Composition containing monomers for optical components, polymerizable composition for optical components, cured product, spectacle lens, and method for producing a composition containing monomers for optical components.

Abstract

One embodiment of the present disclosure relates to a monomer for an optical member, the monomer containing a compound represented by formula (1), wherein the pH is 4.0-7.5 as obtained by the following pH measurement method. (pH measurement method) A sample (80 g), toluene (80 ml), and water (250 ml) are mixed in a separatory funnel, an aqueous phase is separated, and the pH of the aqueous phase is measured.

Description

Technical Field

[0001] The present disclosure relates to a monomer for an optical member A composition containing (hereinafter also simply referred to as "monomer for optical components") , a polymerizable composition for an optical member, a cured product, a spectacle lens, and a method for producing a monomer for an optical member.

Background Art

[0002] As a monomer for an optical member used in a spectacle lens, an episulfide compound is known. By polymerizing and curing the episulfide compound, a resin having high transparency, a high refractive index, and a high Abbe number can be obtained (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] For example, when a polymerizable composition for an optical member containing the episulfide compound shown in Patent Document 1 is thermally polymerized, curing may be insufficient and a soft solid may be obtained, and improvement in polymerizability may be required.

[0005] One embodiment of the present disclosure relates to a monomer for an optical member having excellent polymerizability, a polymerizable composition for an optical member containing the monomer, a cured product thereof, a spectacle lens containing the cured product, and a method for producing a monomer for an optical member.

Means for Solving the Problems

[0006] The present inventor has found that the polymerizability is improved by using a monomer for an optical member showing a pH within a predetermined range.

[0007] One embodiment according to the present disclosure is Formula (1): [ka] (In the formula, X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2.) Contains a compound represented by the formula, This invention relates to monomers for optical components whose pH, obtained by the pH measurement method described below, is between 4.0 and 7.5. (pH measurement method) Mix 80g of the sample, 80ml of toluene, and 250ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase.

[0008] One embodiment of the present disclosure relates to a polymerizable composition for optical components containing the above-mentioned monomer.

[0009] One embodiment of the present disclosure relates to a cured product of the polymerizable composition for optical components described above.

[0010] One embodiment of the present disclosure relates to an eyeglass lens comprising a lens substrate containing the cured product described above.

[0011] One embodiment relating to this disclosure is, Formula (1): [ka] A method for producing a monomer for optical components containing a compound represented by the formula (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2), Formula (2): [ka] The method involves obtaining the compound represented by formula (1) using a compound represented by (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2) and a sulfurizing agent, The compound represented by the formula (1) is washed with water until the pH obtained by the following pH measurement method becomes 4.0 to 7.5, (pH measurement method) 80 g of a sample, 80 ml of toluene, and 250 ml of water are mixed in a separatory funnel, the aqueous phase is separated, and the pH of the aqueous phase is measured. It relates to a method for producing a monomer for an optical member, including this.

Effect of the invention

[0012] According to one embodiment of the present disclosure, it is possible to provide a monomer for an optical member having excellent polymerizability, a polymerizable composition for an optical member containing the monomer, a cured product thereof, an eyeglass lens containing the cured product, and a method for producing a monomer for an optical member.

Mode for carrying out the invention

[0013] Hereinafter, embodiments of the present disclosure (hereinafter referred to as "the present embodiment") will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the gist thereof. In this specification, for example, the notation of a numerical range such as "1 to 100" is intended to include both the lower limit value "1" and the upper limit value "100". The same applies to the notation of other numerical ranges.

[0014] [Monomer for optical member] The monomer for an optical member according to the embodiment of the present disclosure is Formula (1): [[ID=​​​​​​​​​​​​Mix 80g of the sample, 80ml of toluene, and 250ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase.

[0016] According to the embodiments described above, monomers for optical components with excellent polymerizability can be obtained. The excellent polymerizability of the monomer provides effects such as improving the hardness of the monomer composition after curing. In the examples of this specification, hardness after thermal polymerization is shown as one aspect of the evaluation index for polymerizability, but hardness is also affected by other monomers and polymerization conditions, and it is not an absolute evaluation, but rather a relative difference in hardness is observed, so it is judged that polymerizability is improved.

