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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/06—Polythioethers from cyclic thioethers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts

Definitions

• This disclosure relates to polymerizable compositions, cured products, optical materials, eyeglass lenses, compounds, methods for producing polymerizable compositions, and resins.
• Plastic materials with high refractive indexes are becoming increasingly used as optical materials such as eyeglass lenses because they are lighter and less likely to break than inorganic materials such as glass, and can be dyed.
• plastic materials for optical materials include acrylic resins, polycarbonates, thiourethane resins, and episulfide resins, and of these, thiourethane resins and episulfide resins are known as plastic materials that can achieve a high refractive index (see, for example, JP 2019-15922 A).
• Optical materials containing resins generally contain ultraviolet absorbers (UVA) to prevent deterioration due to ultraviolet rays.
• UVA ultraviolet absorbers
• UV absorbers may dissolve out of the resin, and many of the compounds generally used as ultraviolet absorbers are persistent and there are concerns about their accumulation in living organisms, so in recent years they have become substances subject to environmental regulations. Therefore, measures to suppress the release of ultraviolet absorbers from resins have been studied.
• an object of one aspect of the present disclosure is to provide a polymerizable composition that can give a resin in which release of an ultraviolet absorber is suppressed, a method for producing the same, and a cured product, an optical material, and a spectacle lens obtained using the polymerizable composition.
• Another aspect of the present disclosure has an object to provide a compound from which a resin in which release of an ultraviolet absorber is suppressed can be obtained, and a resin in which release of an ultraviolet absorber is suppressed.
• Means for solving the above problems include the following aspects.
• ⁇ 1> At least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound, A polythiol compound, A polymerizable composition comprising a reaction product of a compound represented by the following general formula (1) and a polythiol compound:
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is a functional group containing an ethylenically unsaturated double bond.
• the polyiso(thio)cyanate compound is at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate,
• the polythiol compound is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)
• ⁇ 4> A cured product of the polymerizable composition according to ⁇ 1>.
• ⁇ 5> An optical material comprising the cured product according to ⁇ 4>.
• ⁇ 6> A spectacle lens comprising the optical material according to ⁇ 5>.
• ⁇ 7> A compound which is a reaction product of a compound represented by the following general formula (1) and a polythiol compound:
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is a functional group containing an ethylenically unsaturated double bond.
• Ra8> A compound having a structure represented by the following general formula (2) and a thiol group:
• Ra is a monovalent hydrocarbon group or a halogen
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• R2 is a hydrogen atom or a monovalent hydrocarbon group
• n3 is 0 or 1
• * is a bonding position.
• the present disclosure provides a polymerizable composition that can yield a resin in which the release of an ultraviolet absorber is suppressed, a method for producing the same, and a cured product, optical material, and eyeglass lens obtained using the polymerizable composition.
• the present disclosure provides a compound that can yield a resin in which the release of an ultraviolet absorber is suppressed, and a resin in which the release of an ultraviolet absorber is suppressed.
• a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• Polymerizable composition One embodiment of the present disclosure comprises: At least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound; A polythiol compound,
• the polymerizable composition includes a reaction product of a compound represented by the following general formula (1) and a polythiol compound.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is a functional group containing an ethylenically unsaturated double bond.
• the polymerizable composition of the present disclosure contains, as polymerizable components, at least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound (hereinafter also referred to as a first component), and a polythiol compound (hereinafter also referred to as a second component).
• a resin containing a thiourethane structure can be obtained by reacting an iso(thio)cyanate group, which is a polymerizable functional group of a polyiso(thio)cyanate compound, with a thiol group, which is a polymerizable functional group of a polythiol compound.
• a resin containing a sulfide structure can be obtained by reacting an episulfide group, which is a polymerizable functional group of a polyepisulfide compound, with a thiol group, which is a polymerizable functional group of a polythiol compound.
• the resin (thiourethane resin or episulfide resin) obtained by the polymerization reaction between the first component and the second component has a high refractive index and can be suitably used in applications requiring a high refractive index, such as optical materials.
• the polymerizable composition of the present disclosure contains a reaction product of a compound represented by general formula (1) and a polythiol compound (hereinafter also referred to as a reactive UVA) in addition to the first component and the second component.
