Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
  • C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • 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
  • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto 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
  • C08G18/70—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

Definitions

• the present disclosure relates to polythiol compositions and their applications.
• Plastic lenses which are lenses containing resin, are lighter than inorganic lenses, are less likely to crack, and can be dyed.
• various studies have been made so far on lenses containing thiourethane resin (see, for example, Patent Documents 1 to 3).
• Patent Document 1 JP-A-63-46213
• Patent Document 2 JP-A-2-270859
• Patent Document 3 JP-A-7-252207
• a thiourethane resin is usually produced using a polythiol composition and a polyisocyanate compound as raw materials.
• thiourethane resins there are cases where it is required to further improve the heat resistance.
• An object of one aspect of the present disclosure is to provide a polythiol composition capable of producing a thiourethane resin with excellent heat resistance and its application.
• Means for solving the above problems include the following aspects. ⁇ 1> A polythiol composition containing a polythiol compound, Containing compound C1 having a retention time of 32.0 minutes to 35.0 minutes in high performance liquid chromatography measurement under the following measurement conditions A, The peak area of the compound C1 in the high performance liquid chromatography measurement is 0.50 or more relative to the total peak area of 100 of the compounds contained in the polythiol composition.
• the compound C1 has a molecular weight of 426, The polythiol composition according to ⁇ 1>.
• the compound C1 is a polythiol compound, The polythiol composition according to ⁇ 1> or ⁇ 2>.
• ⁇ 4> Further, it contains compound C2 whose retention time in the high performance liquid chromatography measurement is 16.0 minutes to 19.0 minutes, The peak area of the compound C2 in the high performance liquid chromatography measurement is 1.39 or more with respect to 100 of the total peak area of the compounds contained in the polythiol composition.
• ⁇ 5> Furthermore, it contains a polythiol compound (XA) containing three or more mercapto groups as a main component,
• the peak area in the high performance liquid chromatography measurement of the compound (XB) in which at least one of the three or more mercapto groups in the polythiol compound (XA) is replaced with a group represented by the following formula (N1) is is less than 1.10 with respect to 100 of the total peak area of the compounds contained in the polythiol composition
• the peak area in the high performance liquid chromatography measurement of the compound (XC) in which at least one of the three or more mercapto groups in the polythiol compound (XA) is replaced with a hydroxyl group is the peak area of the compound contained in the polythiol composition. is less than 2.40 for a total peak area of 100;
• the polythiol compound (XA) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane;
• the polythiol composition according to ⁇ 5> is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and at least one selected from the group consisting of
• a polyiso (thio) cyanate compound The polythiol composition according to any one of ⁇ 1> to ⁇ 6>, A polymerizable composition for optical materials containing ⁇ 8>
• the polyiso(thio)cyanate compound includes pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanate), natomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and including at least one selected from the group consisting of phenylene diisocyanates, The polymerizable composition for optical materials
• ⁇ 9> A resin that is a cured product of the polymerizable composition for optical materials according to any one of ⁇ 7> or ⁇ 8>.
• ⁇ 10> A molded article containing the resin according to ⁇ 9>.
• ⁇ 11> An optical material containing the resin according to ⁇ 9>.
• ⁇ 12> A lens containing the resin according to ⁇ 9>.
• a polythiol composition capable of producing a thiourethane resin with excellent heat resistance and its application are provided.
• a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
• the term “step” includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
• the amount of each component contained in the composition is the total amount of the multiple substances present in the composition unless otherwise specified.
• the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. .
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• the polythiol compositions of the present disclosure are A polythiol composition containing a polythiol compound, Containing compound C1 having a retention time of 32.0 minutes to 35.0 minutes in high-performance liquid chromatography measurement (hereinafter also simply referred to as "high-performance liquid chromatography measurement") under the following measurement conditions A,
• the peak area of compound C1 in high performance liquid chromatography measurement is 0.50 or more relative to the total peak area of 100 of the compounds contained in the polythiol composition, A polythiol composition.
• thiourethane resin having excellent heat resistance can be produced.
• polythiol composition means a composition containing at least one polythiol compound.
• the polythiol compound contained in the polythiol composition is also referred to as "polythiol component.”
• the polythiol composition may contain components other than the polythiol compound as impurities.
• the polythiol composition preferably contains at least one polythiol compound as a main component.
• the polythiol composition contains at least one polythiol compound as a main component
• the total content of at least one polythiol compound relative to the total amount of the polythiol composition is 50% or more. do.
• the total content of at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.
• the expression that the composition “includes a certain component (hereinafter referred to as “component X”) as a main component” means the content of component X (when component X consists of two or more compounds means that the total content of two or more compounds) is 50% or more of the total amount of the composition.
• the content of component X, which is the main component, is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more, relative to the total amount of the composition.
• % in the explanation of the term “contained as a main component” is the component relative to the total area of all peaks of the composition (e.g., polythiol composition) determined by high-performance liquid chromatography under the above measurement conditions A. It means the ratio (area %) of the total area of all peaks of X (eg, at least one polythiol compound).
• polythiol compositions include polythiol compositions containing known polythiol compounds.
• the polythiol compound is not particularly limited as long as it contains two or more thiol groups (also known as mercapto groups).
• thiol groups also known as mercapto groups.
• the polythiol compound refer to the above-mentioned known documents (that is, JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, WO 2008/047626, etc.) as appropriate. can.
