WO2020004533A1 - Polythiourethane resin for optical member and optical member - Google Patents

Polythiourethane resin for optical member and optical member Download PDF

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Publication number
WO2020004533A1
WO2020004533A1 PCT/JP2019/025551 JP2019025551W WO2020004533A1 WO 2020004533 A1 WO2020004533 A1 WO 2020004533A1 JP 2019025551 W JP2019025551 W JP 2019025551W WO 2020004533 A1 WO2020004533 A1 WO 2020004533A1
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Prior art keywords
compound
optical member
polythiourethane resin
bis
mass
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PCT/JP2019/025551
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French (fr)
Japanese (ja)
Inventor
匡人 猪狩
照夫 山下
渡邊　強
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ホヤ レンズ タイランド リミテッド
匡人 猪狩
照夫 山下
渡邊　強
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Application filed by ホヤ レンズ タイランド リミテッド, 匡人 猪狩, 照夫 山下, 渡邊　強 filed Critical ホヤ レンズ タイランド リミテッド
Priority to JP2020527620A priority Critical patent/JPWO2020004533A1/en
Publication of WO2020004533A1 publication Critical patent/WO2020004533A1/en

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    • 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
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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 invention relates to a polythiourethane resin for an optical member and an optical member.
  • Polythiourethane resins obtained by curing a polymerizable composition containing a polyiso (thio) cyanate compound and a polythiol compound are widely used as various optical members such as lenses (for example, see Patent Document 1).
  • a resin may be dyed for imparting fashionability or light-shielding properties. If the resin constituting the optical member is inferior in dyeability, it takes a long time for the dyeing process, or it becomes difficult to impart a desired color to the optical member by the dyeing process. Therefore, the desired physical properties of the resin constituting the optical member include excellent dyeability.
  • One embodiment of the present invention provides a polythiourethane resin for an optical member having excellent dyeability.
  • the polythiourethane resin has a bond represented by the following formula 1: Is a resin having a plurality of in the molecule.
  • Z is an oxygen atom or a sulfur atom.
  • Z forms the above bond of an oxygen atom
  • the thiol group reacts with the isothiocyanate group
  • the above bond forms a sulfur atom of Z.
  • the “thiourethane bond” in the present invention and the present specification refers to a bond represented by the above formula 1.
  • * indicates the position where the thiourethane bond is bonded to another adjacent structure.
  • one embodiment of the present invention provides: A polythiourethane resin for optical members having a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more (hereinafter also referred to simply as "polythiourethane resin") Described). About.
  • a polythiourethane resin for an optical member having excellent dyeability it is possible to provide a polythiourethane resin for an optical member having excellent dyeability, and an optical member obtained by dyeing the polythiourethane resin.
  • the polythiourethane resin has a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more.
  • the polythiourethane resin will be described in more detail.
  • the thiourethane bond content of the polythiourethane resin is 30.00% by mass or less, preferably 25.00% by mass or less, based on the mass (100% by mass) of the polythiourethane resin. It is more preferably at most 20.00% by mass. Further, the content of the thiourethane bond is more than 0% by mass, and is 1.00% by mass or more, 2.00% by mass or more, 3.00% by mass or more, 4.00% by mass or more, % Or more, 6.00% or more, or 7.00% or more. It is preferable to lower the content of thiourethane bonds in the polythiourethane resin in order to enhance dyeability.
  • the content of the ester bond is, for example, 30.00% by mass or less or 25.00% by mass or less. It is preferable that the content of the ester bond in the polythiourethane resin is high in order to enhance the dyeability.
  • the content of thiourethane bonds and the content of ester bonds of the polythiourethane resin can be determined by a known method. Further, when the composition of the polymerizable composition for obtaining the polythiourethane resin is known, it is possible to calculate the content of thiourethane bonds and the content of ester bonds of the polythiourethane resin based on the known composition. it can. The thiourethane bond content and the ester bond content of the polythiourethane resin can be adjusted by the composition of the polymerizable composition used to obtain the polythiourethane resin.
