Episulfide compositions, polymerizable compositions, cured products, optical materials, and lenses

Abstract

This episulfide composition contains an optically-active compound A that includes one disulfide bond and two episulfide rings, and one of the two episulfide rings is an episulfide ring 1 that includes an asymmetric carbon atom C*1, and the other of the two episulfide rings is an episulfide ring 2 that includes an asymmetric carbon atom C*2. The optically-active compound A includes: at least one of a compound A-SS in which both C*1 and C*2 are S configurations and a compound A-RR in which both C*1 and C*2 are R configurations; and a compound A-RS in which one of C*1 and C*2 is an R configuration and the other is an S configuration. The ratio of the peak area RS of the compound A-RS to the total peak area T of the compound A-SS, the compound A-RR and the compound A-RS, as measured by HPLC, is 10-70% by area.

Description

Technical Field

[0001] The present disclosure relates to an episulfide composition, a polymerizable composition, a cured product, an optical material, and a lens.

Background Art

[0002] Plastic lenses have rapidly spread in recent years as optical materials for spectacle lenses, camera lenses, etc., because they are lighter and less likely to break than inorganic lenses and can be dyed.

[0003] Among them, optical materials made of resins based on episulfide compounds are widely used because they are excellent in refractive index and the like (see, for example, Patent Document 1).

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-194083

Summary of the Invention

Problems to be Solved by the Invention

[0005] By the way, there are cases where it is required to further suppress haze with respect to a cured product obtained using an episulfide compound and an optical material containing this cured product.

[0006] [[ID=3③]] The present disclosure has been made in view of the above circumstances. An object of the present disclosure is to provide an episulfide composition and a polymerizable composition capable of obtaining a cured product with suppressed haze, and a cured product, an optical material, and a lens with suppressed haze.

Means for Solving the Problems

[0007] Means for solving the above problems include the following embodiments. <1> An episulfide composition containing an optically active compound A, where the optically active compound A includes one disulfide bond and two episulfide rings, and among the two episulfide rings, one is an asymmetric carbon atom C*1 is episulfide ring 1 containing [it], and the other is asymmetric carbon atom C *2 is episulfide ring 2 containing [it], The optically active compound A is the asymmetric carbon atom C *1 and the asymmetric carbon atom C *2 both of which are S-form optically active compound A-SS, and the asymmetric carbon atom C *1 and the asymmetric carbon atom C *2 at least one of optically active compound A-RR in which both are R-form, and the asymmetric carbon atom C *1 and the asymmetric carbon atom C *2 optically active compound A-RS in which one is R-form and the other is S-form, and containing " An episulfide composition in which the ratio of the peak area RS of the optically active compound A-RS to the total peak area T of the optically active compound A-SS, the optically active compound A-RR, and the optically active compound A-RS, measured by high performance liquid chromatography, is 10 area% to 70 area%. <(2)> The episulfide composition according to <(1)>, wherein the ratio of the peak area RS to the total peak area T is more than 50 area% and 70 area% or less. <(3)> The episulfide composition according to <(1)>, wherein the ratio of the peak area RS to the total peak area T is 10 area% to 50 area%. <(4)> The episulfide composition according to any one of <(1)> to <(3)>, wherein the optically active compound A contains a compound represented by the following formula (A1).

[0008]

Chemical formula

[0009] In formula (A1), R 1A ~R 7A are each independently a hydrogen atom or a monovalent hydrocarbon group which may be substituted, m is an integer of 0 to 3, C *1AThis is the chiral carbon atom C in the compound represented by formula (A1). *1 C *2A This is the chiral carbon atom C in the compound represented by formula (A1). *2 There are multiple R 1A ~R 7A And m may be the same or different.

[0010] <5> The content of the optically active compound A is 90% by mass or more of the total amount of the episulfide composition. <1> ~ <4> An episulfide composition as described in any one of the following. <6> <1> ~ <5> A polymerizable composition comprising an episulfide composition described in any one of the above, and a polymerization catalyst. <7> Used in the manufacture of optical materials <6> The polymerizable composition described above. <8> <6> A cured product of the polymerizable composition described above. <9> <6> An optical material comprising a cured product of the polymerizable composition described above. <10> <6> A lens containing a cured product of the polymerizable composition described above. [Effects of the Invention]

[0011] The present disclosure provides episulfide compositions and polymerizable compositions that can yield cured products with suppressed haze, as well as cured products, optical materials, and lenses with suppressed haze. [Modes for carrying out the invention]

[0012] In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the amount of each component in a composition means the total amount of any multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples.

[0013] [Episulfide composition] The episulfide compositions of this disclosure are An episulfide composition containing optically active compound A, Optically active compound A contains one disulfide bond and two episulfide rings, one of which is an asymmetric carbon atom C *1 It is an episulfide ring 1 containing a chiral carbon atom C *2 It is an episulfide ring 2 containing, Optically active compound A is, Chiral carbon atom C *1 and the chiral carbon atom C *2 Optically active compounds A-SS, in which both are S-isomers, and the asymmetric carbon atom C *1 and asymmetric carbon atoms C *2 At least one of the optically active compounds A-RR, both of which are R-isomers, Chiral carbon atom C *1 and the chiral carbon atom C *2 Among them, optically active compound A-RS, in which one is the R-isomer and the other is the S-isomer, Includes, The ratio of the peak area RS of optically active compound A-RS to the total peak area T of optically active compounds A-SS, A-RR, and A-RS, as measured by high-performance liquid chromatography (hereinafter also referred to as the peak area ratio [RS / T]), is 10 area % or higher. 70 area% It is an episulfide composition.