• the polythiol composition of the present disclosure contains compound C1.
• Compound C1 is a compound having a retention time of 32.0 to 35.0 minutes in high performance liquid chromatography measurement under measurement conditions A.
• the polythiol composition of the present disclosure may contain only one type of compound C1, or may contain two or more types.
• Compound C1 may or may not be a polythiol compound, but is preferably a polythiol compound.
• Compound C1 is an effective component for improving the heat resistance of the thiourethane resin produced using the polythiol composition.
• the peak area of the compound C1 relative to the total peak area of 100 of the compounds contained in the polythiol composition in high performance liquid chromatography measurement (hereinafter simply referred to as the "peak area of compound C1") is When it is 0.50 or more, the effect of improving the heat resistance of the produced thiourethane resin is exhibited.
• the upper limit of the peak area of compound C1 is preferably 10.0, more preferably 5.0, from the viewpoint of the hue of the thiourethane resin to be produced.
• the molecular weight of compound C1 is 426, for example.
• the molecular weight referred to here is a value measured by high performance liquid chromatography mass spectrometry under measurement condition B below.
• Measurement condition B As a column, YMC-Pack (registered trademark) C18RS manufactured by YMC Co., Ltd.
• Compound C1 having a molecular weight of 426 and being a polythiol compound includes the following compound (C1-1a), the following compound (C1-1b), the following compound (C1-1c), the following compound (C1-2a), It preferably contains at least one selected from the group consisting of the following compound (C1-2b), the following compound (C1-2c), and the following compound (C1-2d).
• Compound C2 The polythiol composition of the present disclosure preferably further contains compound C2. Thereby, the heat resistance of the manufactured thiourethane resin is further improved.
• Compound C2 is a compound having a retention time of 16.0 to 19.0 minutes in high performance liquid chromatography measurement under measurement conditions A. When the polythiol composition of the present disclosure contains compound C2, only one type of compound C2 may be contained, or two or more types may be contained. Compound C2 may or may not be a polythiol compound.
• the peak area of compound C2 relative to the total peak area of 100 of the compounds contained in the polythiol composition in the high-performance liquid chromatography measurement under measurement conditions A (hereinafter also simply referred to as the "peak area of compound C2") is 1.39 or more. is preferably Thereby, the heat resistance of the manufactured thiourethane resin is further improved.
• the upper limit of the peak area of compound C2 is preferably 10.0, more preferably 5.0, from the viewpoint of the hue of the thiourethane resin to be produced.
• the polythiol composition of the present disclosure preferably further contains a polythiol compound (XA) containing 3 or more mercapto groups as a main component.
• the polythiol compound (XA) is a polythiol compound containing three or more mercapto groups.
• the compound C1 is not included in the scope of the polythiol compound (XA).
• the polythiol composition of the present disclosure contains compound C2, and the aforementioned compound C2 is a "polythiol compound containing three or more mercapto groups", the scope of the polythiol compound (XA) includes: Compound C2 shall not be included.
• the polythiol compound (XA) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and It is preferably at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane.
• 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is a polythiol compound represented by the following formula (1)
• 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane is a polythiol compound represented by the following formula (2)
• 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane is a polythiol compound represented by the following formula (3)
• 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane is a polythiol compound represented by the following formula (4).
• a more preferred embodiment of the polythiol compound (XA) is A mode containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A1") as a main component, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter collectively referred to as "polythiol component A2”) as a main component.
• the polythiol composition of each aspect may contain at least one component other than the main component (for example, other polythiol compounds, components other than the polythiol compound, etc.).
• the peak area of the compound C1 is 0.50 or more from the viewpoint of the heat resistance of the thiourethane resin to be produced. Even in the aspect in which the polythiol compound (XA) contains the polythiol component A1 as a main component, the peak area of the compound C1 is preferably 1.00 or more, more preferably 1.00 or more, from the viewpoint of further improving the heat resistance of the thiourethane resin to be produced. is greater than or equal to 1.20.
• the upper limit of the peak area of the compound C1 is preferably 10.0, more preferably 5, from the viewpoint of the hue of the thiourethane resin to be produced. .0.
• the compound C1 in the embodiment in which the polythiol compound (XA) contains the polythiol component A1 as a main component is preferably the aforementioned compound (C1-1).
• the peak area of the compound C1 is 0.50 or more from the viewpoint of the heat resistance of the thiourethane resin to be produced.
• the peak area of the compound C1 is preferably 2.30 or more, from the viewpoint of further improving the heat resistance of the thiourethane resin to be produced. It is more preferably 2.50 or more, and still more preferably 2.65 or more.
• the upper limit of the peak area of the compound C1 is preferably 10.0, more preferably 5, from the viewpoint of the hue of the thiourethane resin to be produced. .0.
• the compound C1 in the embodiment in which the polythiol compound (XA) contains the polythiol component A2 as a main component is preferably the aforementioned compound (C1-2a), the aforementioned compound (C1-2b), and the aforementioned compound (C1-2c). At least one selected from the group consisting of
• the peak area of the compound C2 is preferably 1.39 or more from the viewpoint of the heat resistance of the thiourethane resin to be produced. Even in the aspect in which the polythiol compound (XA) contains the polythiol component A1 as a main component, the peak area of the compound C2 is more preferably 2.40 or more from the viewpoint of further improving the heat resistance of the thiourethane resin to be produced. , more preferably 2.70 or more, more preferably 2.90 or more.