  • the polythiourethane resin can be produced by curing a polymerizable composition. Next, the polymerizable composition that can be used to obtain the polythiourethane resin will be described in more detail.
  • the thiourethane bond can be formed by a reaction between an iso (thio) cyanate group of the polyiso (thio) cyanate compound and a thiol group of the polythiol compound (hereinafter also referred to as “thiourethane-forming reaction”). Therefore, as the polymerizable composition for obtaining the above polythiourethane resin, a polymerizable composition containing at least a polyiso (thio) cyanate compound and a polythiol compound can be used.
  • an ester bond-containing compound can be used as one or more polymerizable compounds contained in the polymerizable composition. This point will be further described later.
  • polyiso (thio) cyanate compound refers to a compound having two or more iso (thio) cyanate groups per molecule.
  • Iso (thio) cyanate means isocyanate and / or isothiocyanate. Isocyanates are sometimes called isocyanates, and isothiocyanates are sometimes called isothiocyanates.
  • Polythiol compound refers to a compound having two or more thiol groups per molecule.
  • the polyiso (thio) cyanate compound can be an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like.
  • the number of iso (thio) cyanate groups contained in the polyiso (thio) cyanate compound is 2 or more per molecule, preferably 2 to 4, more preferably 2 or 3.
  • the polyiso (thio) cyanate compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like.
  • Specific examples of the polyiso (thio) cyanate compound include hexamethylene diisocyanate, 1,5-pentane diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, and 2,5-bis (isocyanatomethyl) -bicyclo.
  • heptane 2,6-bis (isocyanatomethyl) -bicyclo
  • heptane bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanato) Aliphatic polyisocyanate compounds such as methyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane
  • aromatic polyisocyanates such as xylylene diisocyanate, 1,3-diisocyanatobenzene, tolylene diisocyanate and diphenylmethane diisocyanate Lithocyanate compounds and the like can be mentioned.
  • the polyiso (thio) cyanate compound may be a chlorine-substituted product, a halogen-substituted product such as a bromine-substituted product, an alkyl-substituted product, an alkoxy-substituted product, a nitro-substituted product, a modified prepolymer with a polyhydric alcohol, a carbodiimide-modified product, Urea modified products, buret modified products, dimerization or trimerization reaction products, and the like can also be used.
  • a halogen-substituted product such as a bromine-substituted product, an alkyl-substituted product, an alkoxy-substituted product, a nitro-substituted product
  • a modified prepolymer with a polyhydric alcohol a carbodiimide-modified product
  • Urea modified products buret modified products, dimerization or trimerization reaction products
  • the polymerizable composition can include a cyclic structure-containing compound as the polyiso (thio) cyanate compound.
  • the cyclic structure-containing compound may be a carbocyclic compound, a heterocyclic compound, a monocyclic compound, or a bicyclic or higher polycyclic compound.
  • the polyiso (thio) cyanate compound may include a plurality of cyclic structures.
  • the polyiso (thio) cyanate compound can be an aromatic compound (aromatic polyiso (thio) cyanate compound).
  • the polyiso (thio) cyanate compound can be an ester bond-containing compound.
  • the polyiso (thio) cyanate compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, two to five ester bonds.
  • the content of the polyiso (thio) cyanate compound in the polymerizable composition is, for example, more than 0% by mass and 50.00% by mass or less, preferably 10.00% by mass, based on the mass (100% by mass) of the polymerizable composition. It can be in the range of ⁇ 35.00% by mass.
  • the mass of the polymerizable composition means the mass excluding the solvent when the polymerizable composition contains a solvent.
  • the polythiol compound can be an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like.
  • the number of thiol groups contained in the polythiol compound is two or more per molecule, preferably 2 to 4. Further, the number of thiol groups contained in the polythiol compound is preferably 3 or more per molecule.
