Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
  • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
  • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
  • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
  • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
  • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

• the present disclosure relates to a method for producing a polythiol composition, a polythiol composition, a composition management system for thiourethane resin raw materials, and applications thereof.
• Plastic lenses which are lenses containing resin, are lighter than inorganic lenses, are less likely to crack, and can be dyed.
• Patent Documents 1 to 3 various studies have been made so far on lenses containing thiourethane resin (see, for example, Patent Documents 1 to 3).
• Patent Document 1 JP-A-63-46213
• Patent Document 2 JP-A-2-270859
• Patent Document 3 JP-A-7-252207
• raw materials for producing thiourethane resins (hereinafter also referred to as "raw materials for thiourethane resins")
• polythiol compositions and polyisocyanate compositions are usually used.
• Polyisocyanate compositions are produced, for example, from polyamine compounds.
• a lens containing a thiourethane resin (for example, an eyeglass lens) is manufactured by cutting a molded body containing a thiourethane resin.
• a large amount of cutting powder containing thiourethane resin may be generated as waste in the lens manufacturing process.
• defective molding or defective processing may occur in the process of manufacturing a molded body containing a thiourethane resin.
• used spectacle lenses by consumers may be disposed of as waste. Conventionally, cutting powder, defective molding products, defective processing products, and used spectacle lenses as waste are either burned or buried as industrial waste, and have not been effectively used. Ta.
• a polythiol composition which is a raw material for thiourethane resin, is produced.
• a manufacturing technique a recycled raw material for thiourethane resin (hereinafter also referred to as "raw material for recycled thiourethane resin"), etc. are desired.
• the produced polythiol composition, recycled thiourethane resin raw material, and the like can be used as a raw material for producing a thiourethane resin.
• the produced polythiol composition can be used as a raw material for producing resins other than thiourethane resins, for example, other resins utilizing thiol-ene reaction.
• a technique for producing a polythiol composition, a recycled thiourethane resin raw material, etc. using a thiourethane resin as a starting material without being limited to using the thiourethane resin contained in cutting powder, defective molding products, or defective processing products as a starting material. is desired.
• the thiourethane resin used in the production of the polythiol composition, recycled thiourethane resin raw material, etc. is a mixture of multiple types of thiourethane.
• these collected products are composed of different types of thiourethane resins.
• An object of the present disclosure includes a method for producing a polythiol composition that can produce a polythiol composition having a specific composition ratio using a polythiol composition produced using a thiourethane resin as a starting material, and this production method.
• An object of the present invention is to provide a method for producing a polymerizable composition, a method for producing a cured product, and a polythiol composition containing a polythiol compound derived from a thiourethane resin.
• Another object of the present disclosure is a thiourethane resin raw material composition management system that manages information that enables production of a thiourethane resin raw material having a specific composition ratio using a recycled thiourethane resin raw material, and 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 the polythiol composition, and the polymerizable composition.
• An object of the present invention is to provide a cured product obtained by curing and an optical material containing this cured product.
• 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 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 thiourethane resins.
• 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 the polythiol composition (P), a polythiol composition (Q) containing a polythiol compound (A2) having at least one or more ester bonds in the molecule, and a polyisocyanate composition containing at least one polyisocyanate compound ( B) a thiourethane resin B formed using The method for producing a polythiol composition according to ⁇ 2A>, comprising at least two or more thiourethane resins selected from the group consisting of.
• the polythiol composition (P) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of
• the method for producing a polythiol composition according to ⁇ 3A> which contains at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• the polythiol composition (Q) is pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), Trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate)
• the polyisocyanate composition (A) and the polyisocyanate composition (B) are each independently pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohe
• ⁇ 7A> In the step of generating the polythiol composition (T), at least one polythiol compound contained in the polythiol composition (S) is added to the polythiol composition (S) to form the polythiol composition ( T), the method for producing the polythiol composition according to any one of ⁇ 1A> to ⁇ 6A>.
• ⁇ 8A> In the step of generating the polythiol composition (S), the thiourethane resin in the composition X and an active hydrogen compound are reacted to generate the polythiol composition (S), ⁇ 1A> to A method for producing the polythiol composition according to any one of ⁇ 7A>.
• ⁇ 9A> The method for producing a polythiol composition according to ⁇ 8>, wherein the active hydrogen compound contains at least one selected from the group consisting of amine compounds and alcohol compounds.
• the composition X is at least one selected from the group consisting of resins other than the thiourethane resin, polymerization catalysts, metals, ultraviolet absorbers, internal release agents, plasticizers, dyes, machine oils, and water.
• the polythiol composition (S) and the polythiol composition (T) are each independently 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of
• ⁇ 12A> 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of A polythiol composition comprising at least two polythiol compounds (U) selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane and derived from a thiourethane resin.
• a polyisocyanate composition comprising the polythiol composition (T) obtained by the method for producing a polythiol composition according to any one of ⁇ 1A> to ⁇ 11A>, and at least one polyisocyanate compound.
• a method for producing a polymerizable composition comprising the step of producing a polymerizable composition by mixing (C).
• C the step of producing a polymerizable composition by mixing
• ⁇ 14A> A step of producing a polymerizable composition by the method for producing a polymerizable composition according to ⁇ 13A>; obtaining a cured product by curing the polymerizable composition; A method for producing a cured product containing.
• ⁇ 1B> a first registration unit for registering composition information regarding a recycled thiourethane resin raw material obtained by chemically decomposing the thiourethane resin contained in the collected resin powder; a second registration unit that registers composition information about the 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, from the recycled thiourethane resin raw material a derivation unit for deriving information on the composition for producing the thiourethane resin raw material; A composition management system for thiourethane resin raw materials.
• composition information about the recycled thiourethane resin raw material is Derived from the thiourethane resin, compositional information about a polythiol composition comprising a polythiol compound; compositional information about a polyisocyanate composition containing a polyisocyanate compound; At least one selected from the group consisting of composition information on an intermediate product capable of producing a polythiol composition containing a polythiol compound and composition information on an intermediate product capable of producing a polyisocyanate composition containing a polyisocyanate compound.
• the composition management system for the thiourethane resin raw material according to ⁇ 1B>.
• the recycled thiourethane resin raw material and the thiourethane resin raw material are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of The thiourethane resin raw material composition management system according to ⁇ 1B> or ⁇ 2B>, containing at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• the information about the composition is any one of ⁇ 1B> to ⁇ 3B>, which is information about the composition of the resin raw material to be added to the recycled thiourethane resin raw material in order to produce the thiourethane resin raw material.
• the composition management system for the thiourethane resin raw material according to 1.
• ⁇ 5B> a third registration unit that registers information about the resin powder; a fourth registration unit for registering information on 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 the information about the resin powder registered in the third registration unit; an acquisition unit that acquires information on a method for chemically decomposing the thiourethane resin to be recycled from the fourth registration unit when the determination unit determines that the thiourethane resin is to be recycled;
• the thiourethane resin raw material composition management system according to any one of ⁇ 1B> to ⁇ 4B>, further comprising: ⁇ 6B>
• the determination unit makes the thiourethane resin contained in the resin powder subject to recycling based on a calculated value of life cycle assessment using the information on the resin powder registered in the third registration unit.
• the thiourethane resin raw material composition management system according to ⁇ 5B> which determines that the is not subject to recycling.
• the information on the resin powder includes at least one selected from the group consisting of information on the composition of the resin powder, product information corresponding to the resin powder, and information on the source of the resin powder ⁇ 5B> or The composition management system for the thiourethane resin raw material according to ⁇ 6B>.
• ⁇ 8B> The thiourethane resin raw material composition management system according to any one of ⁇ 1B> to ⁇ 7B>; a production apparatus for producing the thiourethane resin raw material from the recycled thiourethane resin raw material based on the derived information on the composition; A manufacturing system for thiourethane resin raw materials.
• the resin powder contains A decomposition device that decomposes the thiourethane resin that is a production device for producing the thiourethane resin raw material from the recycled thiourethane resin raw material obtained by decomposition of the thiourethane resin in the decomposition device, based on the derived information about the composition; A manufacturing system for thiourethane resin raw materials.
• a step of managing composition information regarding the recycled thiourethane resin raw material obtained by chemically decomposing the thiourethane resin contained in the collected resin powder A step of managing composition information about the thiourethane resin raw material; a step of deriving information on a composition for producing a thiourethane resin raw material from the recycled thiourethane resin raw material based on the composition information on the thiourethane resin raw material and the composition information on the recycled thiourethane resin raw material; Composition control method of thiourethane resin raw material containing.