• the upper limit of the peak area of the compound C2 is preferably 10.0, more preferably 5, from the viewpoint of the hue of the thiourethane resin to be produced. .0.
• the peak area of the compound C2 is preferably 1.39 or more from the viewpoint of the heat resistance of the thiourethane resin to be produced.
• the peak area of the compound C2 is more preferably 1.40 or more, and further Preferably it is 1.41 or more.
• the upper limit of the peak area of the compound C2 is preferably 10.0, more preferably 5, from the viewpoint of the hue of the thiourethane resin to be produced. .0.
• the polythiol composition of the present disclosure contains a polythiol compound (XA) as a main component
• a polythiol compound (XB) as a main component
• the peak area of the compound (XB) in which at least one of the three or more mercapto groups in the polythiol compound (XA) is replaced with a group represented by the following formula (N1) by high-performance liquid chromatography is determined by the polythiol composition.
• the peak area in high performance liquid chromatography measurement of the compound (XC) in which at least one of the three or more mercapto groups in the polythiol compound (XA) is replaced with a hydroxyl group is the total peak area of the compounds contained in the polythiol composition. It is preferably less than 2.40 out of 100.
• Compound (XB) is a compound in which at least one of the three or more mercapto groups in polythiol compound (XA) is replaced with a group represented by formula (N1)
• Compound (XC) is a compound obtained by replacing at least one of the three or more mercapto groups in polythiol compound (XA) with a hydroxyl group.
• the polythiol composition of the present disclosure does not contain compound (XB), or even if it contains compound (XB), the peak area of compound (XB) in high performance liquid chromatography measurement is the total peak of the compounds contained in the polythiol composition It is preferably less than 1.10 with respect to 100 of the area.
• the peak area of the compound (XB) is preferably 100% of the total peak area of the compounds contained in the polythiol composition. is less than 1.10, more preferably less than 0.50, more preferably less than 0.25, and even more preferably less than 0.10.
• the peak area of the compound (XB) is preferably 100% of the total peak area of the compounds contained in the polythiol composition. is less than 1.10, more preferably less than 0.50, and even more preferably less than 0.10.
• the polythiol composition of the present disclosure does not contain compound (XC), or even if it contains compound (XC), the peak area of compound (XC) in high performance liquid chromatography measurement is the total peak of the compounds contained in the polythiol composition It is preferably less than 2.40 for an area of 100.
• the peak area of the compound (XC) is, relative to the total peak area of 100 of the compounds contained in the polythiol composition, It is preferably less than 2.40, more preferably less than 1.20, and even more preferably less than 0.10.
• the peak area of the compound (XC) is, relative to the total peak area of 100 of the compounds contained in the polythiol composition, It is preferably less than 2.40, more preferably less than 2.00, even more preferably less than 1.00, and even more preferably less than 0.10.
• the polythiol composition of the present disclosure when the contents of compound (XB) and compound (XC) are limited as described above, unintended polymerization of polythiol compound (XA) in the polythiol composition is suppressed. , and as a result, thickening is suppressed. Therefore, the polythiol composition of this aspect has an excellent pot life (that is, it has a long pot life).
• Compound (XB) is a compound obtained by replacing at least one of the three or more mercapto groups in polythiol compound (XA) with a group represented by formula (N1) above. Examples of compound (XB) are shown below, but compound (XB) is not limited to the following examples.
• Compound (XC) is a compound obtained by replacing at least one of the three or more mercapto groups in polythiol compound (XA) with a hydroxyl group. Examples of compound (XC) are shown below, but compound (XC) is not limited to the following examples.
• the polythiol composition of the present disclosure may contain other polythiol compounds other than the polythiol compounds described above.
• Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate).
• production method A Method for producing polythiol composition.
• production method A The polythiol composition of the present disclosure described above is produced, for example, by the following production method (hereinafter also referred to as “production method A”).
• Production method A is a method for producing a polythiol composition, including the step of reacting a thiourethane resin and an active hydrogen compound to produce the polythiol composition of the present disclosure.
• the polythiol composition of the present disclosure can be produced using a thiourethane resin as a starting material.
• the thiourethane resin reacts with the active hydrogen compound, the reaction chemically decomposes the thiourethane resin, and the polythiol composition of the present disclosure is obtained as a decomposition product of the thiourethane resin.
• thiourethane resin A thiourethane resin is the starting material in process A.
• the thiourethane resin is not particularly limited. Mention may be made of the thiourethane resins described.
• a thiourethane resin is usually produced as a reaction product of a polyisocyanate compound and a polythiol composition as raw materials.
• thiourethane resins include: Thiourethane resin obtained from high refractive index lens materials MR-6, MR-7, MR-8, MR-8Plus, MR-60, MR-10, MR-20 (manufactured by Mitsui Chemicals, Inc.); EYAS1.60 (manufactured by HOYA Corporation); etc.
• the thiourethane resin is preferably recovered in at least one of the spectacle lens manufacturing process, the spectacle manufacturing process, and the spectacle disposal process. According to this aspect, it is possible to recycle the thiourethane resin, which is the material of the spectacle lenses.