  • polythiol compound examples include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, and 1,6-hexane Dithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4- Dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl thiomalate), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3 Dimer
  • Polythiol compounds containing a sulfur atom in addition to a thiol group such as one of the isomers or a mixture of two or three of these isomers); 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl Containing a sulfur atom in addition to thiol groups such as 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane and 2,5-dimercaptomethyl-1,4-dithiane And the like.
  • the polythiol compound contained in the polymerizable composition can be an aliphatic compound.
  • the polythiol compound can be an ester bond-containing compound.
  • the polythiol compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, 2 to 5 ester bonds.
  • the polythiol compound in one aspect, can be an ester bond-containing aliphatic compound.
  • the content of the polythiol compound in the polymerizable composition is, for example, 20.00 to 80.00% by mass, preferably 30.00 to 70.00% by mass with respect to the mass (100% by mass) of the polymerizable composition. %.
  • the polymerizable composition may include one or more other polymerizable compounds in addition to the polyiso (thio) cyanate compound and the polythiol compound.
  • examples of such a polymerizable compound include a polyene compound.
  • polyene compound refers to a compound having two or more carbon-carbon double bonds per molecule.
  • a cured product of the polymerizable composition containing a polyene compound and a polythiol compound reacts with a carbon-carbon double bond of the polyene compound and a thiol group of the polythiol compound (hereinafter referred to as a “thiol-ene reaction”).
  • the number of carbon-carbon double bonds of the polyene compound is 2 or more, preferably 3 or more, for example, 3 to 5 per molecule.
  • the polyene compound can include a carbon-carbon double bond in a carbon-carbon double bond-containing group such as a (meth) acryl group, a vinyl group, and an allyl group.
  • the types of the carbon-carbon double bond-containing groups contained in the polyene compound may be the same or different.
  • polyene compound examples include vinyl compounds such as divinylbenzene and divinyltoluene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
  • (Meth) acrylates such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate , Diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyl Allyl compounds such as Kishietan like.
  • the polyene compound only one kind of polyene compound may be used, or two or more kinds may be used as a mixture.
  • the polyene compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like.
  • the polyene compound can be a cyclic structure containing compound.
  • the cyclic structure-containing compound may be a carbocyclic compound, a heterocyclic compound, a monocyclic compound, or a bicyclic or higher polycyclic compound. Good.
  • the polyene compound may include a plurality of cyclic structures.
  • the polyene compound can be a heteroalicyclic or heteroaromatic compound, and specifically can be an isocyanuric ring-containing compound or a cyanuric ring-containing compound.
  • the polyene compound can be an ester bond-containing compound.
  • the polyene compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, two to five ester bonds.
  • the content of the polyene compound in the polymerizable composition is, for example, more than 0% by mass and 50.00% by mass or less, preferably 10.00 to 35.00, based on the mass (100% by mass) of the polymerizable composition. % By weight.
  • the polymerizable composition may optionally contain one or more known components such as additives and polymerization catalysts generally used for the production of optical members.
  • the additive include various additives such as an ultraviolet absorber, an antioxidant, and a release agent.
  • an organic phosphorus compound such as a phosphine derivative can be used as an additive. The amount of the additive used can be appropriately set.
  • the polymerizable composition includes, as a polymerization catalyst, a polymerization catalyst that catalyzes a thiourethanation reaction between a polyiso (thio) cyanate compound and a polythiol compound (hereinafter, also referred to as “first polymerization catalyst”). Is preferred.
  • a polymerization catalyst that catalyzes a thiol-ene reaction between the polyene compound and the polyiso (thio) cyanate compound hereinafter also referred to as a “second polymerization catalyst” Is preferably used in combination with the first polymerization catalyst.
  • first polymerization catalyst that catalyzes the thiourethane reaction As the first polymerization catalyst that catalyzes the thiourethane reaction and the second polymerization catalyst that catalyzes the thiol-ene reaction, known polymerization catalysts can be used.
  • the first polymerization catalyst that catalyzes the thiourethanation reaction include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, and tributyltin.