• the reaction product between the compound represented by general formula (1) and the polythiol compound is formed by the reaction of the functional group represented by X in general formula (1) with one of the multiple thiol groups contained in the polythiol compound. Therefore, this reaction product has a thiol group that has not reacted with the functional group represented by X in general formula (1) among the multiple thiol groups contained in the polythiol compound. That is, the reactive UVA has the property of reacting with the first component contained in the polymerizable composition.
• the molecules functioning as UVA are bound to the polymer structure formed by the polymerization reaction of the polymerizable component, and as a result, the molecules functioning as UVA are inhibited from being released outside the resin.
• the specific molecular structure of the compound represented by general formula (1) is not particularly limited as long as it exhibits UVA properties.
• Ra is a monovalent hydrocarbon group or a halogen atom.
• the monovalent hydrocarbon group represented by Ra include an alkyl group having 1 to 3 carbon atoms.
• the halogen atom represented by Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Ra is preferably a halogen atom, and more preferably a chlorine atom or a bromine atom.
• n1 represents the number of Ra and is a number from 0 to 4.
• n1 is preferably an integer from 0 to 2, and more preferably 0 or 1. When the number of Ra is 2 or more, the 2 or more Ra may be the same or different.
• Rb is a monovalent group containing no ethylenically unsaturated double bond.
• Examples of the monovalent group not containing an ethylenically unsaturated double bond represented by Rb include a monovalent hydrocarbon group, an alkoxy group, and a monovalent group containing an ester bond.
• the monovalent hydrocarbon group represented by Rb may be an alkyl group having 1 to 10 carbon atoms.
• the alkyl group may be linear or branched and may have a substituent.
• An example of the substituent is a phenyl group.
• the alkoxy group represented by Rb includes an alkoxy group consisting of an alkyl group having 1 to 10 carbon atoms and an oxygen atom.
• the alkyl group may be linear or branched and may have a substituent.
• An example of the substituent is a phenyl group.
• Rc is an alkylene group having 1 to 10 carbon atoms
• Rd is an alkyl group having 1 to 10 carbon atoms.
• the alkylene group or alkyl group may be linear or branched, and may have a substituent.
• An example of the substituent is a phenyl group.
• Rb is preferably a monovalent hydrocarbon group, and more preferably a hydrocarbon group of Sp3 (for example, a tert-butyl group).
• Rb is preferably an alkoxy group having 3 or more carbon atoms.
• n2 represents the number of Rb and is a number from 0 to 3.
• n2 is preferably an number from 0 to 2, and more preferably 0 or 1. When the number of Rb is 2 or more, the two or more Rb may be the same or different.
• R1 is a divalent hydrocarbon group.
• Examples of the divalent hydrocarbon group represented by R1 include an alkylene group or an aralkylene group having 1 to 10 carbon atoms.
• the alkylene group may be linear or branched, and may contain a cyclic structure.
• the position of R 1 on the aromatic ring may be the para-position, meta-position or ortho-position relative to the OH group.
• X is a functional group containing an ethylenically unsaturated double bond.
• the functional group containing an ethylenically unsaturated double bond represented by X is not particularly limited as long as it is a functional group capable of reacting with a thiol group.
• Specific examples of X include a vinyl group, an acryloyloxy group, and a methacryloyloxy group.
• the type of polythiol compound to be reacted with the compound represented by general formula (1) is not particularly limited. For example, it may be selected from the polythiol compounds described below.
• reaction product between a compound represented by general formula (1) and a polythiol compound is a compound having a structure represented by the following general formula (2) and a thiol group.
• Ra, n1, Rb, n2 and R1 are the same as those of Ra, n1, Rb, n2 and R1 in the general formula (1).
• R2 is a hydrogen atom or a monovalent hydrocarbon group, n3 is 0 or 1, and * is a bonding position.
• R2 is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group.
• the polymerizable composition may contain one or more types of reactive UVAs. That is, the polythiol compound reacted with the compound represented by general formula (1) may be one type or two or more types, and the compound represented by general formula (1) reacted with the polythiol compound may be one type or two or more types.
