Compositions containing monomers for optical components, polymerizable compositions for optical components, cured products, and eyeglass lenses

Abstract

An embodiment according to the present disclosure relates to a monomer for optical members which comprises a compound represented by formula (1) and satisfies that in an examination by gel permeation chromatography, the proportion of the total area P1 of peaks appearing at retention times earlier than a main peak to the total area P2 of all peaks is 3.5% or less.

Description

Technical Field

[0001] The present disclosure relates to monomers for optical members A composition containing (hereinafter also simply referred to as "monomer for optical components") , polymerizable compositions for optical members, cured products, and spectacle lenses.

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, cloudiness may occur during curing, and suppression of the occurrence of cloudiness may be required.

[0005] One embodiment of the present disclosure relates to a monomer for an optical member in which cloudiness due to curing hardly occurs, a polymerizable composition for an optical member containing the monomer, a cured product thereof, and a spectacle lens containing the cured product.

Means for Solving the Problems

[0006] The present inventor has found that by using a monomer for an optical member in which the total value P1 of the peak areas at a retention time before the main peak is not more than a predetermined value with respect to the total value P2 of all the peak areas in measurement by gel permeation chromatography, the occurrence of cloudiness due to curing can be suppressed.

[0007] One embodiment relating to this disclosure is, Formula (1): [ka] 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 group having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2), This invention relates to monomers for optical components in which, in measurements by gel permeation chromatography, the total peak area P1 at the retention time prior to the main peak is 3.5% or less of the total peak area P2.

[0008] One embodiment of the present disclosure relates to a cured product of the polymerizable composition for optical components described above.

[0009] One embodiment of the present disclosure relates to an eyeglass lens comprising a lens substrate containing the cured product described above. [Effects of the Invention]

[0010] According to one embodiment of the present disclosure, it is possible to provide a monomer for optical components that is less prone to clouding due to curing, a polymerizable composition for optical components containing the monomer, a cured product thereof, and an eyeglass lens containing the cured product. [Modes for carrying out the invention]

[0011] The embodiments of this disclosure (hereinafter referred to as "these embodiments") will be described in detail below, but the present invention is not limited thereto, and various modifications are possible without departing from the spirit of the invention. In this specification, for example, the notation of a numerical range "1 to 100" includes both the lower limit "1" and the upper limit "100". The same applies to the notation of other numerical ranges.

[0012] [Monomers for optical components] A monomer for an optical component according to an embodiment of this disclosure is Formula (1):

Chem.

[0013] <Compound (1)> The monomer for an optical member according to this embodiment Formula (1):

Chem.

[0014] As the compound (1), specifically, for example, 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, bis(β-epithiopropylthioethyl) sulfide can be mentioned. Among these, bis(β-epithiopropyl) sulfide and bis(β-epithiopropyl) disulfide are preferable, and bis(β-epithiopropyl) sulfide is more preferable. That is, the compound represented by the formula (1) is the following formula (1-1): [Chemical formula] It is more preferable that it is a compound represented by

[0015] The content (also referred to as purity) of the compound (1) in the monomer for an optical member according to the present embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and even more preferably 99% by mass or more with respect to the total amount of the monomer for an optical member. The upper limit of the content of the compound (1) is not particularly limited, but it may be 100% by mass or less with respect to the total amount of the monomer for an optical member.

[0016] (P1 / P2 ratio) In the monomer for an optical member of the present embodiment, in the measurement by gel permeation chromatography, the total value P1 of the peak areas at a retention time before the main peak is 3.5% or less with respect to the total value P2 of all peak areas. Hereinafter, in the meaning of the ratio of the total value P1 of the peak areas at a retention time before the main peak to the total value P2 of all peak areas, it is also referred to as the "P1 / P2 ratio". Here, "main peak" refers to the peak with the largest peak area in the measurement by gel permeation chromatography. The main peak corresponds to the peak of compound (1). Peaks at the retention time prior to the main peak correspond to the polymers of compound (1). Examples of polymers include dimers, trimers, tetramers, and pentamers. By keeping the P1 / P2 ratio below 3.5%, the occurrence of clouding due to the curing of the monomer for optical components can be suppressed. It has been found that polymerization of monomers for optical components containing this polymer causes clouding due to curing, but it is thought that the occurrence of clouding due to curing can be suppressed by keeping the P1 / P2 ratio below a predetermined value, that is, by reducing the amount of the polymer of compound (1) in the monomer for optical components. The P1 / P2 ratio is preferably 3.0% or less, more preferably 1.5% or less, and even more preferably 1.0% or less, from the viewpoint of suppressing clouding due to hardening. The lower limit of the P1 / P2 ratio is not particularly limited, but it may be 0.1% or more, 0.3% or more, or 0.5% or more.

[0017] Gel permeation chromatography is performed using chloroform as the eluent. Details of the gel permeation chromatography measurement method are described in the examples.

[0018] The P1 / P2 ratio of the monomer for the optical component according to this embodiment can be set to a predetermined range, for example, by adjusting the purification conditions of compound (1). As a purification method, it can be obtained, for example, by the manufacturing method described later.

[0019] Furthermore, monomers for optical components having a P1 / P2 ratio within the above range can be obtained, for example, by the purification method described later.

[0020] [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)"), Washing the compound represented by formula (1) with water (hereinafter also referred to as the "washing step"), 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.

[0021] <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).

[0022] An example of an epihalohydrin is epichlorohydrin.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] The reaction temperature is preferably -5 to 30°C, more preferably 0°C to 20°C, and even more preferably 5 to 15°C.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] <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).