[0017] <Compound (1)> The monomer for the optical component according to this embodiment is Formula (1): [ka] It contains a compound represented by the formula (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2) (hereinafter also referred to as "compound (1)"). X is preferably S. If X is O, then a is preferably 0. The number of carbon atoms in R is preferably 1 to 4, more preferably 2 or 3. Examples of divalent hydrocarbons of R include ethylene, propylene, and butylene groups.

[0018] Examples of compound (1) include bis(β-epithiopropyl) sulfide, bis(β-epithiopropyl) disulfide, bis(β-epithiopropyl) trisulfide, bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane, 1,3-bis(β-epithiopropyloxy)propane, 1,4-bis(β-epithiopropylthio)butane, and bis(β-epithiopropylthioethyl) sulfide. Among these, bis(β-epithiopropyl) sulfide and bis(β-epithiopropyl) disulfide are preferred, and bis(β-epithiopropyl) sulfide is more preferred. In other words, the compound represented by formula (1) is shown in formula (1-1) below: [ka] It is more preferable that the compound is represented by [formula].

[0019] The content (also referred to as purity) of compound (1) in the monomer for optical components according to this embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, based on the total amount of monomer for optical components. The upper limit of the content of compound (1) is not particularly limited, but it may be 100% by mass or less based on the total amount of monomer for optical components.

[0020] (pH) The monomer for optical components according to this embodiment has a pH of 4.0 to 7.5 obtained by the pH measurement method described below. A pH within this range yields a monomer for optical components that exhibits excellent polymerizability. Preferably, the pH is 4.3 to 7.5. A pH within the range of 4.3 to 7.5 further improves polymerizability and suppresses discoloration such as turbidity and yellowing. From the viewpoint of further improving polymerizability and further suppressing turbidity and discoloration, the pH is more preferably 4.4 to 7.0, even more preferably 4.5 to 7.0, and even more preferably 4.6 to 7.0.

[0021] (pH measurement method) Mix 80g of the sample, 80ml of toluene, and 250ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase. The sample mentioned above is a monomer for optical components. pH is measured at 25°C using a pH meter (for example, HORIBA, model number: F52, glass bead electrode (aqueous solution type, model number: 9615S-10D)).

[0022] The pH of the monomer for optical components according to this embodiment can be set to a predetermined range, for example, by adjusting the purification conditions of compound (1). The purification method can be, for example, the manufacturing method described later.

[0023] [Method for producing monomers for optical components] The method for producing monomers for optical components according to this embodiment is: Formula (2): [ka] The process of obtaining the compound represented by formula (1) using a compound represented by (wherein X, a, R, b, and n are the same as defined in formula (1)) (hereinafter also referred to as "the process of producing compound (2)") and a sulfurizing agent (hereinafter also referred to as "the process of producing compound (1)"), The compound represented by formula (1) above is washed with water until the pH obtained by the following pH measurement method is between 4.0 and 7.5 (hereinafter also referred to as the "washing step"), (pH measurement method) Mix 80g of the sample, 80ml of toluene, and 250ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase. Includes. The manufacturing process for compound (2) may precede the manufacturing process for compound (1). According to the above-described embodiment, monomers for optical components with excellent polymerizability can be obtained.

[0024] <Manufacturing process for compound (2)> The manufacturing process for compound (2) includes, for example, a step of reacting an epihalohydrin with a sulfur-based metal compound to obtain compound (2).

[0025] An example of an epihalohydrin is epichlorohydrin.

[0026] Examples of sulfur-based metal compounds include metal hydrosulfides, metal sulfides, and metal polysulfides. Examples of metals include alkali metals. Among these, metal hydrosulfides are preferred, sodium hydrosulfide or potassium hydrosulfide are more preferred, and sodium hydrosulfide is even more preferred.

[0027] The molar ratio of epihalohydrin to sulfur-based metal compound is preferably 5 to 20, more preferably 5 to 15, and even more preferably 5 to 10. Here, the molar ratio of epihalohydrin to sulfur-based metal compound refers to the molar ratio of the amount of epihalohydrin charged to the final amount of sulfur-based metal compound added.

[0028] It is preferable to add a sulfur-based metal compound to the epihalohydrin. The preferred temperature of the epihalohydrin when adding the sulfur-based metal compound is -5 to 30°C.

[0029] The solvent may or may not be used, but its use is preferred. Examples of solvents include water, alcohol, ether, aliphatic hydrocarbon, aromatic hydrocarbon, and halogenated hydrocarbon. Among these, water or alcohol is preferred, alcohol is more preferred, and methanol is even more preferred.