• ⁇ 11B> Determine whether or not the thiourethane resin contained in the resin powder is to be recycled based on the information about the resin powder, and if it is determined that the thiourethane resin is to be recycled, recycle
• ⁇ 12B> Determining whether or not the thiourethane resin contained in the resin powder is subject to recycling based on the calculated value of life cycle assessment using the information on the resin powder, and determining whether the calculated value is predetermined Determining that the thiourethane resin is not subject to recycling if the calculated value is equal to or greater than the value, and determining that the thiourethane resin is not subject to recycling if the calculated value is less than a predetermined value. Composition control method of thiourethane resin raw material.
• the recycled thiourethane resin raw material is converted to the thiourethane resin raw material.
• a method for producing a thiourethane resin raw material comprising the step of producing ⁇ 14B> When it is determined that the thiourethane resin is to be recycled based on the method for managing the composition of the thiourethane resin raw material described in ⁇ 12B>, based on information on a method for chemically decomposing the thiourethane resin decomposing the thiourethane resin contained in the resin powder with a step of producing the thiourethane resin raw material from the regenerated thiourethane resin raw material obtained by decomposition of the thiourethane resin based on the information about the composition derived by the composition control method of the thiourethane resin raw material; A method for producing a thiourethane resin raw material containing.
• ⁇ 1C> 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane , and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane.
• ⁇ 2C> 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane , and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane.
• ⁇ 3C> The polythiol composition according to ⁇ 1C> or ⁇ 2C>; A polyisocyanate composition containing a polyisocyanate compound; A polymerizable composition comprising: ⁇ 4C>
• the polyisocyanate composition is xylylene diisocyanate and 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) in the gas chromatography measurement under the following GC conditions 1 is 0.0 to 1 of the peak area of xylylene diisocyanate.
• the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is 0.0 to 1 of the peak area of xylylene diisocyanate.
• the peak area of the compound (N3) in the gas chromatography measurement under the following GC condition 1 is 0.0 to 1 of the peak area of xylylene diisocyanate.
• the polymerizable composition according to ⁇ 3C> which is 10 ppm or more.
• ⁇ 5C> The polythiol composition according to ⁇ 1C> or ⁇ 2C>; A polyisocyanate composition containing a polyisocyanate compound; A composition set, comprising: ⁇ 6C>
• the polyisocyanate composition is xylylene diisocyanate and 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) in the gas chromatography measurement under the following GC conditions 1 is 0.0 to 1 of the peak area of xylylene diisocyanate.
• the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is 0.0 to 1 of the peak area of xylylene diisocyanate.
• the peak area of the compound (N3) in the gas chromatography measurement under the following GC condition 1 is 0.0 to 1 of the peak area of xylylene diisocyanate.
• ⁇ 7C> Polymerization obtained by mixing the polythiol composition and the polyisocyanate composition contained in the polymerizable composition according to ⁇ 3C> or ⁇ 4C> or the composition set according to ⁇ 5> or ⁇ 6> A cured product obtained by curing a curable composition.
• ⁇ 8C> An optical material containing the cured product according to ⁇ 7C>.
• a method for producing a polythiol composition capable of producing a polythiol composition having a specific composition ratio using a polythiol composition produced using a thiourethane resin as a starting material, including this production method It is possible to provide a method for producing a polymerizable composition, a method for producing a cured product, and a polythiol composition containing a polythiol compound derived from a thiourethane resin.
• a thiourethane resin raw material composition management system that manages information that enables production of a thiourethane resin raw material having a specific composition ratio using a recycled thiourethane resin raw material, and a thiourethane resin raw material having a specific composition ratio It is possible to provide a thiourethane resin raw material production system capable of producing a urethane resin raw material. Furthermore, according to the present disclosure, a composition management method for a thiourethane resin raw material that manages information that enables the production of a thiourethane resin raw material having a specific composition ratio using a recycled thiourethane resin raw material, and a specific composition ratio.
• a method for producing a thiourethane resin raw material that can produce a thiourethane resin raw material having.
• a polythiol composition capable of producing a cured product having desired heat resistance and dyeability a polymerizable composition and a composition set containing the polythiol composition, and curing the polymerizable composition
• a cured product comprising the cured product and an optical material containing this cured product.
• FIG. 1 is a block diagram showing the hardware configuration of a thiourethane resin raw material composition management system in an embodiment of the present disclosure.
• FIG. 1 is a diagram showing the configuration of a production system for a thiourethane resin raw material in an embodiment of the present disclosure;
• FIG. 4 is a diagram showing an example of each information registered in a first registration section to a fourth registration section;
• 1 is a flow chart showing an example of a method for producing a thiourethane resin raw material of the present disclosure.
• a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
• the term “step” includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
• the amount of each component contained in the composition is the total amount of the multiple substances present in the composition unless otherwise specified. means In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• the specific component contained in each composition may be used singly or in combination of two or more.
• 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 the polythiol composition (S) 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.
• a polythiol composition (S) which is a polythiol composition produced using a thiourethane resin as a starting material, is used to produce a polythiol composition (T) having a specific composition ratio.
• the polythiol composition (S) produced using a thiourethane resin as a starting material includes the composition of the thiourethane resin, the conditions for chemical decomposition of the thiourethane resin, and the polythiol in the mixture obtained by chemically decomposing the thiourethane resin.
• the composition of the polythiol composition (S) varies depending on the composition separation method and the like.
• composition of the polythiol composition (S) varies for each production unit, by adjusting the content of at least one polythiol compound contained in the polythiol composition (S), the production unit Variation in composition for each polythiol compound is suppressed.
• a polythiol composition (T) having a specific composition ratio can be produced in each production unit.
• Step of producing polythiol composition (S) The manufacturing method of the present disclosure includes the step of reacting a composition X containing a thiourethane resin to produce a polythiol composition (S) containing two or more polythiol compounds.
• the thiourethane resin contained in the composition X is chemically decomposed to produce a polythiol composition (S) containing two or more polythiol compounds.
• a thiourethane resin is a starting material in the production method of the present disclosure and is included in composition X.
• a thiourethane resin may be a reaction product formed using a polythiol composition comprising at least one polythiol compound and a polyisocyanate composition comprising at least one polyisocyanate compound.
• the thiourethane resin as a starting material may be one type of thiourethane resin, or may contain two or more types of thiourethane resins.
• the thiourethane resin may contain at least one of thiourethane resin A and thiourethane resin B described below.
• 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
• the thiourethane resin A and the thiourethane resin B may each independently be one kind of thiourethane resin, or may contain two or more kinds of thiourethane resins.
• the thiourethane resin A is a reaction product using the polythiol composition (P) and the polyisocyanate composition (A).
• the polythiol composition (P) contains a polythiol compound (A1) that does not have an ester bond in its molecule.
• the polythiol compound (A1) having no intramolecular ester bond is not particularly limited as long as it is a compound having no intramolecular ester bond and containing two or more mercapto groups.
• polythiol compound (A1) having no intramolecular ester bond examples 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-trithiundecane, 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol , tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(
• the polythiol composition (P) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of It may contain at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• the polythiol composition (P) comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, at least one of the above three types of polythiol compounds (preferably a mixture of the above three types of polythiol compounds). ) and at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• the polyisocyanate composition (A) contains at least one polyisocyanate compound.
• the polyisocyanate compound is not particularly limited 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.
• Polyisocyanate composition (A) for example, may be one polyisocyanate compound, may be a mixture of two or more polyisocyanate compounds, one or more polyisocyanate compounds and other components may be a mixture of
• the polyisocyanate composition (A) is 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 It preferably contains at least one polyisocyanate compound selected from the group.
• Polyisocyanate composition (A) includes m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo- It is more preferable to include at least one selected from the group consisting of [2.2.1]-heptane.
• the polyisocyanate composition (A) may contain xylylene diisocyanate such as m-xylylene diisocyanate and p-xylylene diisocyanate.
• xylylene diisocyanate such as m-xylylene diisocyanate and p-xylylene diisocyanate.
• the polyisocyanate composition (A) 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). .
• the peak area of the compound (N1) in the gas chromatography measurement under the following GC conditions 1 is 0.0 to 1 of the peak area of xylylene diisocyanate. It is preferably 20 ppm or more.
• -GC condition 1- Filler; DB-1 (film thickness) 1.5 ⁇ m Column; inner diameter 0.53 mm ⁇ length 60 m (manufactured by Agilent) Oven temperature: from 130°C to 220°C at a rate of 3°C/min, after reaching 220°C, the temperature was raised to 300°C at a rate of 10°C/min.
