Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
  • C07C321/04—Thiols having mercapto groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
  • C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses

Definitions

• the present invention relates to a polythiol, a polymerizable composition for an optical material, an optical material, and methods for producing the same.
• Patent Document 1 discloses a polymerizable composition for optical materials that contains polyisocyanate, polyol, a compound derived from plants, and the like.
• optical materials produced from the polymerizable composition for optical materials disclosed in Patent Document 1 have high haze, and further improvements in terms of optical properties are required.
• One aspect of the present invention aims to provide a plant-derived compound that is suitable for producing optical materials with excellent optical properties.
• one aspect of the present invention is as follows.
• [1] A polythiol in which the hydroxyl group of a plant-derived polyol is thiolated.
• a polymerizable composition for an optical material comprising one or more polythiols according to [1] or [2] and one or more polyiso(thio)cyanates.
• the optical material according to [5] which is a lens.
• a method for producing a polythiol comprising thiolating a hydroxy group of a plant-derived polyol.
• [12] Producing a polythiol by the production method according to [11], and mixing the produced polythiol with one or more polyiso(thio)cyanates;
• a method for producing a polymerizable composition for an optical material comprising the steps of: [13] Producing a polymerizable composition for optical materials by the production method according to [12], and curing the produced polymerizable composition for optical materials to obtain a cured product.
• a method for producing an optical material comprising: [14] The method for producing an optical material according to [13], wherein the optical material is a lens. [15] The method for producing an optical material according to [14], wherein the lens is a spectacle lens.
• Polythiol and its manufacturing method One aspect of the present invention relates to a polythiol obtained by thiolating a hydroxy group of a plant-derived polyol.
• Another aspect of the present invention relates to a method for producing a polythiol, which includes thiolating the hydroxyl groups of a plant-derived polyol.
• plant-derived polyol refers to a polyol obtained from a plant through a single-stage or multi-stage process. Examples of the process include a fermentation process, an extraction process, a separation process, and a reaction process.
• the fact that a polyol contains carbon 14C means that the polyol is a plant-derived polyol.
• the fact that the polyol is plant-derived can be confirmed by performing a measurement in accordance with the standard of ASTM D6866 METHOD B and detecting carbon 14C .
• plant-derived in relation to various compounds described below.
• non-plant-derived as described below refers to a polyol obtained from a raw material other than a plant
• “petroleum-derived” refers to a polyol obtained from a petroleum raw material.
• Plant-derived polyols can be obtained by known methods.
• the hydroxyl groups (OH) of plant-derived polyols can be thiolated by, for example, any of the following methods (1) to (4).
• Polyol is reacted with hydrogen halide (e.g., hydrobromic acid (HBr), hydrochloric acid (HCl), etc.) and thiourea to form an isothiuronium salt, and the isothiuronium salt is then hydrolyzed.
• hydrogen halide e.g., hydrobromic acid (HBr), hydrochloric acid (HCl), etc.
• Methanesulfonyl chloride is reacted with a polyol to obtain a sulfonate.
• tosyl chloride or acetic anhydride is reacted with a polyol to obtain a tosylate or ester.
• the product thus obtained is reacted with a thioacetate (e.g., potassium thioacetate) to obtain a thioester, which is then reduced with a reducing agent (e.g., LiAlH 4 ).
• a reducing agent e.g., LiAlH 4
• an acid e.g., HCl
• the plant-derived polyol in which the hydroxyl groups are thiolated and converted to thiol groups can be, for example, a polyol with 2 to 10 functionalities.
• the functionality of a polyol is the number of hydroxyl groups contained in one polyol molecule.
• polythiols in which the hydroxyl groups of a plant-derived polyol are thiolated all of the hydroxyl groups of the plant-derived polyol may be thiolated, or some of the hydroxyl groups may remain.
• plant-derived polyols include glycerol, sorbitol, isosorbide, sucrose, ⁇ -methyl glycoside, mannitol, 1,4-butanediol, 1,3-butanediol, and 1,3-propanediol.
• the biomass degree which is an index of plant-derived raw materials, can be measured in accordance with the standard of ASTM D6866 METHOD B and calculated by the following formula:
• the biomass degree of a polythiol obtained by thiolating a hydroxy group of a plant-derived polyol can be, for example, 100%.