[0030] The reaction temperature is preferably -5 to 30°C, more preferably 0°C to 20°C, and even more preferably 5 to 15°C.

[0031] The reaction time is preferably 1 minute to 10 hours, more preferably 5 minutes to 5 hours, and even more preferably 10 minutes to 3 hours, after the completion of the addition of the sulfur-based metal compound.

[0032] It is preferable to react the epihalohydrin with a sulfur-based metal compound as described above, and then add a basic compound to the reaction product obtained from the reaction and proceed with the reaction. Examples of basic compounds include amines, alkali metal salts, and alkaline earth metal salts. Among these, alkali metal salts or alkaline earth metal salts are preferred. Examples of alkali metal salts include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide. Examples of alkaline earth metal salts include magnesium carbonate, calcium carbonate, magnesium hydroxide, and calcium hydroxide.

[0033] The basic compound is preferably added such that the molar ratio of the basic compound to the sulfur-based metal compound is preferably 1.0 to 3.5, more preferably 1.2 to 3.0, and even more preferably 1.5 to 3.0. Here, this refers to the molar ratio of the amount of basic compound added to the amount of sulfur-based metal compound added in the previous reaction.

[0034] In reactions with basic compounds, a solvent may or may not be used, but it is preferable to use one. Examples of solvents include water, alcohol, ether, aliphatic hydrocarbon, aromatic hydrocarbon, and halogenated hydrocarbon. Among these, water or alcohol is preferred, alcohol is more preferred, and methanol is even more preferred.

[0035] In reactions with basic compounds, the reaction temperature is preferably -5 to 30°C, more preferably 0°C to 20°C, and even more preferably 5 to 15°C. The reaction time is preferably 1 minute to 10 hours, more preferably 5 minutes to 5 hours, and even more preferably 10 minutes to 3 hours, after the completion of the addition of the basic compound.

[0036] After the reaction is complete, it is preferable to add an organic solvent to extract compound (2). Examples of organic solvents include hydrocarbons, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. Among these, aromatic hydrocarbons or halogenated hydrocarbons are preferred, with toluene, benzene, xylene, dichloromethane, and chloroform being more preferred, and toluene being even more preferred. Furthermore, the obtained organic phase is preferably washed with water to remove basic compounds. The organic phase is washed with water until the pH of the washing water is preferably 10 or less, and more preferably 9 or less. By removing the solvent from the organic phase obtained in this way, the target compound (2) can be obtained.

[0037] <Manufacturing process for compound (1)> In the manufacturing process of compound (1), compound (1) is obtained using compound (2) and a sulfurizing agent. The reaction between compound (2) and the sulfurizing agent derives an epithio group from the epoxy group of compound (2).

[0038] Examples of sulfurizing agents include thiourea and thiocyanates. Examples of thiocyanates include sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, calcium thiocyanate, and lead thiocyanate.

[0039] In the reaction, the amount of sulfurizing agent used relative to the epoxy group of compound (2) is preferably 1 to 5 equivalents, and more preferably 1 to 3 equivalents. The reaction temperature is, for example, 10 to 60°C, but when thiourea is used as the sulfurizing agent, it is preferably 10 to 30°C, and when thiocyanate is used as the sulfurizing agent, it is preferably 30 to 60°C.

[0040] In the manufacturing process of compound (1), it is preferable to use a solvent. Examples of solvents include aromatic solvents, aliphatic solvents, and alcohols. Examples of aromatic solvents include toluene, xylene, chlorobenzene, dichlorobenzene, and nitrobenzene. Examples of aliphatic solvents include dichloromethane, chloroform, and dichloroethane. Examples of alcohols include methanol, ethanol, isopropanol, butanol, methoxyethanol, ethylene glycol, and glycerin. Among these, aromatic solvents or alcohols are preferred, mixed solvents of aromatic solvents and alcohols are more preferred, and mixed solvents of toluene and methanol are even more preferred. In a mixed solvent of an aromatic solvent and an alcohol, the volume ratio of aromatic solvent to alcohol is preferably 20 / 80 to 80 / 20, more preferably 30 / 70 to 70 / 30, and even more preferably 40 / 60 to 60 / 40.

[0041] In the manufacturing process of compound (1), a weak acid may be added to adjust the pH in the reaction system. Examples of weak acids include acetic acid, acetic anhydride, phosphoric acid, and phosphoric anhydride. The amount of weak acid added is preferably 0.1 to 10% by volume, and more preferably 0.3 to 5% by volume, relative to the solvent.

