Manufacturing method of polythiol composition, composition management system of polythiol composition, thiourethane resin raw material, and application thereof

Abstract

The present invention provides a method for producing a polythiol composition, the method comprising: a step for generating a polythiol composition (S), which contains two or more polythiol compounds, by reacting a composition X that contains a thiourethane resin; and a step for producing a polythiol composition (T) from the polythiol composition (S) by adjusting the content of at least one polythiol compound contained in the polythiol composition (S).

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a polythiol composition, a polythiol composition, a composition management system for a thiourethane resin raw material, and applications thereof. [Background technology]

[0002] Plastic lenses, which are lenses containing resin, are lighter and less likely to break than inorganic lenses, and can be dyed, and so in recent years have rapidly become popular for use in eyeglass lenses, camera lenses, and the like. For example, various studies have been conducted on lenses containing thiourethane resins (see, for example, Patent Documents 1 to 3). [Patent Document 1] Japanese Patent Application Laid-open No. 63-46213 [Patent Document 2] Japanese Patent Application Laid-Open No. 2-270859 [Patent Document 3] Japanese Patent Application Laid-Open No. 7-252207 Summary of the Invention [Problem to be solved by the invention]

[0003] As raw materials for producing a thiourethane resin (hereinafter also referred to as "thiourethane resin raw materials"), a polythiol composition and a polyisocyanate composition are usually used. The polyisocyanate composition is produced, for example, from a polyamine compound.

[0004] A lens (for example, a spectacle lens) containing a thiourethane resin is produced by cutting a molded body containing a thiourethane resin. As a result, a large amount of cutting powder containing thiourethane resin may be generated as waste during the lens manufacturing process. Furthermore, in the process of producing a molded article containing a thiourethane resin, defective molded products or defective processed products may occur. Additionally, used eyeglass lenses may be disposed of by consumers as waste. Conventionally, waste materials such as cutting chips, defective molded products, defective processed products, and used eyeglass lenses have been either burned or buried as industrial waste, and have not been effectively utilized. However, from the viewpoint of effective utilization of materials (i.e., recycling), there is a demand for a technology for producing a polythiol composition, which is a thiourethane resin raw material, using waste cutting powder containing thiourethane resin, or defective molding or processing products as a starting material, as well as a recycled thiourethane resin raw material (hereinafter also referred to as "recycled thiourethane resin raw material"). The produced polythiol composition, recycled thiourethane resin raw material, etc. can be used as a raw material for producing thiourethane resin. Alternatively, the produced polythiol composition can also be used as a raw material for producing resins other than thiourethane resins, for example, other resins utilizing a thiol-ene reaction, etc. Furthermore, there is a demand for a technique for producing polythiol compositions, recycled thiourethane resin raw materials, and the like using thiourethane resin as a starting material, in addition to using thiourethane resin contained in cutting processing powder or defective molded or processed products as a starting material.

[0005] The thiourethane resin used in the production of polythiol compositions, recycled thiourethane resin raw materials, etc. is expected to be a mixture of multiple types of thiourethanes. For example, when cutting powder, defective molding products, defective processing products, used eyeglass lenses, etc. are collected, these collected materials are expected to be composed of different types of thiourethane resins. When the thiourethane resin contained in these collected materials is decomposed to produce polythiol compositions, recycled thiourethane resin raw materials, etc., the composition of the produced polythiol compositions, recycled thiourethane resin raw materials, etc. may vary depending on the collected materials. Furthermore, when a polythiol composition, recycled thiourethane resin raw material, etc. is produced by decomposing a thiourethane resin mixed powder obtained by pulverizing collected materials composed of different types of thiourethane resins, the composition of the produced polythiol compositions, recycled thiourethane resin raw materials, etc. may vary for each production unit. Therefore, polythiol compositions, recycled thiourethane resin raw materials, etc. produced by chemically decomposing thiourethane resins vary in composition, making them difficult to use as products as they are.

[0006] An object of the present disclosure is to provide a method for producing a polythiol composition that can produce a polythiol composition having a specific compositional ratio using a polythiol composition produced using a thiourethane resin as a starting material, a method for producing a polymerizable composition and a method for producing a cured product that include this production method, and a polythiol composition that includes a polythiol compound derived from a thiourethane resin. Another object of the present disclosure is to provide a composition management system for thiourethane resin raw materials that manages information that enables the production of thiourethane resin raw materials having specific composition ratios using recycled thiourethane resin raw materials, and a production system for thiourethane resin raw materials that is capable of producing thiourethane resin raw materials having specific composition ratios. Furthermore, another object of the present disclosure is to provide a composition management method for thiourethane resin raw materials that manages information that enables the production of thiourethane resin raw materials having a specific composition ratio using recycled thiourethane resin raw materials, and a manufacturing method for thiourethane resin raw materials that enables the production of thiourethane resin raw materials having a specific composition ratio. Another object of the present disclosure is to provide a polythiol composition capable of producing a cured product having desired heat resistance and dyeability, a polymerizable composition and composition set containing this polythiol composition, a cured product obtained by curing this polymerizable composition, and an optical material containing this cured product. [Means for solving the problem]

[0007] The means for solving the above problems include the following aspects. <1A> A step of reacting a composition X containing a thiourethane resin to produce a polythiol composition (S) containing two or more polythiol compounds; a step of producing a polythiol composition (T) from the polythiol composition (S) by adjusting the content of at least one polythiol compound contained in the polythiol composition (S); A method for producing a polythiol composition, comprising: <2A> The method for producing a polythiol composition according to <1A>, wherein the thiourethane resin contains at least two or more types of thiourethane resins. <3A> The thiourethane resin is A thiourethane resin A formed using a polythiol composition (P) containing a polythiol compound (A1) having no ester bond in the molecule and a polyisocyanate composition (A) containing at least one polyisocyanate compound, and A thiourethane resin B formed using the polythiol composition (P), a polythiol composition (Q) containing a polythiol compound (A2) having at least one ester bond in the molecule, and a polyisocyanate composition (B) containing at least one polyisocyanate compound. The method for producing the polythiol composition according to <2A>, which contains at least two or more thiourethane resins selected from the group consisting of: <4A> The polythiol composition (P) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane The method for producing the polythiol composition according to <3A>, which contains at least one selected from the group consisting of: <5A> The polythiol composition (Q) pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), Trimethylolpropane tris(3-mercaptopropionate) and Pentaerythritol tetrakis(3-mercaptobutyrate) The method for producing the polythiol composition according to <3A> or <4A>, which comprises at least one selected from the group consisting of: <6A> The polyisocyanate composition (A) and the polyisocyanate composition (B) each independently comprise: The method for producing a polythiol composition according to any one of <3A> to <5A>, which contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. <7A> The method for producing a polythiol composition according to any one of <1A> to <6A>, wherein in the step of producing the polythiol composition (T), the polythiol composition (T) is produced by adding at least one polythiol compound contained in the polythiol composition (S) to the polythiol composition (S). <8A> The method for producing a polythiol composition according to any one of <1A> to <7A>, wherein in the step of producing the polythiol composition (S), the thiourethane resin in the composition X is reacted with an active hydrogen compound to produce the polythiol composition (S). <9A> The active hydrogen compound includes at least one selected from the group consisting of an amine compound and an alcohol compound. <8> A method for producing the polythiol composition described in claim 1. <10A> The method for producing a polythiol composition according to any one of <1A> to <9A>, wherein the composition X contains at least one selected from the group consisting of a resin other than the thiourethane resin, a polymerization catalyst, a metal, an ultraviolet absorber, an internal mold release agent, a plasticizer, a dye, machine oil, and water. <11A> The polythiol composition (S) and the polythiol composition (T) each independently comprise: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane The method for producing the polythiol composition according to any one of <1A> to <10A>, which contains at least one selected from the group consisting of: <12A> 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane A polythiol composition comprising at least two polythiol compounds (U) selected from the group consisting of the above and derived from a thiourethane resin. <13A> A method for producing a polymerizable composition, comprising a step of producing a polymerizable composition by mixing the polythiol composition (T) obtained by the method for producing a polythiol composition according to any one of <1A> to <11A> and a polyisocyanate composition (C) containing at least one polyisocyanate compound. <14A> A step of producing a polymerizable composition by the method for producing a polymerizable composition according to <13A>; a step of curing the polymerizable composition to obtain a cured product; A method for producing a cured product comprising the steps of:

[0008] <1B> A first registration unit that registers composition information regarding recycled thiourethane resin raw materials obtained by chemically decomposing the thiourethane resin contained in the recovered resin powder; a second registration unit that registers composition information related to the thiourethane resin raw material; A derivation unit that derives information about a composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material based on composition information about the thiourethane resin raw material registered in the second registration unit and composition information about the recycled thiourethane resin raw material registered in the first registration unit; A composition management system for thiourethane resin raw materials. <2B> The composition information regarding the recycled thiourethane resin raw material is Derived from the thiourethane resin compositional information regarding a polythiol composition comprising a polythiol compound; compositional information regarding a polyisocyanate composition comprising the polyisocyanate compound; compositional information regarding intermediate products capable of producing polythiol compositions comprising polythiol compounds; and Composition information regarding intermediate products capable of producing polyisocyanate compositions containing polyisocyanate compounds The composition management system for a thiourethane resin raw material according to <1B>, wherein the composition management system is at least one selected from the group consisting of: <3B> The recycled thiourethane resin raw material and the thiourethane resin raw material are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane The composition management system for a thiourethane resin raw material according to <1B> or <2B>, which contains at least one selected from the group consisting of: <4B> A composition management system for a thiourethane resin raw material according to any one of <1B> to <3B>, wherein the information on the composition is information on the composition of a resin raw material to be added to the recycled thiourethane resin raw material in order to produce the thiourethane resin raw material. <5B> A third registration unit that registers information about the resin powder; a fourth registration unit that registers information regarding a method for chemically decomposing the thiourethane resin; a determination unit that determines whether or not the thiourethane resin contained in the resin powder is to be recycled based on information about the resin powder registered in the third registration unit; an acquisition unit that acquires, when the determination unit determines that the thiourethane resin is to be recycled, information on a method for chemically decomposing the thiourethane resin to be recycled from the fourth registration unit; The composition management system for a thiourethane resin raw material according to any one of <1B> to <4B>, further comprising: <6B> A composition management system for thiourethane resin raw materials described in <5B>, wherein the determination unit determines whether the thiourethane resin contained in the resin powder is eligible for recycling based on a calculated value of a life cycle assessment using information about the resin powder registered in the third registration unit, and determines that the thiourethane resin is eligible for recycling if the calculated value is equal to or greater than a predetermined value, and determines that the thiourethane resin is not eligible for recycling if the calculated value is less than the predetermined value. <7B> The composition management system for thiourethane resin raw materials described in <5B> or <6B>, wherein the information about the resin powder includes at least one selected from the group consisting of composition information about the resin powder, product information corresponding to the resin powder, and information about the source of the resin powder.

[0009] <8B> A composition management system for a thiourethane resin raw material according to any one of <1B> to <7B>; a manufacturing device that manufactures the thiourethane resin raw material from the recycled thiourethane resin raw material based on the derived information about the composition; A system for producing a thiourethane resin raw material. <9B> A composition management system for a thiourethane resin raw material according to any one of <5B> to <7B>; a decomposition device that decomposes the thiourethane resin contained in the resin powder based on information on a method for chemically decomposing the thiourethane resin acquired from the fourth registration unit when the determination unit determines that the thiourethane resin is to be recycled; a manufacturing device that manufactures the thiourethane resin raw material from the recycled thiourethane resin raw material obtained by decomposing the thiourethane resin in the decomposition device based on the derived information about the composition; A system for producing a thiourethane resin raw material.