[0014] According to the episulfide composition of this disclosure, a cured product with suppressed haze can be obtained. The effect of suppressing haze in cured products is measured by the peak area ratio [RS / T]. 70 It is thought that the fact that area% is below this level is a contributing factor. A peak area ratio [RS / T] of 10 area % or higher is considered to contribute to the curability and handling properties of the episulfide composition.

[0015] <Optically active compound A> The episulfide composition of this disclosure comprises optically active compound A. Optically active compound A is a compound containing one disulfide bond and two episulfide rings. In other words, optically active compound A is a compound that falls under the concept of episulfide compounds (i.e., compounds containing an episulfide ring).

[0016] Of the two episulfide rings in optically active compound A, one is an asymmetric carbon atom C *1 It is an episulfide ring 1 containing a chiral carbon atom C *2 It is an episulfide ring 2 containing [a specific compound]. Optically active compound A is, Chiral carbon atom C *1 and the chiral carbon atom C *2 Optically active compounds A-SS, in which both are S-isomers, and the asymmetric carbon atom C *1 and the chiral carbon atom C *2 At least one of the optically active compounds A-RR, both of which are R-isomers, Chiral carbon atom C *1 and the chiral carbon atom C *2 Among them, optically active compound A-RS, in which one is the R-isomer and the other is the S-isomer, Includes.

[0017] In this disclosure, the term "R-form chiral carbon atom" refers to a chiral carbon atom whose stereoconfiguration is R, and the term "S-form chiral carbon atom" refers to a chiral carbon atom whose stereoconfiguration is S.

[0018] In optically active compound A, the chiral carbon atom C *1 and the chiral carbon atom C *2Of these, the optically active compound A-RS, in which one is the R-isomer and the other is the S-isomer, is preferably the meso-isomer. The optically active compound A-RS is a meso compound because of the asymmetric carbon atom C *1A It is an S-isomer and has an asymmetric carbon atom C *2A Compounds in which the R-isomer and an asymmetric carbon atom C *1A It is an R-isomer and has a chiral carbon atom C *2A This means that the compound in the S-isomer is the same compound.

[0019] As described above, optically active compound A comprises at least one of optically active compound A-SS and optically active compound A-RR. Optically active compound A more preferably contains both optically active compound A-SS and optically active compound A-RR.

[0020] Optically active compound A preferably includes a compound represented by the following formula (A1).

[0021] [ka]

[0022] In formula (A1), R 1A ~R 7A Each is independently a hydrogen atom or an optionally substituted monovalent hydrocarbon group, m is an integer from 0 to 3, and C *1A This is the chiral carbon atom C in the compound represented by formula (A1). *1 C *2A This is the chiral carbon atom C in the compound represented by formula (A1). *2 There are multiple R 1A ~R 7A And m may be the same or different.

[0023] In formula (A1), R 1A ~R 7AExamples of substituted monovalent hydrocarbon groups represented by each of the above include halogen atoms, thiol groups (i.e., mercapto groups), alkoxy groups, alkylthio groups, hydroxyl groups, and the like. In formula (A1), R 1A ~R 7A The number of carbon atoms in each of the optionally substituted monovalent hydrocarbon groups is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, even more preferably 1 or 2, and even more preferably 1, including the number of carbon atoms of the substituents if they are present. R in equation (A1) 1A ~R 7A The "may be substituted monovalent hydrocarbon group" represented in each of the above is preferably an alkyl group having 1 to 6 carbon atoms (i.e., an unsubstituted alkyl group), more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl group or an ethyl group, and even more preferably a methyl group. In formula (A1), R 1A ~R 7A Each of these is preferably a hydrogen atom.

[0024] In equation (A1), m is an integer between 0 and 3. m is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 1.

[0025] In formula (A1), C *1A This is the chiral carbon atom C in the compound represented by formula (A1). *1 C *2A This is the chiral carbon atom C in the compound represented by formula (A1). *2 That is the case. C *1A and C *2A Each of these may be an asymmetric carbon atom in the S-form or an asymmetric carbon atom in the R-form. Optically active compound A is, A compound represented by formula (A1), C *1A and C *2A Compounds in which both are S-forms (A1SS), and compounds represented by formula (A1), C*1A and C *2A At least one (more preferably both) of the compounds (A1RR) in which both are R-isomers, A compound represented by formula (A1), C *1A and C *2A A compound (A1RS) in which one of the compounds is the R-isomer and the other is the S-isomer, It is more preferable to include it.

[0026] The content of the optically active compound A described above is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the episulfide composition.

[0027] Furthermore, the total content of optically active compound A-SS, optically active compound A-RR, and optically active compound A-RS is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the episulfide composition.

