessary. Examples of the application method include dip coating, spray coating, flow coating, shower coating, roll coating, spin coating, gravure coating, microgravure coating, comma roll coating, Mayer bar coating, slot bicoat, air knife coating, lip coating, kiss coating, brush coating, etc. The removal of the solvent is not particularly limited, but can be carried out at, for example, 0 to 200°C.

[0078] The type of the substrate is not particularly limited, and may be resin, glass, metal, ceramic, or the like.

[0079] The film thickness of the optical component may be 0.1 μm or more, 1 μm or more, or 3 μm or more, and may be 1 m or less, 500 μm or less, or 200 μm or less.

[0080] <Optical article having optical component> Examples of optical articles having optical components such as the above-mentioned coatings include, but are not limited to, optical devices such as high refractive index light emitting diodes (LEDs) and image sensors; high refractive index materials such as anti-reflection films, lenses, and lens coatings; and optical instruments such as telescopes, binoculars, microscopes, cameras, endoscopes (fiberscopes), planetariums, length measuring instruments, comparators, range finders, spectrometers, interferometers, and polarimeters.

[0081] Although the embodiments have been described above, it will be understood that various changes in form and detail can be made without departing from the spirit and scope of the claims.

Example

[0082] Hereinafter, embodiments of the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.

[0083] The test method is as follows.

[0084] <NMR Measurement> The identification of the compound was performed using NMR. 400 MHz-NMR manufactured by JEOL Ltd., JOEL ECS-400K or 400 MHz-NMR manufactured by JEOL Ltd., JOEL ECZ-400 was used.

[0085] <SEC Measurement> It was carried out under the following equipment and conditions. HLC-8320GPC manufactured by Tosoh Corporation Column; TSKgel SuperMultipore HZ-M × 2 (4.6 mm I.D. × 15 cm × 2) Standard; Polystyrene SRM706 (NIST) Eluent; THF Detector; RI; Polarity (+), Response (0.5 s) UV; Wavelength (254 nm), Polarity (+), Response (0.5 s)

[0086] <Refractive Index> The refractive index of the iodine-containing polymer was measured by forming the iodine-containing polymer on a silicon wafer, measuring 30 points with a laser having a wavelength of 632 nm using an ellipsometer (SE-101 manufactured by Photonic Lattice Co., Ltd.), and averaging them. The results are shown in the following table.

[0087] <Heat Resistance> Using a TGA measuring device (Shimadzu Model TGA-50 / 50H), measurements were performed in a nitrogen gas atmosphere at a temperature range of 25°C to 450°C at a heating rate of 10°C / min. The temperature T at which a 5% weight loss was observed was d are shown in the table below.

[0088] <Molding processability test> The obtained iodine-containing polymer was molded using a vacuum press (manufactured by Imoto Manufacturing, manual hydraulic vacuum heating press). The resin was placed in a mold, sandwiched between metal plates (aluminum plates), and placed in a vacuum press, where the pressure was reduced to 0.1 MPa or less, and then heated until the molding temperature reached 200°C. After the molding temperature was reached, the press pressure was increased to 2 MPa and heated for 2 minutes. The press pressure was then increased over 3 minutes, and molding was performed while maintaining 15 MPa for 5 minutes. After molding, the pressure was returned to atmospheric pressure and cooled to room temperature. The moldability was evaluated according to the following criteria. ○: A uniform film can be formed, and the resulting film can be separated from the substrate. ×: An uneven film is formed and / or the film is damaged when attempting to separate from the substrate, making it impossible to separate as a film.

[0089] [Synthesis of Monomer (1) Precursor (TIPE)] TIFF2024156489000001.tif36170100ml eggplant flask was charged with 10mmol (4.71g) of 2,4,6-triiodophenol, 12mmol (3.90g) of cesium carbonate as a base catalyst, 0.5mmol (0.16g) of tetrabutylammonium bromide (TBAB) as a catalyst, and 20ml of N-Methyl-pyrolidone (NMP) as a solvent. The mixture was pre-stirred at 60℃ for 1 hour, then 15mmol (1.2g) of 2-chloroethanol was added and stirred at 60℃ for another 24 hours. A yellow solid was obtained. Evaporation was performed and ethyl acetate was added. The salt was removed by filtration, and separation operations (1N HCl, sat. NaHCO3, sat. NaCl) were performed three times each. The organic layer was dehydrated with MgSO4 and dried under reduced pressure to obtain 4.46 g of a yellow powder solid (2,4,6-triiodophonoxyethanol (TIPE)). The yield was 81%.

[0090] [Synthesis of Monomer (1) (TIPEA)] TIFF2024156489000002.tif3517050mmol (25.7g) of 2,4,6-triiodophonoxyethanol (TIPE) obtained in the above synthesis, 70mmol (7.08g) of triethylamine, and 150ml of dichloromethane (DCM) as a solvent were placed in a 100ml eggplant flask, and 75mmol (6.74g) of acrylic chloride diluted with 7ml of dichloromethane (DCM) was added in an ice bath and stirred at room temperature for 8 hours. A yellow solid was obtained. The solid was eluted with a developing solvent of chloroform:hexane = 3:1 by column chromatography, and dried under reduced pressure to obtain 14.89g of white solid powder (2,4,6-triiodo2-phenyloxyethyl acrylate (TIPEA)). The yield was 52%.