[0010] <10B> A step of managing composition information regarding recycled thiourethane resin raw materials obtained by chemically decomposing the thiourethane resin contained in the recovered resin powder; managing composition information relating to the thiourethane resin raw material; A step of deriving information regarding a composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material based on composition information regarding the thiourethane resin raw material and composition information regarding the recycled thiourethane resin raw material; A method for managing the composition of a thiourethane resin raw material comprising: <11B> A composition management method for a thiourethane resin raw material according to <10B>, which determines whether the thiourethane resin contained in the resin powder is eligible for recycling based on information about the resin powder, and if it is determined that the thiourethane resin is eligible for recycling, determines information about a method for chemically decomposing the thiourethane resin eligible for recycling. <12B> A composition management method for a thiourethane resin raw material according to <11B>, which determines whether the thiourethane resin contained in the resin powder is eligible for recycling based on a calculated value of a life cycle assessment using information about the resin powder, and determines that the thiourethane resin is eligible for recycling if the calculated value is equal to or greater than a predetermined value, and determines that the thiourethane resin is not eligible for recycling if the calculated value is less than the predetermined value.

[0011] <13B> A method for producing a thiourethane resin raw material, comprising a step of producing the thiourethane resin raw material from the recycled thiourethane resin raw material, based on information about the composition derived by the method for managing the composition of a thiourethane resin raw material according to any one of <10B> to <12B>. <14B> When it is determined that the thiourethane resin is to be recycled based on the composition management method for a thiourethane resin raw material described in <12B>, decomposing the thiourethane resin contained in the resin powder based on information on a method for chemically decomposing the thiourethane resin; A step of producing the thiourethane resin raw material from the recycled thiourethane resin raw material obtained by decomposing the thiourethane resin based on information about the composition derived by the method for managing the composition of the thiourethane resin raw material; A method for producing a thiourethane resin raw material comprising:

[0012] <1C> A polythiol composition X1 containing a polythiol component B which is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and a polythiol composition X2 containing a polythiol component A that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; A polythiol composition, wherein the peak area of ​​the polythiol component A is 30 area % or more and 99 area % or less of the total peak area of ​​the polythiol composition, as measured by high performance liquid chromatography. <2C> A polythiol composition X1 containing a polythiol component B which is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and a polythiol composition X2 containing a polythiol component A that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; A polythiol composition in which the peak area of ​​the polythiol component A is 30 area % or more and 99 area % or less of the total peak area of ​​the polythiol composition X1 and the polythiol composition X2, as measured by high performance liquid chromatography. <3C> The polythiol composition according to <1C> or <2C>, a polyisocyanate composition containing a polyisocyanate compound; A polymerizable composition comprising: <4C> The polyisocyanate composition, Xylylene diisocyanate, At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3): Including, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, The polymerizable composition according to <3C>, wherein, when the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1: -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and hold for 6 minutes after reaching 280°C. Split ratio: Pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate content)

[0013] [ka]

[0014] <5C> The polythiol composition according to <1C> or <2C>, a polyisocyanate composition containing a polyisocyanate compound; A composition set comprising: <6C> The polyisocyanate composition, Xylylene diisocyanate, At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3): Including, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, The composition set according to <5C>, wherein, when the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1: -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and hold for 6 minutes after reaching 280°C. Split ratio: Pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate content) [ka]

[0015] <7C> The polymerizable composition according to <3C> or <4C>, or <5> or <6> A cured product obtained by curing a polymerizable composition obtained by mixing the polythiol composition and the polyisocyanate composition contained in the composition set described in 1. <8C> An optical material comprising the cured product according to <7C>. [Effects of the Invention]

[0016] According to the present disclosure, it is possible to provide a method for producing a polythiol composition that can produce a polythiol composition having a specific compositional ratio using a polythiol composition produced using a thiourethane resin as a starting material, a method for producing a polymerizable composition and a method for producing a cured product that include this production method, and a polythiol composition that includes a polythiol compound derived from a thiourethane resin.

[0017] According to the present disclosure, it is possible to provide a composition management system for thiourethane resin raw materials that manages information on the ability to produce thiourethane resin raw materials having specific composition ratios using recycled thiourethane resin raw materials, and a manufacturing system for thiourethane resin raw materials that is capable of producing thiourethane resin raw materials having specific composition ratios. Furthermore, according to the present disclosure, it is possible to provide a composition management method for thiourethane resin raw material that manages information that enables the production of thiourethane resin raw material having a specific composition ratio using recycled thiourethane resin raw material, and a manufacturing method for thiourethane resin raw material that enables the production of thiourethane resin raw material having a specific composition ratio. Furthermore, according to the present disclosure, it is possible to provide a polythiol composition capable of producing a cured product having desired heat resistance and dyeability, a polymerizable composition and composition set containing this polythiol composition, a cured product obtained by curing this polymerizable composition, and an optical material containing this cured product. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a block diagram showing the hardware configuration of a composition management system for a thiourethane resin raw material in one embodiment of the present disclosure. [Figure 2] FIG. 1 is a diagram showing the configuration of a production system for a thiourethane resin raw material according to an embodiment of the present disclosure. [Figure 3] FIG. 4 is a diagram showing an example of each piece of information registered in a first registration unit to a fourth registration unit. [Figure 4] 1 is a flowchart illustrating an example of a method for producing a thiourethane resin raw material according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0019] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, the specific components contained in each composition may be one type alone or a combination of two or more types.

[0020] <Method of producing polythiol composition> The method for producing a polythiol composition of the present disclosure includes a step of reacting a composition X containing a thiourethane resin to produce a polythiol composition (S) containing two or more polythiol compounds, and a step of producing a polythiol composition (T) from the polythiol composition (S) by adjusting the content of at least one polythiol compound contained in the polythiol composition (S).

[0021] In the method for producing a polythiol composition disclosed herein, a polythiol composition (T) having a specific composition ratio can be produced using a polythiol composition (S) that is a polythiol composition produced using a thiourethane resin as a starting material. For example, the composition of a polythiol composition (S) produced using a thiourethane resin as a starting material varies depending on the composition of the thiourethane resin, the conditions for chemical decomposition of the thiourethane resin, the method for separating the polythiol composition from the mixture obtained by chemical decomposition of the thiourethane resin, and the like. Even if the composition of the polythiol composition (S) varies for each production unit, the variation in the composition of the polythiol compound for each production unit can be suppressed by adjusting the content of at least one polythiol compound contained in the polythiol composition (S). A polythiol composition (T) having a specific composition ratio can be produced for each production unit.

[0022] [Step of Producing Polythiol Composition (S)] The manufacturing method of the present disclosure includes a step of reacting a composition X containing a thiourethane resin to produce a polythiol composition (S) containing two or more polythiol compounds. In the step of producing the polythiol composition (S), the thiourethane resin contained in composition X is chemically decomposed to produce the polythiol composition (S) containing two or more polythiol compounds.

[0023] (thiourethane resin) The thiourethane resin is a starting material in the manufacturing method of the present disclosure and is contained in composition X. The thiourethane resin may be a reaction product formed using a polythiol composition containing at least one polythiol compound and a polyisocyanate composition containing at least one polyisocyanate compound.

[0024] The thiourethane resin that is the starting material may be one type of thiourethane resin, or may contain two or more types of thiourethane resins.

[0025] The thiourethane resin may contain at least one of thiourethane resin A and thiourethane resin B described below. Thiourethane resin A formed using a polythiol composition (P) containing a polythiol compound (A1) having no ester bond in the molecule and a polyisocyanate composition (A) containing at least one polyisocyanate compound. A thiourethane resin B formed using the polythiol composition (P), a polythiol composition (Q) containing a polythiol compound (A2) having at least one ester bond in the molecule, and a polyisocyanate composition (B) containing at least one polyisocyanate compound.

[0026] The thiourethane resin A and the thiourethane resin B may each independently be one type of thiourethane resin, or may contain two or more types of thiourethane resins.

[0027] The thiourethane resin A is a reaction product using the polythiol composition (P) and the polyisocyanate composition (A).

[0028] The polythiol composition (P) contains a polythiol compound (A1) having no ester bonds in the molecule. The polythiol compound (A1) having no ester bonds in the molecule is not particularly limited as long as it has no ester bonds in the molecule and contains two or more mercapto groups. Examples of the polythiol compound (A1) having no ester bond in the molecule include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, methanedithiol, 1,2-ethanedithiol, 1,3-dimethyl-2,4-dimethyl-1,5-dimethyl-1,6-dimethyl-1,7-dimethyl-1,8-dimethyl-1,9-dimethyl-2,10-dimethyl-1,9-dimethyl-2,1 ... , 2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, etc. The polythiol compound (A1) having no ester bond in the molecule may be one type alone or a combination of two or more types.

[0029] The polythiol composition (P) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane That is, the polythiol composition (P) may contain at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one of the above three types of polythiol compounds (preferably a mixture of the above three types of polythiol compounds), and 2,5-dimercaptomethyl-1,4-dithiane.

[0030] The polyisocyanate composition (A) contains at least one polyisocyanate compound. There are no particular limitations on the polyisocyanate compound, as long as it is a compound containing two or more isocyanate groups. The polyisocyanate composition (A) preferably contains a polyisocyanate compound as a main component. The polyisocyanate composition (A) may be, for example, one type of polyisocyanate compound, a mixture of two or more types of polyisocyanate compounds, or a mixture of one or more types of polyisocyanate compounds with other components.

[0031] The polyisocyanate composition (A) is It is preferable that the polyisocyanate composition contains at least one polyisocyanate compound selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0032] The polyisocyanate composition (A) more preferably contains at least one selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane.

[0033] The polyisocyanate composition (A) may contain a xylylene diisocyanate such as m-xylylene diisocyanate or p-xylylene diisocyanate. When the polyisocyanate composition (A) contains xylylene diisocyanate, it may further contain at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3):

[0034] [ka]

[0035] When the polyisocyanate composition (A) contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is preferably 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate. -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID

[0036] The peak area of ​​the compound (N1) is more preferably 5.0 ppm or more, even more preferably 50 ppm or more, and particularly preferably 100 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1000 ppm or less relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0037] When the polyisocyanate composition (A) contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1. -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and hold for 6 minutes after reaching 280°C. Split ratio: Pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate (XDI) content)

[0038] The peak area of ​​the compound (N2) is more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and even more preferably 0.6 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and even more preferably 60 ppm or less relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.

[0039] When the polyisocyanate composition (A) contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the above-mentioned GC condition 1 is preferably 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1. The peak area of ​​the compound (N3) is more preferably 0.1 ppm or more, even more preferably 3.0 ppm or more, and even more preferably 5.0 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, even more preferably 100 ppm or less, and even more preferably 75 ppm or less relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0040] The acid content of the polyisocyanate composition (A) is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm. The lower limit of the acid content of the polyisocyanate composition (A) is not particularly limited, but the lower limit is, for example, 1 ppm. The acid content of the polyisocyanate composition (A) can be measured in accordance with the method described in paragraph 0091 of WO 2021 / 256417.

[0041] Thiourethane resin B is a reaction product using polythiol composition (P), polythiol composition (Q), and polyisocyanate composition (B). The preferred form of polythiol composition (P) used to produce thiourethane resin B is the same as the preferred form of polythiol composition (P) used to produce thiourethane resin A described above.

[0042] The polythiol composition (Q) contains a polythiol compound (A2) having at least one ester bond in the molecule. The polythiol compound (A2) having at least one ester bond in the molecule is not particularly limited as long as it is a compound having an ester bond in the molecule and containing two or more mercapto groups. Examples of the polythiol compound (A2) having at least one ester bond in the molecule include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and diethylene glycol bis(3-mercaptopropionate). The polythiol compound (A2) having at least one ester bond in the molecule may be a single compound or a combination of two or more compounds.

[0043] The polythiol composition (Q) is pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), Trimethylolpropane tris(3-mercaptopropionate) and Pentaerythritol tetrakis(3-mercaptobutyrate) It may contain at least one selected from the group consisting of:

[0044] The polyisocyanate composition (B) contains at least one polyisocyanate compound. A preferred embodiment of the polyisocyanate composition (B) is the same as the preferred embodiment of the polyisocyanate composition (A).

[0045] The thiourethane resin used in the manufacturing method of the present disclosure is preferably recovered during at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses, and may be a mixture of thiourethane resins recovered during at least one of the aforementioned processes. This embodiment allows for the recycling of thiourethane resin, which is a material for eyeglass lenses. where: The manufacturing process of eyeglass lenses means the process of producing resin by compounding monomers, which are resin raw materials, and then subjecting them to cast polymerization, and / or the process of cutting a resin molded body to obtain eyeglass lenses. The eyeglass manufacturing process refers to the process of combining eyeglass lenses with other components such as eyeglass frames to manufacture eyeglasses. The eyeglasses disposal process refers to the process of disposing of eyeglasses that have been manufactured but are no longer needed, used eyeglasses, etc. In either process, thiourethane resin, a material for eyeglass lenses, can be generated as waste.