• the process of manufacturing an eyeglass lens means a process of preparing a resin by preparing a monomer that is a resin raw material and subjecting it to cast polymerization, and/or a process of cutting a resin molding to obtain an eyeglass lens.
• the manufacturing process of spectacles means the process of manufacturing spectacles by combining spectacle lenses and other members such as spectacle frames,
• the process of discarding eyeglasses means a process of discarding manufactured but unnecessary eyeglasses, used eyeglasses, and the like.
• thiourethane resin which is a material for spectacle lenses, can be generated as a waste product.
• a thiourethane resin produced in at least one of these processes is used as a starting material, and this thiourethane resin is reacted with an active hydrogen compound to obtain a polythiol composition of the present disclosure as a decomposition product of the thiourethane resin.
• the production method A by using the used thiourethane resin for the production of the polythiol composition, it is possible to reduce the amount of the thiourethane resin that is incinerated and discarded. It is possible to reduce the generation of greenhouse gases such as carbon dioxide, nitrogen monoxide and sulfur dioxide; and air pollutants such as sulfur oxides and nitrogen oxides. In addition, since thiourea is not used in the production of the polythiol compound, there is no production of waste water containing thiourea, making the production method environmentally friendly.
• production method A is effective as a method for recycling thiourethane resin.
• the polythiol composition of the present disclosure containing compound C1 is obtained. This point is effective in ensuring the traceability of materials.
• the starting material preferably contains cutting waste (for example, cutting powder and/or cutting pieces; the same shall apply hereinafter) containing thiourethane resin.
• cutting waste for example, cutting powder and/or cutting pieces; the same shall apply hereinafter
• the thiourethane resin and the active hydrogen compound are reacted by contacting the cutting waste containing the thiourethane resin and the active hydrogen compound.
• the reactivity between the active hydrogen compound and the thiourethane resin in the starting material is excellent, so that the polythiol composition can be produced more effectively.
• the active hydrogen compound functions as a decomposing agent for the starting thiourethane resin. From the viewpoint of the above functions, the active hydrogen compound is preferably at least one selected from the group consisting of amine compounds and alcohol compounds.
• the amine compound is preferably an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 to 6 (preferably 1 to 3, more preferably 1 or 2). .
• the molecular weight of the amine compound is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and still more preferably 200 or less.
• the lower limit of the molecular weight of the amine compound is, for example, 45 or more, preferably 59 or more, more preferably 60 or more.
• Examples include amine compounds containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 or 2 and having a molecular weight of 300 or less.
• amine compounds include alkylamines having 2 to 10 carbon atoms, aralkylamines having 7 to 10 carbon atoms (eg, benzylamine), dialkylamines having 2 to 10 carbon atoms (eg, di-n-butylamine ), alkyldiamines having 2 to 10 carbon atoms (e.g., ethylenediamine, bis(2-aminoethyl) ether), alkyltriamines having 2 to 10 carbon atoms (e.g., bis(2-aminoethyl)amine), 2 to 10 carbon atoms, 10 hydroxyalkylamines (eg, monoethanolamine), bis(hydroxyalkyl)amines having 2 to 10 carbon atoms (eg, bis(hydroxyethyl)amine), cyclic amines having 2 to 10 carbon atoms (eg, morpholine), Secondary amines such as alkyl(hydroxyalkyl)amines having 2 to 10 carbon atoms (eg, benzy
• the alcohol compound may be a monoalcohol compound containing only one hydroxy group, or a polyol compound containing two or more hydroxy groups.
• the molecular weight of the alcohol compound is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and still more preferably 200 or less.
• the lower limit of the molecular weight of the alcohol compound is, for example, 40 or more, preferably 50 or more, more preferably 60 or more.
• the alcohol compound preferably includes an alcohol compound having a boiling point of 135°C to 250°C (hereinafter also referred to as "alcohol compound A").
• the boiling point means the boiling point under 1 atmosphere (101325 Pa).
• the proportion of alcohol compound A in the total amount of alcohol compounds is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and still more preferably 80% by mass to 100% by mass. be.
• reaction solvent In the step of producing the polythiol composition, it is preferable to react the thiourethane resin and the active hydrogen compound in the presence of the reaction solvent.
• the reaction solvent include hydrocarbon compounds having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), ether compounds having 4 to 12 carbon atoms, ketone compounds having 3 to 12 carbon atoms, and 4 carbon atoms. Ester compounds having 1 to 12 carbon atoms, alcohol compounds having 2 to 12 carbon atoms, and nitrile compounds having 2 to 12 carbon atoms are preferred.
• the hydrocarbon compound is preferably hexane, heptane, octane, nonane, decane, xylene, mesitylene, or toluene, more preferably heptane, octane, nonane, xylene, mesitylene, or toluene, and particularly preferably , xylene or toluene.
• the ether compound is preferably diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane or 1,4-dioxane, and particularly preferably dimethoxyethane.
• the ketone compound is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, or 2-octanone, and particularly preferably methyl isobutyl ketone.
• the above ester compound is preferably ethyl acetate, butyl acetate, or pentyl acetate, and particularly preferably pentyl acetate.
• the above alcohol compound is preferably ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-octanol, 2-octanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, or methyl cellosolve, Benzyl alcohol or ethylene glycol is particularly preferred.
• the nitrile compound is preferably acetonitrile or propionitrile, particularly preferably acetonitrile.
