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
  • C08G18/08—Processes
• • 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.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is OH, SH, or NHR2
• R2 is a hydrogen atom or a hydrocarbon group.
• 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 any one of ⁇ 1> to ⁇ 3>.
• An optical material comprising the cured product according to ⁇ 4>.
• ⁇ 6> A spectacle lens comprising the optical material according to ⁇ 5>.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is OH, SH, or NHR2
• R2 is a hydrogen atom or a hydrocarbon group.
• ⁇ 10> A compound having a structure represented by the following general formula (3) and an episulfide group:
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• R2 is a hydrogen atom or a hydrocarbon group
• * is a bonding position
• Y is a hydrogen atom or a bonding position.
• a method for producing a polymerizable composition comprising: mixing the compound according to any one of ⁇ 7> to ⁇ 10>, at least one compound selected from a polyiso(thio)cyanate compound and a polyepisulfide compound, 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 that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is O, S, or NR2
• R2 is a hydrogen atom or a hydrocarbon group
• * is a bonding position
• Y is a hydrogen atom or 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 contains a compound represented by the following general formula (1) or a reaction product of a compound represented by the following general formula (1) with a polyiso(thio)cyanate compound or a polyepisulfide compound.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is OH, SH, or NHR2
• R2 is a hydrogen atom or a hydrocarbon group.
• 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, in addition to the first component and the second component, a compound represented by general formula (1) or a reaction product of a compound represented by general formula (1) with a polyiso(thio)cyanate compound or a polyepisulfide compound (hereinafter also referred to as a reactive UVA). That is, the reactive UVAs can be classified into three types: (1) a compound represented by general formula (1), (2) a reaction product of a compound represented by general formula (1) with a polyiso(thio)cyanate compound, and (3) a reaction product of a compound represented by general formula (1) with a polyepisulfide compound.
• the compound represented by the general formula (1) has OH, SH or NH 2 represented by X (that is, a functional group capable of reacting with the polymerizable functional group of the first component).
• the reaction product of the compound represented by general formula (1) and a polyiso(thio)cyanate compound has, among a plurality of iso(thio)cyanate groups contained in the polyiso(thio)cyanate compound, an iso(thio)cyanate group that has not reacted with the functional group represented by X in general formula (1).
• a reaction product of a compound represented by general formula (1) and a polyepisulfide compound has, among a plurality of episulfide groups contained in the polyepisulfide compound, an episulfide group that has not reacted with a functional group represented by X in general formula (1). That is, the three types of reactive UVAs described above have the property of reacting with either the first component or the second component contained in the polymerizable composition. Therefore, in the resin obtained from the polymerizable composition containing the reactive UVA, 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 that does not contain OH, SH, or NHR2 .
• Examples of the monovalent group not containing OH, SH, or NHR2 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 OH, SH or NHR2 , where R2 is a hydrogen atom or a hydrocarbon group.
• R2 is a hydrogen atom or a hydrocarbon group.
• X is OH, SH or NHR2 .
• X is preferably SH.
• the type of polyiso(thio)cyanate compound or polyepisulfide compound to be reacted with the compound represented by general formula (1) is not particularly limited. For example, it may be selected from the polyiso(thio)cyanate compounds or polyepisulfide compounds described below.
• Examples of the reaction product of the compound represented by general formula (1) and a polyiso(thio)cyanate compound include compounds having a structure represented by the following general formula (2) and an iso(thio)cyanate group.
• Examples of the reaction product of the compound represented by general formula (1) and a polyepisulfide compound include compounds having a structure represented by the following general formula (3) and an episulfide group.
• Ra, n1, Rb, n2 and R1 are the same as those of Ra, n1, Rb, n2 and R1 in the general formula (1).
• X is O, S or NR2
• R2 is a hydrogen atom or a hydrocarbon group
• * is a bonding position
• Y is a hydrogen atom or a bonding position.
• the polymerizable composition may contain one or more types of reactive UVAs. That is, the polyiso(thio)cyanate compound or polyepisulfide compound to be 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) to be reacted with the polyiso(thio)cyanate compound or polyepisulfide compound may be one type or two or more types.
• the polyiso(thio)cyanate compound or polyepisulfide compound to be reacted with the compound represented by general formula (1) may be the same as or different from the polyiso(thio)cyanate compound or polyepisulfide compound contained as a polymerizable component in the polymerizable composition.
• the polymerizable composition may contain, as the reactive UVA, either the compound represented by general formula (1) or the reaction product of the compound represented by general formula (1) and the first component, or may contain both.
• 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 polyiso(thio)cyanate compound or polyepisulfide 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 represented by the following general formula (1), or a compound that is a reaction product of a compound represented by general formula (1) with a polyiso(thio)cyanate compound or an episulfide compound.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is OH, SH, or NHR2
• R2 is a hydrogen atom or a hydrocarbon group.
• One embodiment of the present disclosure is a compound having a structure represented by the following general formula (2) and an iso(thio)cyanate group.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is O, S, or NR2
• R2 is a hydrogen atom or a hydrocarbon group
• * is a bonding position.
• One embodiment of the present disclosure is a compound having a structure represented by general formula (3) and an episulfide group.
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• R2 is a hydrogen atom or a hydrocarbon group
• * is a bonding position
• Y is a hydrogen atom or 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 is a method for producing a polymerizable composition, comprising a step of mixing the compound of the present disclosure described above (reactive UVA), at least one selected from a polyiso(thio)cyanate compound and a polyepisulfide compound (first component), and a polythiol compound (second component).