[0046] The thiourethane resin used in the manufacturing method of the present disclosure may be a powder containing a thiourethane resin (hereinafter also referred to as "thiourethane resin powder").

[0047] The thiourethane resin powder is not particularly limited, and may be, for example, cutting powder of a molded product containing a thiourethane resin and / or the above cutting powder that has been sieved. The cutting dust of a molded article containing a thiourethane resin is generated, for example, when an optical material (for example, a lens) is manufactured by cutting a molded article containing a thiourethane resin. The thiourethane resin powder may also be a lump powder obtained by crushing and / or pulverizing a molded body containing a thiourethane resin.

[0048] Composition X may contain components other than the thiourethane resin, such as a component added to promote the reaction when producing a thiourethane resin by reacting a polythiol composition and a polyisocyanate composition, a component added to impart some functionality to the thiourethane resin produced, a component necessary for chemical decomposition of the thiourethane resin, etc. For example, composition X may contain at least one member selected from the group consisting of a resin other than the thiourethane resin, a polymerization catalyst, a metal, an ultraviolet absorber, an internal mold release agent, a plasticizer, a dye, machine oil, and water.

[0049] In the step of producing the polythiol composition (S), it is preferable to produce the polythiol composition (S) by reacting the thiourethane resin in the composition X with an active hydrogen compound.

[0050] The active hydrogen compound functions as a decomposing agent for the thiourethane resin, which is the starting material. From the viewpoint of the above-mentioned functions, the active hydrogen compound is preferably at least one selected from the group consisting of amine compounds and alcohol compounds.

[0051] -Amine 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 of 1 to 6 (preferably 1 to 3, more preferably 1 or 2) amino groups and monoalkylamino groups.

[0052] From the viewpoint of further improving the reactivity with the thiourethane resin, the molecular weight of the amine compound is preferably 1000 or less, more preferably 500 or less, even more preferably 300 or less, and particularly 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, and more preferably 60 or more.

[0053] Examples of preferred amine compounds include: Examples of such amine compounds include those containing at least one of an amino group and a monoalkylamino group, and having a total of 1 or 2 amino groups and monoalkylamino groups, and having a molecular weight of 300 or less.

[0054] Specific examples of the amine compound include alkylamines having 2 to 10 carbon atoms, aralkylamines having 7 to 10 carbon atoms (e.g., benzylamine), dialkylamines having 2 to 10 carbon atoms (e.g., 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), hydroxyalkylamines having 2 to 10 carbon atoms (e.g., monoethanolamine), bis(hydroxyalkyl)amines having 2 to 10 carbon atoms (e.g., bis(hydroxyethyl)amine), cyclic amines having 2 to 10 carbon atoms (e.g., morpholine), and secondary amines such as alkyl(hydroxyalkyl)amines having 2 to 10 carbon atoms (e.g., methylethanolamine, isopropylethanolamine). The amine compound is preferably benzylamine, di-n-butylamine, ethylenediamine, or monoethanolamine.

[0055] -Alcohol compounds- The alcohol compound may be a monoalcohol compound containing only one hydroxy group, or a polyol compound containing two or more hydroxy groups.

[0056] From the viewpoint of further improving the reactivity with the thiourethane resin, the molecular weight of the alcohol compound is preferably 1000 or less, more preferably 500 or less, even more preferably 300 or less, and particularly 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, and more preferably 60 or more.

[0057] 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").

[0058] In this disclosure, boiling point means the boiling point at 1 atmosphere (101325 Pa).

[0059] 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 even more preferably 80% by mass to 100% by mass.

[0060] As an alcohol compound, Preferred are benzyl alcohol, phenethyl alcohol, 2-octanol, 2-ethyl-1-hexanol, 1-decanol, 1-nonanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, propylene glycol, and ethylene glycol; More preferably, it is benzyl alcohol, phenethyl alcohol, 1-decanol, 1-nonanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, propylene glycol, or ethylene glycol; More preferred are benzyl alcohol, phenethyl alcohol, 2-octanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, and propylene glycol.

[0061] -Amount of amine compound- When an amine compound is used in the step of producing the polythiol composition (S), the charge mass ratio of the amine compound to the thiourethane resin (i.e., charge mass ratio [amine compound / thiourethane resin]) can be appropriately adjusted, but is preferably 0.05 or more and less than 10. When the charge mass ratio [amine compound / thiourethane resin] is 0.05 or more, the production of the polythiol composition is further promoted. When the charge mass ratio [amine compound / thiourethane resin] is less than 10, the amine compound remaining in the reaction mixture can be further suppressed. The mass ratio of the charged amine compound to the thiourethane resin is preferably 0.075 to 5, and more preferably 0.10 to 1.

[0062] In the step of producing the polythiol composition (S), the number of millimoles of the amine compound charged per 1 g of the thiourethane resin is preferably 1.0 mmol / g to 30 mmol / g, more preferably 2.0 mmol / g to 20 mmol / g, and even more preferably 3.0 mmol / g to 10.0 mmol / g.

[0063] In the step of producing the polythiol composition (S), the charge equivalent of the amine compound relative to the thiourethane resin (charge equivalent [amine compound / thiourethane resin]) is preferably 1.0 to 2.0, more preferably more than 1.0 and not more than 1.8, and even more preferably more than 1.0 and not more than 1.6. When the charge equivalent [amine compound / thiourethane resin] is 1.0 or more, the production of the polythiol composition is further promoted. When the charge equivalent [amine compound / thiourethane resin] is 2.0 or less, the amount of the amine compound remaining in the reaction mixture can be further reduced. Here, the charge equivalent of the amine compound relative to the thiourethane resin (charge equivalent [amine compound / thiourethane resin]) means the ratio of the total number of amino groups and monoalkylamino groups in the charged amine compound to the total number of thiourethane bonds in the charged thiourethane resin.

[0064] In the step of producing the polythiol composition (S), it is preferable to react the thiourethane resin with the amine compound in the presence of a reaction solvent. The reaction solvent is preferably a hydrocarbon compound having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), an ether compound having 4 to 12 carbon atoms, a ketone compound having 3 to 12 carbon atoms, an ester compound having 4 to 12 carbon atoms, an alcohol compound having 2 to 12 carbon atoms, or a nitrile compound having 2 to 12 carbon atoms. The compound used as the reaction solvent may be one kind or two or more kinds.

[0065] The reaction temperature between the thiourethane resin and the amine compound can be adjusted appropriately. The thiourethane resin and the amine compound are preferably reacted under temperature conditions (ie, reaction temperature) of 50°C to 150°C (more preferably 60°C to 145°C, and even more preferably 70°C to 140°C).

[0066] The reaction time between the thiourethane resin and the amine compound can be adjusted appropriately, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and even more preferably 1 to 10 hours.

[0067] -Amount of alcohol compound added- When an alcohol compound is used in the step of producing the polythiol composition (S), the mass ratio of the alcohol compound to the thiourethane resin (i.e., the mass ratio of the alcohol compound to the thiourethane resin) can be adjusted appropriately, but is preferably 0.10 to 20. When the charge mass ratio [alcohol compound / thiourethane resin] is 0.10 or more, the production of the polythiol composition is further promoted. When the charge mass ratio [alcohol compound / thiourethane resin] is 20 or less, the alcohol compound remaining in the reaction mixture can be further suppressed. The charge mass ratio [alcohol compound / thiourethane resin] is more preferably 0.30 to 15, and even more preferably 0.40 to 10.

[0068] In the step of producing the polythiol composition (S), the number of millimoles of the alcohol compound charged per 1 g of the thiourethane resin is preferably 1.0 mmol / g to 100 mmol / g, more preferably 2.0 mmol / g to 80 mmol / g, even more preferably 5.0 mmol / g to 60 mmol / g, and particularly preferably 25 mmol / g to 37.5 mmol / g.

[0069] In the step of producing the polythiol composition (S), the charge equivalent of the alcohol compound relative to the thiourethane resin (charge equivalent [alcohol compound / thiourethane resin]) is preferably 1 to 25, more preferably 1.2 to 20, even more preferably 1.5 to 15, and particularly preferably 10 to 15. When the charge equivalent [alcohol compound / thiourethane resin] is 1 or more, the production of the polythiol composition is further promoted. When the charge equivalent (alcohol compound / thiourethane resin) is 25 or less, the alcohol compound remaining in the reaction mixture can be further suppressed. Here, the charge equivalent of the alcohol compound relative to the thiourethane resin (charge equivalent [alcohol compound / thiourethane resin]) means the ratio of the number of hydroxy groups in the charged alcohol compound to the total number of thiourethane bonds in the charged thiourethane resin.

[0070] In the step of producing the polythiol composition (S), the thiourethane resin and the alcohol compound are preferably reacted in the presence of a tertiary amine compound. The tertiary amine compound is thought to function as a decomposition aid. The tertiary amine compound is not particularly limited. The tertiary amine compound may be a chain amine compound or a cyclic amine compound. The tertiary amine compound may be one type or a combination of two or more types.

[0071] In particular, when the thiourethane resin contains the aforementioned thiourethane resin B, it is preferable to react the thiourethane resin with an alcohol compound in the presence of a tertiary amine compound. This suppresses unintended side reactions of the polythiol compound (A2) having at least one ester bond in the molecule, which may occur upon chemical decomposition of the thiourethane resin B, and tends to result in a polythiol composition (S) with high purity.

[0072] The molecular weight of the tertiary amine compound is preferably 1,000 or less, more preferably 500 or less, even more preferably 300 or less, and even more preferably 200 or less. The lower limit of the molecular weight of the tertiary amine compound is, for example, 59 or more, and preferably 70 or more.

[0073] Tertiary amine compounds include: Preferred are N,N-dimethylethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 4-(2-hydroxyethyl)morpholine, 1,4-diazabicyclo[2,2,2]octane (abbreviation: DABCO), diazabicyclononene, and diazabicycloundecene; More preferably, it is N,N-dimethylethanolamine, N,N-diethylaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 1,4-diazabicyclo[2,2,2]octane, diazabicyclononene, or diazabicycloundecene; More preferred are N,N-dimethylethanolamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, N-ethylmorpholine, and 1,4-diazabicyclo[2,2,2]octane.

[0074] In the step of producing the polythiol composition (S), the charged mass ratio of the tertiary amine compound to the alcohol compound (i.e., the charged mass ratio [tertiary amine compound / alcohol compound]) can be adjusted as appropriate, but is preferably 0.001 to 2.00. The charge mass ratio [tertiary amine compound / alcohol compound] is more preferably 0.002 to 1.50, and even more preferably 0.004 to 1.20.

[0075] In the step of producing the polythiol composition (S), the molar ratio of the tertiary amine compound to the alcohol compound (i.e., the molar ratio of the tertiary amine compound to the alcohol compound) can be adjusted as appropriate, but is preferably 0.001 to 3.00. The charging molar ratio [tertiary amine compound / alcohol compound] is more preferably 0.002 to 2.50, even more preferably 0.003 to 2.00, even more preferably 0.004 to 1.50, and even more preferably 0.004 to 1.00.

[0076] In the step of producing the polythiol composition (S), it is preferable to react the thiourethane resin with the alcohol compound in the presence of a reaction solvent. The reaction solvent is preferably a hydrocarbon compound having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), an ether compound having 4 to 12 carbon atoms, a ketone compound having 3 to 12 carbon atoms, an ester compound having 4 to 12 carbon atoms, an alcohol compound having 2 to 12 carbon atoms, or a nitrile compound having 2 to 12 carbon atoms. The compound used as the reaction solvent may be one kind or two or more kinds.

[0077] The reaction temperature between the thiourethane resin and the alcohol compound can be adjusted appropriately. The thiourethane resin and the alcohol compound are preferably reacted under temperature conditions (ie, reaction temperature) of 70°C to 200°C (more preferably 90°C to 180°C, and even more preferably 100°C to 170°C).