• the polythiol compound reacted with the compound represented by general formula (1) may be the same as or different from the polythiol compound contained as a polymerizable component in the polymerizable composition.
• the amount of the compound represented by formula (1) contained in the polymerizable composition is not particularly limited and can be selected depending on the application of the polymerizable composition, etc. From the viewpoint of obtaining sufficient ultraviolet absorbing performance, the amount of the compound represented by general formula (1) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, even more preferably 0.5 part by mass or more, and particularly preferably 1.0 part by mass or more, relative to 100 parts by mass of the total mass of the polymerizable components.
• the amount of the compound represented by general formula (1) is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less, relative to 100 parts by mass of the total mass of the polymerizable components.
• the above “amount of the compound represented by general formula (1)” does not include the amount of the polythiol compound that has reacted with the compound represented by general formula (1).
• a polyiso(thio)cyanate compound means a compound having two or more isocyanate groups or isothiocyanate groups in one molecule.
• the polymerizable composition may contain only one type of polyiso(thio)cyanate compound, or two or more types of polyiso(thio)cyanate compounds.
• the polyiso(thio)cyanate compound may include a dimer, a trimer, or a prepolymer.
• Examples of these polyiso(thio)cyanate compounds include the compounds exemplified in WO 2011/055540.
• polyiso(thio)cyanate compound examples include an aliphatic polyiso(thio)cyanate compound, an alicyclic polyiso(thio)cyanate compound, an aromatic polyiso(thio)cyanate compound, and a heterocyclic polyiso(thio)cyanate compound.
• the composition may contain one or more types of polyiso(thio)cyanate compounds.
• Alicyclic polyiso(thio)cyanate compounds refer to polyiso(thio)cyanate compounds that contain an alicyclic structure and may contain a heterocyclic structure.
• Aromatic polyiso(thio)cyanate compounds refer to polyiso(thio)cyanate compounds that contain an aromatic structure and may contain an alicyclic structure and a heterocyclic structure.
• Heterocyclic polyiso(thio)cyanate compounds refer to polyiso(thio)cyanate compounds that contain a heterocyclic structure and do not contain an alicyclic structure or an aromatic structure.
• the polyiso(thio)cyanate compound preferably includes at least one selected from the group consisting of an aliphatic polyiso(thio)cyanate compound, an alicyclic polyiso(thio)cyanate compound, an aromatic polyiso(thio)cyanate compound, and a heterocyclic polyiso(thio)cyanate compound.
• the polyiso(thio)cyanate compound preferably includes at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, 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; More preferably, the mixture contains at least one selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-h
• a polyepisulfide compound means a compound having two or more episulfide groups in one molecule.
• the polymerizable composition may contain only one type of polyepisulfide compound, or two or more types of polyepisulfide compounds.
• Specific examples of the polyepisulfide compound include compounds represented by the following formula:
• Y represents a linear divalent hydrocarbon group having 1 to 4 carbon atoms, a branched divalent hydrocarbon group having 2 to 4 carbon atoms, a cyclic divalent hydrocarbon group having 3 to 6 carbon atoms, a 1,4-dithiane group, an arylene group, or an aralkylene group; m represents an integer of 0 to 2; and n represents an integer of 0 to 3. Y may contain a substituent or may be unsubstituted.
• Y preferably represents a linear divalent hydrocarbon group having 1 to 4 carbon atoms, a branched divalent hydrocarbon group having 2 to 4 carbon atoms, or a cyclic divalent hydrocarbon group having 3 to 6 carbon atoms, and more preferably represents a linear divalent hydrocarbon group having 1 to 4 carbon atoms.
• m preferably represents 0 or 1, and more preferably represents 0.
• n preferably represents 0 or 1, and more preferably represents 1.
• the polyepisulfide compound preferably contains at least one selected from the group consisting of bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) disulfide, and 2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane.
• the polyepisulfide compound has a refractive index of 1.60 to 1.80 for sodium D lines (i.e., light with a wavelength of 589.3 nm) at 20°C.
• a polythiol compound means a compound having two or more thiol groups in one molecule.