• 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 mixing of the reactive UVA, the first component and the second component may be carried out in one step or in two steps.
• the reactive UVA and the first component may be mixed together and then the second component may be mixed therewith.
• the compound represented by general formula (1) is used as the reactive UVA, after mixing the compound represented by general formula (1) with the first component, all or a part of the compound represented by general formula (1) may react with the first component to become a reaction product.
• One embodiment of the present disclosure is a resin having a structure represented by the following general formula (2) or general formula (3).
• Ra is a monovalent hydrocarbon group or a halogen atom
• n1 is a number from 0 to 4
• Rb is a monovalent group that does not contain OH, SH, or NHR2
• n2 is a number from 0 to 3
• R1 is a divalent hydrocarbon group
• X is O, S, or NR2
• R2 is a hydrogen atom or a hydrocarbon group
• * is a bonding position
• Y is a hydrogen atom or 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.
• 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.
• polyepisulfide compounds 10.0 parts by mass of bis(2,3-epithiopropyl)disulfide (manufactured by Mitsui Chemicals, Inc.), 0.002 parts by mass of N,N-dimethylcyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.01 parts by mass of N,N-dicyclohexylmethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were used, and as polythiol compounds, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was used.
• a polymerizable composition for producing a resin molded body was obtained by mixing 0.99 parts by mass of a mixture of 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (manufactured by Mitsui Chemicals, Inc.) 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.
• Example 1 Polymerization was carried out in the same manner as in Comparative Example 1, except that the ultraviolet absorbing agent was changed to 0.075 parts by mass of UVA-OH, to obtain a flat plate-shaped resin molded product having a thickness of 3.0 mm. Before the polymerizable composition was poured into the mold, it was measured by FT-IR (using IR Spirit manufactured by Shimadzu Corporation; the same applies below) to confirm the formation of urethane bonds (a new peak appeared at 1600-1750 cm -1 ). From this result, it was confirmed that a reaction product between UVA-OH and the polyisocyanate compound was generated in the polymerizable composition.
• FT-IR using IR Spirit manufactured by Shimadzu Corporation; the same applies below
• Example 2 Polymerization was carried out in the same manner as in Comparative Example 2, except that the ultraviolet absorber was changed to 0.15 parts by mass of UVA-OH, to obtain a flat plate-shaped resin molded product having a thickness of 3.0 mm. Before the polymerizable composition was poured into the mold, the polymerizable composition was measured by FT-IR to confirm the formation of a urethane bond (a new peak appeared at 1600-1750 cm -1 ). From this result, it was confirmed that a reaction product between UVA-OH and the polyisocyanate compound was generated in the polymerizable composition.
• Example 3 Polymerization was carried out in the same manner as in Comparative Example 3, except that the ultraviolet absorber was changed to 0.075 parts by mass of UVA-OH, to obtain a flat plate-shaped resin molded product having a thickness of 3.0 mm. Before the polymerizable composition was poured into the mold, it was measured by FT-IR to confirm the formation of urethane bonds (a new peak appeared at 1600-1750 cm -1 ).
• Example 4 Polymerization was carried out in the same manner as in Comparative Example 1, except that the ultraviolet absorbing agent was changed to 0.20 parts by mass of UVA-SH, to obtain a resin molded product in the form of a flat plate having a thickness of 3.0 mm. Before the polymerizable composition was poured into the mold, the polymerizable composition was measured by FT-IR to confirm the formation of a thiourethane bond (a new peak appeared at 1600-1750 cm -1 ). From this result, it was confirmed that a reaction product between UVA-SH and the polyisocyanate compound was generated in the polymerizable composition.
• Example 5 Polymerization was carried out in the same manner as in Comparative Example 2, except that the ultraviolet absorbing agent was changed to 0.20 parts by mass of UVA-SH, to obtain a flat plate-shaped resin molded product having a thickness of 3.0 mm. Before the polymerizable composition was poured into the mold, the polymerizable composition was measured by FT-IR to confirm the formation of a thiourethane bond (a new peak appeared at 1600-1750 cm -1 ). From this result, it was confirmed that a reaction product between UVA-SH and the polyisocyanate compound was generated in the polymerizable composition.
• Example 6 Polymerization was carried out in the same manner as in Comparative Example 3, except that the ultraviolet absorbing agent was changed to 0.20 parts by mass of UVA-SH, to obtain a flat plate-shaped resin molded product having a thickness of 3.0 mm. Before the polymerizable composition was poured into the mold, the polymerizable composition was measured by FT-IR to confirm the formation of a thiourethane bond (a new peak appeared at 1600-1750 cm -1 ). From this result, it was confirmed that a reaction product between UVA-SH and the polyisocyanate compound was generated in the polymerizable composition.
• Example 7 Polymerization was carried out in the same manner as in Comparative Example 4, except that the ultraviolet absorbing agent was changed to 0.11 parts by mass of UVA-SH, to obtain a flat plate-shaped resin molded product having a thickness of 3.0 mm.
• the resin molded product after annealing was measured by FT-IR, and it was confirmed that the mercapto group peak (2400-2600 cm ⁇ 1 ) had disappeared. From this result, it was confirmed that UVA-SH had reacted with the polyepisulfide compound in the resin molded product.
• UVA-OH and UVA-SH obtained in Synthesis Examples 1 and 2 both had low light transmittance in the ultraviolet range (especially at 380 nm), demonstrating their performance as ultraviolet absorbents.
• 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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