[0028] Furthermore, the total content of compound (A1SS), compound (A1RR), and compound (A1RS) is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the episulfide composition.

[0029] <Peak area ratio [RS / T]> In the episulfide compositions of this disclosure, the peak area ratio [RS / T] (i.e., the ratio of the peak area RS of optically active compound A-RS to the total peak area T of optically active compounds A-SS, A-RR, and A-RS, as measured by high-performance liquid chromatography) is 10 area % to 70 area %.

[0030] The measurement conditions for the peak area ratio [RS / T] by high-performance liquid chromatography (HPLC) are as shown in the examples below.

[0031] In the episulfide composition of this disclosure, the haze of the cured product of the episulfide composition of this disclosure is suppressed by having a peak area ratio [RS / T] of 70 area % or less. In the episulfide composition of this disclosure, having a peak area ratio [RS / T] of 10 area % or more improves the curability and handling properties of the episulfide composition of this disclosure.

[0032] In this disclosure, the concept of a cured product of the episulfide composition of this disclosure includes not only cured products obtained by curing only the episulfide composition of this disclosure, but also cured products obtained by curing the polymerizable composition of this disclosure described later (i.e., a polymerizable composition comprising the episulfide composition of this disclosure and a polymerization catalyst). Furthermore, in this disclosure, the concept of curability of the episulfide composition of this disclosure includes not only the curability of the episulfide composition of this disclosure alone, but also the curability of the polymerizable composition of this disclosure described later (i.e., a polymerizable composition comprising the episulfide composition of this disclosure and a polymerization catalyst).

[0033] As mentioned above, the peak area ratio [RS / T] should be between 10 area% and 70 area%. From the viewpoint of further improving the maximum bending stress of the cured episulfide composition, the peak area ratio [RS / T] is preferably 20 area% to 70 area%, more preferably 50 area% to 70 area%, and even more preferably more than 50 area% and 70 area or less.

[0034] Furthermore, the peak area ratio [RS / T] may be between 10 area and 50 area.

[0035] <Other ingredients> The episulfide compositions of this disclosure may contain other components besides optically active compound A. Other components include the reaction solvent used in the synthesis of optically active compound A, and reaction by-products (impurities) generated during the synthesis.

[0036] <Application> There are no particular limitations on the uses of the episulfide compositions disclosed herein. The episulfide composition of this disclosure can produce cured products of episulfide compounds (specifically, optically active compound A) that have a high refractive index, and is therefore suitably used, for example, in the manufacture of optical materials. Optical materials will be discussed later.

[0037] [Polymerizable composition] The polymerizable composition of this disclosure contains the episulfide composition of this disclosure described above and a polymerization catalyst. The polymerizable composition of this disclosure contains the episulfide composition of this disclosure described above, and therefore exhibits excellent polymerizability.

[0038] <Polymerization catalyst> The polymerizable composition of this disclosure contains a polymerization catalyst. The polymerization catalyst contained in the polymerizable composition may be one type or two or more types.

[0039] Examples of polymerization catalysts include tertiary amine compounds, phosphine compounds, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts, and the like. For example, one can refer to paragraphs 0029 to 0033 of Japanese Patent Publication No. 2002-194083 as a polymerization catalyst.

[0040] Preferably, the polymerization catalyst is a tertiary amine compound or a phosphine compound. As for tertiary amine compounds, Triethylamine, Tri-n-butylamine, Tri-n-hexylamine, N,N-diisopropylethylamine, Triethylenediamine, Triphenylamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, Triethanolamine, N-ethyldiethanolamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, Tribenzylamine, N-methyldibenzylamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-diethylcyclohexylamine, N,N-dicyclohexylethylamine, N,N-dimethylbutylamine, N,N-dicyclohexylbutylamine, N-methylmorpholine, N-isopropylmorpholine, Pyridine, Quinoline, N,N-dimethylaniline, N,N-diethylaniline, α-picoline, β-picoline, γ-picoline, 2,2'-bipyridyl, 1,4-dimethylpiperazine, Tetramethylethylenediamine, Hexamethylenetetramine, 1,8-Diazabicyclo(5,4,0)-7-Undecene, Examples include 2,4,6-tris(N,N-dimethylaminomethyl)phenol.

[0041] As for phosphine compounds, Trimethylphosphine, Triethylphosphine, Tri-n-propylphosphine, Triisopropylphosphine, Tri-n-butylphosphine, Triphenylphosphine, Tribenzylphosphine, 1,2-bis(diphenylphosphin)ethane, 1,2-bis(dimethylphosphin)ethane, These are some examples.

[0042] The polymerizable composition of this disclosure contains a polymerization catalyst, preferably 0.01% to 5% by mass, more preferably 0.01% to 2% by mass, and even more preferably 0.03% to 1% by mass, based on the total amount of the polymerizable composition.

[0043] <Thiol compounds> The polymerizable composition of this disclosure preferably further contains a thiol compound. If the polymerizable composition of this disclosure contains a thiol compound, the episulfide composition Things and A resin (i.e., a cured product) can be obtained by polymerizing a thiol compound with [the other compound]. The resulting resin may have superior resin properties. If the polymerizable composition of this disclosure contains a thiol compound, the contained thiol compound may be one type or two or more types.