• the compound used as the reaction solvent may be of one type or two or more types.
• the step of producing a polythiol composition is preferably a step of reacting a thiourethane resin and an active hydrogen compound to produce a polythiol composition and a polyamine compound.
• a decomposition reaction occurs in which the thiourethane resin is decomposed into a polythiol composition and a polyamine compound by an active hydrogen compound as a decomposing agent.
• the active hydrogen compound is an amine compound
• the decomposition reaction is an aminolysis reaction
• the active hydrogen compound is an alcohol compound
• the decomposition reaction is an alcoholysis reaction.
• the step of generating a polythiol composition includes contacting a resin mixture containing a thiourethane resin with an active hydrogen compound to react the thiourethane resin in the resin mixture with the active hydrogen compound to form a polythiol composition. It may be a step of generating
• a resin mixture containing a thiourethane resin further contains components other than the thiourethane resin.
• Components other than the thiourethane resin include resins other than the thiourethane resin, inorganic materials for lens production (for example, glass), and the like.
• Resins other than the thiourethane resin are not particularly limited. for example; A hybrid material of a thiourethane resin and a urethane resin, produced by adding a polyol compound to raw materials when producing a thiourethane resin; A hybrid material of a thiourethane resin and a urea resin, produced by adding a polyamine compound to raw materials when producing a thiourethane resin; etc. are also included in the scope of resin mixtures containing thiourethane resins and resins other than thiourethane resins.
• Polyolefin film that protects the surface of resin moldings for making eyeglass lenses
• a hard coat or primer coat that protects the surface of a resin molded body for making eyeglass lenses
• a resin material for fixing a resin molded body when cutting a resin molded body for making eyeglass lenses, Tape or tape glue used to fix the glass mold used when making a resin molded body for making eyeglass lenses, etc. are also mentioned.
• the resin mixture preferably contains, as a resin other than the thiourethane resin, at least one selected from the group consisting of polycarbonate resin, polyallyl carbonate resin, acrylic resin, urethane resin, and episulfide resin. These resins, like thiourethane resins, are also resins that can be used as materials for spectacle lenses.
• the resin mixture containing the thiourethane resin is preferably recovered in at least one of the spectacle lens manufacturing process, the spectacle manufacturing process, and the spectacle disposal process.
• the spectacle lens manufacturing process, the spectacle manufacturing process, and the spectacle disposal process are as described above.
• the resin mixture containing the thiourethane resin preferably contains cutting waste containing the thiourethane resin.
• the step of producing a polythiol composition is a step of reacting a thiourethane resin with an active hydrogen compound to produce the polythiol composition of the present disclosure to obtain a reaction mixture containing the polythiol composition as the target product. good too.
• Components other than the polythiol composition in the reaction mixture include the reaction solvent described above, residues of raw materials (thiourethane resin and/or active hydrogen compound), impurities contained in the raw materials, and the like.
• Production method A may include a separation step of separating the target polythiol composition from the reaction mixture containing the polythiol composition.
• the separation method in the separation step is not particularly limited, and known methods can be applied. Separation methods in the separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (for example, column chromatography), and the like. A plurality of methods may be used in combination as the separation method.
• a method for separating the polythiol composition includes a method of extracting with an organic solvent or an inorganic solvent capable of dissolving the polythiol compound.
• Common purification methods such as column purification, distillation purification, recrystallization purification, and salt extraction are used as methods for purifying the polythiol composition.
• the separation step includes filtering the reaction mixture containing the polythiol composition and the polyamine derivative to obtain the polythiol composition as a filtrate. and/or obtaining as filtrate a mixture containing a polyurea compound that is a polyamine derivative.
• the separating step comprises obtaining a filtrate comprising the polythiol composition as a filtrate
• separating the polythiol composition from the filtrate provides the polythiol composition.
• filtering a reaction mixture comprising the polythiol composition and the polyamine compound to obtain a filtrate comprising the polythiol composition
• obtaining an aqueous extract containing an alkali metal salt of the polythiol composition by adding a base containing an alkali metal to the filtrate containing the polythiol composition and then adding water for extraction; adding an acid to an aqueous extract containing an alkali metal salt of the polythiol composition to obtain an aqueous liquid containing the polythiol composition
• Obtaining an extract containing the polythiol composition by adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to an aqueous liquid containing the polythiol composition for extraction; separating the polythiol composition from an extract containing the polythiol
• An acid is then added here to return the alkali metal salt of the polythiol composition to the polythiol composition.
• the polythiol composition is extracted from the resulting aqueous liquid containing the polythiol composition with the extraction solvent to obtain an extract containing the polythiol composition.
• the polythiol composition is separated from the obtained extract containing the polythiol composition. According to this example, even when the filtrate containing the polythiol composition contains many components other than the polythiol composition, a polythiol composition having a higher purity of the polythiol component as the main component can be obtained.
• the alkali metal in the alkali metal-containing base is preferably sodium, potassium or lithium, more preferably sodium or potassium.
• Bases containing alkali metals include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.
• a base containing an alkali metal can be added to the filtrate in the form of an alcohol solution (methanol solution, ethanol solution, etc.), if necessary.
• the acid added to the water extract containing the alkali metal salt of the polythiol composition includes hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, and the like.
• the number of extraction solvents may be one, or two or more.
• preferred modes of the extraction solvent are the same as the preferred modes of the reaction solvent described above.