  • Organic tin compounds such as fluoride and dimethyltin dibromide can be mentioned.
  • the polymerizable composition can contain, for example, the first polymerization catalyst in an amount of 0.01 to 0.50% by mass based on the mass (100% by mass) of the polymerizable composition.
  • the second polymerization catalyst that catalyzes the thiol-ene reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis-2.
  • the polymerizable composition can be prepared by mixing the various components described above simultaneously or sequentially in an arbitrary order.
  • the preparation method is not particularly limited, and a known method for preparing a polymerizable composition can be employed. Further, the polymerizable composition may be prepared without adding a solvent, or may be prepared by adding an arbitrary amount of a solvent. As the solvent, one or more known solvents that can be used for the polymerizable composition can be used.
  • the polyiso (thio) cyanate compound, polythiol compound, and polyene compound described above are all polymerizable compounds, and the above polymerizable composition is cured by polymerizing these compounds to obtain a cured product (polythiourethane resin). ) Can be obtained.
  • the polythiourethane resin thus obtained can be used as various optical members.
  • the optical member include various lenses such as a spectacle lens, a telescope lens, a binocular lens, a microscope lens, an endoscope lens, and an imaging system lens of various cameras.
  • the “lens” in the present invention and the present specification includes a “lens substrate” in which one or more layers are arbitrarily laminated.
  • cast polymerization is preferable.
  • the polymerizable composition is injected into a cavity of a mold having two cavities facing each other at a predetermined interval and a cavity formed by closing the space, and the polymerizable composition is injected into the cavity.
  • the polymerization (curing reaction) of the polymerizable compound contained in the above can be performed to obtain a cured product.
  • molds usable for casting polymerization refer to, for example, paragraphs 0012 to 0014 of JP-A-2009-262480 and FIG. 1 of the same.
  • a molding die in which a gap between two molds is closed by a gasket as a sealing member is shown, but a tape may be used as the sealing member.
  • the casting polymerization can be performed as follows.
  • the polymerizable composition is injected into the mold cavity from an injection port provided on the side surface of the mold.
  • the polymerizable compound contained in the polymerizable composition is preferably polymerized (cured reaction) by heating, whereby the polymerizable composition is cured, and a cured product in which the internal shape of the cavity is transferred can be obtained.
  • the polymerization conditions are not particularly limited, and can be appropriately set according to the composition of the polymerizable composition and the like.
  • the mold in which the polymerizable composition has been injected into the cavity can be heated at a heating temperature of 20 to 150 ° C.
  • the temperature such as a heating temperature for casting polymerization refers to an ambient temperature at which a mold is placed.
  • the temperature can be increased at an arbitrary rate, and the temperature can be decreased (cooled) at an arbitrary rate.
  • the cured product inside the cavity is released from the mold.
  • the cured product can be released from the mold by removing the upper and lower molds and the gasket or tape forming the cavity in any order.
  • the cured product (polythiourethane resin) released from the mold can be used as an optical member after post-processing as necessary, and can be used as, for example, various lenses (for example, a lens substrate).
  • a cured product used as a lens base material for an eyeglass lens is usually, after release, annealing, dyeing, a grinding process such as a rounding process, a polishing process, a primer coat layer for improving impact resistance, and a surface. It can be applied to a post-process such as a process of forming a coat layer such as a hard coat layer for increasing hardness.
  • various functional layers such as an antireflection layer and a water-repellent layer can be formed on the lens substrate. For each of these steps, a known technique can be applied.
  • an eyeglass lens in which the lens substrate is the above polythiourethane resin can be obtained.
  • spectacles can be obtained by attaching this spectacle lens to a frame.
  • the above polythiourethane resin can be preferably subjected to a dyeing treatment.
  • the polythiourethane resin can exhibit excellent dyeability.
  • the dyeing treatment can be performed, for example, by immersing the cured product in a dyeing bath containing a dye.