[0044] Examples of thiol compounds include aliphatic thiols and aromatic thiols.

[0045] As for aliphatic thiols, Pentaerythritol tetrakis (2-mercaptothioglycolate), Pentaerythritol tetrakis (3-mercaptopropionate), Trimethylolpropantrys (2-mercaptothioglycolate), Trimethylolpropanetris (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-Dimercaptomethyl-1,4-Dithiane, 2,5-Bis[(2-mercaptoethyl)thiomethyl]-1,4-Dithiane, 1,3-Cyclohexanedithiol, 1,4-Cyclohexanedithiol, Bis(mercaptomethyl) sulfide, Bis(mercaptomethyl) disulfide, Bis(mercaptoethyl) sulfide, Bis(mercaptoethyl) disulfide, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and Tetrakis(mercaptomethylthio)propane At least one selected from the group consisting of is preferred. However, aliphatic thiols are not limited to these specific examples.

[0046] As aromatic thiols, benzylthiol, Xylylenedithiol, 1,3-bis(mercaptoethyl)benzene, 1,4-Bis(mercaptoethyl)benzene 2,5-toluenedithiol, 3,4-toluenedithiol, Thiophenol, 1,2-Dimercaptobenzene, 1,3-Dimercaptobenzene, 1,4-Dimercaptobenzene, and 1,2-Bis(mercaptomethyl)benzene At least one selected from the group consisting of is preferred. However, aromatic thiols are not limited to these specific examples.

[0047] As the thiol compound, a compound having two or more thiol groups (i.e., mercapto groups) (hereinafter also referred to as "polythiol compound") is preferred.

[0048] Furthermore, when the polymerizable composition of this disclosure contains a thiol compound, it is preferable that the thiol compound contains an aliphatic polythiol (i.e., an aliphatic thiol that is a polythiol compound). In this case, the proportion of aliphatic polythiol in the total amount of the thiol compound is preferably 50% by mass, more preferably 60% by mass or more, and even more preferably 80% by mass or more. There is no particular upper limit on the percentage of aliphatic thiols mentioned above. The percentage of aliphatic thiols may be 100% by mass, less than 100% by mass, 99% by mass or less, or 95% by mass or less.

[0049] Thiol compounds are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and It is more preferable to include at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "polythiol A"). In this case, the proportion of polythiol A in the total amount of the thiol compound is preferably 50% by mass, more preferably 60% by mass or more, and even more preferably 80% by mass or more. There is no particular upper limit on the proportion of polythiol A mentioned above. The proportion of polythiol A may be 100% by mass, less than 100% by mass, 99% by mass or less, or 95% by mass or less.

[0050] Thiol compounds are 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and It is more preferable to include at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "polythiol A1"). In this case, the proportion of polythiol A1 in the total amount of the thiol compound is preferably 50% by mass, more preferably 60% by mass or more, and even more preferably 80% by mass or more. There is no particular upper limit on the proportion of polythiol A1 mentioned above. The proportion of polythiol A1 may be 100% by mass, less than 100% by mass, 99% by mass or less, or 95% by mass or less.

[0051] If the episulfide composition of this disclosure contains a thiol compound, the content of the thiol compound is ,workman Pistolfid composition The amount is preferably 1% to 50% by mass, more preferably 2% to 30% by mass, even more preferably 3% to 20% by mass, and even more preferably 5% to 15% by mass, relative to the total amount.

[0052] For thiol compounds, see paragraph 0039 of International Publication 2018 / 079829.

[0053] <Other ingredients> The polymerizable compositions of this disclosure may contain other components in addition to those described above. Other components include isocyanate compounds, epoxy compounds, alcohol compounds (e.g., polyol compounds), mercapto organic acids, resins (e.g., acrylic resins, olefin resins, etc.), crosslinking agents, light stabilizers, UV absorbers, antioxidants, color inhibitors, dyes, fillers, and internal release agents. Other known ingredients can be used. For other components, refer to, for example, Japanese Patent Publication No. 2002-194083 as appropriate.

[0054] <Application> There are no particular limitations on the use of the polymerizable composition disclosed herein. The polymerizable composition of this disclosure can produce cured products that have a high refractive index, and is therefore suitably used, for example, in the manufacture of optical materials. Optical materials will be described later.

[0055] [Cured product] The cured product of this disclosure is a cured product of the polymerizable composition of this disclosure. The cured product of this disclosure is, for example, a monomer in the polymerizable composition of this disclosure. - The polymerizable composition of the present disclosure is obtained by curing through polymerization. In this case, the cured product of the present disclosure includes a resin obtained by polymerization of monomers in the polymerizable composition of the present disclosure. The resulting resin has resin characteristics sex It excels in [this area].