• Biomass ratio number of carbon atoms derived from plants / (number of carbon atoms derived from plants + number of carbon atoms derived from non-plants) x 100
• One aspect of the present invention relates to a polymerizable composition for an optical material, which comprises one or more polythiols obtained by thiolating hydroxy groups of a plant-derived polyol, and one or more polyiso(thio)cyanates.
• Another aspect of the present invention relates to a method for producing a polymerizable composition for optical materials, which includes producing a polythiol by the above-mentioned production method, and mixing the produced polythiol with one or more polyiso(thio)cyanates.
• One or more of the polythiols produced by the above-mentioned production method can be mixed with one or more of the polyiso(thio)cyanates.
• the above-mentioned polymerizable composition for optical materials can be used to produce polythiourethane-based optical materials by reacting polythiol with polyiso(thio)cyanate.
• polyiso(thio)cyanate is used to include polyisocyanate and polyisothiocyanate.
• isocyanate is sometimes called isocyanate
• isothiocyanate is sometimes called isothiocyanate.
• Polyiso(thio)cyanate is a polyfunctional compound having two or more iso(thio)cyanate groups in one molecule.
• the thiol group of the polythiol reacts with the iso(thio)cyanate group of the polyiso(thio)cyanate, and the following bond is generated in the molecule:
• Z represents an oxygen atom or a sulfur atom. * indicates the bonding position with the adjacent structure.
• the thiol group reacts with an isocyanate group to form the above bond in which X is an oxygen atom, and the thiol group reacts with an isocyanate group to form the above bond in which X is a sulfur atom.
• a reaction product (resin) containing a plurality of such bonds in one molecule is referred to as "polythiourethane.”
• the polyiso(thio)cyanate may be a plant-derived polyiso(thio)cyanate or a non-plant-derived (e.g., petroleum-derived) polyiso(thio)cyanate.
• various polyiso(thio)cyanates such as aliphatic polyiso(thio)cyanates, alicyclic polyiso(thio)cyanates, and aromatic polyiso(thio)cyanates can be used.
• the number of iso(thio)cyanate groups contained in one molecule of the polyiso(thio)cyanate is 2 or more, preferably 2 to 4, and more preferably 2 or 3.
• polyiso(thio)cyanates include the various compounds exemplified as polyiso(thio)cyanate compounds in paragraph 0052 of Japanese Patent No. 5319037.
• Preferred polyiso(thio)cyanates include hexamethylene diisocyanate, 1,5-pentane diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,5-bis(isocyanatomethyl)cyclohexane, 1,6-bis(isocyanatomethyl)cyclohexane, 1,7-bis(is
• polyiso(thio)cyanates may be substituted with halogens such as chlorine and bromine, alkyl, alkoxy, and nitro, or prepolymers modified with polyhydric alcohols, carbodiimide, urea, and biuret modifications, or dimerization or trimerization reaction products. These compounds may be used alone or in combination of two or more.
• a "polymerizable composition for optical materials” is a polymerizable composition used in the manufacture of optical materials
• a “polymerizable composition” is a composition containing one or more polymerizable compounds.
• the polymerizable composition for optical materials contains one or more polythiols obtained by thiolating the hydroxyl groups of plant-derived polyols, and one or more polyiso(thio)cyanates, and may or may not contain one or more other polymerizable compounds.
• a "polymerizable compound” is a compound that can undergo a polymerization reaction, and polythiols and polyiso(thio)cyanates are polymerizable compounds.
• a specific example of the other polymerizable compounds is a polyol.
• a specific example of the other polymerizable compounds is a polythiol other than the polythiol obtained by thiolating the hydroxyl groups of plant-derived polyols.
• polystyrene resin When the polymerizable composition for optical materials contains a polyol as another polymerizable compound, such polyol may be a plant-derived polyol or a non-plant-derived (e.g., petroleum-derived) polyol, with plant-derived polyols being preferred.
• plant-derived polyols include glycerol, sorbitol, isosorbide, sucrose, ⁇ -methyl glycoside, mannitol, 1,4-butanediol, 1,3-butanediol, and 1,3-propanediol.