• the peak area of the compound (N1) is more preferably 5.0 ppm or more, still more preferably 50 ppm or more, and particularly preferably 100 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, still more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and still more preferably 1000 ppm or less relative to the peak area 1 of xylylene diisocyanate. .
• the peak area of the compound (N1) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.
• the peak area of the compound (N2) in the gas chromatography measurement under the following GC conditions 2 is 0.0 to 1 of the peak area of xylylene diisocyanate. 05 ppm or more is preferable.
• -GC condition 2- Column: HP-50+, inner diameter 0.25 mm ⁇ length 30 m ⁇ film thickness 0.25 ⁇ m (manufactured by Hewlett-Packard) Oven temperature; raised from 50°C to 280°C at a rate of 10°C/min, and held for 6 minutes after reaching 280°C.
• the peak area of the compound (N2) is more preferably 0.1 ppm or more, still more preferably 0.3 ppm or more, still more preferably 0.6 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, still more preferably 100 ppm or less, still more preferably 80 ppm or less, still more preferably 70 ppm or less, with respect to the peak area 1 of xylylene diisocyanate. It is preferably 60 ppm or less.
• the peak area of the compound (N2) can be measured according to the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.
• the peak area of the compound (N3) in the gas chromatography measurement under the above-mentioned GC condition 1 is 0 with respect to the peak area of xylylene diisocyanate 1 .10 ppm or more is preferred.
• the peak area of the compound (N3) is more preferably 0.1 ppm or more, still more preferably 3.0 ppm or more, still more preferably 5.0 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, still more preferably 100 ppm or less, and still more preferably 75 ppm or less relative to the peak area 1 of xylylene diisocyanate. .
• the peak area of the compound (N3) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.
• the acid content of the polyisocyanate composition (A) is preferably 3000 ppm or less, more preferably 2000 ppm or less, still more preferably 1000 ppm or less, still more preferably 100 ppm or less, still more preferably 50 ppm or less, still more preferably 30 ppm or less, still more preferably less than 15 ppm.
• the lower limit of the acid content of the polyisocyanate composition (A) is not particularly limited, the lower limit is, for example, 1 ppm.
• the acid content of the polyisocyanate composition (A) can be measured according to the method described in paragraph 0091 of WO2021/256417.
• the thiourethane resin B is a reaction product using the polythiol composition (P), the polythiol composition (Q) and the polyisocyanate composition (B).
• Preferred forms of the polythiol composition (P) used to produce the thiourethane resin B are the same as preferred forms of the polythiol composition (P) used to produce the thiourethane resin A described above.
• the polythiol composition (Q) contains a polythiol compound (A2) having at least one or more ester bonds in the molecule.
• the polythiol compound (A2) having at least one or more ester bonds in the molecule is not particularly limited as long as it is a compound that has an ester bond in the molecule and contains two or more mercapto groups.
• Polythiol compounds (A2) having at least one or more ester bonds in the molecule include, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), trimethylolpropane tris (3 -mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptopropionate) and the like.
• the polythiol compound (A2) having at least one or more ester bonds in the molecule may be used singly or in combination of two or more.
• 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
• the polyisocyanate composition (B) contains at least one polyisocyanate compound. Preferred forms of the polyisocyanate composition (B) are the same as those of the polyisocyanate composition (A).
• the thiourethane resin used in the manufacturing method of the present disclosure is preferably recovered in at least one of the eyeglass lens manufacturing process, the eyeglass manufacturing process, and the eyeglass disposal process. may be a mixture of thiourethane resins recovered in at least one of According to this aspect, the recycling of the thiourethane resin, which is the material of the spectacle lenses, is realized.
• the process of manufacturing an eyeglass lens means a process of preparing a resin by preparing a monomer that is a resin raw material and subjecting it to cast polymerization, and/or a process of cutting a resin molding to obtain an eyeglass lens.
• the manufacturing process of spectacles means the process of manufacturing spectacles by combining spectacle lenses and other members such as spectacle frames
• the process of discarding eyeglasses means the process of discarding manufactured but unnecessary eyeglasses, used eyeglasses, and the like.
• thiourethane resin which is a material for spectacle lenses, can be generated as a waste product.
• the thiourethane resin used in the production method of the present disclosure may be powder containing thiourethane resin (hereinafter also referred to as "thiourethane resin powder").
• the thiourethane resin powder is not particularly limited, and for example, cutting powder of a molded body containing thiourethane resin and/or sieved cutting powder may be used. Cutting powder of a molded body containing a thiourethane resin is generated, for example, when a molded body containing a thiourethane resin is cut to produce an optical material (for example, a lens). Further, the thiourethane resin powder may be lump-like powder obtained by crushing and/or pulverizing a compact containing thiourethane resin.
• Composition X may contain components other than the thiourethane resin, for example, a component added to promote the reaction when the polythiol composition and the polyisocyanate composition are reacted to produce a thiourethane resin. , a component added to impart some function to the thiourethane resin to be produced, a component required for chemical decomposition of the thiourethane resin, and the like.
• composition X contains at least one selected from the group consisting of resins other than thiourethane resins, polymerization catalysts, metals, ultraviolet absorbers, internal release agents, plasticizers, dyes, machine oils, and water. You can stay.
• the step of producing the polythiol composition (S) it is preferable to react the thiourethane resin in the composition X with the active hydrogen compound to produce the polythiol composition (S).
• the active hydrogen compound functions as a decomposing agent for the starting thiourethane resin.
• the active hydrogen compound is preferably at least one selected from the group consisting of amine compounds and alcohol compounds.
• the amine compound is preferably an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 to 6 (preferably 1 to 3, more preferably 1 or 2). .
• the molecular weight of the amine compound is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and 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, more preferably 60 or more.
• Examples include amine compounds containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 or 2 and having a molecular weight of 300 or less.
• amine compounds include alkylamines having 2 to 10 carbon atoms, aralkylamines having 7 to 10 carbon atoms (eg, benzylamine), dialkylamines having 2 to 10 carbon atoms (eg, di-n-butylamine), C2-C10 alkyldiamine (e.g., ethylenediamine, bis(2-aminoethyl)ether), C2-C10 alkyltriamine (e.g., bis(2-aminoethyl)amine), C2-10 hydroxyalkylamine (e.g., monoethanolamine), bis(hydroxyalkyl)amine having 2 to 10 carbon atoms (e.g., bis(hydroxyethyl)amine), cyclic amine having 2 to 10 carbon atoms (e.g., morpholine), carbon number Secondary amines such as 2 to 10 alkyl(hydroxyalkyl)amines (eg, methylethanolamine, isopropylethanolamine) and the like.
• the alcohol compound may be a monoalcohol compound containing only one hydroxy group, or a polyol compound containing two or more hydroxy groups.
• the molecular weight of the alcohol compound is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and 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, more preferably 60 or more.
• the alcohol compound preferably includes an alcohol compound having a boiling point of 135°C to 250°C (hereinafter also referred to as "alcohol compound A").
• the boiling point means the boiling point under 1 atmosphere (101325 Pa).
• the proportion of alcohol compound A in the total amount of alcohol compounds is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and still more preferably 80% by mass to 100% by mass. be.
• the charged mass ratio of the amine compound to the thiourethane resin i.e., charged mass ratio [amine compound/thiourethane resin]
• the charged mass ratio [amine compound/thiourethane resin] is preferably 0.05 or more and less than 10.
• the charged mass ratio [amine compound/thiourethane resin] is 0.05 or more, the production of the polythiol composition is further promoted.
• the charged mass ratio [amine compound/thiourethane resin] is less than 10, the residual amine compound in the reaction mixture can be further suppressed.
• the charged mass ratio [amine compound/thiourethane resin] is preferably from 0.075 to 5, more preferably from 0.10 to 1.
• the number of millimoles of the amine compound charged with respect to 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. g, more preferably 3.0 mmol/g to 10.0 mmol/g.
• the charge equivalent of the amine compound to the thiourethane resin is preferably 1.0 to 2.0, more preferably It is more than 1.0 and 1.8 or less, more preferably more than 1.0 and 1.6 or less.
• the charge equivalent [amine compound/thiourethane resin] is 1.0 or more, the production of the polythiol composition is further promoted.
• the charge equivalent [amine compound/thiourethane resin] is 2.0 or less, the residual amine compound in the reaction mixture can be further suppressed.
• the charged equivalent of the amine compound to the thiourethane resin is the total number of thiourethane bonds in the charged thiourethane resin. It means the ratio of the total number of amino groups.