[0056] There are no particular limitations on the method for polymerizing the monomers in the polymerizable composition of this disclosure (i.e., the method for producing the cured product of this disclosure). One example of a method for polymerizing monomers in the polymerizable composition of this disclosure is casting polymerization. In casting polymerization, the polymerizable composition of this disclosure is first injected between molding molds held together by gaskets or tape. At this time, degassing, filtration, etc. may be performed as necessary. Next, the polymerizable composition injected between the molding molds is polymerized to cure the polymerizable composition between the molding molds, thereby obtaining a cured product. Then, the cured product is removed from the molding molds to obtain a cured product. Polymerization of the above monomers may be carried out by heating the polymerizable composition of this disclosure. This heating can be carried out, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, or the like.

[0057] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition of this disclosure are set appropriately, taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, the shape of the mold, etc. Examples of polymerization temperatures include -50°C to 150°C and 10°C to 150°C. Polymerization times can range from 1 hour to 200 hours, 1 hour to 80 hours, and so on.

[0058] The cured product of this disclosure may be obtained by performing a treatment such as annealing after polymerization of the monomer. Typical annealing temperatures include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0059] Since the cured product of this disclosure is a cured product of a polymerizable composition containing an episulfide compound, it may have a high refractive index. The refractive index (nd) of the cured product of this disclosure is preferably 1.71 or higher, more preferably 1.72 or higher, and even more preferably 1.73 or higher.

[0060] Furthermore, by changing the molding mold used during casting polymerization, cured products of various shapes can be obtained. Therefore, the cured product of this disclosure can be suitably used, for example, as a material for optical materials such as eyeglass lenses, camera lenses, and light-emitting diodes (LEDs); as a material for transparent resin components; and so on.

[0061] [Optical materials] The optical materials of this disclosure (e.g., lenses; the same applies hereinafter) include the cured products of this disclosure. The optical materials of this disclosure may consist of the cured products of this disclosure, or may include the cured products of this disclosure and other elements. Other elements include other components, a coating layer applied to the cured product of this disclosure, and so on.

[0062] The optical materials of this disclosure may have a high refractive index because they include cured products of episulfide compositions. The refractive index (nd) of the optical material of this disclosure is preferably 1.71 or higher, more preferably 1.72 or higher, and even more preferably 1.73 or higher.

[0063] Examples of optical materials in this disclosure include eyeglass lenses, camera lenses, polarizing lenses, and light-emitting diodes (LEDs).

[0064] -Eyeglass Lenses- Below, we will describe eyeglass lenses as an example of the optical materials described herein. The spectacle lens includes a cured product of the present disclosure molded into a desired lens shape. The spectacle lens preferably further includes a coating layer provided on one or both sides of the cured material.

[0065] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers can be used individually or in multiple layers. When applying coating layers to both sides of a cured object, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.

[0066] The components of the coating layer can be selected as appropriate depending on the purpose. The components of the coating layer include, for example, resins (e.g., urethane resin, epoxy resin, polyester resin, melamine resin, polyvinyl acetal resin, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, and the like.

[0067] For eyeglass lenses and coating layers, you can refer to the descriptions in publicly available documents such as Japanese Patent Publication No. 2002-194083 and International Publication No. 2017 / 047745 as appropriate. [Examples]

[0068] The following are examples of the embodiments of this disclosure, but this disclosure is not limited to the following embodiments. In the following, "%" represents mass percentage. "(SS)", "(RR)", and "(RS)" refer to combinations of S-forms, R-forms, and R-forms, respectively.

[0069] [Preparation of Composition 1 containing episulfide compound (A1-1) as the main component] In this manufacturing example, a racemic epichlorohydrin was used as the starting material to produce composition 1, which mainly contains an episulfide compound (A1-1) (hereinafter also simply referred to as "(A1-1)") as the target product. Here, (A1-1) is a mixture of the RR isomer (hereinafter referred to as "(A1-1RR)"), the SS isomer (hereinafter referred to as "(A1-1SS)"), and the RS isomer (hereinafter referred to as "(A1-1RS)"). (A1-1RR) is an example of optically active compound A, more specifically, the chiral carbon atom C in formula (A1) *1 and the chiral carbon atom C *2 All of these are examples of compounds in which the R-isomer exists. (A1-1SS) is an example of optically active compound A, and more specifically, in formula (A1), the chiral carbon atom C *1 and the chiral carbon atom C *2 All of these are examples of compounds in which the S-isomer is present. (A1-1RS) is an example of optically active compound A, more specifically, the chiral carbon atom C in formula (A1) *1 and the chiral carbon atom C *2 This is an example of a compound in which one of the compounds is the R-isomer and the other is the S-isomer.

[0070] [ka]

[0071] The following describes in detail an example of the production of composition 1, which contains (A1-1) as the main component.

[0072] <Synthesis of intermediate a1, which is a racemic 3-chlor-1-mercapto-2-propanol> The starting material, racemic epichlorohydrin, was reacted with H2S to produce intermediate a1, which is racemic 3-chlor-1-mercapto-2-propanol (see reaction scheme below).