[0078] The reaction time between the thiourethane resin and the alcohol compound can be adjusted appropriately, but is preferably 0.1 to 50 hours, more preferably 0.5 to 30 hours, even more preferably 1 to 20 hours, and particularly preferably 4 to 7 hours.

[0079] By reacting composition X containing a thiourethane resin in the manner described above, a polythiol composition (S) containing two or more polythiol compounds can be obtained. The polythiol compounds contained in polythiol composition (S) correspond to at least some of the polythiol compounds used in producing the thiourethane resin. For example, when the thiourethane resin contains thiourethane resin A and thiourethane resin B, polythiol composition (S) preferably contains two or more polythiol compounds contained in at least one of polythiol composition (P) and polythiol composition (Q).

[0080] Examples of the polythiol compound contained in the polythiol composition (S) include the above-mentioned thiol compounds classified as polythiol compounds (A1) having no ester bond in the molecule or polythiol compounds (A2) having at least one ester bond in the molecule.

[0081] The polythiol composition (S) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane It may contain at least one selected from the group consisting of:

[0082] By reacting composition X containing a thiourethane resin, components other than the polythiol composition (S) containing two or more polythiol compounds can also be obtained. By reacting composition X containing a thiourethane resin, a mixture of the polythiol composition (S) and a polycarbamate composition containing a polycarbamate compound or a polyurea composition containing a polyurea compound can be obtained. For example, when a thiourethane resin is reacted with an amine compound, a polyurea composition containing a polyurea compound is obtained, and when a thiourethane resin is reacted with an alcohol compound, a polycarbamate composition containing a polycarbamate compound is obtained. The polythiol compound or its derivative obtained by chemically decomposing the thiourethane resin may be partially decomposed by the action of an alcohol compound, an amine compound, or the like.

[0083] The polycarbamate composition containing the above-mentioned polycarbamate compound, the polyurea composition containing the polyurea compound, the decomposition product of the polythiol compound or its derivative obtained by chemically decomposing the thiourethane resin, and the like may be separated from the polythiol composition (S) by a known method. Examples of the separation method include filtration, decantation, extraction, distillation, dissolution, drying (including drying under reduced pressure), purification (for example, column chromatography), etc. A plurality of separation methods may be used in combination. For example, a method of extracting with an organic solvent or inorganic solvent capable of dissolving a specific component in a mixture containing the polythiol composition (S) and the polycarbamate composition or polyurea composition can be mentioned. In addition, an acid, a base, etc. may be used when extracting with an organic solvent or inorganic solvent. As a method for purifying specific components, general purification methods such as column purification, distillation purification, recrystallization purification, and salt extraction are used.

[0084] [Step of Producing Polythiol Composition (T)] The manufacturing method of the present disclosure includes a step of producing a polythiol composition (T) from the polythiol composition (S) by adjusting the content of at least one polythiol compound contained in the polythiol composition (S). By including the step of producing the polythiol composition (T), variation in the composition of the polythiol compounds among production units is suppressed, and a polythiol composition (T) having a specific composition ratio can be produced in each production unit.

[0085] In the step of producing the polythiol composition (T), it is preferable to produce the polythiol composition (T) by, for example, the following method (1) or (2). (1) At least one polythiol compound contained in the polythiol composition (S) is added to the polythiol composition (S) to produce the polythiol composition (T). (2) At least one polythiol compound contained in the polythiol composition (S) is at least partially removed from the polythiol composition (S) to produce the polythiol composition (T).

[0086] From the viewpoint of facilitating the production of the polythiol composition (T), it is preferable to produce the polythiol composition (T) by the above method (1). The composition of the polythiol compounds in the polythiol composition (T) can be confirmed from, for example, the ratio of the peak area of ​​a specific polythiol compound to the total peak area of ​​all peaks of the polythiol composition, or the ratio of the peak area of ​​a specific polythiol compound to the peak area of ​​another polythiol compound, as measured by high-performance liquid chromatography as shown in the Examples described below. A calibration curve showing the relationship between the composition of the polythiol composition and the aforementioned peak area ratio may be prepared using a polythiol composition with a known composition. Furthermore, the amount of polythiol compound to be added to the polythiol composition (S), or the amount of polythiol compound to be removed from the polythiol composition (S), may be determined by comparing the prepared calibration curve with the results of measurement of the polythiol composition (S) by high-performance liquid chromatography.

[0087] The composition of the polythiol composition (T) to be produced is not particularly limited, and the ratio of the polythiol compounds contained in the polythiol composition (T) may be adjusted depending on the application of the polythiol composition (T).

[0088] Examples of the polythiol compound contained in the polythiol composition (T) include the above-mentioned thiol compounds classified as polythiol compounds (A1) having no ester bond in the molecule or polythiol compounds (A2) having at least one ester bond in the molecule.

[0089] The polythiol composition (T) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane It may contain at least one selected from the group consisting of:

[0090] <Method of producing polymerizable composition> The method for producing a polymerizable composition of the present disclosure includes a step of producing a polymerizable composition by mixing the polythiol composition (T) obtained by the method for producing a polythiol composition of the present disclosure described above with a polyisocyanate composition (C) containing at least one polyisocyanate compound.

[0091] The method for producing a polymerizable composition of the present disclosure uses a polythiol composition (T) having a specific compositional ratio obtained by the method for producing a polythiol composition of the present disclosure. As a result, the polymerizable composition obtained by the method for producing a polymerizable composition of the present disclosure can produce a cured product with little variation in various properties (e.g., optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.) for each polymerizable composition. Therefore, the polymerizable composition obtained by the method for producing a polymerizable composition according to the present disclosure is particularly suitable as a composition for producing a thiourethane resin for optical materials.

[0092] In the step of producing a polymerizable composition, the polythiol composition (T) is mixed with a polyisocyanate composition (C) containing at least one polyisocyanate compound to produce the polymerizable composition. The preferred configuration of the polyisocyanate composition (C) is the same as the preferred configuration of the polyisocyanate composition (A) described above.

[0093] The mixing ratio of the polythiol composition (T) and the polyisocyanate composition (C) is not particularly limited. The ratio of the charged mass of the polythiol composition (T) to the charged mass of the polyisocyanate composition (C) (i.e., charged mass [polythiol composition (T) / polyisocyanate composition (C)]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, even more preferably 0.50 to 1.50, and still more preferably 0.70 to 1.30. Furthermore, the molar ratio of mercapto groups contained in the polythiol composition (T) to isocyanato groups contained in the polyisocyanate composition (C) (mercapto groups / isocyanato groups) is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3.

[0094] The total mass of the polythiol composition (T) and the polyisocyanate composition (C) charged is not particularly limited. For example, the total mass of the charged polythiol composition (T) and the polyisocyanate composition (C) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the polymerizable composition to be produced.

[0095] When mixing the polythiol composition (T) and the polyisocyanate composition (C), the polythiol composition (T) and the polyisocyanate composition (C) may be mixed with other components, if necessary. After mixing at least the polythiol composition (T) and the polyisocyanate composition (C), other components may be added to the mixture. Examples of these other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, and inorganic pigments.

[0096] Examples of the polymerization catalyst include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0097] As the internal mold release agent, an acidic phosphate ester can be used. Examples of the acidic phosphate ester include a phosphate monoester and a phosphate diester, and these can be used alone or in combination of two or more.

[0098] Examples of the resin modifier include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, olefin compounds including (meth)acrylate compounds, etc. Here, the (meth)acrylate compound means at least one of an acrylate compound and a methacrylate compound.

[0099] The above-mentioned components can be mixed in a conventional manner, and the mixing method is not particularly limited.

[0100] <Method of manufacturing the cured product> The method for producing a cured product of the present disclosure includes a step of producing a polymerizable composition by the method for producing a polymerizable composition of the present disclosure, and a step of curing the polymerizable composition to obtain a cured product.

[0101] In the step of obtaining a cured product, the polymerizable composition is cured to obtain a cured product. The polymerizable composition can be cured by polymerizing the monomers in the polymerizable composition (for example, the polythiol composition (T) and the polyisocyanate composition (C)). As a pretreatment for polymerization, the polymerizable composition may be subjected to filtration, degassing, or the like. The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition are appropriately set in consideration of the composition of the composition, the type and amount of the monomers in the composition, the type and amount of the polymerization catalyst in the composition, and the properties of the mold when a mold described below is used. The polymerization temperature may be, for example, from -50°C to 150°C, or from 10°C to 150°C. The polymerization time may be, for example, 1 hour to 200 hours, or 1 hour to 80 hours.

[0102] In the step of obtaining a cured product, a polymer obtained by polymerizing a monomer may be subjected to a treatment such as annealing to obtain a cured product. The annealing temperature may be 50°C to 150°C, 90°C to 140°C, or 100°C to 130°C.

[0103] The uses of the cured product are not particularly limited, and examples include optical materials such as lenses, and molded articles other than optical materials.

[0104] <Polythiol composition> (First aspect) The polythiol composition according to the first aspect of the present disclosure comprises: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-Dimercaptomethyl-1,4-dithiane and a polythiol compound (U) derived from a thiourethane resin. The polythiol composition of the present disclosure contains a polythiol compound (U) derived from a thiourethane resin and is a polythiol composition produced using a thiourethane resin as a starting material. The polythiol composition of the present disclosure can be obtained, for example, by reacting a composition X containing a thiourethane resin as described in the process for producing the polythiol composition (S). The thiol composition of the present disclosure preferably contains polythiol composition X1 (a composition containing polythiol component A described below) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (polythiol component B described below). A cured product having desired heat resistance and dyeability can be produced by including polythiol component A and polythiol component B. For example, increasing the content of polythiol component A tends to improve heat resistance, and increasing the content of polythiol component B tends to improve dyeability.

[0105] (Second aspect) The polythiol composition according to a second embodiment of the present disclosure includes a polythiol composition X1 including a polythiol component A that is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and a polythiol composition X2 containing a polythiol component B that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; In high performance liquid chromatography measurement, the peak area of ​​the polythiol component A is 30 area % or more and 99 area % or less of the total peak area of ​​the polythiol composition, which makes it possible to produce a cured product with desired heat resistance and dyeability. The polythiol composition according to the second embodiment may or may not contain a polythiol compound derived from a thiourethane resin (for example, the above-mentioned polythiol compound (U)).

[0106] The peak area of ​​polythiol component A is preferably 10 area % or more and 99 area % or less, and more preferably 30 area % or more and 99 area % or less, of the total peak area of ​​the polythiol composition.

[0107] The polythiol composition according to the second embodiment may contain a polythiol composition (another polythiol composition) other than the polythiol composition X1 and the polythiol composition X2. The peak area of ​​the other polythiol composition may be 30 area % or less, or may be 10 area % or less, relative to the total peak area of ​​the polythiol composition. The lower limit of the peak area of ​​the other polythiol composition is not particularly limited as long as it is 0 area % or more.

[0108] (Third aspect) The polythiol composition according to a third embodiment of the present disclosure includes a polythiol composition X1 including a polythiol component B that is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and a polythiol composition X2 containing a polythiol component A that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; In high performance liquid chromatography measurement, the peak area of ​​the polythiol component A is 30 area % or more and 99 area % or less of the total peak area of ​​the polythiol composition X1 and the polythiol composition X2, which makes it possible to produce a cured product having the desired heat resistance and dyeability. The polythiol composition according to the third embodiment may or may not contain a polythiol compound derived from a thiourethane resin (for example, the above-mentioned polythiol compound (U)).

[0109] The peak area of ​​polythiol component A is preferably 10 area % or more and 99 area % or less, and more preferably 30 area % or more and 99 area % or less, of the total peak area of ​​polythiol composition X1 and polythiol composition X2.

[0110] <Polymerizable composition> The polymerizable composition of the present disclosure includes the polythiol composition of the present disclosure described above and a polyisocyanate composition including a polyisocyanate compound. The preferred forms of the polyisocyanate composition are the same as the preferred forms of the polyisocyanate compositions (A) to (C) described above.

[0111] <Composition set> The set of compositions of the present disclosure includes the polythiol composition of the present disclosure and a polyisocyanate composition containing a polyisocyanate compound. The set of compositions can prepare the polymerizable composition of the present disclosure by mixing the polythiol composition and the polyisocyanate composition. The preferred forms of the polyisocyanate composition are the same as the preferred forms of the polyisocyanate compositions (A) to (C) described above.