• the composition may contain one type of polythiol compound or two or more types of polythiol compounds.
• polythiol compounds include the compounds exemplified in WO 2016/125736.
• the polythiol compound may be 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl ...
• the compound contains at least one selected from the group consisting of bis(mercaptomethylthio)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane, More preferably, the monomer comprises at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-
• the polythiol compound has a refractive index of 1.60 to 1.80 for sodium D lines (i.e., light with a wavelength of 589.3 nm) at 20°C.
• the polymerizable composition may contain other ingredients in addition to the polymerizable component and the reactive UVA.
• other components include a polymerization catalyst, an internal release agent, a resin modifier, a base generator, a chain extender, a crosslinking agent, a radical scavenger, a light stabilizer, an antioxidant, an oil-soluble dye, a filler, an adhesion improver, an antibacterial agent, an antistatic agent, a dye, a fluorescent brightening agent, a fluorescent pigment, and an inorganic pigment.
• polymerization catalysts include tertiary amine compounds, inorganic or organic acid salts of tertiary amine compounds, metal compounds, quaternary ammonium salts, and organic sulfonic acids.
• internal release agents include acidic phosphate esters.
• acidic phosphate esters include monophosphate esters and diphosphate esters, and each can be used alone or in combination of two or more types.
• resin modifiers include alcohol compounds, amine compounds, epoxy compounds, organic acids or their anhydrides, (meth)acrylate compounds, olefin compounds, etc.
• the total content thereof may be 0.1 ppm by mass to 70% by mass, 1 ppm by mass to 30% by mass, 10 ppm by mass to 10% by mass, or 0.1% by mass to 5% by mass, based on the total mass of the polymerizable composition.
• the cured product is a cured product of the above-mentioned polymerizable composition.
• the cured product of the present disclosure is in a state where the molecule functioning as UVA is bonded to a polymer structure formed by a polymerization reaction of a polymerizable component. Therefore, the release of the component functioning as UVA to the outside is suppressed.
• the cured product of the present disclosure includes a polymer structure formed by a polymerization reaction of at least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound as a polymerizable component with a polythiol compound, and therefore has a high refractive index and excellent transparency.
• the cured product of the present disclosure can be obtained, for example, by heating the polymerizable composition at a temperature at which a polymerization reaction of the polymerizable component occurs.
• the cured product of the present disclosure has photocurability, the cured product can be obtained by irradiating the polymerizable composition with light having a wavelength at which a polymerization reaction of the polymerizable component occurs. Heating and light irradiation may be combined.
• optical materials and eyeglass lenses One embodiment of the present disclosure is an optical material including the cured product described above. Specific examples of optical materials include optical adhesives, coatings, optical waveguides, films, lenses, anti-reflective films, microlenses, microlens arrays, wafer-level lenses, imaging lenses for cameras (such as vehicle-mounted cameras, digital cameras, PC cameras, mobile phone cameras, and surveillance cameras), eyeglass lenses, light beam focusing lenses, light diffusing lenses, and camera flash lenses.
• a spectacle lens comprising the optical material described above.
• One embodiment of the present disclosure is a compound that is a reaction product of a compound represented by the following general formula (1) and a polythiol compound.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is a functional group containing an ethylenically unsaturated double bond.
• One embodiment of the present disclosure is a compound having a structure represented by the following general formula (2) and a thiol group.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• R2 is a hydrogen atom or a monovalent hydrocarbon group
• n3 is 0 or 1
• * is a bonding position.
• the compounds disclosed herein are suitable for use in the manufacture of resins obtained by curing polymerizable components or articles containing the same.
• details and preferred aspects of the compounds disclosed herein please refer to the details and preferred aspects of the reactive UVA contained in the polymerizable composition described above.
• One embodiment of the present disclosure includes a method for preparing a mixture comprising the steps of preparing a mixture of the compound of the present disclosure and a polythiol compound; and mixing the mixture with at least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound.
• the above method produces a cured product that suppresses UVA emission.
• the details and preferred aspects of each compound used in the method of the present disclosure are the same as those of each compound described above.