[0073] [ka]

[0074] The following are detailed instructions. In a reaction flask equipped with a stirring rod, thermometer, gas inlet tube, and condenser, racemic epichlorohydrin (462.4 g; 5.00 mol), methanol (800 ml), and a 48% by mass NaSH aqueous solution (6.0 g; the amount of NaSH is 2.9 g) were charged. While stirring, the internal temperature was maintained at 0-5°C, and hydrogen sulfide gas (277.5 g; 7.500 mol) was blown into the reaction system through the gas inlet tube over 2 hours. The mixture was then aged at 5°C for 3 hours to react epichlorohydrin with hydrogen sulfide and obtain a reaction solution. After desolvating methanol from the obtained reaction solution, Smith's distillation was performed on the concentrated solution, and intermediate a1 (i.e., racemic 3-chlor-1-mercapto-2-propanol) with a purity of 99% was obtained on the distillate side.

[0075] <Synthesis of intermediate b1, a racemic halohydrin compound> Using intermediate a1 obtained above as the starting material, intermediate b1, a racemic halohydrin, was obtained (see reaction scheme below).

[0076] [ka]

[0077] The following are detailed instructions. To the intermediate a1 (553.9 g; 4.330 mol) obtained above, pure water (445.1 g), sodium bicarbonate (380.8 g), and methanol (123.6 g) were added. While stirring under a nitrogen atmosphere and maintaining the internal temperature at 10°C, bromine (362.1 g; 2.266 mol) was added dropwise over 10 hours. The resulting liquid was allowed to mature by continuously stirring it for 1 hour while maintaining an internal temperature of 10°C, thereby obtaining a reaction solution containing intermediate b1.

[0078] <Synthesis of intermediate c1, a racemic epoxy compound> Using the intermediate c1 obtained above as the starting material, we obtained intermediate c1, which is a racemic epoxy compound (see reaction scheme below).

[0079] [ka]

[0080] The following are detailed instructions. To the reaction solution containing the intermediate b1 obtained above, toluene (93.4 g) was added, and while stirring and maintaining an internal temperature of 10°C, 25% by mass NaOH aqueous solution (824.2 g; 5.151 mol) was added dropwise over 3 hours. Further stirring was continued for 3 hours while maintaining an internal temperature of 10°C, and the mixture was allowed to mature. Next, 203.3g of pure water was added and the mixture was stirred for 15 minutes to separate the organic layer from the aqueous layer, and then the aqueous layer was drained. 71.2g of 13% by mass NaCl aqueous solution was added to the remaining organic layer and stirred to separate the organic layer from the aqueous layer. Acetic acid was then added while stirring until the pH of the aqueous layer reached 5-6. The aqueous layer was then drained. The remaining organic layer was concentrated under reduced pressure to obtain a crude product (365.3 g; purity 97.6%) containing racemic bis(2,3-epoxypropyl) disulfide (i.e., intermediate c1).

[0081] <Synthesis of intermediate d1, which is the thironium salt of a racemic mixture> Intermediate d1, a thironium salt of the racemic mixture, was synthesized by thironium chloride of intermediate c1 described above.

[0082] [ka]

[0083] The following are detailed instructions. In a separate flask, 72.0 g (1.2 mol) of acetic acid, 313.0 g (4.111 mol) of thiourea, 684.1 g of pure water, and 533.3 g of methanol were added. While maintaining the internal temperature at 15°C as a base solution, the crude solution containing the above intermediate c1 (365.3 g; 2.000 mol as the amount of intermediate c1) was added dropwise from dropping funnel 1, and 88% by mass of formic acid (157.0 g) was added dropwise from dropping funnel 2, over a period of 5 hours. After these additions were completed, the mixture was stirred for a further 3 hours while maintaining the internal temperature at 15°C to obtain a reaction solution containing intermediate d1, which is a racemic thironium salt.

[0084] <Preparation of crude product containing episulfide compound (A1-1)> Using the reaction solution containing the above intermediate d1, a crude product containing the episulfide compound (A1-1) (hereinafter also referred to as "crude (A1-1)") was prepared (see reaction scheme below).

[0085] [ka]

[0086] The following are detailed instructions. 760.7 g of methyl isobutyl ketone (MIBK) was added in a single dose to a flask containing the reaction mixture d1 described above. Then, 679.7 g of 10% aqueous ammonia (equivalent to 3.991 mol of ammonia) was added dropwise over 2 hours, and the mixture was aged for another 2 hours while stirring, maintaining an internal temperature of 10°C. The resulting liquid was allowed to stand, and the aqueous layer was discarded after separation. The remaining organic layer was washed with 1056.7 g of 13% by mass NaCl aqueous solution and 6 g of 10% by mass ammonia aqueous solution, and then washed with 1056.7 g of 13% by mass NaCl aqueous solution, 11.9 g of acetic acid, and 126.7 g of methanol. By concentrating the organic layer after washing under reduced pressure, a crude product containing the episulfide compound (A1-1) (hereinafter also referred to as crude (A1-1)) (393.3 g) was obtained.

[0087] <Purification (Preparation of Composition 1 containing episulfide compound (A1-1) as the main component)> The crude (A1-1) described above was purified by column chromatography to obtain composition 1, which mainly contains the purified episulfide compound (A1-1) and trace amounts of impurities.