• reaction solvents include hydrocarbon compounds having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), ether compounds having 4 to 12 carbon atoms, ketone compounds having 3 to 12 carbon atoms, and 4 carbon atoms. ⁇ 12 ester compounds, C2-12 alcohol compounds, or C2-12 nitrile compounds are preferred.
• the compound used as the reaction solvent may be of one type or two or more types.
• reaction temperature between the thiourethane resin and the amine compound can be adjusted as appropriate. It is preferable to react the thiourethane resin and the amine compound under temperature conditions (that is, reaction temperature) of 50° C. to 150° C. (more preferably 60° C. to 145° C., still more preferably 70° C. to 140° C.).
• the reaction time between the thiourethane resin and the amine compound can be adjusted as appropriate, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and still more preferably 1 to 1 hour. 10 hours.
• the charged mass ratio of the alcohol compound to the thiourethane resin (that is, the charged mass ratio [alcohol compound/thiourethane resin]) can be adjusted as appropriate. is preferably 0.10 to 20. When the charged mass ratio [alcohol compound/thiourethane resin] is 0.10 or more, the production of the polythiol composition is further promoted. When the charged mass ratio [alcohol compound/thiourethane resin] is 20 or less, the residual alcohol compound in the reaction mixture can be further suppressed.
• the charged mass ratio [alcohol compound/thiourethane resin] is more preferably 0.30 to 15, still more preferably 0.40 to 10.
• the number of millimoles of the alcohol compound charged with respect to 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. g, more preferably 5.0 mmol/g to 60 mmol/g, particularly preferably 25 mmol/g to 37.5 mmol/g.
• the charged equivalent of the alcohol compound to the thiourethane resin is preferably 1 to 25, more preferably 1.2 to 20, more preferably 1.5-15, particularly preferably 10-15.
• the charged equivalent [alcohol compound/thiourethane resin] is 1 or more, the production of the polythiol composition is further promoted.
• the charge equivalent [alcohol compound/thiourethane resin] is 25 or less, the residual alcohol compound in the reaction mixture can be further suppressed.
• the charged equivalent of the alcohol compound to the thiourethane resin is the number of hydroxy groups in the charged alcohol compound with respect to the total number of thiourethane bonds in the charged thiourethane resin. means ratio.
• the thiourethane resin and the alcohol compound are preferably reacted in the presence of a tertiary amine compound.
• the tertiary amine compound is believed to function as a decomposition aid. There are no particular restrictions on the tertiary amine compound.
• the tertiary amine compound may be a chain amine compound or a cyclic amine compound. Tertiary amine compounds may be used alone or in combination of two or more.
• the thiourethane resin contains the thiourethane resin B described above, it is preferable to react the thiourethane resin and the alcohol compound in the presence of a tertiary amine compound.
• a tertiary amine compound unintended side reactions of the polythiol compound (A2) having at least one or more ester bonds in the molecule, which may occur due to chemical decomposition of the thiourethane resin B, are suppressed, resulting in a highly pure polythiol composition ( S) tends to be obtained.
• 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, still more preferably 200 or less.
• the lower limit of the molecular weight of the tertiary amine compound is, for example, 59 or more, preferably 70 or more.
• the charged mass ratio of the tertiary amine compound to the alcohol compound i.e., charged mass ratio [tertiary amine compound/alcohol compound]
• the charged mass ratio [tertiary amine compound/alcohol compound] is more preferably 0.002 to 1.50, still more preferably 0.004 to 1.20.
• the charge molar ratio of the tertiary amine compound to the alcohol compound can be appropriately adjusted, but is preferably is between 0.001 and 3.00.
• the charge molar ratio [tertiary amine compound/alcohol compound] is more preferably from 0.002 to 2.50, still more preferably from 0.003 to 2.00, still more preferably from 0.004 to 1.00. 50, more preferably 0.004 to 1.00.
• reaction solvents include hydrocarbon compounds having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), ether compounds having 4 to 12 carbon atoms, ketone compounds having 3 to 12 carbon atoms, and 4 carbon atoms. ⁇ 12 ester compounds, C2-C12 alcohol compounds, or C2-C12 nitrile compounds are preferred.
• the compounds used as the reaction solvent may be of one type or two or more types.
• reaction temperature between the thiourethane resin and the alcohol compound can be adjusted as appropriate. It is preferable to react the thiourethane resin and the alcohol compound under temperature conditions (that is, reaction temperature) of 70° C. to 200° C. (more preferably 90° C. to 180° C., still more preferably 100° C. to 170° C.).
• the reaction time between the thiourethane resin and the alcohol compound can be adjusted as appropriate, but is preferably 0.1 hour to 50 hours, more preferably 0.5 hours to 30 hours, and still more preferably 1 hour to 20 hours, particularly preferably 4 to 7 hours.
• a polythiol composition (S) containing two or more polythiol compounds is obtained by reacting the composition X containing the thiourethane resin as described above.
• the polythiol compound contained in the polythiol composition (S) corresponds to at least part of the polythiol compound used for producing the thiourethane resin.
• the polythiol composition (S) contains two or more of the polythiol composition (P) and the polythiol composition (Q). It preferably contains a polythiol compound.
• the polythiol compound contained in the polythiol composition (S) is classified into, for example, a polythiol compound (A1) having no ester bond in the molecule or a polythiol compound (A2) having at least one ester bond in the molecule. and the thiol compounds described above.
• the polythiol composition (S) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of It may contain at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• Components other than the polythiol composition (S) containing two or more polythiol compounds can be obtained by reacting the composition X containing the thiourethane resin.
• a mixture of the polythiol composition (S) and the polycarbamate composition containing the polycarbamate compound or the polyurea composition containing the polyurea compound may be obtained by reacting the composition X containing the thiourethane resin.
• a polyurea composition containing a polyurea compound is obtained, and when a thiourethane resin and an alcohol compound are reacted, a polycarbamate composition containing a polycarbamate compound is obtained.
• a polythiol compound or a derivative thereof obtained by chemically decomposing a thiourethane resin may be partially decomposed by the action of an alcohol compound, an amine compound, or the like.
• the polycarbamate composition containing the polycarbamate compound described above, the polyurea composition containing the polyurea compound, the polythiol compound obtained by chemically decomposing the thiourethane resin or the decomposed product of its derivative, etc. can be converted into the polythiol composition by a known method. It may be separated from (S). Methods of separation include filtration, decantation, extraction, distillation, dissolution, drying (including drying under reduced pressure), purification (eg, column chromatography), and the like. As a separation method, a plurality of methods may be used in combination.
• a method of extracting with an organic solvent or an inorganic solvent capable of dissolving specific components in a mixture containing the polythiol composition (S) and the polycarbamate composition or the polyurea composition can be mentioned.
• an acid, a base, or the like may be used.
• a method for purifying a specific component general purification methods such as column purification, distillation purification, recrystallization purification, and salt extraction are used.
• the production 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). include.
• a step of producing a polythiol composition (T) variation in the composition of the polythiol compound in each production unit is suppressed, and the polythiol composition (T) having a specific composition ratio is produced in each production unit. be able to.
• a polythiol composition (T) is produced by adding at least one polythiol compound contained in the polythiol composition (S) to the polythiol composition (S).
• At least a portion of at least one polythiol compound contained in the polythiol composition (S) is removed from the polythiol composition (S) to produce the polythiol composition (T).
• the composition of the polythiol compound in the polythiol composition (T) is the ratio of the peak area of a specific polythiol compound to the total peak area of all peaks of the polythiol composition, measured by high-performance liquid chromatography as shown in Examples below. , the ratio of the peak area of another polythiol compound to the peak area of a specific polythiol compound, and the like. Using a polythiol composition whose composition is known, a calibration curve showing the relationship between the composition of the polythiol composition and the aforementioned peak area ratio may be prepared.
• the amount of the polythiol compound added to the polythiol composition (S), or the polythiol composition may be determined.
• 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 according to the application of the polythiol composition (T).
• the polythiol compound contained in the polythiol composition (T) is classified into, for example, a polythiol compound (A1) having no ester bond in the molecule or a polythiol compound (A2) having at least one ester bond in the molecule. and the thiol compounds described above.
• the polythiol composition (T) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of It may contain at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• the method for producing a polymerizable composition of the present disclosure includes the polythiol composition (T) obtained by the above-described method for producing a polythiol composition of the present disclosure, and a polyisocyanate composition containing at least one polyisocyanate compound ( and C) to produce a polymerizable composition.
• the method for producing a polymerizable composition of the present disclosure uses a polythiol composition (T) having a specific composition ratio obtained by the method for producing a polythiol composition of the present disclosure.