• the method for preparing a mixture containing the compound of the present disclosure i.e., a reaction product of the compound represented by general formula (1) and a polythiol compound
• a polythiol compound i.e., a reaction product of the compound represented by general formula (1) and a polythiol compound
• a compound represented by general formula (1) may be mixed with an excess amount of a polythiol compound relative to the compound represented by general formula (1), and placed under conditions in which X in general formula (1) reacts with a thiol group, thereby obtaining a mixture in which a portion of the polythiol compound has reacted with the compound represented by general formula (1).
• the method for mixing the mixture containing the compound of the present disclosure and the polythiol compound with at least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound is not particularly limited.
• a polythiol compound may be further mixed in this step.
• ⁇ resin ⁇ One embodiment of the present disclosure is a resin having a structure represented by the following general formula (2):
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group not containing an ethylenically unsaturated double bond
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• R2 is a hydrogen atom or a monovalent hydrocarbon group
• n3 is 0 or 1
• * is a bonding position.
• the resin disclosed herein has molecules that function as UVA bound to the polymer structure. This suppresses the emission of UVA compared to when the molecules that function as UVA are not bound to the polymer structure.
• the type of resin of the present disclosure is not particularly limited. From the viewpoint of obtaining a high refractive index, the resin of the present disclosure preferably contains at least one selected from a thiourethane structure and a sulfide structure.
• Example 1 Into the reactor at 25 ° C., 3.0 parts by mass of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd., structure below) as an ultraviolet absorber, 160.0 parts by mass of toluene, and 96.0 parts by mass of polythiol composition (A) were charged. Furthermore, under a nitrogen atmosphere, 0.55 parts by mass of 2,2'-azobis(isobutyronitrile (AIBN, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a radical reaction initiator was charged at 25 ° C. and stirred. The temperature was raised from 25 ° C. to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours. The disappearance of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol was confirmed by HPLC analysis.
• the water layer was separated by a liquid separation operation to obtain a toluene extract.
• This toluene extract was washed three times with 80 parts by mass of water at 40 ° C. to obtain a toluene solution of a polythiol composition.
• the toluene was removed from the obtained toluene solution by a rotary evaporator.
• the obtained mixture was subjected to removal of low boiling point components by a vacuum pump and filtration by a 3 micron PTFE membrane filter in this order to obtain 91.9 parts by mass of a polythiol/UVA composition in which a part of the polythiol compound had reacted with an ultraviolet absorber.
• the content of UVA in the entire polythiol/UVA composition was 3.3% by mass.
• the obtained polymerizable composition was degassed at 600 Pa for 1 hour and then filtered through a 1 ⁇ m Teflon (registered trademark) filter.
• the filtered polymerizable composition was poured into a mold consisting of a pair of glass plates fixed with tape. This mold was placed in an oven, and the temperature inside the oven was raised from 10°C to 120°C over 38 hours to harden the polymerizable composition.
• the hardened product was removed from the mold and annealed at 120°C for 2 hours to obtain a flat resin molded product with a thickness of 3.0 mm.
• Example 2 Into the reactor at 25 ° C., 0.75 parts by mass of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (Tokyo Chemical Industry Co., Ltd.) as an ultraviolet absorber, 40.0 parts by mass of toluene, and 24.7 parts by mass of polythiol composition (B) were charged. Further, under a nitrogen atmosphere, 0.046 parts by mass of 2,2'-azobis(isobutyronitrile) (AIBN, Fujifilm Wako Pure Chemical Industries, Ltd.) as a radical reaction initiator was charged at 25 ° C. and stirred. The temperature was raised from 25 ° C. to 80 ° C., and the reaction was carried out at 80 ° C.
• 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol Tokyo Chemical Industry Co., Ltd.
• 40.0 parts by mass of toluene 40.0 parts by mass of toluene,
• toluene 100 parts by mass of toluene was added, and 40 parts by mass of 35% hydrochloric acid was added and stirred at 40 ° C.
• the water layer was separated by a liquid separation operation to obtain a toluene extract.
• This toluene extract was washed three times with 40 parts by mass of water at 40 ° C. to obtain a toluene solution of a polythiol composition.
• the toluene was removed from the obtained toluene solution by a rotary evaporator.