[0088] [ka]

[0089] The following are detailed instructions. The crude (A1-1) described above was dissolved in a large amount of methylcyclohexane, and some undissolved components were removed. The resulting solution of (A1-1) was purified by passing it through a silica gel column. The silica gel column fraction was concentrated and subjected to a low-boiling decongestant treatment to obtain composition 1, which mainly contained purified (A1-1) and trace amounts of impurities.

[0090] [Separation of composition 1 containing (A1-1) as the main component (production of crystalline composition and liquid composition)] Composition 1, which contains (A1-1) obtained above as the main component, A crystalline composition containing (A1-1RR) and (A1-1SS) as the main components, A liquid composition containing (A1-1RS) as the main component, It was separated into two parts. The following explains the detailed procedure.

[0091] The composition 1 obtained above was placed in a transparent glass bottle and refrigerated at 5°C for one week to allow it to crystallize. After storage, the state of composition 1 was that the upper part was a clear liquid, and the lower part had white crystals settled. This stored composition 1 was separated into a supernatant liquid (upper part) and a crystalline portion (lower part) by decantation.

[0092] The crystalline portion described above was placed in ethyl acetate cooled to below -25°C and slowly sludged. Then, the stirring was stopped and the mixture was placed in a freezer at -25°C for 24 hours (hereinafter, this operation will be referred to as "ethyl acetate sludge"). Next, the slurry liquid after ethyl acetate sludge was quickly filtered, and the crystalline portion remaining as filtrate was recovered. The ethyl acetate sludge and filtration operations described above were repeated two more times for the recovered crystalline portion. As described above, the crystalline portion obtained by repeating the ethyl acetate sludge and filtration operations a total of three times was dried in a desiccator under high vacuum for 24 hours to obtain a crystalline composition mainly containing (A1-1RR) and (A1-1SS). The optical isomer ratio of (A1-1) in the crystalline composition was analyzed as described below.

[0093] On the other hand, the supernatant liquid was concentrated under reduced pressure and further subjected to deboiling treatment to obtain a liquid composition mainly containing (A1-1RS). The optical isomer ratio of (A1-1) in the liquid composition was analyzed as described below.

[0094] [Analysis of optical isomer ratios in crystalline and liquid compositions] The components of (A1-1) in the crystalline composition and (A1-1) in the liquid composition were analyzed by high-performance liquid chromatography (HPLC) under the following measurement conditions. The results are shown in Table 1.

[0095] - HPLC measurement conditions - Column… Daicel Chemicals Optical Resolution Column AD-H φ0.46cm × 25cm × 2 in series Mobile phase: Hexane:Isopropyl alcohol (IPA) = 98:2 (volume ratio) Flow rate...0.7ml / min Oven temperature: 29℃ Measurement wavelength...215nm

[0096] [Table 1]

[0097] As shown in Table 1, the total peak area T (= peak area RS + peak area RR + peak area SS), peak area RR + peak area SS, and peak area RS were determined for (A1-1) in the crystalline composition and (A1-1) in the liquid composition, respectively. Specifically, the analysis results of the crystalline composition showed that the peak area RR + peak area SS was large, confirming that the main components of the crystalline composition were (A1-1RR) and (A1-1SS). On the other hand, the large peak area RS in the analysis of the liquid composition confirmed that the main component of the liquid composition is (A1-1RS).

[0098] [Examples 1-3 and Comparative Example 1] <Manufacturing of Episulfide Composition> By appropriately blending the above crystalline composition and the above liquid composition, the episulfide compositions of Examples 1 to 3 and Comparative Example 1 shown in Table 2 were obtained. The conditions for component analysis in each episulfide composition were the same as those for component analysis performed on the crystalline and liquid compositions, respectively.

[0099] <Manufacturing of polymerizable compositions> Polymerizable compositions were prepared using the episulfide compositions of Examples 1-3 and Comparative Example 1, as described below. Dicyclohexylmethylamine (15 mg) and dimethylcyclohexylamine (3 mg) as polymerization catalysts, and TINUVIN PS (manufactured by BASF Japan) (0.165 g) as an ultraviolet absorber were placed in a conical beaker. One of the episulfide compositions (15.000 g) from Examples 1-3 and Comparative Example 1 was then placed in the beaker and stirred. After confirming that the TINUVIN PS had dissolved by this stirring, a mixture of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecane (1.500 g) [polythiol composition] was placed in the beaker and mixed to obtain a polymerizable composition.

[0100] <Manufacturing of cured products (resin molded articles)> The polymerizable composition obtained above was filtered through a TEFE filter with a retained particle size of 3 μm. The resulting filtrate (i.e., polymerizable composition) was subjected to degassing under reduced pressure at 15°C to 25°C for 1 hour. The degassed polymerizable composition was poured between a pair of glass molds fixed with tape. A pair of glass molds for producing 2 mm flat plates was used as the "pair of glass molds fixed with tape". Next, a pair of glass molds into which the polymerizable composition had been injected were placed in an oven. Next, the oven temperature was first maintained at 30°C for 10 hours, then increased from 30°C to 120°C over 8 hours, then maintained at 120°C for 2 hours, and then decreased from 120°C to 60°C over 1 hour. Through this process, the monomers (i.e., episulfide compounds and polythiol compounds) in the polymerizable composition were polymerized, and a cured product of the polymerizable composition (i.e., a resin molded body) was formed between a pair of glass molds. Subsequently, by releasing the resin molded body from a pair of glass molds, a flat resin molded body with a thickness of 2 mm was obtained as a cured product of the polymerizable composition.