• T polythiol composition
• various properties e.g., optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.]
• the polymerizable composition obtained by the method for producing a polymerizable composition of the present disclosure is particularly suitable as a composition for producing thiourethane resins for optical materials.
• the polymerizable composition is produced by mixing the polythiol composition (T) and the polyisocyanate composition (C) containing at least one polyisocyanate compound.
• Preferred configurations of the polyisocyanate composition (C) are the same as those of the polyisocyanate composition (A) described above.
• 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) is preferably 0. It is 10 to 10.0, more preferably 0.20 to 5.00, still more preferably 0.50 to 1.50, still more preferably 0.70 to 1.30.
• the molar ratio of the mercapto groups contained in the polythiol composition (T) to the isocyanato groups in the polyisocyanate composition (C) is preferably 0.5 to 3.0. It is more preferably 6 to 2.0, even more preferably 0.8 to 1.3.
• the total charged mass of the polythiol composition (T) and the polyisocyanate composition (C) is not particularly limited.
• the total charged mass is preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, relative to the total amount of the polymerizable composition to be produced.
• the polythiol composition (T) and the polyisocyanate composition (C) When mixing the polythiol composition (T) and the polyisocyanate composition (C), if necessary, mix the polythiol composition (T) and the polyisocyanate composition (C) with other components. good too.
• other components After mixing at least the polythiol composition (T) and the polyisocyanate composition (C), other components may be added to the mixture. These other components include polymerization catalysts, internal release agents, resin modifiers, chain extenders, cross-linking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers. , adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and the like.
• polymerization catalysts include tertiary amine compounds, inorganic or organic acid salts thereof, metal compounds, quaternary ammonium salts, organic sulfonic acids, and the like.
• Acidic phosphate ester can be used as the internal release agent.
• Acidic phosphates include phosphate monoesters and phosphate diesters, each of which can be used alone or in combination of two or more.
• resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, organic acid anhydrides, olefin compounds including (meth)acrylate compounds, and the like.
• the (meth)acrylate compound means at least one of an acrylate compound and a methacrylate compound.
• the above-described ingredients can be mixed according to a conventional method, and the mixing method is not particularly limited.
• the method for producing a cured product of the present disclosure includes a step of producing a polymerizable composition by a method for producing a polymerizable composition of the present disclosure, and a step of obtaining a cured product by curing the polymerizable composition. .
• a cured product is obtained by curing the polymerizable composition.
• Curing of the polymerizable composition can be performed by polymerizing the monomers (for example, the polythiol composition (T) and the polyisocyanate composition (C)) in the polymerizable composition.
• the polymerizable composition may be subjected to treatment such as filtration and degassing.
• the polymerization conditions e.g., polymerization temperature, polymerization time, etc.
• the polymerization conditions include the composition of the composition, the type and amount of monomers in the composition, and the amount of polymerization catalyst in the composition.
• the polymerization temperature include -50°C to 150°C, 10°C to 150°C, and the like.
• the polymerization time is, for example, 1 hour to 200 hours, 1 hour to 80 hours, and the like.
• a cured product may be obtained by subjecting a polymer obtained by polymerization of monomers to a treatment such as annealing.
• Annealing temperatures include 50° C. to 150° C., 90° C. to 140° C., 100° C. to 130° C., and the like.
• the use of the cured product is not particularly limited, and examples include optical materials such as lenses and molded articles other than optical materials.
• the polythiol composition according to the first aspect of the present disclosure comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and a polythiol composition X1 containing at least one selected from the group consisting of It contains at least two polythiol compounds (U) selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane and 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 is obtained, for example, by reacting composition X containing a thiourethane resin as described in the step of producing polythiol composition (S).
• the thiol composition of the present disclosure contains polythiol composition X1 (composition containing polythiol component A described later) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (polythiol component B described later). is preferred.
• a cured product having desired heat resistance and dyeability By containing the polythiol component A and the polythiol component B, a cured product having desired heat resistance and dyeability can be produced. 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.
• the polythiol composition according to the second aspect of the present disclosure comprises 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11- A polythiol component that is at least one selected from the group consisting of dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
• the peak area of the polythiol component A is 30 area % or more and 99 area % or less with respect to the total peak area of the polythiol composition.
• the polythiol composition according to the second aspect may or may not contain a polythiol compound derived from a thiourethane resin (for example, the aforementioned polythiol compound (U)).
• the peak area of the polythiol component A is preferably 10 area% or more and 99 area% or less, more preferably 30 area% or more and 99 area% or less, relative to the total peak area of the polythiol composition.
• the polythiol composition according to the second aspect may contain a polythiol composition (another polythiol composition) other than the polythiol composition X1 and the polythiol composition X2.
• the peak area of other polythiol compositions may be 30 area % or less, or 10 area % or less, relative to the total peak area of the polythiol composition.
• the lower limit of the peak area of other polythiol compositions is not particularly limited as long as it is 0 area % or more.
• the polythiol composition according to the third aspect of the present disclosure comprises 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11- A polythiol component that is at least one selected from the group consisting of dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
• 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.
• the polythiol composition according to the third aspect may or may not contain a polythiol compound derived from a thiourethane resin (for example, the aforementioned polythiol compound (U)).
• the peak area of the polythiol component A is preferably 10 area% or more and 99 area% or less, and preferably 30 area% or more and 99 area% or less, with respect to the total peak area of the polythiol composition X1 and the polythiol composition X2. more preferred.
• the polymerizable composition of the present disclosure includes the aforementioned polythiol composition of the present disclosure and a polyisocyanate composition containing a polyisocyanate compound.
• Preferred forms of the polyisocyanate composition are the same as the preferred forms of the polyisocyanate compositions (A) to (C) described above.
• a set of compositions of the present disclosure includes a polythiol composition of the present disclosure described above and a polyisocyanate composition comprising a polyisocyanate compound.
• a set of compositions can be prepared by mixing the polythiol composition and the polyisocyanate composition to prepare the aforementioned polymerizable compositions of the present disclosure.
• Preferred forms of the polyisocyanate composition are the same as the preferred forms of the polyisocyanate compositions (A) to (C) described above.
• the cured product of the present disclosure is obtained by curing a polymerizable composition obtained by mixing the polythiol composition and the polyisocyanate composition included in the polymerizable composition of the present disclosure described above or the composition set of the present disclosure described above.
• Applications of the cured product of the present disclosure include optical materials (for example, lenses).
• the thiourethane resin raw material composition management system of the present disclosure includes a first registration unit that registers composition information about a recycled thiourethane resin raw material obtained by chemically decomposing the thiourethane resin contained in the collected resin powder. a second registration unit for registering composition information about the thiourethane resin raw material; composition information about the thiourethane resin raw material registered in the second registration unit; and the recycled thiourethane registered in the first registration unit. composition information about the resin raw material;
• composition management system for thiourethane resin raw materials of the present disclosure
• composition management system is a first A registration unit and a second registration unit for registering composition information (hereinafter, also referred to as “composition information (2)”) regarding the thiourethane resin raw material are provided.
• the derivation unit provided in the composition management system uses the composition information (1) and the composition information (2) to provide information on the composition for producing the thiourethane resin raw material from the recycled thiourethane resin raw material (hereinafter referred to as “composition information ( 3)”) is derived.
• composition information (3) By obtaining the composition information (3), it becomes possible to produce a thiourethane resin raw material having a specific composition ratio from the recycled thiourethane resin raw material.
• Recycled thiourethane resin raw material manufactured from thiourethane resin as a starting material depends on the composition of the thiourethane resin, the conditions during decomposition of the thiourethane resin, and the regenerated thiourethane resin raw material in the mixture obtained by decomposing the thiourethane resin.
• the composition of the recycled thiourethane resin raw material varies depending on the separation method and the like. In this way, 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 production of a thiourethane resin raw material having a specific composition ratio.
• each composition information (3) corresponding to the different composition information (1) is obtained,
• a thiourethane resin raw material having a specific composition ratio a thiourethane resin raw material satisfying the specific composition information (2)
• the thiourethane resin contained in the collected resin powder includes a reaction product formed using a polythiol composition containing at least one polythiol compound and a polyisocyanate composition containing at least one polyisocyanate compound. be done.
• the thiourethane resin contained in the resin powder may be one kind of thiourethane resin, or may contain two or more kinds of thiourethane resins.
• a 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 there is a method of reacting the thiourethane resin with an active hydrogen compound, as described later.
• composition information (composition information (1)) on the recycled thiourethane resin raw material includes, for example, composition information on components obtained by chemically decomposing the thiourethane resin, reaction components obtained by further reaction of the components, composition information and the like.