• the obtained mixture was subjected to removal of low boiling point components by a vacuum pump and filtration by a 3 micron PTFE membrane filter in this order, to obtain 20.6 parts by mass of a polythiol/UVA composition in which a part of the polythiol compound had reacted with an ultraviolet absorber.
• the content of UVA in the entire polythiol/UVA composition was 3.6% by mass.
• a polymerizable composition was prepared in the same manner as in Example 1, except that the amount of m-xylylene diisocyanate was changed to 51 parts by mass and the amount of polythiol/UVA composition was changed to 49 parts by mass, and a resin molded body was obtained.
• Example 3 Into the reactor at 25 ° C., 1.50 parts by mass of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (manufactured by Tokyo Chemical Industry Co., Ltd.; ultraviolet absorber), 40.0 parts by mass of toluene, and 23.9 parts by mass of polythiol composition (C) were charged. Furthermore, under a nitrogen atmosphere, 0.092 parts by mass of 2,2'-azobis(isobutyronitrile) (AIBN, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was charged as a radical reaction initiator at 25 ° C. and stirred. The temperature was raised from 25 ° C.
• AIBN 2,2'-azobis(isobutyronitrile
• the toluene was removed from the obtained toluene solution by a rotary evaporator.
• the obtained mixture was subjected to removal of low boiling point components by a vacuum pump and filtration by a 3 micron PTFE membrane filter in this order to obtain 22.8 parts by mass of a polythiol/UVA composition in which a part of the polythiol compound had reacted with an ultraviolet absorber.
• the content of UVA in the entire polythiol/UVA composition was 6.6% by mass.
• a polyisocyanate composition mainly composed of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 0.06 parts by mass of dibutyltin dichloride as a curing catalyst, and 0.10 parts by mass of an acidic phosphate ester (Zereck UN, Stepan) as an internal mold release agent were mixed and dissolved at 20°C.
• Example 4 Into the reactor at 25 ° C., 0.60 parts by mass of 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol (Tokyo Chemical Industry Co., Ltd.) as an ultraviolet absorber, 15.0 parts by mass of toluene, and 5.0 parts by mass of polythiol composition (B) were charged. Further, 0.10 parts by mass of 2,2'-azobis(isobutyronitrile) (AIBN, Fujifilm Wako Pure Chemical Industries, Ltd.) as a radical reaction initiator was charged at 25 ° C. under a nitrogen atmosphere and stirred. The temperature was raised from 25 ° C. to 80 ° C., and the reaction was carried out at 80 ° C. for 6 hours.
• 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol Tokyo Chemical Industry Co., Ltd.
• AIBN 2,2'-azobis(isobutyronitrile)
• toluene 30 parts by mass of toluene was added, and 7.0 parts by mass of 35% hydrochloric acid was added and stirred at 40 ° C.
• the water layer was separated by a liquid separation operation to obtain a toluene extract.
• This toluene extract was washed three times with 10 parts by mass of water at 40 ° C. to obtain a toluene solution of a polythiol composition.
• the toluene was removed from the obtained toluene solution by a rotary evaporator.
• the obtained mixture was subjected to removal of low boiling point components by a vacuum pump and filtration by a 3 micron PTFE membrane filter in this order to obtain 2.7 parts by mass of a polythiol/UVA composition in which a part of the polythiol compound had reacted with an ultraviolet absorber.
• the content of UVA in the entire polythiol/UVA composition was 22% by mass.
• the obtained polymerizable composition was degassed at 600 Pa for 1 hour and then filtered through a 1 ⁇ m Teflon (registered trademark) filter.
• the filtered polymerizable composition was poured into a mold consisting of a pair of glass plates fixed with tape. This mold was placed in an oven, and the temperature inside the oven was raised from 10°C to 120°C over 20 hours to harden the polymerizable composition.
• the cured product was removed from the mold and annealed at 120°C for 2 hours to obtain a flat resin molded product with a thickness of 3.0 mm.