• the polymerizable composition for optical materials contains a polythiol other than a polythiol obtained by thiolating the hydroxyl groups of a plant-derived polyol as another polymerizable compound, such a polythiol can be a non-plant-derived (e.g., petroleum-derived) polythiol.
• non-plant-derived (e.g., petroleum-derived) polythiol examples include a mixture of 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), etc.
• non-plant-derived (e.g., petroleum-derived) polythiol examples include a mixture of 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-d
• non-plant-derived polyol is not limited to the above specific examples.
• Non-plant-derived (e.g., petroleum-derived) polythiols can be synthesized by known methods.
• synthesis method reference can be made to, for example, Japanese Patent No. 3444682, Japanese Patent No. 6632493, Japanese Patent No. 6588639, Japanese Patent No. 4928543, Japanese Patent No. 6851763, Japanese Patent Publication No. 63-46213, Japanese Patent Publication No. 2005-336104, and Japanese Patent Publication No. 59-152367.
• the polymerizable composition for optical materials can be prepared by mixing the various components described above.
• the polymerizable composition for optical materials can contain, for example, 10% by mass or more (for example, 10 to 50% by mass) of the polythiol obtained by thiolating the hydroxyl group of the plant-derived polyol relative to the total amount of the polymerizable composition for optical materials, 100% by mass.
• the content of the polyol can be, for example, 10% by mass or less (for example, 1 to 10% by mass) relative to 100% by mass of the total amount of the polymerizable composition for optical materials.
• the content of such a polythiol can be, for example, 20% by mass or less (for example, 1 to 20% by mass) relative to 100% by mass of the total amount of the polymerizable composition for optical materials.
• one or more other components other than the various components described above may be mixed.
• specific examples of such other components include, for example, a reaction catalyst for the reaction between polythiol and polyiso(thio)cyanate.
• a reaction catalyst for the reaction between polythiol and polyiso(thio)cyanate for other components that can be mixed, see, for example, paragraphs 0055, 0057, and 0058 to 0064 of Japanese Patent No. 5319037.
• one or more additives that are generally commercially available as additives for various resins such as polythiourethane resins can also be used.
• the polymerizable composition for optical materials can be prepared by mixing the various components described above simultaneously or sequentially in any order.
• the preparation method is not particularly limited, and any method known as a method for preparing a polymerizable composition can be used without any restrictions.
• optical material and its manufacturing method One aspect of the present invention relates to an optical material which is a cured product obtained by curing the above-mentioned polymerizable composition for an optical material.
• Another aspect of the present invention relates to a method for producing an optical material, which includes producing a polymerizable composition for optical materials by the above-mentioned production method, and curing the produced polymerizable composition for optical materials to obtain a cured product.
• the optical material can be a lens such as a spectacle lens.
• the curing reaction of the polymerizable composition for optical materials can be carried out by various curing processes capable of curing the polymerizable composition.
• cast polymerization is preferred.
• a curable composition is injected into a mold cavity having two molds facing each other at a predetermined distance and a cavity formed by blocking the distance, and the curable composition is polymerized (cured) in the cavity to obtain a cured product.
• a mold that can be used for cast polymerization, see, for example, paragraphs 0012 to 0014 of JP 2009-262480 A and FIG. 1 of the same publication. In the above publication, a mold in which the gap between the two molds is blocked by a gasket as a sealing member is shown, but tape can also be used as the sealing member.
• the cast polymerization can be carried out as follows.
• the polymerizable composition is injected into the mold cavity through an injection port provided on the side of the mold.
• the polymerizable composition is polymerized (cured) preferably by heating to harden the polymerizable composition, and a hardened product with the internal shape of the cavity transferred thereto can be obtained.
• the polymerization conditions are not particularly limited and can be set appropriately depending on the composition of the polymerizable composition.
• the mold in which the polymerizable composition has been injected into the cavity can be heated at a heating temperature of 10 to 150°C for about 1 to 72 hours, but is not limited to these conditions.
• the temperature such as the heating temperature related to the cast polymerization refers to the atmospheric temperature (for example, the temperature inside the furnace) in which the mold is placed.