[0101] <Rating> (Haze of hardened material) The cured material obtained above (i.e., a flat resin molded body with a thickness of 2 mm) was subjected to haze measurement using NDH2000 (Nippon Denshoku Kogyo) in accordance with JIS K7361-1 "Test method for total light transmittance of transparent plastic materials", JIS K7105 "Test method for optical properties of plastics", and JIS K7136 "Method for determining haze of transparent plastic materials". Based on the obtained haze, the haze of the cured product was evaluated according to the following evaluation criteria. The results are shown in Table 2. In the evaluation criteria below, rank A indicates the best suppression of haze in the cured product.

[0102] -Evaluation criteria for haze in hardened materials- A: The haze is less than 3. B: Haze is between 3 and 20. C: Hayes is 20 or higher

[0103] (Maximum point stress when hardened material is bent) For Examples 1 to 3, in addition to evaluating the haze of the cured material as described above, the maximum bending stress of the cured material was also evaluated. From the cured material obtained above (i.e., a flat resin molded body with a thickness of 2 mm), a test piece measuring 65 mm in length and 25 mm in width was cut out. The cut surface of the cut test piece was polished with an 800-grit file to obtain a flat test piece measuring 65 mm in length, 25 mm in width, and 2 mm in thickness. The obtained flat plate-shaped test specimens were subjected to a three-point bending test using an Autograph (manufactured by SHIMAZU Corporation), with the width of the base on which the flat plate-shaped test specimens were placed set to 34 mm. The maximum point stress in this three-point bending test was determined, and the maximum point stress was evaluated based on the evaluation criteria below. The results are shown in Table 2. In the evaluation criteria below, the rank that best represents the maximum bending stress of the hardened material is AA.

[0104] -Evaluation criteria for maximum bending stress of hardened materials- AA: Maximum point stress is 125 N / mm2 That's all. A: Maximum point stress is 100 N / mm 2 More than 125N / mm 2 Less than B: Maximum point stress is 90 N / mm 2 Above 100 N / mm 2 Less than C: Maximum point stress is 90 N / mm 2 Less than

[0105] [Table 2]

[0106] As shown in Table 2, in Examples 1 to 3, where episulfide compositions with a peak area ratio (RS / T) of 10 area to 70 area were used, haze in the cured product was suppressed. In contrast, in Comparative Example 1, where the peak area ratio [RS / T] was greater than 70 area%, haze in the cured product could not be suppressed.

[0107] Of Examples 1 to 3, Example 1, in which the peak area ratio [RS / T] was greater than 50 area and less than or equal to 70 area, showed superior performance in terms of the maximum bending stress of the cured product.

[0108] The disclosure of Japanese Patent Application No. 2023-009655, filed on 25 January 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. An episulfide composition containing optically active compound A, The optically active compound A comprises one disulfide bond and two episulfide rings, wherein one of the two episulfide rings is an asymmetric carbon atom C ＊１ It is an episulfide ring 1 containing a chiral carbon atom C ＊２ It is an episulfide ring 2 containing, The optically active compound A is The aforementioned chiral carbon atom C ＊１ and the aforementioned asymmetric carbon atom C ＊２ Optically active compound A-SS, in which both are S-isomers, and the asymmetric carbon atom C ＊１ and the aforementioned asymmetric carbon atom C ＊２ At least one of the optically active compound A-RR, both of which are R-isomers, The aforementioned chiral carbon atom C ＊１ and the aforementioned asymmetric carbon atom C ＊２ Among them, optically active compound A-RS, in which one is the R-isomer and the other is the S-isomer, Includes, The ratio of the peak area RS of optically active compound A-RS to the total peak area T of optically active compound A-SS, optically active compound A-RR, and optically active compound A-RS, as measured by high-performance liquid chromatography, is greater than 50 area and less than or equal to 70 area. The optically active compound A is a compound represented by the following formula (A1): Episulfide composition. 【Chemistry 1】 [In formula (A1), each of R1A to R7A is a hydrogen atom, m is an integer of 0 or 1, C*1A is the chiral carbon atom C*1 in the compound represented by formula (A1), and C*2A is the chiral carbon atom C*2 in the compound represented by formula (A1).]

2. The episulfide composition according to claim 1, wherein the content of the optically active compound A is 90% by mass or more of the total amount of the episulfide composition.

3. A polymerizable composition comprising the episulfide composition according to claim 1 or claim 2, and a polymerization catalyst.

4. A polymerizable composition according to claim 3, used in the manufacture of optical materials.

5. A cured product of the polymerizable composition according to claim 3.

6. An optical material comprising a cured product of the polymerizable composition according to claim 3.

7. A lens comprising a cured product of the polymerizable composition described in claim 3.

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