• Example 5 Into a reactor at 25 ° C., 0.63 parts by mass of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (Tokyo Chemical Industry Co., Ltd., structure below) as an ultraviolet absorber, 30.0 parts by mass of toluene, 20.0 parts by mass of polythiol composition (A), and 0.043 parts by mass of 1,4-diazabicyclo[2.2.2]octane (Fujifilm Wako Pure Chemical Industries, Ltd.) as a reaction initiator were charged at 25 ° C., and stirred under a nitrogen atmosphere. The temperature was raised from 25 ° C.
• 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole Tokyo Chemical Industry Co., Ltd., structure below
• 30.0 parts by mass of toluene 30.0 parts by mass of toluene
• the obtained mixture was subjected to removal of low boiling point components by a vacuum pump and filtration by a 3 micron PTFE membrane filter in this order to obtain 20.4 parts by mass of a polythiol/UVA composition in which a part of the polythiol compound had reacted with an ultraviolet absorber.
• the content of UVA in the entire polythiol/UVA composition was 3.1% by mass.
• a polymerizable composition was prepared in the same manner as in Example 1, except that 48 parts by mass of the obtained polythiol/UVA composition was used, and a resin molded body was obtained.
• Example 6 Into a reactor at 25 ° C., 0.67 parts by mass of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) as an ultraviolet absorber, 30.0 parts by mass of toluene, 5.0 parts by mass of polythiol composition (B), and 0.046 parts by mass of 1,4-diazabicyclo[2.2.2]octane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a reaction initiator were charged at 25 ° C., and stirring was performed under a nitrogen atmosphere. The temperature was raised from 25 ° C.
• the toluene was removed from the obtained toluene solution by a rotary evaporator.
• the obtained mixture was subjected to removal of low boiling point components by a vacuum pump and filtration by a 3 micron PTFE membrane filter in this order to obtain 3.4 parts by mass of a polythiol/UVA composition in which a part of the polythiol compound had reacted with an ultraviolet absorber.
• the content of UVA in the entire polythiol/UVA composition was 19.7% by mass.
• a polymerizable composition was prepared in the same manner as in Example 4, except that 0.99 parts by mass of the obtained polythiol/UVA composition was used, and a resin molded body was obtained.
• ⁇ Comparative Example 2 51 parts by mass of m-xylylene diisocyanate as a polyisocyanate compound, 0.015 parts by mass of dibutyltin dichloride as a curing catalyst, 0.10 parts by mass of an acidic phosphate ester (Zereck UN, Stepan Co., Ltd.) as an internal mold release agent, and 1.5 parts by mass of Biosorb 583 (Kyodo Pharmaceutical Co., Ltd.) as an ultraviolet absorber were mixed and dissolved at 20° C. 49 parts by mass of polythiol composition (B) was mixed into this mixture to obtain a polymerizable composition as a homogeneous liquid. Using the obtained polymerizable composition, a resin molded body was obtained in the same manner as in Example 1.
• a polymerizable composition for producing a resin molded body was obtained by mixing 10.0 parts by mass of bis(2,3-epithiopropyl)disulfide (manufactured by Mitsui Chemicals, Inc.) as a polyepisulfide compound, 0.002 parts by mass of N,N-dimethylcyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.01 parts by mass of N,N-dicyclohexylmethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.99 parts by mass of polythiol composition (B), and 0.11 parts by mass of a compound having the following structure (Tinuvin PS, manufactured by BASF Japan Ltd.) as an ultraviolet absorber, as a homogeneous liquid.
• the obtained polymerizable composition was degassed at 600 Pa for 1 hour and then filtered through a 1 ⁇ m Teflon (registered trademark) filter.
• the filtered polymerizable composition was poured into a mold consisting of a pair of glass plates fixed with tape. This mold was placed in an oven, and the temperature inside the oven was raised from 10°C to 120°C over 20 hours to harden the polymerizable composition.
• the hardened product was removed from the mold and annealed at 120°C for 2 hours to obtain a flat resin molded product with a thickness of 3.0 mm.
• Transmittance (T%) of 5.0 mg (approximately 500 ppm reproduction) 0.03%
• Transmittance (T%) of 0.5 mg (approximately 50 ppm reproduction) 20.5%
• Transmittance (T%) of 0.05 mg (approximately 5 ppm reproduction) 91.2%

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