[0112] <Cured product> The cured product of the present disclosure is obtained by curing the polymerizable composition of the present disclosure or a polymerizable composition obtained by mixing the polythiol composition and the polyisocyanate composition contained in the composition set of the present disclosure. Applications of the cured product of the present disclosure include optical materials (e.g., lenses).

[0113] <Composition management system for thiourethane resin raw materials> The composition management system for thiourethane resin raw material disclosed herein comprises a first registration unit that registers composition information regarding recycled thiourethane resin raw material obtained by chemically decomposing thiourethane resin contained in recovered resin powder, a second registration unit that registers composition information regarding the thiourethane resin raw material, and a derivation unit that derives information regarding the composition for producing thiourethane resin raw material from the recycled thiourethane resin raw material based on the composition information regarding the thiourethane resin raw material registered in the second registration unit and the composition information regarding the recycled thiourethane resin raw material registered in the first registration unit.

[0114] The composition management system for thiourethane resin raw material (hereinafter also referred to as the "composition management system") of the present disclosure includes a first registration unit that registers composition information related to recycled thiourethane resin raw material (hereinafter also referred to as "composition information (1)"), and a second registration unit that registers composition information related to thiourethane resin raw material (hereinafter also referred to as "composition information (2)"). Furthermore, the derivation unit included in the composition management system uses composition information (1) and composition information (2) to derive information related to the composition for producing thiourethane resin raw material from recycled thiourethane resin raw material (hereinafter also referred to as "composition information (3)"). By obtaining composition information (3), it becomes possible to produce thiourethane resin raw material having a specific composition ratio from recycled thiourethane resin raw material.

[0115] The composition of recycled thiourethane resin raw materials produced using thiourethane resin as a starting material varies depending on the composition of the thiourethane resin, the conditions for decomposing the thiourethane resin, and the method for separating the recycled thiourethane resin raw material from the mixture obtained by decomposing the thiourethane resin. Even if the composition of the recycled thiourethane resin raw material varies for each production unit, it is possible to obtain composition information (3) that enables the production of thiourethane resin raw materials with specific composition ratios. For example, by obtaining different composition information (1) and specific composition information (2) from each piece of composition information (3) corresponding to the different composition information (1), and combining the recycled thiourethane resin raw materials corresponding to the different composition information (1) with the respective pieces of composition information (3), it becomes possible to reproducibly produce thiourethane resin raw materials with specific composition ratios (thiourethane resin raw materials that satisfy the specific composition information (2)).

[0116] The thiourethane resin contained in the recovered resin powder can be a reaction product formed using a polythiol composition containing at least one polythiol compound and a polyisocyanate composition containing at least one polyisocyanate compound. The thiourethane resin contained in the resin powder can be one type of thiourethane resin or can contain two or more types of thiourethane resin. Recycled thiourethane resin raw material can be obtained by chemically decomposing the thiourethane resin contained in the resin powder. As a method for chemically decomposing the thiourethane resin, a method of reacting the thiourethane resin with an active hydrogen compound can be mentioned, as described below.

[0117] Examples of composition information (composition information (1)) regarding recycled thiourethane resin raw materials include composition information regarding components obtained by chemically decomposing thiourethane resin, and composition information regarding reactive components obtained by further reacting those components. In the present disclosure, various pieces of information may be assigned an identification ID, and the identification ID may be linked to various pieces of composition information, and the identification ID may be linked to various pieces of composition information and other information as necessary.

[0118] Specifically, the composition information (1) is derived from a thiourethane resin. compositional information regarding a polythiol composition comprising a polythiol compound; compositional information regarding a polyisocyanate composition comprising the polyisocyanate compound; compositional information regarding intermediate products capable of producing polythiol compositions comprising polythiol compounds; and Composition information regarding intermediate products capable of producing polyisocyanate compositions containing polyisocyanate compounds It is preferable that the compound is at least one selected from the group consisting of:

[0119] Examples of polythiol compositions containing polythiol compounds include: a polythiol compound exemplified as the polythiol compound (A1) not having an ester bond in the molecule; Examples of the polythiol compound include a composition containing at least one selected from the polythiol compounds exemplified above as the polythiol compound (A2) having at least one ester bond in the molecule.

[0120] Examples of polyisocyanate compositions containing polyisocyanate compounds include: Examples of the polyisocyanate composition include a composition containing at least one selected from the polyisocyanate compounds exemplified above for the polyisocyanate composition (A).

[0121] Examples of intermediate products capable of producing a polythiol composition containing a polythiol compound include components obtained by further reacting or decomposing a polythiol compound produced by chemically decomposing a thiourethane resin. When the polythiol compound produced by chemically decomposing the thiourethane resin is a polythiol compound having at least one ester bond in the molecule, examples of intermediate products that can produce the polythiol composition include alcohol compounds having one or more hydroxy groups, carboxylic acids having one or more carboxy groups, and derivatives such as salts of these.

[0122] Examples of intermediate products that can produce a polyisocyanate composition containing a polyisocyanate compound include components that are produced by chemically decomposing a thiourethane resin and then further reacting or decomposing the polyisocyanate compound. For example, when a thiourethane resin is reacted with an amine compound to chemically decompose the thiourethane resin, an intermediate product capable of producing a polyisocyanate composition includes a polyurea composition containing a polyurea compound. When a thiourethane resin is reacted with an alcohol compound to chemically decompose the thiourethane resin, an intermediate product capable of producing a polyisocyanate composition includes a polycarbamate composition containing a polycarbamate compound.

[0123] Regarding a polyurea composition containing a polyurea compound, the polyurea compound may be reacted with an amine compound or the like to obtain a polyamine compound, and then the polyamine compound or a derivative thereof may be reacted with phosgene, thereby producing a polyisocyanate composition containing a polyisocyanate compound.

[0124] Regarding the polycarbamate composition containing a polycarbamate compound, the polycarbamate compound may be reacted with an amine compound or the like to obtain a polyamine compound, and then the polyamine compound or a derivative thereof may be reacted with phosgene, thereby producing a polyisocyanate composition containing a polyisocyanate compound.

[0125] Composition information (2) is compositional information regarding a polythiol composition comprising a polythiol compound; compositional information regarding a polyisocyanate composition comprising the polyisocyanate compound; compositional information regarding intermediate products capable of producing polythiol compositions comprising polythiol compounds; and Composition information regarding intermediate products capable of producing polyisocyanate compositions containing polyisocyanate compounds It is preferable that the compound is at least one selected from the group consisting of:

[0126] In the composition information (1) registered in the first register and the composition information (2) registered in the second register, the recycled thiourethane resin raw material and the thiourethane resin raw material are: The polythiol composition X1 described above, and 2,5-Dimercaptomethyl-1,4-dithiane It is preferable that the composition contains at least one selected from the group consisting of:

[0127] The composition information (1) and the composition information (2) used to obtain information on the composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material discharged by the discharge unit (composition information (3)) are both: compositional information regarding a polythiol composition comprising a polythiol compound; compositional information regarding a polyisocyanate composition comprising the polyisocyanate compound; compositional information regarding intermediate products capable of producing a polythiol composition comprising a polythiol compound; or The composition information is preferably information about an intermediate product that can produce a polyisocyanate composition containing a polyisocyanate compound.

[0128] Composition information (3) is (a) Information on the composition of a resin raw material to be added to the recycled thiourethane resin raw material in order to produce the thiourethane resin raw material, (b) It may be information about the composition of resin components to be removed from the recycled thiourethane resin raw material in order to produce the thiourethane resin raw material. From the viewpoint of facilitating the production of the thiourethane resin raw material, the composition information (3) is preferably the information (a) above.

[0129] For example, when composition information (1) and composition information (2) are composition information relating to a polythiol composition containing a polythiol compound, composition information (3) is preferably information relating to the composition of a polythiol composition containing a polythiol compound, which is a resin component added to the polythiol composition.

[0130] The composition of the resin raw material to be added to the recycled thiourethane resin raw material, or the composition of the resin component to be removed from the recycled thiourethane resin raw material, may be determined using a chromatographic device such as a high-performance liquid chromatograph (HPLC) device.

[0131] In the composition information (1) registered in the first registration unit, the recovered resin powder is preferably recovered in at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses, and may be a mixture of thiourethane resins recovered in at least one of the aforementioned processes. By using the composition information (1) of this form, the thiourethane resin, which is the material for eyeglass lenses, can be recycled.

[0132] The recovered resin powder may contain components other than the thiourethane resin, for example, components other than the thiourethane resin that can be used in composition X described above.

[0133] The composition management system of the present disclosure may further include a third registration unit that registers information about the recovered resin powder, and a fourth registration unit that registers information about a method for chemically decomposing the thiourethane resin contained in the recovered resin powder. The composition management system may further include a determination unit that determines whether the thiourethane resin contained in the resin powder is eligible for recycling based on the information about the resin powder registered in the third registration unit, and may further include an acquisition unit that, when the determination unit determines that the thiourethane resin is eligible for recycling, acquires from the fourth registration unit information about a method for chemically decomposing the thiourethane resin eligible for recycling.

[0134] The information about the resin powder registered in the third registration unit preferably includes at least one selected from the group consisting of composition information about the resin powder, product information corresponding to the resin powder, and information about the source of the resin powder.

[0135] Information regarding methods for chemically decomposing the thiourethane resin contained in the resin powder to be registered in the fourth registration section (hereinafter also referred to as "information regarding the decomposition method") includes information including a combination of the composition of a specific thiourethane resin and a decomposition method for the thiourethane resin that is suitable for that composition.

[0136] Examples of information related to the decomposition method include information on the type and amount of active hydrogen compound (e.g., amine compound, alcohol compound, etc.) used in the decomposition of the specific thiourethane resin, information on the type and amount of other components (e.g., decomposition aid, solvent, etc.) used in the decomposition, information on the temperature and reaction time of the decomposition reaction, etc. The information related to the decomposition method may include information on a method for separating a specific resin component from a product obtained by decomposing the specific thiourethane resin.

[0137] Methods for separating a specific resin component include filtration, decantation, extraction, distillation, dissolution, drying (including drying under reduced pressure), purification (for example, column chromatography), and combinations of these.

[0138] The determination unit may determine whether the thiourethane resin contained in the resin powder is to be recycled based on a calculated value of a life cycle assessment using information about the resin powder registered in the third registration unit. For example, the determination unit may determine that the thiourethane resin is to be recycled if the calculated value is equal to or greater than a predetermined value, and may determine that the thiourethane resin is not to be recycled if the calculated value is less than the predetermined value.

[0139] The calculation of life cycle assessment (LCA) can be performed according to a conventional method, and there are no particular restrictions. For example, if the recovered resin powder is recovered in at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses, the calculated value of LCA may be obtained taking into account the entire life cycle of the eyeglass lenses.

[0140] The thiourethane resin raw material may be produced from the recycled thiourethane resin raw material based on composition information (3) derived using the composition management system of the present disclosure by a method to be described later or the like.

[0141] An example of an embodiment of the technology of the present disclosure will be described below with reference to the drawings. Note that the same or equivalent components and parts in each drawing are given the same reference numerals. Furthermore, the sizes of the components in each drawing are conceptual, and the relative size relationships between the components are not limited to these.

[0142] The composition management system 100 according to an embodiment of the present disclosure can be configured as a hardware device. Fig. 1 is a block diagram showing the hardware configuration of the composition management system 100 according to an embodiment of the present disclosure. Note that the composition management system 100 is not limited to physical hardware, and may be a cloud server in a virtual environment, or functions may be distributed across multiple servers.

[0143] 1, the composition management system 100 includes a CPU (Central Processing Unit) 11, a ROM (Read Only Memory) 12, a RAM (Random Access Memory) 13, a storage 14, an input unit 15, a display unit 16, and a communication interface (I / F) 17. Each component is connected to each other via a bus 19 so as to be able to communicate with each other.

[0144] The CPU 11 is a central processing unit that executes various programs and controls each part. The CPU 11 reads the programs from the ROM 12 or the storage 14 and executes the programs using the RAM 13 as a work area. The CPU 11 controls each of the above components and performs various arithmetic processing in accordance with the programs stored in the ROM 12 or the storage 14.