• the reaction solvent and the extraction solvent may be the same or different.
• the separation step comprises obtaining a mixture comprising the polyurea compound as a filtrate or a residue from decantation or extraction
• the active hydrogen compound preferably amine compound and/or alcohol compound
• the polyurea compound and the active hydrogen compound in the mixture are allowed to react, thereby producing a polyamine compound as a raw material for a thiourethane resin.
• the polyamine compound as a raw material for the thiourethane resin can be obtained.
• Production method A may include other steps than the above steps, if necessary.
• Other steps include, for example; a sieving step of sieving the thiourethane resin prior to the step of forming the polythiol composition; washing the thiourethane resin prior to forming the polythiol composition; crushing and/or pulverizing the thiourethane resin prior to forming the polythiol composition; etc. More specific examples of other steps are shown below.
• Manufacturing method A is Before the step of generating the polythiol composition, the cutting waste containing the thiourethane resin is classified to obtain a powder containing the thiourethane resin having a smaller average particle size than the cutting waste. It's okay.
• the powder and the active hydrogen compound are brought into contact with each other to allow the thiourethane resin in the powder to react with the active hydrogen compound.
• Classification methods include sieving, centrifugation, and the like.
• the following sieving process can be referred to for the aspect of performing sieving as classification.
• Manufacturing method A is Before the step of generating the polythiol composition, a sieving step of sieving the cutting powder containing the thiourethane resin to obtain a powder containing the thiourethane resin that has passed through the sieve may be included.
• the powder and the active hydrogen compound are brought into contact to react the thiourethane resin in the powder and the active hydrogen compound.
• the nominal opening of the sieve defined by JIS Z-8801-1:2019 is, for example, 0.1 mm to 20 mm, preferably 0.1 mm to 10 mm, more preferably 0.1 mm to 5 mm, and further It is preferably 0.1 mm to 2 mm, more preferably 0.3 mm to 2 mm, still more preferably 0.5 mm to 1.5 mm.
• the method for producing a polythiol composition according to production method A comprises: A washing step of washing the powder containing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent may be included before the step of producing the polythiol composition.
• a washing step of washing the powder containing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent may be included before the step of producing the polythiol composition.
• the powder washed in the washing step is brought into contact with the active hydrogen compound, whereby the thiourethane resin in the powder and the active hydrogen compound are brought into contact with each other. React with a hydrogen compound.
• the number of hydrocarbon compounds used as the washing solvent may be one, or two or more. Preferred aspects of the hydrocarbon compound as the washing solvent are the same as the above-described preferred aspects of the hydrocarbon compound as the reaction solvent. However, the reaction solvent and the washing solvent may be the same or different.
• the washing method in the washing step is not particularly limited, and a known method such as adding the above washing solvent to the thiourethane resin powder and mixing can be applied.
• the manufacturing method A includes the sieving process and the washing process described above, it is preferable to perform the sieving process and the washing process in this order. In this case, since it is not necessary to wash the cutting powder that has not passed through the sieve, the amount of washing solvent used can be further reduced.
• polymerizable composition for optical material The polymerizable composition for optical materials of the present disclosure (hereinafter also referred to as “polymerizable composition of the present disclosure") is A polyiso (thio) cyanate compound, the aforementioned polythiol composition of the present disclosure; contains
• the polymerizable composition of the present disclosure contains the polythiol composition of the present disclosure described above, it exhibits the same effects as the polythiol composition of the present disclosure.
• polyiso (thio) cyanate compound The polyiso(thio)cyanate compound is not particularly limited as long as it is a compound having at least two iso(thio)cyanate groups in one molecule.
• Specific examples of polyiso (thio) cyanate compounds include: Tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate , aliphatic polyisocyanate compounds such as xylylene diisocyanate; isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, dicyclohexy
• Polyiso(thio)cyanate compounds include halogen-substituted products such as chlorine-substituted products and bromine-substituted products thereof, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols, and carbodiimides. Modified products, urea modified products, buret modified products, dimerization or trimerization reaction products, etc. can also be used.
• Polyisocyanate compounds are preferred, pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1] - containing at least one selected from heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and phenylene diisocyanate is preferred.
• the mixing ratio of the polythiol composition and the polyiso(thio)cyanate compound is not particularly limited.
• the molar ratio of the mercapto group of the polythiol compound and the iso(thio)cyanate group of the polyiso(thio)cyanate compound contained in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and preferably 0.8 to 1.3 More preferred.
• the mixing ratio is within the above range, it tends to be possible to satisfy various performances such as refractive index and heat resistance required for a plastic lens or the like in a well-balanced manner.
• the polymerizable composition of the present disclosure may contain components other than the polythiol composition and the polyiso(thio)cyanate compound.
• Other ingredients include polymerization catalysts, internal release agents, resin modifiers, chain extenders, cross-linking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion Blue ink agents such as property improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments are included.
• polymerization catalysts include tertiary amine compounds, inorganic or organic acid salts thereof, metal compounds, quaternary ammonium salts, organic sulfonic acids, and the like.
• An acidic phosphate ester can be used as the internal release agent.
• acidic phosphates include phosphate monoesters and phosphate diesters, each of which can be used alone or in combination of two or more.
• resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, olefin compounds including (meth)acrylate compounds, and the like.