• the various information may be assigned an identification ID, may be associated with the identification ID and various composition information, and may be associated with the identification ID, various composition information, and other information as necessary. may be associated with the information of
• the composition information (1) is derived from a thiourethane resin, compositional information about a polythiol composition comprising a polythiol compound; Compositional information about a polyisocyanate composition containing a polyisocyanate compound, At least one selected from the group consisting of composition information on an intermediate product capable of producing a polythiol composition containing a polythiol compound and composition information on an intermediate product capable of producing a polyisocyanate composition containing a polyisocyanate compound. is preferred.
• polythiol composition containing a polythiol compound Polythiol compounds exemplified in the polythiol compound (A1) having no ester bond in the molecule; A composition containing at least one selected from the polythiol compounds exemplified in the polythiol compound (A2) having at least one or more ester bonds in the molecule;
• polyisocyanate composition containing a polyisocyanate compound A composition containing at least one selected from the polyisocyanate compounds exemplified in the above-mentioned polyisocyanate composition (A) can be mentioned.
• Intermediate products capable of producing a polythiol composition containing a polythiol compound include a component obtained by further reacting or decomposing a polythiol compound produced by chemically decomposing a thiourethane resin.
• the intermediate product capable of producing the polythiol composition is a hydroxy group.
• Intermediate products capable of producing a polyisocyanate composition containing a polyisocyanate compound include a component obtained by further reacting or decomposing a polyisocyanate compound produced by chemically decomposing a thiourethane resin.
• 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.
• an intermediate product capable of forming a polyisocyanate composition includes a polycarbamate composition containing a polycarbamate 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 its derivative may be reacted with phosgene. Thereby, a polyisocyanate composition containing a polyisocyanate compound can be produced.
• the polycarbamate compound may be reacted with an amine compound or the like to obtain a polyamine compound, and then the polyamine compound or its derivative may be reacted with phosgene. Thereby, a polyisocyanate composition containing a polyisocyanate compound can be produced.
• Composition information (2) is compositional information about a polythiol composition comprising a polythiol compound; compositional information about a polyisocyanate composition containing a polyisocyanate compound; At least one selected from the group consisting of composition information on an intermediate product capable of producing a polythiol composition containing a polythiol compound and composition information on an intermediate product capable of producing a polyisocyanate composition containing a polyisocyanate compound. is preferred.
• the recycled thiourethane resin raw material and the thiourethane resin raw material are The aforementioned polythiol composition X1 and It preferably contains at least one selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane.
• composition information (1) and the composition information (2) used to obtain the information (composition information (3)) on the composition for producing the thiourethane resin raw material from the recycled thiourethane resin raw material derived by the lead-out unit are both , compositional information about a polythiol composition comprising a polythiol compound; compositional information about a polyisocyanate composition containing a polyisocyanate compound;
• the composition information is preferably compositional information relating to an intermediate product capable of producing a polythiol composition containing a polythiol compound or compositional information relating to an intermediate product capable of producing a polyisocyanate composition containing a polyisocyanate compound.
• Composition information (3) is (a) may be information on the composition of the resin raw material to be added to the recycled thiourethane resin raw material in order to produce the thiourethane resin raw material; (b) Information on the composition of the resin component 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.
• composition information (1) and composition information (2) are composition information about a polythiol composition containing a polythiol compound
• composition information (3) is a resin component added to the polythiol composition
• the information relates to the composition of a polythiol composition containing a polythiol compound.
• 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 is determined using a chromatographic device such as a high performance liquid chromatograph (HPLC) device.
• HPLC high performance liquid chromatograph
• the collected resin powder is collected in at least one of the eyeglass lens manufacturing process, the eyeglass manufacturing process, and the eyeglass disposal process.
• it may be a mixture of thiourethane resins recovered in at least one of the aforementioned processes.
• the recovered resin powder may contain components other than the thiourethane resin, for example, it may contain components other than the thiourethane resin that can be used in the composition X described above.
• the composition management system of the present disclosure includes a third registration unit that registers information about the collected resin powder, and a fourth registration unit that registers information about a method for chemically decomposing the thiourethane resin contained in the collected resin powder. You may further have a part.
• the composition management system may further include a determination unit that determines whether or not the thiourethane resin contained in the resin powder is subject to recycling based on the information on the resin powder registered in the third registration unit. Often, when the determination unit determines that the thiourethane resin is to be recycled, the acquisition unit acquires information on a method for chemically decomposing the thiourethane resin to be recycled from the fourth registration unit. You may have more.
• the information on the resin powder registered in the third registration unit includes at least one selected from the group consisting of information on the composition of the resin powder, product information corresponding to the resin powder, and information on the source of the resin powder. is preferred.
• Information on the method of chemically decomposing the thiourethane resin contained in the resin powder registered in the 4th registration department includes the composition of the specific thiourethane resin and the composition Information including the combination with the decomposition method of the thiourethane resin suitable for
• Information on the decomposition method includes, for example, information such as the type and amount of active hydrogen compound (e.g., amine compound, alcohol compound, etc.) used to decompose a specific thiourethane resin, other components used for decomposition (e.g., , decomposition aid, solvent, etc.), information such as the amount used, temperature of the decomposition reaction, information such as the reaction time, and the like.
• Information on the decomposition method may include information on a method for separating a specific resin component from a product obtained by decomposing a specific thiourethane resin.
• Methods for separating specific resin components include filtration, decantation, extraction, distillation, dissolution, drying (including drying under reduced pressure), purification (eg column chromatogram), combined use of these, and the like.
• the judging unit judges whether or not the thiourethane resin contained in the resin powder is subject to recycling based on the calculated value of the life cycle assessment using the information on the resin powder registered in the third registration unit. good too. For example, the determination unit determines that the thiourethane resin is to be recycled when the calculated value is equal to or greater than a predetermined value, and the thiourethane resin is recycled when the calculated value is less than the predetermined value. It may be determined to be non-recyclable.
• Life cycle assessment (LCA) calculations can be performed according to standard methods, and there are no particular restrictions. For example, when the collected resin powder is collected in at least one of the spectacle lens manufacturing process, the spectacle manufacturing process, and the spectacle disposal process, the calculated value of LCA is the life of the spectacle lens. It may be determined by considering the entire cycle.
• the thiourethane resin raw material may be produced from the recycled thiourethane resin raw material based on the composition information (3) derived using the composition management system of the present disclosure by the method described later.
• the composition management system 100 which is an embodiment of the present disclosure, can be configured as a hardware device.
• FIG. 1 is a block diagram showing the hardware configuration of a composition management system 100 according to one embodiment of the present disclosure.
• the hardware is not limited to physical hardware, and may be a cloud server in a virtual environment or the like, and functions may be distributed among a plurality of servers.
• 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 section 15, a display section 16, and a communication interface. (I/F) 17.
• CPU Central Processing Unit
• ROM Read Only Memory
• RAM Random Access Memory
• storage 14 an input section 15, a display section 16, and a communication interface. (I/F) 17.
• I/F communication interface.
• the CPU 11 is a central processing unit that executes various programs and controls each section.
• the CPU 11 reads a program from the ROM 12 or the storage 14 and executes the program using the RAM 13 as a work area.
• the CPU 11 performs control of each configuration and various arithmetic processing according to programs stored in the ROM 12 or the storage 14 .
• the ROM 12 stores various programs and various data.
• the RAM 13 temporarily stores programs or data as a work area.
• the storage 14 is configured by a storage device such as a HDD (Hard Disk Drive) or SSD (Solid State Drive), and stores various programs including an operating system and various data.
• HDD Hard Disk Drive
• SSD Solid State Drive
• the ROM 12 may store a program related to determination of recycling, a program related to determination of the decomposition method of the thiourethane resin, and the like, and the storage 14 may store various information.
• the input unit 15 includes a pointing device such as a mouse and a keyboard, and is used for various inputs.
• the display unit 16 is, for example, a liquid crystal display, and displays various information.
• the display unit 16 may employ a touch panel system and function as the input unit 15 .
• the communication interface 17 is an interface for communicating with other devices such as terminals.
• the communication uses, 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).
• FIG. 2 is a diagram showing the configuration of a production system for thiourethane resin raw materials in an embodiment of the present disclosure.
• FIG. 2 shows the functional configuration of the composition management system provided in the manufacturing system.
• the manufacturing system 200 includes a composition management system 100 , a decomposition device 30 , an analysis device 40 and a manufacturing device 50 .
• acquisition, transmission and reception of each information are represented by dotted lines, and supply of various raw materials, products, etc. are represented by solid lines.