[0042] (Washing process) In the washing step, compound (1) is washed with water until the pH obtained by the pH measurement method described above is 4.0 to 7.5. By washing with water until the pH is 4.0 to 7.5 in this step, a monomer for optical components containing compound (1) with excellent polymerizability is obtained. The washing with water is preferably carried out until the pH is 4.3 to 7.5 from the viewpoint of obtaining a monomer for optical components with excellent polymerizability, more preferably 4.4 to 7.0, even more preferably 4.5 to 7.0, and even more preferably 4.6 to 7.0 from the viewpoint of further improving polymerizability and further suppressing turbidity and discoloration.

[0043] The cleaning process is not particularly limited, but for example, it can be carried out by a method having the following steps in this order. (i) A step in which an aromatic solvent and an aqueous alkali metal salt solution are added to the reaction solution obtained in the manufacturing process of compound (1), and the aqueous phase and organic phase are separated. (ii) A step of washing the organic phase with an acidic aqueous solution. (iii) Washing the organic phase with water (iv) Washing the organic phase with an aqueous sodium bicarbonate solution. (v) Washing the organic phase with water

[0044] In (ii) to (v), washing means separating the formed aqueous phase from the organic phase.

[0045] (ii) removes impurities dissolved in the organic phase and makes the organic phase weakly acidic. Examples of the acidic aqueous solution in (ii) include dilute sulfuric acid aqueous solution and dilute hydrochloric acid aqueous solution. The concentration of the acidic aqueous solution is preferably 0.1 to 3% by mass, and more preferably 0.3 to 2% by mass. The number of washes in (ii) is preferably 1 to 4 times, and more preferably 2 or 3 times.

[0046] (iii) removes impurities dissolved in the organic phase. The water in (iii) is, for example, distilled water or deionized water. The number of washes in (iii) is preferably 1 to 10 times, more preferably 2 to 8 times, and even more preferably 4 to 6 times.

[0047] (iv) removes impurities dissolved in the organic phase and restores the organic phase to a weakly acidic pH. The concentration of the sodium bicarbonate aqueous solution is preferably 0.001 to 0.1% by mass, and more preferably 0.005 to 0.05% by mass. The number of washes in (iv) is preferably 1 to 3 times, and more preferably 1 time.

[0048] The pH of the organic phase is adjusted by (v). The water in (v) is, for example, distilled water or deionized water. The number of washes in (v) is preferably 1 to 3 times, and more preferably 1 time.

[0049] After the above procedure, the solvent is removed by distillation to obtain a monomer for optical components containing the target compound (1). Before removing the solvent by distillation, the organic phase and a drying agent may be mixed and filtered. Examples of drying agents include sodium sulfate and magnesium sulfate.

[0050] Applications of the monomer for optical components in this embodiment include, for example, eyeglass lenses (materials for lens substrates), prisms, optical fibers, information recording substrates, and filters. Among these applications, eyeglass lenses are preferred, and lens substrates are more preferred. The monomer for optical components in this embodiment is polymerized alone or together with other monomers to be used as an episulfide resin.

[0051] (Episulfide resin) The episulfide resin is a cured product of a polymerizable composition for optical components (hereinafter also simply referred to as "polymerizable composition") containing the monomer for optical components of this embodiment. The monomer content for optical components in this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more in the polymerizable composition. The monomer content for optical components in this embodiment is not particularly limited to an upper limit, but may be 100% by mass or less, 98% by mass or less, or 96% by mass or less.

[0052] The polymerizable composition may contain other monomers. Examples of other monomers include other epithio compounds, sulfur, and polythiol compounds.

[0053] (Other epithio compounds) Epithio compounds are compounds that contain an episulfide group (epithio group). Other epithio compounds include, for example, episulfide compounds having a linear or branched aliphatic skeleton different from compound (1), episulfide compounds having an alicyclic skeleton, episulfide compounds having an aromatic skeleton, and episulfide compounds having a dithiane ring skeleton.

[0054] Examples of episulfide compounds having a linear or branched aliphatic skeleton different from compound (1) include 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropylthio)propane, 1,2-bis[(2-β-epithiopropylthioethyl)thio]-3-(β-epithiopropylthio)propane, tetrakis(β-epithiopropylthiomethyl)methane, and 1,1,1-tris(β-epithiopropylthiomethyl)propane.