• the polymerizable composition of the present disclosure can be obtained by mixing the above components.
• the resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure described above.
• the resin of the present disclosure is obtained by curing the polymerizable composition of the present disclosure described above.
• Curing of the polymerizable composition can be carried out by polymerizing the monomers (specifically, the polythiol composition and the polyiso(thio)cyanate compound; hereinafter the same) in the polymerizable composition.
• the polymerizable composition may be subjected to treatment such as filtration and degassing.
• Polymerization conditions e.g., polymerization temperature, polymerization time, etc.
• Polymerization catalyst for polymerizing the monomers in the polymerizable composition include the composition of the composition, the type and amount of monomers in the composition, and the type of polymerization catalyst in the composition.
• the polymerization temperature include -50°C to 150°C, 10°C to 150°C, and the like.
• the polymerization time is, for example, 1 hour to 200 hours, 1 hour to 80 hours, and the like.
• a polymer obtained by polymerization of monomers may be subjected to a treatment such as annealing to obtain the resin.
• Annealing temperatures include 50° C. to 150° C., 90° C. to 140° C., 100° C. to 130° C., and the like.
• the molded article of the present disclosure contains the resin of the present disclosure.
• the molded article of the present disclosure is obtained by curing the polymerizable composition of the present disclosure, similarly to the resin of the present disclosure. Preferred conditions for curing the polymerizable composition, ie, polymerization of the monomers in the polymerizable composition, are as described above.
• Cast polymerization is an example of a preferred method for producing the molded article of the present disclosure.
• the polymerizable composition is injected between molding molds held by gaskets, tapes, or the like. At this time, if necessary, defoaming treatment, filtration treatment, or the like may be performed.
• the composition is cured between the molding molds to obtain a cured product.
• the cured product is removed from the molding mold to obtain a molded body containing the resin.
• Polymerization of the above monomers may be carried out by heating the polymerizable composition. This heating can be performed, for example, by using a heating device having a mechanism for heating the object to be heated in an oven, in water, or the like.
• the optical material of the present disclosure contains the resin of the present disclosure.
• the optical material of the present disclosure like the resin of the present disclosure, is obtained by curing the polymerizable composition of the present disclosure. Preferred conditions for curing the polymerizable composition, ie, polymerization of the monomers in the polymerizable composition, are as described above.
• Optical materials include lenses (eg, eyeglass lenses, camera lenses, polarized lenses), light emitting diodes (LEDs), and the like.
• lenses eg, eyeglass lenses, camera lenses, polarized lenses
• LEDs light emitting diodes
• the optical material of the present disclosure may include a coating layer formed on one side or both sides of the resin of the present disclosure (or a molded article containing the resin of the present disclosure).
• coating layers include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water repellent layer.
• Each of these coating layers may be formed independently, or may be formed by stacking a plurality of coating layers. When the coating layer is formed on both sides, the same coating layer may be formed on each side, or different coating layers may be formed on each side.
• the components of the coating layer can be appropriately selected depending on the purpose.
• Components of the coating layer include, for example, resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, Pigments, antistatic agents and the like can be mentioned.
• room temperature means 25°C unless otherwise specified.
• the purity (%) of the polythiol component A1 in the polythiol composition means the peak of the polythiol component A1 with respect to the total peak area of the compounds contained in the polythiol composition, which is obtained by high-performance liquid chromatography under the measurement conditions A described above. It means the area ratio (area %).
• Table 1 shows the above HPLC of polythiol composition X1, The peak area ratio of the polythiol component A1 (specifically, the peak area ratio to the total peak area of the compounds contained in the polythiol composition. Same below.), Peak area ratio of compound C1, Peak area ratio of compound C2, The peak area ratio of compound (XB) and the peak area ratio of compound (XC) are shown.
• Polythiol component A1 is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• Compound C1 is a polythiol compound with a molecular weight of 426 and a retention time of 32.0 to 35.0 minutes
• Compound C2 is a polythiol compound having a retention time of 16.0 minutes to 19.0 minutes
• compound (XB) represents at least one of the mercapto groups in polythiol component A1 by formula (N1).
• Compound (XC) is a compound in which at least one of the mercapto groups in polythiol component A1 is replaced with a hydroxyl group.
• each compound is the result of high performance liquid chromatography (HPLC) measurement under measurement condition A described above, the result of liquid chromatography mass spectrometry measurement under measurement condition B described above, and the polythiol component A1, which is the main component. was deduced based on the structure of Compound C1 in this Comparative Example 1 and Example 1 described later is presumed to be the compound (C1-1) described above.
• HPLC high performance liquid chromatography
• the polymerizable composition was filtered under reduced pressure with a PTFE (polytetrafluoroethylene) filter, and then sufficiently degassed under a reduced pressure of 600 Pa until foaming was no longer observed.
• the degassed polymerizable composition was injected between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven and the temperature inside the oven was set at 10°C. Next, the temperature inside the oven was raised from 10° C. to 120° C. over 38 hours.
• the monomers (polyisocyanate compound and polythiol composition) in the polymerizable composition after degassing are polymerized, and the molded article containing the thiourethane resin R1 (that is, the polymerizable composition A hardened product) was formed.
• the inside of the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and then the molded body was removed from the pair of glass molds to obtain a molded body.
• a lens was manufactured by cutting the molded body obtained above.