• 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 .
• composition information (1) on 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 with the analyzer 40. The information is transmitted from the analyzer 40 to the composition management system 100 and sent to the first registration unit 21. be registered.
• the composition information (1) is composition information about the recycled thiourethane resin raw material obtained by decomposing the resin powder containing the thiourethane resin in the decomposition device 30, and includes the type of the resin powder, the decomposition method of the thiourethane resin, and the like. differ by A plurality of pieces of composition information (1) may be registered in the first registration unit 21. For example, even if the pieces of composition information (1) differ in the type of resin powder, decomposition method of thiourethane resin, etc., good.
• composition information (2) on 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 be the product.
• a plurality of pieces of composition information (2) may be registered in the first registration unit 22 according to differences in consumers, applications, and the like.
• Information about the collected resin powder is registered in the third registration unit 23 .
• Information on the resin powder includes information on the composition of the resin powder, information on products corresponding to the resin powder, information on the source of the resin powder, and the like.
• the information about the 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.
• the fourth registration unit 24 information (information on the decomposition method) on the method of chemically decomposing the thiourethane resin contained in the resin powder is registered.
• the derivation unit 25 uses the composition information (1) registered in the first registration unit 21 and the composition information (2) registered in the second registration unit 22 to obtain a thiourethane resin raw material from the recycled thiourethane resin raw material. Information about the composition (composition information (3)) is derived. If multiple pieces of composition information (1) or composition information (2) are registered, one of the pieces of registration information is selected, and composition information ( 3) should be derived.
• composition information (3) is information on the composition of the resin raw material to be added to the recycled thiourethane resin raw material in order to produce the thiourethane resin raw material
• the composition information (3) is the thiourethane resin raw material that will be the product. It is sufficient if the composition information of the component obtained by subtracting the composition of the recycled thiourethane resin raw material from the composition of is included.
• composition information (3) obtained by the derivation unit 25 is transmitted to the manufacturing apparatus 50.
• the determination unit 26 determines whether or not the thiourethane resin contained in the resin powder is to be recycled. For example, a life cycle assessment (LCA) calculation may be used to determine whether the thiourethane resin is subject to recycling.
• LCA life cycle assessment
• the acquisition unit 27 acquires information on the decomposition method from the fourth registration unit 24 when the determination unit 26 determines that the thiourethane resin is to be recycled.
• the acquired information about the decomposition method is selected based on the information about the resin powder, preferably based on the composition information of the resin powder.
• the information on the decomposition method acquired by the acquisition unit 27 is transmitted to the decomposition device 30 .
• the resin powder determined to be recycled 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 the information on the decomposition method acquired 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 for decomposition, and the like.
• the decomposing device 30 may include a separating section for separating a specific resin component from the product obtained by decomposing the thiourethane resin. A purified recycled thiourethane resin raw material is obtained in the separation unit.
• a portion of the regenerated 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 for analyzing the recycled thiourethane resin raw material. Analysis of the recycled thiourethane resin raw material provides composition information (composition information (1)) on the recycled thiourethane resin raw material.
• the analyzer 40 may be any device capable of obtaining compositional information on the recycled thiourethane resin raw material, and may be equipped with a chromatograph such as a high-performance liquid chromatograph (HPLC), for example.
• HPLC high-performance liquid chromatograph
• the analysis device 40 is equipped with an HPLC device, information on peaks at specific retention times corresponding to resin components that may be contained in the regenerated thiourethane resin raw material may be obtained in advance.
• the type of resin contained in the regenerated thiourethane resin raw material can be specified.
• the ratio of the peak area corresponding to a specific resin component to the total peak area of the resin components contained in the regenerated thiourethane resin raw material may be obtained. Thereby, the ratio of the specific resin component contained in the recycled thiourethane resin raw material can be obtained.
• composition information (1) includes the composition information of the resin components obtained by an HPLC device or the like
• composition information (2) also includes the composition information of the resin components obtained by the HPLC device or the like.
• composition information (3) it is possible to easily derive information (composition information (3)) on the composition for producing the thiourethane resin raw material from the recycled thiourethane resin raw material from the difference between the composition information (1) and the composition information (2). can.
• composition information (1) obtained by the analyzer 40 is transmitted to the composition management system 100 and registered in the first registration unit 21 . Further, based on the composition information (1) and the composition information (2) registered in the second registration unit 22, the composition information (3) is derived.
• 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 by the derivation unit 25 is transmitted to the manufacturing apparatus 50 .
• the manufacturing apparatus 50 includes a control section 51 , a supply section 52 and a manufacturing section 53 . Various processes in the manufacturing apparatus 50 are executed by the CPU.
• the control unit 51 has a function of controlling the supply unit 52 and adjusting the resin raw material supplied to the production unit 53 based on the received composition information (3).
• the supply unit 52 has a configuration for supplying the production unit 53 with the resin raw material used in the production of the thiourethane resin raw material.
• the composition information (3) includes the composition information of the component obtained by subtracting the composition of the recycled thiourethane resin raw material from the composition of the thiourethane resin raw material to be the product, the resin raw material corresponding to the subtracted component is supplied to the manufacturing department 53. supplied.
• the resin raw material supplied to the supply unit 52 may be appropriately determined according to the composition of the recycled thiourethane resin raw material and the composition of the thiourethane resin raw material.
• the manufacturing department 53 is configured to manufacture thiourethane resin raw materials using recycled thiourethane resin raw materials and resin raw materials. For example, a recycled thiourethane resin raw material and a resin raw material are mixed to obtain a thiourethane resin raw material as a product.
• FIG. 4 is a flow chart showing an example of a method for producing a thiourethane resin raw material of the present disclosure. Each step in FIG. 4 may be performed using a thiourethane resin raw material manufacturing system such as the manufacturing system 200 shown in FIG. 2, or may be performed without using a thiourethane resin raw material manufacturing system.
• step S102 it is determined whether or not the thiourethane resin contained in the resin powder is subject to recycling based on the information on the resin powder. At this time, it may be determined whether or not the thiourethane resin contained in the resin powder is subject to recycling based on the calculated value of the life cycle assessment using the information on the resin powder.
• step S104 When it is determined in step S104 that the thiourethane resin is to be recycled, information on the decomposition method of the thiourethane resin to be recycled is determined.
• step S106 the thiourethane resin targeted for recycling is decomposed.
• a recycled thiourethane resin raw material is obtained.
• composition information (composition information (1)) on the recycled thiourethane resin raw material is acquired.
• the composition information relating to the obtained recycled thiourethane resin raw material may be managed, and the composition information relating to the thiourethane resin raw material (composition information (2)) may be managed.
• step S110 information for manufacturing urethane resin raw materials is acquired. Specifically, based on the composition information (1) and the composition information (2), information on the composition (composition information (3 )).
• step S112 a thiourethane resin raw material is produced from the regenerated thiourethane resin raw material obtained in step S106 based on the composition information (3).
• room temperature means 25°C unless otherwise specified.
• Example 1 After manufacturing a molded body containing thiourethane resin R1, the manufactured molded body was cut to obtain thiourethane resin powder R1.
• a method using an alcohol compound was determined in consideration of the composition of the thiourethane resin powder R1.
• the thiourethane resin powder R1 was decomposed using an alcohol compound to obtain a polythiol composition containing a polythiol compound. Details are given below.
• the polymerizable composition was filtered under reduced pressure with a PTFE (polytetrafluoroethylene) filter, and then sufficiently degassed under a reduced pressure of 600 Pa until foaming was no longer observed.
• the degassed polymerizable composition was injected between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven and the temperature inside the oven was set at 10°C. Next, the temperature inside the oven was raised from 10° C. to 120° C. over 38 hours.
• the monomers (polyisocyanate composition and polythiol composition) in the polymerizable composition after degassing are polymerized, and a molded body containing the thiourethane resin R1 (that is, polymerizable A cured product of the composition) was formed.
• the inside of the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and then the molded body was removed from the pair of glass molds to obtain a molded body.
• thiourethane resin powder R1 (Production of thiourethane resin powder R1) A lens was manufactured by cutting the molded body obtained above. The cutting powder generated at this time was collected to obtain thiourethane resin powder R1 (that is, powder containing thiourethane resin R1).
• polythiol composition (S) containing polythiol compound A1 and polythiol compound A2.
• polythiol composition containing the polythiol compound A1 and the polythiol composition containing the polythiol compound A2 may be separated using the aforementioned separation technique.
• the polythiol composition containing the separated polythiol compound A1 or the polythiol composition containing the polythiol compound A2 was used as the main component of the specific polythiol component 1 obtained in Experimental Example 2 described later, or the experiment described later.