[0145] The ROM 12 stores various programs and various data. The RAM 13 temporarily stores programs or data as a working area. The storage 14 is configured with a storage device such as an HDD (Hard Disk Drive) or an SSD (Solid State Drive) and stores various programs including the operating system and various data.

[0146] In this embodiment, the ROM 12 may store a program relating to the determination of recycling, a program relating to the determination of the decomposition method of the thiourethane resin, and the storage 14 may store various types of information.

[0147] The input unit 15 includes a pointing device such as a mouse and a keyboard, and is used to perform various inputs.

[0148] The display unit 16 is, for example, a liquid crystal display, and displays various information. The display unit 16 may function as the input unit 15 by adopting a touch panel system.

[0149] The communication interface 17 is an interface for communicating with other devices such as terminals, etc. For this communication, for example, a wired communication standard such as Ethernet (registered trademark) or FDDI, or a wireless communication standard such as 4G, 5G, or Wi-Fi (registered trademark) is used.

[0150] Although the present specification has been described as an embodiment in which the program is pre-installed, the program may also be provided by being stored on a computer-readable recording medium.

[0151] Next, an embodiment of a composition management system and a production system for a thiourethane resin raw material (hereinafter also referred to as a "production system") equipped with the composition management system will be described with reference to Figure 2. Figure 2 is a diagram showing the configuration of a production system for a thiourethane resin raw material in one embodiment of the present disclosure. Figure 2 shows the functional configuration of the composition management system equipped in the production system.

[0152] [Example of a manufacturing system] The production system 200 includes a composition management system 100, a decomposition apparatus 30, an analysis apparatus 40, and a production apparatus 50. In Fig. 2, the acquisition, transmission, and reception of information are indicated by dotted lines, and the supply of various raw materials, products, and the like is indicated by solid lines.

[0153] The composition management system 100 includes a first registration unit 21, a second registration unit 22, a third registration unit 23, a fourth registration unit 24, a derivation unit 25, a determination unit 26, and an acquisition unit 27. The derivation unit 25, the determination unit 26, and the acquisition unit 27 are configured to specify the functions of the CPU 11, and the processing of each unit is executed by the CPU 11.

[0154] Composition information (composition information (1)) relating to the recycled thiourethane resin raw material is registered in the first registration unit 21. The composition information (1) is information obtained by analyzing the recycled thiourethane resin raw material using the analysis device 40, and this information is transmitted from the analysis device 40 to the composition management system 100 and registered in the first registration unit 21. The composition information (1) is composition information relating to the recycled thiourethane resin raw material obtained by decomposing resin powder containing thiourethane resin using the decomposition device 30, and varies depending on the type of resin powder, the decomposition method of the thiourethane resin, etc. A plurality of pieces of composition information (1) may be registered in the first registration unit 21; for example, the type of resin powder, the decomposition method of the thiourethane resin, etc. may differ among the plurality of pieces of composition information (1).

[0155] Composition information (composition information (2)) relating to the thiourethane resin raw material is registered in the second registration unit 22. The composition information (2) is composition information (product information in FIG. 2) relating to the thiourethane resin raw material that will become the product, and this information is input into the composition management system 100 and registered in the second registration unit 22. The first registration unit 22 may have multiple pieces of composition information (2) registered depending on the consumer, application, etc.

[0156] Information about the collected resin powder is registered in the third registration unit 23. Examples of the information about the resin powder include composition information about the resin powder, product information corresponding to the resin powder, and information about the source of the resin powder. Information about a specific resin powder may be a combination of multiple pieces of information. Information about the resin powder may be registered in the third registration unit 23 for each collected resin powder.

[0157] The fourth registration section 24 has registered therein information on a method for chemically decomposing the thiourethane resin contained in the resin powder (information on the decomposition method).

[0158] The derivation unit 25 derives information (composition information (3)) regarding the composition for producing thiourethane resin raw material from recycled thiourethane resin raw material from the composition information (1) registered in the first registration unit 21 and the composition information (2) registered in the second registration unit 22. If multiple pieces of composition information (1) or composition information (2) are registered, one piece of registered information can be selected, and composition information (3) can be derived from the selected composition information (1) and composition information (2).

[0159] When the composition information (3) is information regarding the composition of a resin raw material to be added to a recycled thiourethane resin raw material in order to produce a thiourethane resin raw material, the composition information (3) may include composition information of the components obtained by subtracting the composition of the recycled thiourethane resin raw material from the composition of the thiourethane resin raw material that will become the product.

[0160] The composition information (3) obtained in the output section 25 is transmitted to the manufacturing device 50.

[0161] The determination unit 26 determines whether or not the thiourethane resin contained in the resin powder is to be recycled based on the information about the resin powder registered in the third registration unit 23. For example, it may be determined whether or not the thiourethane resin is to be recycled by calculation of a life cycle assessment (LCA).

[0162] When the determination unit 26 determines that the thiourethane resin is to be recycled, the acquisition unit 27 acquires information on the decomposition method from the fourth registration unit 24. The acquired information on the decomposition method is selected based on the information on the resin powder, and preferably based on the composition information of the resin powder.

[0163] The information on the decomposition method acquired by the acquisition unit 27 is transmitted to the decomposition device 30.

[0164] Resin powder determined to be eligible for recycling is supplied to the decomposition device 30. The decomposition device 30 is a device that decomposes the thiourethane resin contained in the resin powder based on information regarding the decomposition method obtained from the fourth registration unit. The decomposition device 30 is supplied with an active hydrogen compound used to decompose the thiourethane resin contained in the resin powder, other components used in the decomposition, etc. The decomposition device 30 may be equipped with a separation unit that separates specific resin components from the product obtained by decomposing the thiourethane resin. The separation unit produces purified recycled thiourethane resin raw material.

[0165] A portion of the recycled thiourethane resin raw material obtained by decomposing the thiourethane resin in the decomposition device 30 is supplied to the analysis device 40. The analysis device 40 is a device that analyzes the recycled thiourethane resin raw material. By analyzing the recycled thiourethane resin raw material, composition information (composition information (1)) regarding the recycled thiourethane resin raw material is obtained.

[0166] The analysis device 40 may be any device that can obtain composition information of the recycled thiourethane resin raw material, and may be equipped with, for example, a chromatographic device such as a high performance liquid chromatograph (HPLC) device. For example, if the analysis device 40 is equipped with an HPLC device, information about peaks at specific retention times corresponding to resin components that may be contained in the recycled thiourethane resin raw material may be acquired in advance. This makes it possible to identify the type of resin contained in the recycled thiourethane resin raw material when analyzing the recycled thiourethane resin raw material by HPLC. When analyzing the recycled thiourethane resin raw material by HPLC, the ratio of the peak area corresponding to a specific resin component to the total peak area of ​​the resin components contained in the recycled thiourethane resin raw material may be determined, thereby determining the proportion of the specific resin component contained in the recycled thiourethane resin raw material.

[0167] When composition information (1) includes composition information of resin components obtained by an HPLC device or the like, composition information (2) also preferably includes composition information of resin components obtained by an HPLC device or the like. This makes it possible to easily derive information on the composition for producing a thiourethane resin raw material from a recycled thiourethane resin raw material (composition information (3)) from the difference between composition information (1) and composition information (2).

[0168] The composition information (1) obtained by the analysis device 40 is transmitted to the composition management system 100 and registered in the first registration unit 21. Furthermore, based on the composition information (1) and the composition information (2) registered in the second registration unit 22, the composition information (3) is derived.

[0169] An example of each piece of information registered in the first to fourth registration units 21 to 24 is shown in Fig. 3. Note that the information registered in each registration unit is not limited to that shown in Fig. 3.

[0170] The recycled thiourethane resin raw material obtained by decomposing the thiourethane resin in the decomposition device 30 is supplied to the manufacturing device 50. The composition information (3) derived in the extraction unit 25 is transmitted to the manufacturing device 50. The manufacturing device 50 includes a control unit 51, a supply unit 52, and a manufacturing unit 53. Various processes in the manufacturing device 50 are executed by a CPU.

[0171] The control unit 51 has a function of controlling the supply unit 52 to adjust the resin raw material to be supplied to the production unit 53 based on the received composition information (3).

[0172] The supply unit 52 is configured to supply the resin raw material used in the production of the thiourethane resin raw material to the production unit 53. For example, if the composition information (3) includes composition information of the components obtained by subtracting the composition of the recycled thiourethane resin raw material from the composition of the thiourethane resin raw material that will become the product, the resin raw material corresponding to the subtracted components is supplied to the production unit 53.

[0173] The resin raw material supplied to supply unit 52 may be appropriately determined depending on the composition of the recycled thiourethane resin raw material and the composition of the thiourethane resin raw material. Examples include the aforementioned polythiol composition containing a polythiol compound, a polyisocyanate composition containing a polyisocyanate compound, an intermediate product capable of producing a polythiol composition containing a polythiol compound, and an intermediate product capable of producing a polythiol composition containing a polythiol compound.

[0174] The manufacturing unit 53 is configured to manufacture a thiourethane resin raw material using a recycled thiourethane resin raw material and a resin raw material. For example, the recycled thiourethane resin raw material and the resin raw material are mixed to obtain a thiourethane resin raw material that will become a product.

[0175] An example of a method for managing the composition of a thiourethane resin raw material (hereinafter also referred to as a composition management method) according to the present disclosure and an example of a method for producing a thiourethane resin raw material according to the present disclosure will be described below with reference to Figure 4. Figure 4 is a flowchart showing an example of a method for producing a thiourethane resin raw material according to the present disclosure. Each step in Figure 4 may be performed using a system for producing a thiourethane resin raw material, such as production system 200 shown in Figure 2, or may be performed without using a system for producing a thiourethane resin raw material.

[0176] [Example of composition control method and example of manufacturing method of thiourethane resin raw material] In one example of a method for producing a thiourethane resin raw material, information about the collected resin powder is obtained in step S100.

[0177] Next, in step S102, it is determined whether the thiourethane resin contained in the resin powder is to be recycled based on the information about the resin powder. At this time, it may be determined whether the thiourethane resin contained in the resin powder is to be recycled based on a calculated value of a life cycle assessment using the information about the resin powder.

[0178] In step S104, when it is determined that the thiourethane resin is to be recycled, information on a method for decomposing the thiourethane resin to be recycled is determined.

[0179] In step S106, the thiourethane resin to be recycled is decomposed, thereby obtaining a recycled thiourethane resin raw material.

[0180] In step S108, composition information (composition information (1)) related to the recycled thiourethane resin raw material is acquired. The acquired composition information related to the recycled thiourethane resin raw material may be managed, and further, composition information (composition information (2)) related to the thiourethane resin raw material may be managed.

[0181] In step S110, information for producing a urethane resin raw material is acquired. Specifically, information (composition information (3)) regarding the composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material obtained in step S106 is acquired based on composition information (1) and composition information (2).

[0182] In step S112, a thiourethane resin raw material is produced from the recycled thiourethane resin raw material obtained in step S106 based on the composition information (3).

[0183] By carrying out the above steps, a thiourethane resin raw material having a specific composition ratio can be produced. [Example]

[0184] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples. Hereinafter, "room temperature" means 25°C unless otherwise specified.

[0185] [Experimental Example 1] After producing a molded body containing thiourethane resin R1, the molded body was machined to obtain thiourethane resin powder R1. Regarding the method for decomposing thiourethane resin powder R1, a method using an alcohol compound was decided upon, taking into account the composition of thiourethane resin powder R1. Then, thiourethane resin powder R1 was decomposed using the alcohol compound to obtain a polythiol composition containing a polythiol compound. Details are provided below.