• the temperature can be increased at any heating rate and decreased (cooled) at any cooling rate.
• the hardened product inside the cavity is released from the mold.
• the upper and lower molds and the gasket or tape forming the cavity can be removed in any order to release the cured product from the mold.
• the cured product released from the mold can preferably be used as an eyeglass lens (specifically, a lens substrate).
• the cured product used as the lens substrate for eyeglass lenses can usually be subjected to post-processing such as annealing, grinding processes such as a rounding process, a polishing process, and a coating layer formation process such as a primer coating layer for improving impact resistance and a hard coating layer for increasing surface hardness. Furthermore, various functional layers such as an anti-reflection layer and a water-repellent layer can be formed on the lens substrate. For all of these processes, known techniques can be applied without any restrictions. In this way, an eyeglass lens whose lens substrate is the above-mentioned cured product can be obtained. Furthermore, eyeglasses can be obtained by attaching this eyeglass lens to a frame.
• the biomass degree of the optical material can be, for example, 20% or more.
• the biomass degree of the optical material can be 100%, or can be 100% or less, 90% or less, 80% or less, 70% or less, 60% or less, or 50% or less.
• Optical materials with a high biomass degree are desirable from the perspective of utilizing non-fossil resources.
• the biomass degree can be determined by known methods.
• a specific example of a method for calculating the biomass degree of an optical material can be the method described in the Examples section below.
• the optical material can exhibit a high refractive index.
• the refractive index ne of the optical material can be 1.50 or more, or 1.55 or more.
• the refractive index ne of the optical material can be 1.76 or less.
• the refractive index ne is the refractive index at a wavelength of 546.1 nm.
• Example 1 (1) Thiolation of hydroxyl groups of plant-derived polyol 100 ml of pure water, 570.9 g (7.5 mol) of thiourea, and 911.4 g (9.0 mol) of 36% by mass hydrochloric acid were added to 92.1 g (1.0 mol) of plant-derived glycerol, and the mixture was stirred for 9 hours under reflux at 110 ° C. After cooling to room temperature, 400 ml of toluene was added, and 1801.2 g (13.5 mol) of 30% by mass aqueous sodium hydroxide solution was gradually added to carry out hydrolysis at 60 ° C. for 4 hours.
• This mixed homogeneous solution was degassed at 200 Pa for 1 hour, and then filtered through a 5.0 ⁇ m PTFE (polytetrafluoroethylene) filter.
• the mixture was poured into a lens mold consisting of a glass mold having a diameter of 75 mm, -4.00D and 0.00D, and a tape.
• the mold was placed in an electric furnace and gradually heated from 15° C. to 100° C. over 20 hours, and then maintained at 100° C. for 2 hours to carry out a polymerization reaction. After the polymerization reaction was completed, the mold was removed from the electric furnace and released to obtain a lens. The obtained lens was further annealed for 3 hours in an annealing furnace at an internal temperature of 100° C.
• Example 2 Lenses were produced in the same manner as above, except that the XDI in Example 1 was changed to a mixture of petroleum-derived 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and petroleum-derived 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane (hereinafter referred to as "petroleum-derived NBDI").
• Example 3 (1) Thiolation of hydroxyl groups of plant-derived polyol 50 g (342 mmol) of plant-derived isosorbide and 500 mL of dry dichloromethane were added to a reaction vessel. After that, the mixture was cooled to 0° C., 48 mL (342 mmol) of triethylamine was added, and 27.2 mL (419 mmol) of methanesulfonic acid was added dropwise to the solution over 15 minutes. The mixture was then warmed to room temperature and stirred for 2 hours. The organic layer was washed and the water was removed, and the solvent was removed under reduced pressure to obtain 80 g (265 mmol) of reaction intermediate A.
• reaction intermediate A 80 g (265 mmol) of reaction intermediate A and 500 mL of dimethylacetamide (DMA) were added and stirred at room temperature for 30 minutes, and then 60 g (530 mmol) of potassium thioacetate was added and stirred at 120° C. for 3 hours. The organic layer was washed and the water was removed, and the solvent was removed under reduced pressure to obtain 44 g (168 mmol) of reaction intermediate B.