• a polythiol composition (S) may be obtained by mixing with a polythiol composition containing the specific polythiol component 2 obtained in Example 3 as a main component.
• the molded article containing the thiourethane resin R2 (i.e., the cured product of the polymerizable composition) was carried out in the same manner as in Experimental Example 1, except that the temperature in the oven was raised from 25°C to 120°C over 24 hours. was formed to obtain a molded body.
• thiourethane resin powder R2 (Production of thiourethane resin powder R2) A lens was manufactured by cutting the molded body obtained above. The cutting powder generated at this time was collected to obtain thiourethane resin powder R2 (that is, powder containing thiourethane resin R2).
• the washed thiourethane resin powder R2 was entirely charged into a 500 mL flask equipped with a cooling tube, and monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (14.81 g; 0.242 mol) and toluene 361 g were added. was added, and the reaction mixture containing the polythiol composition was obtained by heating and stirring at 100° C. for 3 hours.
• the resulting reaction mixture was cooled to 30° C. and then filtered to remove solids.
• the resulting filtrate was washed twice with 150 mL of 1N 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.
• a silica gel column was used to remove highly polar by-products, and then the toluene was distilled off using a rotary evaporator.
• the resulting mixture was subjected to removal of low boiling point components with a vacuum pump and filtration through a 3 micron PTFE membrane filter in this order to give 4,8-dimercaptomethyl-1,11-dimercapto-3, 6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6 ,9-trithiaundecane (specific polythiol component 1) was obtained.
• a molded article containing the thiourethane resin R3 (that is, a cured product of the polymerizable composition) was formed in the same manner as in Experimental Example 1 to obtain a molded article.
• a polyisocyanate composition containing m-xylylene diisocyanate (XDI) was measured by gas chromatography under each of the GC conditions 1 and 2 described above.
• the peak area of the compound (N1) is 0.20 ppm or more (specifically 600 ppm) with respect to the peak area 1 of xylylene diisocyanate
• the peak area of the compound (N2) is 0.05 ppm or more (specifically 18 ppm) with respect to the peak area 1 of xylylene diisocyanate
• the peak area of compound (N3) was 0.10 ppm or more (specifically 100 ppm) with respect to the peak area 1 of xylylene diisocyanate.
• thiourethane resin powder R3 (Production of thiourethane resin powder R3) A lens was manufactured by cutting the molded body obtained above. The cutting powder generated at this time was collected to obtain thiourethane resin powder R3 (that is, powder containing thiourethane resin R3).
• the washed thiourethane resin powder R3 was entirely charged into a 500 mL flask equipped with a cooling tube, and monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (81 g; 1.326 mol) and toluene 386 g were added.
• monoethanolamine manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• toluene 386 g were added.
• the reaction mixture containing the polythiol composition was obtained by heating and stirring at 100° C. for 3 hours.
• the resulting reaction mixture was cooled to 30° C. and then filtered to remove solids.
• the resulting filtrate was washed twice with 150 mL of 1N 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.
• a silica gel column was used to remove highly polar by-products, and then the toluene was distilled off using a rotary evaporator.
• a polythiol composition (S) is obtained.
• monoethanolamine was used to separately chemically decompose the thiourethane resin powder R2 and the thiourethane resin powder R3, but the present disclosure is not limited to this configuration.
• a mixed powder obtained by mixing thiourethane resin powder R2 and thiourethane resin powder R3 may be chemically decomposed using an amine compound such as monoethanolamine or an alcohol compound.
• the proportion (% by area) of polythiol component A in the polythiol composition refers to a mixed polythiol obtained by mixing polythiol composition AX and polythiol composition BX, measured by high performance liquid chromatography under the following conditions. means the ratio (area %) of the peak area of the polythiol component A to the total peak area of the polythiol components A and B1 to B3.
• the proportion (% by mass) of the polythiol composition AX means the proportion (% by mass) of the polythiol composition AX in the sum of the masses of the polythiol composition AX and the polythiol composition BX.
• the ratio (% by mass) of the polythiol composition AX is measured by high performance liquid chromatography under the following conditions. , the ratio (% area) of the peak area of the polythiol component A to the total peak area of the polythiol components A and B1 to B3 in the polythiol composition. Then, for the mixed polythiol obtained by mixing the polythiol composition AX and the polythiol composition BX whose mass ratio is unknown, the peak area ratio (area%) of the polythiol component A was determined by high performance liquid chromatography under the following conditions.
• the ratio (% by mass) of the polythiol composition AX may be obtained based on a calibration curve created from the values of the ratio (% by area).
• the ratio (% by mass) of the polythiol composition BX and the high performance liquid chromatography under the following conditions were measured.
• a calibration curve may be created from the ratio (area %) of the total peak area of the polythiol components B1 to B3 to the total peak area of the polythiol components A and B1 to B3 in the polythiol composition.
• the mixed polythiol obtained by mixing the polythiol composition AX and the polythiol composition BX whose mass ratio is unknown is subjected to high-performance liquid chromatography under the following conditions. %), and the ratio (% by mass) of the polythiol composition BX may be calculated based on a calibration curve created from the values of the ratio (area %).
• polythiol component B1 to A polythiol composition BX containing B3 was mixed at the ratio shown in Table 1 and analyzed by high performance liquid chromatography.
• the ratio of polythiol component A was as shown in Table 1 below.
• the proportion (% by mass) of the polythiol composition AX in any mixture of the polythiol composition AX and the polythiol composition BX can be expressed by the following formula (1).
• Proportion of polythiol composition AX (% by mass) 100 ⁇ (0.0102 ⁇ ratio of polythiol component A (% by area) ⁇ 0.0317).
• polythiol composition AX was added to the polythiol composition of Experimental Example 13 at the mixing ratio shown in Table 3 to prepare 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 ratio of polythiol composition AX was measured by calculating with a calibration curve. Table 3 shows the results.
• the composition (51.6 parts by mass) and the polythiol composition (48.4 parts by mass) prepared in Experimental Example 13 were added and mixed with stirring at room temperature for 1 hour to obtain a transparent homogeneous solution, a polymerizable composition. got Next, the polymerizable composition was filtered under reduced pressure with a PTFE (polytetrafluoroethylene) filter, and then sufficiently degassed under a reduced pressure of 600 Pa until foaming was no longer observed. The degassed polymerizable composition was injected between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven and the temperature inside the oven was set to 25°C. Next, the temperature inside the oven was raised from 25° C. to 120° C. over 24 hours.
• PTFE polytetrafluoroethylene
• the monomers (polyisocyanate compound and polythiol composition) in the polymerizable composition after degassing are polymerized, and the molded article containing the thiourethane resin R4 (that is, the polymerizable composition A hardened product) was formed.
• the inside of the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and then the molded body was removed from the pair of glass molds to obtain a molded body.
• the resulting molded article had good transparency, no distortion, and a good appearance.
• a performance test was performed on the molded article obtained above.
• the performance test items were optical physical properties (refractive index and Abbe number), heat resistance, and hue. Each test was carried out by the following test methods.
• ⁇ Refractive index (ne), Abbe number ( ⁇ e) Using a Shimadzu Pulfrich refractometer KPR-30, the refractive index (ne, nF′, nC′) were measured, and the refractive index (ne) and Abbe number ( ⁇ e) were obtained.
• thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, the glass transition temperature (Tg) is measured by the TMA penation method (50 g load, pin tip 0.5 mm ⁇ , temperature increase rate 10 ° C./min), and is an index of heat resistance. and ⁇ specific gravity: Measured by the Archimedes method. Table 4 shows the results.
• the composition can be adjusted by analyzing a polythiol composition whose composition is unknown and adding a known polythiol compound or a polythiol composition with a known composition to a polythiol composition whose composition is known, and a specific composition It was shown that a polythiol composition having can be produced with good reproducibility. Furthermore, by using a polythiol composition having a specific composition, it was possible to produce molded articles with small variations in various properties with good reproducibility.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Sustainable Development (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Polyurethanes Or Polyureas (AREA)

Priority Applications (2)

Applications Claiming Priority (4)

Publications (1)

Family

ID=87564493

Family Applications (1)

Country Status (2)

Citations (3)

• 2023
  • 2023-02-09 JP JP2023580323A patent/JPWO2023153484A1/ja active Pending
  • 2023-02-09 WO PCT/JP2023/004438 patent/WO2023153484A1/ja active Application Filing

Patent Citations (3)

Also Published As

Similar Documents

Legal Events