• Refractive index (ne) Using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive index (ne) at a wavelength of 546.1 nm (mercury e-line) was measured at 20°C.
• - Specific gravity d Measured by the Archimedes method at 20°C.
• Example 1 ⁇ Production of polythiol composition> - Preparation of thiourethane resin powder - Cutting powder generated during lens manufacturing (that is, cutting) in Comparative Example 1 was collected to obtain thiourethane resin powder R1 (that is, powder containing thiourethane resin R1).
• a polythiol composition was separated from the reaction mixture by subjecting the reaction mixture obtained in the reaction step to a separation step including extraction and the like. Details will be described below.
• the reaction mixture obtained in the reaction step was cooled to 60° C. and then filtered to remove solids. 144.3 g of a 31% sodium hydroxide aqueous solution was added to the obtained filtrate, and the mixture was stirred at 25°C. To this, 150 g of water was added to extract soluble components, and the resulting water extract was washed with 50 g of toluene at 25°C. Stirred. A soluble component was extracted with toluene to obtain a toluene extract.
• the toluene extract was washed with 160 g of water at 40° C., then washed with 160 g of 0.1% aqueous ammonia at 40° C., and then washed twice with 160 g of water at 40° C. to obtain polythiol.
• a toluene solution of the composition was obtained.
• Toluene was distilled off from the resulting toluene solution using a rotary evaporator.
• the resulting mixture was subjected to removal of low boiling point components with a vacuum pump and filtration through a 1 micron PTFE membrane filter in this order to give 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. (That is, polythiol component A1) was obtained as a main component of 86.2 g of the polythiol composition (above, separation step).
• a polymerizable composition, a molded article, and a lens were produced in the same manner as in Comparative Example 1, except that the polythiol composition X1 used in Comparative Example 1 was changed to the polythiol composition obtained in Example 1.
• Example 1 contains compound C1 having a retention time of 32.0 minutes to 35.0 minutes, and the peak area of compound C1 in the high performance liquid chromatography measurement is the sum of the compounds contained in the polythiol composition.
• Example 1 using a polythiol composition having a peak area of 100 of 0.50 or more compared with Comparative Example 1 using a polythiol composition having a peak area of compound C1 of less than 0.50, the heat resistance A thiourethane resin with excellent properties (that is, a lens with a high Tg) could be produced.
• a mixture of the polythiol composition of Comparative Example 1 and the polythiol composition of Example 1 is also useful.
• the peak area of compound C1 is 0.50.
• the polymerizable composition was filtered under reduced pressure with a PTFE (polytetrafluoroethylene) filter, and then sufficiently degassed under a reduced pressure of 600 Pa until foaming was no longer observed.
• the degassed polymerizable composition was injected between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven and the temperature inside the oven was set to 25°C. Next, the temperature inside the oven was raised from 25° C. to 120° C. over 24 hours.
• the monomers (polyisocyanate compound and polythiol composition) in the polymerizable composition after degassing are polymerized, and the molded article containing the thiourethane resin R2 (that is, the polymerizable composition A hardened product) was formed.
• the inside of the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and then the molded body was removed from the pair of glass molds to obtain a molded body of Reference Example 1.
• a lens of Reference Example 1 was manufactured by cutting the molded article of Reference Example 1 obtained above.
• Example 2 ⁇ Production of polythiol composition> Cutting powder generated during the manufacture (ie, cutting) of the lens in Reference Example 1 was collected to obtain thiourethane resin powder R2 (ie, powder containing thiourethane resin R2).
• the resulting mixture was subjected to removal of low boiling point components by a vacuum pump and filtration through a 1 micron PTFE membrane filter in this order to give 4,8-dimercaptomethyl-1,11-dimercapto-3, 6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6 ,9-trithiaundecane (that is, polythiol component A2) as a main component was obtained (19.49 g, separation step).
• HPLC High Performance Liquid Chromatography
• Table 2 shows the above HPLC of the polythiol composition, The peak area ratio of the polythiol component A2 (specifically, the peak area ratio to the total peak area of the compounds contained in the polythiol composition. Same below.), Peak area ratio of compound C1, Peak area ratio of compound C2, The peak area ratio of compound (XB) and the peak area ratio of compound (XC) are shown.
• Polythiol component A2 includes 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tri thiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
• Compound C1 is a polythiol compound with a molecular weight of 426 and a retention time of 32.0 to 35.0 minutes;
• Compound C2 is a polythiol compound having a retention time of 16.0 minutes to 19.0 minutes, and compound (XB) represents at least one of the mercapto groups in polythiol component A2 by formula (N1).
• Compound (XC) is a compound in which at least one of the mercapto groups in polythiol component A2 is replaced with a hydroxyl group.
• the structure of each compound is the result of high performance liquid chromatography (HPLC) measurement under measurement condition A described above, the result of liquid chromatography mass spectrometry measurement under measurement condition B described above, and the polythiol component A2, which is the main component.
• HPLC high performance liquid chromatography
• a polymerizable composition, a molded article, and a lens were produced in the same manner as in Reference Example 1, except that the polythiol composition X2 used in Reference Example 1 was changed to the polythiol composition obtained in Example 2.
• Example 2 using a polythiol composition with a peak area of 100 or more of 0.50 or more, a thiourethane resin with excellent heat resistance (that is, a lens with a high Tg) could be produced.

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