[0055] Examples of episulfide compounds having an alicyclic skeleton include 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, and bis[4-(β-epithiopropylthio)cyclohexyl]sulfide.

[0056] Examples of episulfide compounds having an aromatic skeleton include 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfine, and 4,4-bis(β-epithiopropylthio)biphenyl.

[0057] Examples of episulfide compounds having a dithiane ring skeleton include 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethyl)-1,4-dithiane, and 2,3,5-tri(β-epithiopropylthioethyl)-1,4-dithiane.

[0058] The content of other epithio compounds may be 1 to 30% by mass, 5 to 20% by mass, or 8 to 15% by mass in the polymerizable composition.

[0059] The polymerizable composition preferably contains sulfur or a polythiol compound in combination with an epithio compound. The sulfur content in the polymerizable composition is preferably 1% by mass or more, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass.

[0060] Examples of polythiol compounds include ester compounds of polyol compounds and mercapto group-containing carboxylic acid compounds, linear or branched aliphatic polythiol compounds, polythiol compounds having an alicyclic structure, and polythiol compounds having an aromatic ring structure.

[0061] In ester compounds of polyol compounds and mercapto group-containing carboxylic acid compounds, the polyol compound can be a compound having two or more hydroxyl groups in its molecule. Examples of polyol compounds include ethylene glycol, diethylene glycol, propanediol, propanetriol, butanediol, trimethylolpropane, bis(2-hydroxyethyl) disulfide, pentaerythritol, and dipentaerythritol. Examples of mercapto group-containing carboxylic acid compounds include thioglycolic acid, mercaptopropionic acid, thiolactic acid compounds, and thiosalicylic acid. Examples of ester compounds of polyol compounds and mercapto group-containing carboxylic acid compounds include ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(2-mercaptoacetate), and 1,4-butanediol bis(3-mercaptopropionate). Examples include topropionate, trimethylolpropantris (2-mercaptoacetate), trimethylolpropantris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoacetate), and dipentaerythritol hexakis (3-mercaptopropionate).

[0062] Examples of linear or branched aliphatic polythiol compounds include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethyloxybutane-1,2-dithiol, 2,3-dimercapto-1-propanol, 1,2 -Dimercaptopropyl methyl ether, 2,3-Dimercaptopropyl methyl ether, 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2,2-Bis(mercaptomethyl)-1,3-propanedithiol, Bis(mercaptomethylthio)methane, Tris(mercaptomethylthio)methane, Bis(2-mercaptoethylthio)methane, 1,2-Bis(mercaptomethylthio)ethane, 1,2-Bis(2-mercaptoethylthio) O)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,1,2,2-tetrakis(mercaptoethylthio)ethane, 1,1,3,3-tetrakis(mercaptoethylthio)propane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tetrakis(mercaptoethylthio)propane, bis(2-mercaptoethyl)ether, bis(2-mercaptoethyl Examples include bis(2-mercaptoethyl) disulfide, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, and 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol.

[0063] Examples of polythiol compounds having an alicyclic structure include 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, methylcyclohexanedithiol, bis(mercaptomethyl)cyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 2,5-bis(mercaptomethyl)-1,4-dithiane, and 4,8-bis(mercaptomethyl)-1,3-dithiane.

[0064] Examples of polythiol compounds having an aromatic ring structure include 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 4,4'-dimercaptobiphenyl, and 4,4'-dimercapto Examples include bibenzyl, 2,5-toluenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1,3-di(p-methyloxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane. These may be used individually or in combination of two or more types.

[0065] When used in combination with an epithio compound, the polythiol compound content is preferably 2 to 50% by mass, more preferably 4 to 40% by mass, even more preferably 4 to 30% by mass, even more preferably 4 to 20% by mass, and even more preferably 4 to 10% by mass, of the polymerizable component.

[0066] The polymerizable composition preferably contains a polymerization catalyst. Examples of polymerization catalysts include nitrogen-containing compounds.

[0067] Examples of nitrogen-containing compounds include tertiary amines, quaternary ammonium salts, imidazole compounds, and pyrazole compounds. Tertiary amines are preferably hindered amines.

[0068] Examples of tertiary amines include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, N-methylmorpholine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine, and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0069] Examples of hindered amines include 1,2,2,6,6-pentamethyl-4-piperidinol, 1,2,2,6,6-pentamethyl-4-hydroxyethyl-4-piperidinol, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, a mixture of methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis(1,2,2,6,6 Examples include pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate.