  • the dyeing bath can be prepared, for example, by diluting a commercially available dye with a solvent as necessary.
  • known additives such as a surfactant can be added to the dyeing bath as needed.
  • the temperature of the dye bath can be, for example, in the range from 30 to 100 ° C.
  • the immersion time of the cured product in the dyeing bath is not particularly limited, but is, for example, about 1 minute to 1 hour.
  • a heat treatment may be performed to fix the dye.
  • the heating temperature in this heat treatment (for example, the ambient temperature in the furnace of the heating furnace for performing the heat treatment) is, for example, 30 ° C. to 120 ° C., and the heat treatment time is, for example, 15 minutes to 2 hours, but is not particularly limited.
  • washing and one or more of the post-processes exemplified above can be performed.
  • One embodiment of the present invention relates to an optical member obtained by dyeing the polythiourethane resin.
  • the above description can be referred to for details regarding the above-mentioned polythiourethane resin and optical members such as dyeing treatment.
  • PETMA pentaerythritol tetrakis (2-mercaptoacetate)
  • a plastic lens having a center thickness of 2 mm was produced.
  • the plastic lens thus produced has a thiourethane bond content of 38.42% by mass and an ester bond content of 22.54% by mass.
  • Example 1 A 300 ml eggplant-shaped flask was charged with 10.9 g of 2,4-tolylene diisocyanate (TDI) as a polyiso (thio) cyanate compound and 32.8 g of triallyl isocyanurate (TAIC) as a polyene compound, and triphenylphosphine as an organic phosphorus compound.
  • TDI 2,4-tolylene diisocyanate
  • TAIC triallyl isocyanurate
  • triphenylphosphine an organic phosphorus compound.
  • TPP butoxyethyl acid phosphate
  • JP-506H butoxyethyl acid phosphate
  • dimethyltin dichloride 0.01 g
  • 2,2′-azobis-2,4-dimethyl 0.02 g of valeronitrile was added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C.
  • PETMA pentaerythritol tetrakis (2-mercaptoacetate)
  • a plastic lens having a center thickness of 2 mm was produced.
  • the plastic lens thus manufactured has a thiourethane bond content of 9.41% by mass and an ester bond content of 22.89% by mass.
  • Example 2 In a 300 ml eggplant-shaped flask, 22.0 g of 2,4-tolylene diisocyanate (TDI) as a polyiso (thio) cyanate compound and 22.0 g of triallyl isocyanurate (TAIC) as a polyene compound were charged, and triphenylphosphine was used as an organic phosphorus compound.
  • TDI 2,4-tolylene diisocyanate
  • TAIC triallyl isocyanurate
  • TPP butoxyethyl acid phosphate
  • JP-506H butoxyethyl acid phosphate
  • dimethyltin dichloride 0.02 g
  • 2,2′-azobis-2,4-dimethyl 0.02 g of valeronitrile was added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C.
  • PETMA pentaerythritol tetrakis (2-mercaptoacetate)
  • a plastic lens having a center thickness of 2 mm was produced.
  • the plastic lens thus manufactured has a thiourethane bond content of 18.98% by mass and an ester bond content of 22.78% by mass.
  • Example 3 A 300 ml eggplant-shaped flask was charged with 33.2 g of 2,4-tolylene diisocyanate (TDI) as a polyiso (thio) cyanate compound and 11.1 g of triallyl isocyanurate (TAIC) as a polyene compound, and triphenylphosphine as an organic phosphorus compound.
  • TDI 2,4-tolylene diisocyanate
  • TAIC triallyl isocyanurate
  • triphenylphosphine an organic phosphorus compound.
  • TPP butoxyethyl acid phosphate
  • JP-506H manufactured by Johoku Chemical Co., Ltd.
  • dimethyltin dichloride 0.03 g
  • 2,2′-azobis-2,4-dimethyl 0.02 g of valeronitrile was added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C.
  • PETMA pentaerythritol tetrakis (2-mercaptoacetate)
  • a plastic lens having a center thickness of 2 mm was produced.