[0035] Examples of sulfurizing agents include thiourea and thiocyanates. Examples of thiocyanates include sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, calcium thiocyanate, and lead thiocyanate.

[0036] 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.

[0037] 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.

[0038] 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 and phosphoric acid. 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.

[0039] (Washing process) In the washing process, compound (1) is washed with water. This process reduces the amount of polymer contained in the monomer for optical components.

[0040] 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

[0041] In (ii) to (v), washing means separating the formed aqueous phase from the organic phase.

[0042] (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.

[0043] (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. By increasing the number of washes in (iii), polymers precipitate in the water, and the amount of polymers in the monomer for the optical component can be reduced.

[0044] (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. By going through this step and the wash in (v) described below, polymers precipitate in the water, and the amount of polymers in the monomer for the optical component is reduced.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] (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.

[0049] The polymerizable composition may contain other monomers. Examples of other monomers include other epithio compounds, sulfur, and polythiol compounds.

[0050] (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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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).

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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 or more, 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, in the polymerizable component.

[0063] The polymerizable composition preferably contains a polymerization catalyst. Examples of polymerization catalysts include nitrogen-containing compounds.

[0064] Examples of nitrogen-containing compounds include tertiary amines, quaternary ammonium salts, imidazole compounds, and pyrazole compounds. Tertiary amines are preferably hindered amines.

[0065] 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).

[0066] 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.

[0067] 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.

[0068] 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.

[0069] [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].

[0070] 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.

[0071] 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.

[0072] After polymerization is complete, the lens substrate may be released from the mold and annealed. The annealing temperature is preferably 100 to 150°C.

[0073] 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.

[0074] This specification discloses the following embodiments. <1> Formula (1): [ka] 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 group having 1 to 10 carbon atoms, b is an integer from 0 to 1, and n is an integer from 0 to 2), A monomer for optical components, wherein, in measurements by gel permeation chromatography, the sum of peak areas P1 at the retention time prior to the main peak is 3.5% or less of the sum of all peak areas P2. <2> The sum of the peak areas P1 is 1.0% or less of the sum of all peak areas P2. <1> Monomers for optical components as described above. <3> The compound represented by formula (1) is given by the following formula (1-1): [ka] The compound represented by <1> or <2> The monomers listed. <4> <1> ~ <3> A polymerizable composition for optical components comprising any of the monomers described in one of the following. <5> <4> A cured product of the polymerizable composition for optical components described above. <6> <5> An eyeglass lens comprising a lens substrate containing the cured product described above. [Examples]

[0075] 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.

[0076] [Measurement method] <Gel Permeation Chromatography (GPC)> Measurements were performed using a gel permeation chromatography apparatus (Showa Denko K.K. "GPC104", detector: RI "RI-74s", pump: DU-H2000). Approximately 0.2 g of the sample was dissolved in 20 mL of chloroform to prepare the measurement sample. Chloroform was used as the eluent, with KF-401HQ and KF-402HQ used as the sample column and KF-600RH as the reference column. Measurements were performed under conditions of column temperature 40°C and flow rate 1.00 mL / min. The ratio of the area of ​​each component to the total observed peak area was calculated.

[0077] [evaluation] <Cloudy> The polymerizable compositions obtained by thermal polymerization using the method described in the examples were observed against a black background with the samples illuminated from above by a fluorescent lamp, and evaluated according to the following criteria. (Evaluation Criteria) A: No cloudy weather observed. B: Some cloudiness is observed in parts. C: The opposite side is visible, but cloudiness is observed. D: Milky white, making it impossible to see the opposite side.

[0078] <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 composition of the obtained bis(β-epithiopropylthio) sulfide was analyzed by GPC measurement and is shown in Table 1.

[0079] (polymerization) 79.92 parts by mass of bis-(β-epithiopropyl) sulfide and 14.00 parts by mass of sulfur were added to a 300 ml round-bottom flask, and degassing was carried out for 60 minutes while heating to 60°C. Then, 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 and in a sealed state, after which it was cooled to 20°C, and 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.

[0080] <Example 2> In Example 2, 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, the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution, and 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 composition of the obtained bis(β-epithiopropylthio)sulfide was analyzed by GPC measurement 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.

[0081] <Example 3> In Example 3, 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, the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution, and 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 GPC 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.

[0082] <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, the organic phase was washed twice with 150 ml of 1% by mass aqueous sulfuric acid solution, and then washed once more with 250 ml of water. The subsequent washing with aqueous sodium bicarbonate solution and washing with water were omitted, but otherwise, bis(β-epithiopropylthio)sulfide was obtained in the same manner as in Example 1. The composition of the obtained bis(β-epithiopropylthio)sulfide was analyzed by GPC measurement 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.

[0083] [Table 1]

[0084] From these results, it can be seen that monomers for optical components with a P1 / P2 ratio of 3.5% or less are less prone to clouding due to curing.

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 group 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, in measurement by gel permeation chromatography, the total value P1 of peak areas at the retention time prior to the main peak is 3.5% or less of the total value P2 of all peak areas.

2. A composition comprising the monomer for optical components according to claim 1, wherein the total value of the peak areas P1 is 1.0% or less of the total value of all peak areas P2.

3. 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 .

4. A polymerizable composition for optical components comprising a composition containing the monomer described in any one of claims 1 to 3.

5. A cured product of the polymerizable composition for optical components according to claim 4.

6. An eyeglass lens comprising a lens substrate containing the cured product described in claim 5.

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