[0070] An example of a quaternary ammonium salt is tetraethylammonium hydroxide. Examples of imidazole compounds include imidazole, 1-methyl-2-mercapto-1H-imidazole, 1,2-dimethylimidazole, benzylmethylimidazole, and 2-ethyl-4-imidazole. Examples of pyrazole compounds include pyrazole and 3,5-dimethylpyrazole. Among these, tertiary amines such as hindered amines, imidazole compounds, and pyrazole compounds are preferred, imidazole compounds are more preferred, and 1-methyl-2-mercapto-1H-imidazole is even more preferred.

[0071] The amount of polymerization catalyst added to the polymerizable composition is preferably 0.001 to 2 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.007 to 0.5 parts by mass, per 100 parts by mass of the total amount of polymerizable components.

[0072] [Method for manufacturing lens substrates for eyeglass lenses] The lens substrate for eyeglass lenses is not particularly limited, but for example, A step of curing the polymerizable composition described above, and The process of annealing the resin after curing. It is obtained by a manufacturing method that includes [the following].

[0073] Polymerization is preferably carried out by casting polymerization. The lens substrate can be obtained, for example, by injecting a polymerizable composition into a mold that combines a glass or metal mold with a tape or gasket and then carrying out polymerization.

[0074] Polymerization conditions can be appropriately set depending on the polymerizable composition. The polymerization start temperature is preferably 0 to 50°C, more preferably 10 to 40°C. It is preferable to raise the temperature from the polymerization start temperature and then heat to cure and form the polymer. For example, the maximum temperature to which the temperature is raised is usually 110 to 130°C.

[0075] After polymerization is complete, the lens substrate may be released from the mold and annealed. The annealing temperature is preferably 100 to 150°C.

[0076] As described above, according to this embodiment, a monomer for optical components with excellent polymerizability can be obtained. Furthermore, according to this embodiment, a monomer for optical components can be obtained in which clouding and yellowing of the cured product are suppressed. Therefore, because good polymerizability is obtained and clouding and yellowing are suppressed, it can be suitably used as an optical material such as a lens substrate for eyeglass lenses.

[0077] This specification discloses the following embodiments. <1> Formula (1): [ka] (In the formula, X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2.) Contains a compound represented by the formula, A monomer for optical components, having a pH of 4.0 to 7.5 obtained by the pH measurement method described below. (pH measurement method) Mix 80g of the sample, 80ml of toluene, and 250ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase. <2> The compound represented by formula (1) is given by the following formula (1-1): [ka] The compound represented by <1> The monomers listed. <3> The aforementioned pH is 4.3 to 7.5. <1> or <2> The monomers listed. <4> The aforementioned pH is 4.5 to 7.0. <1> or <2> The monomers listed. <5> <1> ~ <4> A polymerizable composition for optical components comprising any of the monomers described in one of the following. <6> <5> A cured product of the polymerizable composition for optical components described above. <7> <6> An eyeglass lens comprising a lens substrate containing the cured product described above. <8> Formula (1): [ka] A method for producing a monomer for optical components containing a compound represented by the formula (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2), Formula (2): [ka] The method involves obtaining the compound represented by formula (1) using a compound represented by (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2) and a sulfurizing agent, The compound represented by formula (1) above is washed with water until the pH obtained by the following pH measurement method is between 4.0 and 7.5, (pH measurement method) Mix 80g of the sample, 80ml of toluene, and 250ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase. A method for producing monomers for optical components, including the above. [Examples]

[0078] The present invention will be described in more detail below using examples and comparative examples. However, the present invention is not limited in any way by the following examples.

[0079] [Measurement method] <ph> 80 g of the obtained monomer for optical components, 80 ml of toluene, and 250 ml of water were mixed in a separatory funnel, and the aqueous phase was separated. The pH of the obtained aqueous phase was measured at 25°C using a pH meter (HORIBA, model number: F52 (glass bead electrode, aqueous solution system, model number: 9615S-10D)).

[0080] [evaluation] <Polymerizable> The polymerizable compositions were observed and their polymerizability evaluated after thermal polymerization of polymerizable compositions using the method described in the examples. (Evaluation Criteria) A: A hard resin was obtained by thermal polymerization. B: It was a soft resin that hardened through thermal polymerization. C: Did not harden even with thermal polymerization.