• DMA dimethylacetamide
• reaction intermediate B 44 g (168 mmol) of reaction intermediate B and 500 mL of anhydrous THF were added to a 1 L flask and stirred at room temperature for 30 minutes, then nitrogen gas was sealed and cooled to 0 ° C., 7.4 g (168 mmol) of LiAlH 4 was added and stirred for 1 hour.
• the reaction solution was diluted with THF (tetrahydrofuran), dehydrated with sodium sulfate, and the supernatant was concentrated under reduced pressure to obtain a crude product.
• THF tetrahydrofuran
• ISH 1,4:3,6-dianhydro-2,5-dithio-D-mannitol
• Lens preparation 6 0.5 parts by mass of petroleum-derived XDI, 0.01 parts by mass of dimethyltin dichloride, 0.20 parts by mass of "JP-506H” (manufactured by Johoku Chemical Industry Co., Ltd.), and 0.5 parts by mass of "Seesorb 707” (manufactured by Shipro Kasei Co., Ltd.) were mixed and dissolved. Furthermore, 19.6 parts by mass of TTG obtained in (1) of Example 1 and 20.0 parts by mass of ISH obtained in (1) of Example 3 were added and mixed to obtain a mixed homogeneous solution. After this, lenses were prepared in the same manner as in Example 1.
• Example 4 A lens was produced in the same manner as in Example 3, except that XDI was changed to petroleum-derived NBDI.
• Example 5 Lenses were produced in the same manner as in Example 3, except that TTG was changed to petroleum-derived polythiol 1 (a mixture of 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) synthesized by a known method.
• petroleum-derived polythiol 1 a mixture of 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
• Example 6 A lens was produced in the same manner as in Example 4, except that TTG was changed to petroleum-derived polythiol 1 synthesized by a known method.
• Example 7 66.9 parts by mass of petroleum-derived XDI, 0.01 parts by mass of dimethyltin dichloride, 0.20 parts by mass of "JP-506H” (manufactured by Johoku Chemical Industry Co., Ltd.), and 0.5 parts by mass of "Seesorb 707” (manufactured by Shipro Kasei Co., Ltd.) were mixed and dissolved. Furthermore, 27.8 parts by mass of TTG obtained in (1) of Example 1 and 5.3 parts by mass of plant-derived 1,3-butanediol were added and mixed, and stirring was continued until a transparent homogenous solution was obtained. After this, lenses were produced in the same manner as in Example 1.
• Example 8 A lens was produced in the same manner as in Example 7, except that XDI was changed to petroleum-derived NBDI.
• the monomer ratios (molar ratios) of the polymerizable compositions of Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 1.
• petroleum-derived polyisocyanates were used as the polyisocyanates, but it is of course possible to use plant-derived polyisocyanates.
• biomass ratio ⁇ [parts by mass of (b) ⁇ biomass degree of (b) / 100] + [parts by mass of (c) ⁇ biomass degree of (c) / 100] ⁇ / [total mass (parts by mass) of (a) + (b) + (c) + (d)]
• (a) to (d) are as follows:
• c) Plant-derived polyol
• d Petroleum-derived polythiol
• the biomass degree of (c) was measured according to the standard of ASTM D6866 METHOD B and calculated by the following formula. The biomass degree of each plant-derived polyol was 100%.
• Biomass ratio number of carbon atoms derived
• a projection inspection was carried out using an appearance inspection device (Optical Modulex SX-UI251HQ manufactured by Ushio Inc.) for each lens of Examples 1 to 8 and Comparative Examples 5 and 6.
• a high pressure UV lamp (USH-102D manufactured by Ushio Inc.) was used as the light source, a white screen was placed at a distance of 1 m from the light source, the lens to be evaluated was inserted between the light source and the screen, and the projected image on the screen was observed and evaluated according to the following criteria.
• Evaluation Criteria A: There are absolutely no linear irregularities in the projected image.
• B There is a faint linear irregularity in the projection image.
• C There is a strong linear irregularity in the projection image.
• D There is significant linear irregularity in the projection image.
• One aspect of the present invention is useful in the technical fields of various optical materials.

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