[0186] (Production of molded body containing thiourethane resin R1) In a flask equipped with a stirrer, Dibutyltin dichloride as a polymerization catalyst (amount added: 600 ppm by mass based on the total amount of the polyisocyanate composition described below, the polythiol composition X2 described below, and the polythiol composition Y described below), Tinuvin 329 (manufactured by BASF Japan Ltd., 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol) is a UV absorber (amount added: 500 ppm by mass based on the total amount of the polyisocyanate composition described below, the polythiol composition X2 described below, and the polythiol composition Y described below), Zelec-UN (manufactured by Stepan; acidic phosphate ester) as a release agent (amount added: 1000 ppm by mass based on the total amount of the polyisocyanate composition described below, the polythiol composition X2 described below, and the polythiol composition Y described below), A polyisocyanate composition comprising a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane (amount added: 50.6 parts by mass), A polythiol composition X2 (addition amount: 25.6 parts by mass) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (polythiol compound A1), Polythiol composition Y (addition amount: 23.8 parts by mass) containing pentaerythritol tetrakis(3-mercaptopropionate) (polythiol compound A2) as the main component, The mixture was stirred and mixed at room temperature (25°C) for 1 hour to obtain a polymerizable composition which was a transparent homogeneous solution.

[0187] Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter and then thoroughly degassed under a reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds secured with tape, and the pair of glass molds was then placed in an oven, with the oven temperature set to 10°C. The oven temperature was then raised from 10°C to 120°C over 38 hours. Through this process, the monomers (polyisocyanate composition and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded product containing thiourethane resin R1 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Subsequently, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. The molded product was then removed from the pair of glass molds to obtain a molded product.

[0188] (Production of thiourethane resin powder R1) The molded article obtained above was cut to produce a lens. The cutting powder generated during this process was collected to obtain thiourethane resin powder R1 (i.e., powder containing thiourethane resin R1).

[0189] (Decomposition of thiourethane resin powder R1 by alcohol compounds) -Reaction process- The entire amount of thiourethane resin powder R1 (210 g) obtained in Experimental Example 1 was placed in a 2-L flask equipped with a condenser. Benzyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (557 g; 5.15 mol) and 1,4-diazabicyclo-[2.2.2]-octane [abbreviation: DABCO] (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (5.80 g; 51.7 mmol) were added thereto, and the mixture was heated and stirred at 150°C for 5 hours to obtain a reaction liquid containing a polycarbamate composition, polythiol compound A1, and polythiol compound A2. The polycarbamate composition in the reaction solution can be separated using the separation techniques described above, resulting in a polythiol composition (S) containing polythiol compound A1 and polythiol compound A2. Alternatively, the polythiol composition containing polythiol compound A1 and the polythiol composition containing polythiol compound A2 may be separated using the separation techniques described above. The separated polythiol composition containing polythiol compound A1 or the polythiol composition containing polythiol compound A2 may be mixed with a polythiol composition containing specific polythiol component 1 as a main component obtained in Experimental Example 2 described below, or a polythiol composition containing specific polythiol component 2 as a main component obtained in Experimental Example 3 described below, to obtain polythiol composition (S).

[0190] [Experimental Example 2] After producing a molded body containing thiourethane resin R2, the molded body was machined to obtain thiourethane resin powder R2. Regarding the method for decomposing thiourethane resin powder R2, a method using an amine compound was decided upon, taking into account the composition of thiourethane resin powder R2. Then, thiourethane resin powder R2 was decomposed using the amine compound to obtain a polythiol composition containing a polythiol compound. Details are provided below.

[0191] (Production of molded body containing thiourethane resin R2) In a flask equipped with a stirrer, Dimethyltin dichloride (trade name: Nestin P, manufactured by Honjo Chemical Co., Ltd.) as a polymerization catalyst (100 ppm by mass based on the total amount of the polymerizable composition to be obtained), Zelec-UN (Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass based on the total amount of the polymerizable composition to be obtained), m-xylylene diisocyanate (XDI) (50.8 parts by mass), which is a polyisocyanate compound; a polythiol composition X1 (49.2 parts by mass) containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (specific polythiol component 1); The mixture was stirred and mixed at room temperature for 1 hour to obtain a polymerizable composition which was a transparent homogeneous solution. Next, a molded body containing thiourethane resin R2 (i.e., a cured product of the polymerizable composition) was formed in the same manner as in Experimental Example 1, except that the temperature inside the oven was raised from 25°C to 120°C over 24 hours, and a molded body was obtained.

[0192] (Production of thiourethane resin powder R2) The molded article obtained above was cut to produce a lens. The cutting powder generated during this process was collected to obtain thiourethane resin powder R2 (i.e., powder containing thiourethane resin R2).

[0193] (Decomposition of thiourethane resin powder R2 by monoethanolamine) Thiourethane resin powder R2 (30 g) obtained in Experimental Example 2 was weighed out. To this thiourethane resin powder R2 (30 g), toluene was added, the mixture was stirred and washed, and then the toluene was removed by filtration. This procedure was repeated three times.

[0194] The entire amount of the washed thiourethane resin powder R2 was placed in a 500 mL flask equipped with a condenser, and monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (14.81 g; 0.242 mol) and 361 g of toluene were added thereto. The mixture was heated and stirred at 100°C for 3 hours to obtain a reaction mixture containing a polythiol composition.

[0195] The resulting reaction mixture was cooled to 30°C, and then the solid matter was removed by filtration. The resulting filtrate was washed twice with 150 mL of 1 N hydrochloric acid to remove excess amine from the filtrate. The resulting liquid was washed twice with 100 mL of water to obtain a toluene solution of the polythiol composition. From the obtained toluene solution, highly polar by-products were removed using a silica gel column, and then the toluene was distilled off using a rotary evaporator. The obtained mixture was subjected to removal of low boiling point components using a vacuum pump and filtration using a 3-micron PTFE membrane filter in this order to obtain a polythiol composition X1 containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (specific polythiol component 1).

[0196] [Experimental Example 3] After producing a molded body containing thiourethane resin R3, the molded body was machined to obtain thiourethane resin powder R3. Regarding the method for decomposing thiourethane resin powder R3, a method using an amine compound was decided upon, taking into account the composition of thiourethane resin powder R3. Then, thiourethane resin powder R3 was decomposed using the amine compound to obtain a polythiol composition containing a polythiol compound. Details are provided below.

[0197] (Production of Molded Article Containing Thiourethane Resin R3) In a flask equipped with a stirrer, Dibutyltin dichloride as a polymerization catalyst (100 ppm by mass based on the total amount of the polymerizable composition to be obtained), Zelec-UN (Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass based on the total amount of the polymerizable composition to be obtained), a polyisocyanate composition (52 parts by mass) containing m-xylylene diisocyanate (XDI); A polythiol composition X2 (48 parts by mass) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (specific polythiol component 2) as a main component; The mixture was stirred and mixed at room temperature (25°C) for 1 hour to obtain a polymerizable composition which was a transparent homogeneous solution. Next, a molded article containing thiourethane resin R3 (that is, a cured product of the polymerizable composition) was formed in the same manner as in Experimental Example 1, and a molded article was obtained. The polyisocyanate composition containing m-xylylene diisocyanate (XDI) was subjected to gas chromatography measurement under the above-mentioned GC conditions 1 and 2. As a result, the peak area of ​​the compound (N1) is 0.20 ppm or more (specifically, 600 ppm) relative to the peak area of ​​xylylene diisocyanate; The peak area of ​​the compound (N2) is 0.05 ppm or more (specifically, 18 ppm) relative to the peak area of ​​xylylene diisocyanate, The peak area of ​​the compound (N3) was 0.10 ppm or more (specifically, 100 ppm) relative to the peak area of ​​xylylene diisocyanate.

[0198] (Production of thiourethane resin powder R3) The molded article obtained above was cut to produce a lens. The cutting powder generated during this process was collected to obtain thiourethane resin powder R3 (i.e., powder containing thiourethane resin R3).

[0199] (Decomposition of thiourethane resin powder R3 by monoethanolamine) Thiourethane resin powder R3 (200 g) obtained in Experimental Example 3 was weighed out. Toluene was added to this thiourethane resin powder R3 (200 g), followed by stirring and washing, and then filtering to remove the toluene, and this procedure was repeated three times.

[0200] The entire amount of the washed thiourethane resin powder R3 was placed in a 500 mL flask equipped with a condenser, and monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (81 g; 1.326 mol) and 386 g of toluene were added thereto. The mixture was heated and stirred at 100°C for 3 hours to obtain a reaction mixture containing a polythiol composition.

[0201] The resulting reaction mixture was cooled to 30°C, and then the solid matter was removed by filtration. The resulting filtrate was washed twice with 150 mL of 1 N hydrochloric acid to remove excess amine from the filtrate. The resulting liquid was washed twice with 100 mL of water to obtain a toluene solution of the polythiol composition. From the resulting toluene solution, highly polar by-products were removed using a silica gel column, and then the toluene was distilled off using a rotary evaporator. The resulting mixture was subjected to removal of low-boiling components using a vacuum pump and filtration using a 3-micron PTFE membrane filter, in that order, to obtain a polythiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (specific polythiol component 2) as the main component.

[0202] Polythiol composition (S) is obtained by mixing the polythiol composition mainly composed of specific polythiol component 1 obtained in Experimental Example 2 with the polythiol composition mainly composed of specific polythiol component 2 obtained in Experimental Example 3. In Experimental Examples 2 and 3, thiourethane resin powder R2 and thiourethane resin powder R3 were each chemically decomposed separately using monoethanolamine, but the present disclosure is not limited to this configuration. For example, a mixed powder of thiourethane resin powder R2 and thiourethane resin powder R3 may be chemically decomposed using an amine compound such as monoethanolamine or an alcohol compound.

[0203] Hereinafter, the proportion (area %) of polythiol component A in the polythiol composition refers to the ratio (area %) of the peak area of ​​polythiol component A to the total peak area of ​​polythiol components A and B1 to B3, measured by high performance liquid chromatography under the following conditions for a mixed polythiol obtained by mixing polythiol composition AX and polythiol composition BX. Hereinafter, the proportion (mass %) of polythiol composition AX means the proportion (mass %) of polythiol composition AX in the sum of the masses of polythiol composition AX and polythiol composition BX. For a mixed polythiol obtained by mixing polythiol composition AX and polythiol composition BX having a specific mass ratio, a calibration curve may be created from the proportion (mass%) of polythiol composition AX and the ratio (area%) of the peak area of ​​polythiol component A to the total peak area of ​​polythiol components A and B1 to B3 in the polythiol composition, as measured by high-performance liquid chromatography under the following conditions: Then, for a mixed polythiol obtained by mixing polythiol composition AX and polythiol composition BX whose mass ratio is unknown, the ratio (area%) of the peak area of ​​polythiol component A may be determined by high-performance liquid chromatography under the following conditions, and the proportion (mass%) of polythiol composition AX may be determined based on a calibration curve created from the value of this ratio (area%). Furthermore, for a mixed polythiol obtained by mixing polythiol composition AX and polythiol composition BX having a specific mass ratio, a calibration curve may be prepared from the proportion (mass%) of polythiol composition BX and the ratio (area%) of the total peak area of ​​polythiol components B1 to B3 to the total peak area of ​​polythiol components A and B1 to B3 in the polythiol composition, as measured by high performance liquid chromatography under the following conditions: Then, for a mixed polythiol obtained by mixing polythiol composition AX and polythiol composition BX whose mass ratio is unknown, the ratio (area%) of the total peak area of ​​polythiol components B1 to B3 may be determined by high performance liquid chromatography under the following conditions, and the proportion (mass%) of polythiol composition BX may be determined based on a calibration curve prepared from the value of this ratio (area%). (High performance liquid chromatography conditions) Column: YMC-Pack ODS-A (particle size S: 3 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm) Mobile phase: acetonitrile / 0.01 mol potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Column temperature: 40℃ Flow rate: 1.0mL / min Detector: UV detector, wavelength 230 nm Preparation of measurement solution: Dissolve and mix 100 mg of sample in 5 mL of acetonitrile. Injection volume: 2μL

[0204] [Experimental Examples 4-7] (Creating a calibration curve) Polythiol composition AX, which was produced by the method described in Example A-1 of WO 2014-027427 and contained 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (polythiol component A) as the main component, and polythiol composition BX, which was produced by the method described in Example C-1 of WO 2014-027428 and contained 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (polythiol components B1 to B3) as the main components, were mixed in the proportions shown in Table 1 and analyzed by high-performance liquid chromatography. The proportion of polythiol component A was found to be as shown in Table 1 below.