[0081] <White turbidity control> The polymerizable compositions were thermally polymerized using the method described in the examples, and the degree of turbidity was evaluated according to the following criteria. (Evaluation Criteria) A: No clouding was observed in the resin cured by thermal polymerization. B: Although cloudiness was observed in the resin cured by thermal polymerization, the resin had scattered cloudy spots and was transparent. C: White cloudiness was observed in the resin that hardened by thermal polymerization, and the entire resin was cloudy and white. -: Did not harden even with thermal polymerization.

[0082] <Coloring suppression> The polymerizable compositions were thermally polymerized using the method described in the examples, and the degree of coloration was evaluated according to the following criteria. (Evaluation Criteria) A: The resin hardened by thermal polymerization was colorless and transparent. B: The resin that hardened due to thermal polymerization was pale yellow. C: The resin that hardened due to thermal polymerization was yellow.

[0083] <Example 1> (Monomer production) 46.4 g of epichlorohydrin was slowly added dropwise to 20 ml of methanol containing 8.0 g of 70% sodium hydroxide by mass, while stirring at 0-5°C, and the mixture was then stirred for 1 hour. Next, 14.0 g of sodium hydroxide was added dropwise to 40 ml of water, while stirring at 5-10°C, and the mixture was then stirred for 1 hour. After the reaction was complete, the mixture was extracted with 200 ml of toluene, followed by repeated washing with 200 ml of water, and then the toluene solvent was removed by distillation to obtain bis(glycidyl) sulfide. Next, 36.6 g of the obtained bis(glycidyl) sulfide and 39.96 g of thiourea were dissolved in 43.3 ml of toluene and 43.3 ml of methanol, and 0.52 ml of acetic acid was added. The mixture was reacted at room temperature (25°C) for 16 hours. 80 ml of toluene was added to the reaction mixture, and 250 ml of water in which 0.5 g of NaCl was dissolved was added. The aqueous phase and the organic phase were separated using a separatory funnel, and the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution. Subsequently, the organic phase was washed five times with 250 ml of water. Then, the organic phase was washed once with 250 ml of 0.01% by mass aqueous sodium bicarbonate solution, and further washed with 250 ml of water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by distillation to obtain bis(β-epithiopropylthio) sulfide as a white solid monomer for optical components. The pH of the obtained bis(β-epithiopropylthio) sulfide was measured and is shown in Table 1.

[0084] (polymerization) Add 79.92 parts by mass of bis-(β-epithiopropyl) sulfide and 14.00 parts by mass of sulfur to a 300 ml round-bottom flask and heat to 60°C. Degassing was performed while heating for 60 minutes. Subsequently, 0.467 parts by mass of 1-methyl-2-mercapto-1H-imidazole was added, and a preliminary reaction was carried out at 60°C for 60 minutes with stirring under atmospheric pressure in a sealed state. After cooling to 20°C, 0.13 parts by mass of dibutyltin dichloride was added to stop the preliminary reaction. In a separate container, 6.08 parts by mass of bis-(2-mercaptoethyl) sulfide, 0.001 parts by mass of acidic phosphate ester "JP506H" (trade name, manufactured by Johoku Chemical Industry Co., Ltd.), and 0.020 parts by mass of tetrabutylphosphonium bromide were added and mixed and dissolved. This mixture was then added to the pre-reacted mixture, and degassed while stirring at 20°C to obtain a homogeneous solution. Next, the mixture was injected into glass sample bottles (6cc capacity, 14mm inner diameter) while being filtered through a 3-micron polyethylene terephthalate filter, and polymerized and cured in an oven by raising the temperature from 30°C to 100°C over 24 hours to obtain a resin. The obtained resin was evaluated visually, and the results are shown in Table 1.

[0085] <Example 2> In Example 2, 43.3 ml of toluene was added to the reaction mixture, and 250 ml of water in which 0.5 g of NaCl was dissolved was added. The aqueous phase and organic phase were separated using a separatory funnel, and the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution. The organic phase was then washed five times with 250 ml of water. Bis(β-epithiopropylthio)sulfide was obtained in the same manner as in Example 1, except that subsequent washing with aqueous sodium bicarbonate solution and washing with water were not performed. The pH of the obtained bis(β-epithiopropylthio)sulfide was measured and is shown in Table 1. The obtained bis(β-epithiopropylthio) sulfide was polymerized using the same method as in Example 1, and various evaluations were performed, which are shown in Table 1.