[0091] [Example 1: Synthesis of iodine-containing polymer (poly(TIPEA))] TIFF2024156489000003.tif36169In a 10 ml eggplant flask, 6 mmol (3.41 g) of 2,4,6-triiodo2-phenyloxyethyl acrylate (TIPEA) obtained in the above synthesis, 0.18 mmol (0.029 g) of azobisisobutyronitrile (AIBN) as a polymerization initiator, and 1.8 ml of dimethylformamide (DMF) as a solvent were placed, degassed and air-dried, and stirred in a 60°C oil bath for 20 hours. After reprecipitation with diethyl ether and membrane filtration, the mixture was dried under reduced pressure to obtain 3 g of iodine-containing polymer. The yield was 88%.

[0092] [Example 2: Synthesis of iodine-containing polymer (poly(TIPEA-co-EEA))] TIFF2024156489000004.tif511680.95mmol of TIPEA obtained in the above synthesis, 0.05mmol of 2-(2-Ethoxyethoxy)ethyl Acrylate (EEA), 0.3ml of THF, and AIBN (3mol% based on the total amount of TIP-AC and EEA) were placed in a polymerization tube, degassed and sealed, and stirred for 20h in a 60℃ oil bath. After dilution with THF, the mixture was reprecipitated with diethyl ether, filtered through a membrane, and dried under reduced pressure to obtain an iodine-containing polymer. The obtained iodine-containing polymer was subjected to thermogravimetry, solubility test, and refractive index measurement.

[0093] [Examples 3 to 5: Synthesis of iodine-containing polymer (poly(TIPEA-co-EEA))] Poly(TIPEA-co-EEA) was synthesized in the same manner as in Example 2, except that the molar ratio of TIPEA to EEA was changed as shown in the table below.

[0094] [Comparative Example 1: Synthesis of iodine-containing polymer (poly(TIPA))] Instead of TIPEA, Except for using the same molar amount of TIPA (triiodophenyl acrylate) represented by TIFF2024156489000005.tif4523, poly(TIPA) was synthesized in the same manner as in Example 1. TIPA was synthesized by the method described in JP-A-2022-131503.

[0095] [Comparative Example 2: Synthesis of iodine-containing polymer poly(TIPA-EEA)] Instead of TIPEA, Poly(TIPA-EEA) was synthesized in the same manner as in Example 3, except that the same molar amount of TIPA represented by TIFF2024156489000006.tif4523 was used.

[0096] [result] The composition and measurement results of the obtained iodine-containing polymer are shown in the table below. [Table 1] TIFF2024156489000007.tif38158 [Industrial Applicability]

[0097] The iodine-containing polymer of the present disclosure can be used in optical devices such as high refractive index light-emitting diodes (LEDs) and image sensors; high refractive index materials such as high refractive index polymer materials for antireflection films, lens materials, and lens coating films; and optical instruments such as telescopes, binoculars, microscopes, cameras, endoscopes (fiberscopes), planetariums, length measuring instruments, comparators, range finders, spectrometers, interferometers, and polarimeters.

Claims

1. formula: CH 2 =C(-X １ )-C(=O)-Y １ -(L １ O) ｐ -TIP [In the formula, TIP is a triiodophenyl group, X １ is a hydrogen atom, a methyl group, or a halogen atom, Y １ is —O— or —NH—, L １ are each independently an alkylene group having 1 to 10 carbon atoms, p is 1 or more and 5 or less. An optical material comprising an iodine-containing polymer containing a repeating unit derived from a triiodophenyl group-containing acrylic monomer (1) represented by the formula:

2. L １ are each independently an alkylene group having 1 to 4 carbon atoms, 2. The optical material according to claim 1, wherein p is 1 to 3.

3. -Y １ —(L １ O) ｐ -が formula: -O-CH ２ CH ２ -O- The optical material according to claim 1 , wherein

4. The optical material according to claim 1 , which is suitable for molding.

5. The optical material according to claim 1 , which is for forming a free-standing film.

6. The iodine-containing polymer is formula: CH 2 =C(-X ２ )-C(=O)-Y ２ -R [In the formula, X ２ is a hydrogen atom, a methyl group, or a halogen atom, Y ２ is —O— or —NH—, R is an organic group having 2 to 30 carbon atoms. The optical material according to claim 1, which has a repeating unit derived from a triiodophenyl group-free acrylic monomer (2) represented by the following formula:

7. 7. The optical material according to claim 6, wherein R is an alkylene group or a (poly)oxyalkylene group.

8. 2. The optical material according to claim 1, wherein the content of the repeating unit derived from the monomer (1) in the iodine-containing polymer is 75% by weight or more.

9. The optical material according to claim 1 , wherein the iodine-containing polymer has a structure derived from a molecular weight control agent.

10. An optical component comprising the optical material according to any one of claims 1 to 9.

11. The optical component according to claim 10 , which is a molded product of the optical material.

12. 11. The optical component according to claim 10, which is a free-standing film.

13. A method for producing an optical component, comprising a step of molding the optical material according to any one of claims 1 to 9.

14. The method for manufacturing an optical component according to claim 13 , further comprising the steps of: forming a film of an optical material by performing the molding process on a substrate; and separating the film from the substrate.

15. An optical article comprising the optical component according to claim 10.