[0205] [Table 1]

[0206] From these results, the proportion (mass %) of polythiol composition AX in a mixture of any two polythiol compositions AX and BX can be expressed by the following formula (1). The proportion of polythiol composition AX (mass %) can be expressed as 100×(0.0102×proportion of polythiol component A (area %)−0.0317).

[0207] [Experimental Examples 8-12] (Analysis of polythiol composition AX in a polythiol composition of unknown composition) When a polythiol composition of unknown composition (corresponding to polythiol composition (S)) was analyzed by high performance liquid chromatography, the proportion of polythiol component A was found to be as shown in Table 2. The proportion (mass%) of polythiol composition AX calculated from the calibration curves prepared in Experimental Examples 4 to 6 was found to be as shown in Table 2. The data on the proportion of polythiol component A and the proportion of polythiol composition AX shown in Table 2 correspond to the composition information on the recycled thiourethane resin raw material.

[0208] [Table 2]

[0209] [Experimental Examples 13-18] (Adjusting the ratio of polythiol composition AX) Based on the results of Experimental Examples 8 and 9, the proportion of the polythiol composition whose composition was unknown (the polythiol composition whose composition was determined in Experimental Examples 8 and 9) was set to 40 parts by mass, and the remaining 60 parts by mass was made up of polythiol composition AX and BX, resulting in a proportion of polythiol composition AX of 74% by mass of the total. Specifically, polythiol compositions AX and BX were added to the polythiol composition of Experimental Example 8 and the polythiol composition of Experimental Example 9, as shown in Table 3 below, to prepare the polythiol compositions (corresponding to polythiol composition (T)) of Experimental Examples 13 to 16, respectively. Furthermore, polythiol composition AX was added to the polythiol composition of Experimental Example 13 in the mixing ratio shown in Table 3, to prepare the polythiol compositions of Experimental Examples 17 and 18, respectively. The polythiol compositions of Experimental Examples 13 to 18 were analyzed by high-performance liquid chromatography, and the proportion of polythiol composition AX was measured by calculation using a calibration curve. The results are shown in Table 3.

[0210] [Table 3]

[0211] As shown in Table 3, in Experimental Examples 13 to 18, the proportions of polythiol component A and polythiol composition AX were almost the same. This demonstrated that a polythiol composition having a specific composition can be produced with good reproducibility from a polythiol composition of unknown composition. In Table 3, the information regarding the parts by mass of polythiol composition AX and polythiol composition BX to be mixed with the polythiol composition of unknown composition corresponds to the information regarding the composition for producing a thiourethane resin raw material from a recycled thiourethane resin raw material.

[0212] [Experimental Example 19] (Production of molded body containing thiourethane resin) In a flask equipped with a stirrer, dimethyltin dichloride (trade name: Nestin P, manufactured by Honjo Chemical Co., Ltd.) serving as a polymerization catalyst (100 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition), Zelec-UN (manufactured by Stepan; acidic phosphate ester) serving as a release agent (1000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition), a polyisocyanate composition (51.6 parts by mass) containing m-xylylene diisocyanate (XDI), and the polythiol composition (48.4 parts by mass) prepared in Experimental Example 13 were added, and the mixture was stirred and mixed at room temperature for 1 hour to obtain a transparent, homogeneous solution of a polymerizable composition. Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then thoroughly degassed under a reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds secured with tape, and the pair of glass molds were then placed in an oven, with the temperature inside the oven set to 25°C. The temperature inside the oven was then raised from 25°C to 120°C over 24 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded product containing thiourethane resin R4 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Subsequently, the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and the molded body was then removed from the pair of glass molds to obtain a molded body. The obtained molded article had good transparency, was free from distortion, and had a good appearance.

[0213] The molded article obtained above was subjected to a performance test. The performance test items were optical properties (refractive index and Abbe number), heat resistance, and color hue. Each test was carried out using the following test methods. Refractive index (ne), Abbe number (νe): Using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive indices (ne, nF', nC') were measured at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line), respectively, and the refractive index (ne) and Abbe number (νe) were calculated. ·Heat resistance: The glass transition temperature (Tg) was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10°C / min) and used as an index of heat resistance. ·specific gravity: Measurement was performed by the Archimedes method. The results are shown in Table 4.

[0214] [Experimental Examples 20-26] The same procedure as in Experimental Example 19 was carried out, except that the amount of the polyisocyanate composition containing m-xylylene diisocyanate (XDI) was changed as shown in Table 4, and the polythiol composition and its amount were changed as shown in Table 4. The results are shown in Table 4.

[0215] [Experimental Example 27] (Production of molded body containing thiourethane resin) In a flask equipped with a stirrer, the polymerization catalyst dimethyltin dichloride (trade name: Nestin P, manufactured by Honjo Chemical Co., Ltd.) (600 ppm by mass based on the total amount of the polyisocyanate composition and the polythiol composition), the mold release agent Zelec-UN (manufactured by Stepan; acidic phosphate ester) (1200 ppm by mass based on the total amount of the polyisocyanate composition and the polythiol composition), an isocyanate composition (NBDI) (53.8 parts by mass) mainly composed of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and the polythiol composition (46.2 parts by mass) prepared in Experimental Example 13 were added, but the same operation as in Experimental Example 19 was performed. The results are shown in Table 4.

[0216] [Experimental Examples 28-35] The same procedure as in Experimental Example 27 was performed except that the amount of the polyisocyanate composition containing NBDI was changed as shown in Table 4, and the polythiol composition and its amount were changed as shown in Table 4. The results are shown in Table 4.

[0217] [Table 4]

[0218] From the above, it has been shown that by analyzing a polythiol composition whose composition is unknown, and adding a known polythiol compound or a polythiol composition whose composition is known to a polythiol composition whose composition is known, the composition can be adjusted, and a polythiol composition having a specific composition can be produced with good reproducibility.Furthermore, by using a polythiol composition having a specific composition, it is possible to produce a molded body with small variations in various performances with good reproducibility.

[0219] The disclosures of Japanese Patent Application Nos. 2022-19033 and 2022-19034, filed on February 9, 2022, are incorporated herein by reference in their entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. [Explanation of symbols]

[0220] 21 First Registration Section 22 Second Registration Section 23 Third Registration Section 24 Fourth Registration Section 25 Derivation part 26 Judgment section 27 Acquisition Department 30 Decomposition equipment 40 Analyzer 50 Manufacturing equipment 100 Composition Management System 200 Manufacturing System

Claims

1. a step of reacting a composition X containing a thiourethane resin to produce a polythiol composition (S) containing two or more polythiol compounds; a step of producing a polythiol composition (T) from the polythiol composition (S) by adjusting the content of at least one polythiol compound contained in the polythiol composition (S); Including, The thiourethane resin comprises a polythiol composition (P) containing a polythiol compound (A1) having no ester bond in the molecule, a polythiol composition (Q) containing a polythiol compound (A2) having at least one ester bond in the molecule, and a thiourethane resin B formed using a polyisocyanate composition (B) containing at least one polyisocyanate compound (A2), The step of producing the polythiol composition (S) includes reacting the thiourethane resin in the composition X with an alcohol compound in the presence of a tertiary amine compound. A method for producing a polythiol composition.

2. The method for producing a polythiol composition according to claim 1 , wherein the thiourethane resin comprises at least two or more types of thiourethane resins.

3. 3. The method for producing a polythiol composition according to claim 1 or 2, wherein in the step of producing the polythiol composition (T), the polythiol composition (T) is produced by adding at least one polythiol compound contained in the polythiol composition (S) to the polythiol composition (S).

4. 3. The method for producing a polythiol composition according to claim 1 or 2, wherein the composition X includes at least one selected from the group consisting of a resin other than the thiourethane resin, a polymerization catalyst, a metal, an ultraviolet absorber, an internal mold release agent, a plasticizer, a dye, machine oil, and water.

5. The polythiol composition (S) and the polythiol composition (T) each independently include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol composition X1 containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and 2,5-dimercaptomethyl-1,4-dithiane The method for producing the polythiol composition according to claim 1 or claim 2, comprising at least one selected from the group consisting of:

6. 3. A method for producing a polymerizable composition, comprising a step of producing a polymerizable composition by mixing the polythiol composition (T) obtained by the method for producing a polythiol composition according to claim 1 or 2 with a polyisocyanate composition (C) containing at least one polyisocyanate compound.

7. a polythiol composition X1 containing a polythiol component B which is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and a polythiol composition X2 containing a polythiol component A that is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; A polythiol composition, wherein the peak area of ​​the polythiol component A is 30 area % or more and 99 area % or less of the total peak area of ​​the polythiol composition X1 and the polythiol composition X2, as measured by high performance liquid chromatography.

8. The polythiol composition of claim 7; a polyisocyanate composition containing a polyisocyanate compound; A polymerizable composition comprising:

9. The polyisocyanate composition Xylylene diisocyanate, at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); Including, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, 9. The polymerizable composition according to claim 8, wherein, when the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1: -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm x length 60 m (Agilent) Oven temperature: Raise from 130°C to 220°C at 3°C / min, and after reaching 220°C, raise the temperature at 10°C / min to 300°C. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm × length 30 m × film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at 10°C / min, and hold for 6 minutes after reaching 280°C. Split ratio: Pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0 mass% dichloromethane solution Injection volume: 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (content of xylylene diisocyanate) 【Chemistry 1】

10. The polythiol composition of claim 7; a polyisocyanate composition containing a polyisocyanate compound; A composition set comprising:

11. The polyisocyanate composition Xylylene diisocyanate, at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); Including, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, The composition set according to claim 10, wherein when the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1: -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm x length 60 m (Agilent) Oven temperature: Raise from 130°C to 220°C at 3°C / min, and after reaching 220°C, raise the temperature at 10°C / min to 300°C. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm × length 30 m × film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at 10°C / min, and hold for 6 minutes after reaching 280°C. Split ratio: Pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0 mass% dichloromethane solution Injection volume: 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (content of xylylene diisocyanate) 【Chemistry 2】

12. A cured product obtained by curing a polymerizable composition obtained by mixing the polythiol composition and the polyisocyanate composition contained in the polymerizable composition according to claim 8 .

13. An optical material comprising the cured product according to claim 12.

14. a first registration unit that registers composition information relating to a recycled thiourethane resin raw material obtained by chemically decomposing the thiourethane resin contained in the recovered resin powder; a second registration unit that registers composition information related to the thiourethane resin raw material; A derivation unit that derives information about the composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material based on the composition information about the thiourethane resin raw material registered in the second registration unit and the composition information about the recycled thiourethane resin raw material registered in the first registration unit; Equipped with The thiourethane resin comprises a polythiol composition (P) containing a polythiol compound (A1) having no ester bond in the molecule, a polythiol composition (Q) containing a polythiol compound (A2) having at least one ester bond in the molecule, and a thiourethane resin B formed using a polyisocyanate composition (B) containing at least one polyisocyanate compound, Chemically decomposing the thiourethane resin includes reacting the thiourethane resin with an alcohol compound in the presence of a tertiary amine compound. A composition management system for thiourethane resin raw materials.

15. The composition management system for a thiourethane resin raw material according to claim 14; a manufacturing device that manufactures the thiourethane resin raw material from the recycled thiourethane resin raw material based on the derived information about the composition; A system for producing a thiourethane resin raw material.

16. a step of managing composition information regarding the recycled thiourethane resin raw material obtained by chemically decomposing the thiourethane resin contained in the recovered resin powder; managing composition information relating to the thiourethane resin raw material; A step of deriving information regarding a composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material based on composition information regarding the thiourethane resin raw material and composition information regarding the recycled thiourethane resin raw material; Including, The thiourethane resin comprises a polythiol composition (P) containing a polythiol compound (A1) having no ester bond in the molecule, a polythiol composition (Q) containing a polythiol compound (A2) having at least one ester bond in the molecule, and a thiourethane resin B formed using a polyisocyanate composition (B) containing at least one polyisocyanate compound, Chemically decomposing the thiourethane resin includes reacting the thiourethane resin with an alcohol compound in the presence of a tertiary amine compound. A method for controlling the composition of thiourethane resin raw materials.

17. A method for producing a thiourethane resin raw material, comprising a step of producing the thiourethane resin raw material from the recycled thiourethane resin raw material based on information about the composition derived by the method for managing the composition of a thiourethane resin raw material according to claim 16.

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