[0086] <Example 3> In Example 3, 43.3 ml of toluene was added to the obtained reaction mixture, and 250 ml of water in which 0.5 g of NaCl was dissolved was added. The aqueous phase and the organic phase were separated using a separatory funnel, and the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution. The organic phase was then washed four times with 250 ml of water. Bis(β-epithiopropylthio)sulfide was obtained in the same manner as in Example 1, except that subsequent washing with aqueous sodium bicarbonate solution and washing with water were not performed. The pH of the obtained bis(β-epithiopropylthio)sulfide was measured and is shown in Table 1. The obtained bis(β-epithiopropylthio) sulfide was polymerized using the same method as in Example 1, and various evaluations were performed, which are shown in Table 1.

[0087] <Example 4> In Example 4, 43.3 ml of toluene was added to the obtained reaction mixture, and 250 ml of water in which 0.5 g of NaCl was dissolved was added. The aqueous phase and the organic phase were separated using a separatory funnel, and the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution. The organic phase was then washed twice again with 250 ml of water. Bis(β-epithiopropylthio)sulfide was obtained in the same manner as in Example 1, except that subsequent washing with aqueous sodium bicarbonate solution and washing with water were not performed. The pH of the obtained bis(β-epithiopropylthio)sulfide was measured and is shown in Table 1. The obtained bis(β-epithiopropylthio) sulfide was polymerized using the same method as in Example 1, and various evaluations were performed, which are shown in Table 1.

[0088] <Comparative Example 1> In Comparative Example 1, 43.3 ml of toluene was added to the obtained reaction mixture, and 250 ml of water in which 0.5 g of NaCl was dissolved was added. The aqueous phase and organic phase were separated using a separatory funnel, and the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution. The organic phase was then washed once more with 250 ml of water. The subsequent washing with aqueous sodium bicarbonate solution and washing with water were omitted, except that the procedure was the same as in Example 1 to obtain bis(β-epithiopropylthio)sulfide. The pH of the obtained bis(β-epithiopropylthio)sulfide was measured and is shown in Table 1. The obtained bis(β-epithiopropylthio) sulfide was polymerized using the same method as in Example 1, and various evaluations were performed, which are shown in Table 1.

[0089] [Table 1]

[0090] From these results, it can be seen that monomers for optical components with a pH of 4.0 or higher exhibit excellent polymerizability. Furthermore, monomers for optical components with a pH of 4.3 or higher exhibit even better polymerizability, suppress the occurrence of turbidity, and further suppress discoloration. Moreover, monomers for optical components with a pH of 4.5 or higher exhibit even better polymerizability, greater transparency, and further suppression of discoloration.< / ph>

Claims

1. Formula (1): 【Chemistry 1】 The compound contains the compound represented by (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2), A composition containing a monomer for optical components, wherein the pH obtained by the pH measurement method described below is between 4.0 and 7.

5. (pH measurement method) Mix 80 g of the sample, 80 ml of toluene, and 250 ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase.

2. The compound represented by formula (1) is given by the following formula (1-1): 【Chemistry 2】 A composition comprising the monomer described in claim 1, which is a compound represented by .

3. A composition comprising the monomer according to claim 1, wherein the pH is 4.3 to 7.

5.

4. A composition comprising the monomer according to claim 1, wherein the pH is 4.5 to 7.

0.

5. A polymerizable composition for optical components comprising a composition containing the monomer described in any one of claims 1 to 4.

6. A cured product of the polymerizable composition for optical components according to claim 5.

7. An eyeglass lens comprising a lens substrate containing the cured product described in claim 6.

8. Formula (1): 【Transformation 3】 A method for producing a composition containing a monomer for optical components that contains a compound represented by the formula (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2), Formula (2): 【Chemistry 4】 The method involves obtaining the compound represented by formula (1) using a compound represented by (wherein X is S or O, a is an integer from 0 to 1, R is a divalent hydrocarbon having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2) and a sulfurizing agent, The compound represented by formula (1) above is washed with water until the pH obtained by the following pH measurement method is between 4.0 and 7.5, (pH measurement method) Mix 80 g of the sample, 80 ml of toluene, and 250 ml of water in a separatory funnel, separate the aqueous phase, and measure the pH of the aqueous phase. A method for producing a composition containing monomers for optical components.

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