  • the plastic lens thus produced has a thiourethane bond content of 28.74% by mass and an ester bond content of 22.66% by mass.
  • Each of the plastic lenses of Examples 1 to 3 and the plastic lens of Comparative Example 1 is a polythiourethane resin prepared from a polymerizable composition containing a polyiso (thio) cyanate compound and a polythiol compound.
  • the plastic lenses of Examples 1 to 3 having a content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more had better dyeability (higher dyeing density) than the plastic lens of Comparative Example 1. )showed that.
  • Such plastic lenses of Examples 1 to 3 are suitable as various optical members such as spectacle lenses which are desired to have excellent dyeability.
  • the polymerizable compositions 1 to 4 contain various polymerizable compounds in a molar ratio such that the total amount of the isocyanate groups of the polyiso (thio) cyanate compound can react with the thiol groups contained in the polythiol compound.
  • the thiourethane bond content is a value calculated by the following formula, assuming that all the isocyanate groups of the polyiso (thio) cyanate compound react to form a thiourethane bond.
  • Thiourethane bond content (mass of thiourethane bond formed / total weight of polymerizable composition) ⁇ 100
  • PETMA which is a polythiol compound contained in the polymerizable compositions 1 to 4, contains an ester bond.
  • a polythiourethane resin for an optical member having a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more.
  • the polythiourethane resin can exhibit high dyeability.
  • the content of the ester bond in the polythiourethane resin can be in the range of 15.00 to 30.00% by mass.
  • the polythiourethane resin can be a cured product obtained by curing a polymerizable composition containing a polyene compound, a polyiso (thio) cyanate compound, and a polythiol compound.
  • the polyene compound may be a cyclic structure-containing compound.
  • the cyclic structure can be an isocyanuric ring.
  • the polyene compound can be an allyl compound.
  • the polyene compound may be a compound containing three or more carbon-carbon double bonds per molecule.
  • the polythiol compound can be an aliphatic compound.
  • the polythiol compound can be an ester bond-containing compound.
  • the polythiol compound may be a compound containing three or more thiol groups per molecule.
  • the polyiso (thio) cyanate compound can be an aromatic compound.
  • the optical member may be a lens.
  • the lens may be a spectacle lens.
  • an optical member obtained by dyeing the polythiourethane resin.
  • One embodiment of the present invention is useful in the field of manufacturing various optical members such as spectacle lenses.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Eyeglasses (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

A polythiourethane resin for an optical member containing 30.00% by mass or less of a thiourethane bond and 15.00% by mass or more of an ester bond.

Description

光学部材用ポリチオウレタン樹脂および光学部材Polythiourethane resin for optical member and optical member
　本発明は、光学部材用ポリチオウレタン樹脂および光学部材に関する。 The present invention relates to a polythiourethane resin for an optical member and an optical member.
　ポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物を硬化させて得られるポリチオウレタン樹脂は、レンズ等の各種光学部材として広く用いられている（例えば特許文献１参照）。 Polythiourethane resins obtained by curing a polymerizable composition containing a polyiso (thio) cyanate compound and a polythiol compound are widely used as various optical members such as lenses (for example, see Patent Document 1).
特開平７－２５２２０７号公報JP-A-7-252207
　光学部材を製造する際、ファッション性や遮光性付与等のために樹脂を染色することがある。光学部材を構成する樹脂が染色性に劣るものであると、染色処理に長時間を要したり、染色処理により光学部材に所望の色を付与することが困難となる。したがって、光学部材を構成する樹脂に望まれる物性としては、染色性に優れることが挙げられる。 樹脂 When manufacturing an optical member, a resin may be dyed for imparting fashionability or light-shielding properties. If the resin constituting the optical member is inferior in dyeability, it takes a long time for the dyeing process, or it becomes difficult to impart a desired color to the optical member by the dyeing process. Therefore, the desired physical properties of the resin constituting the optical member include excellent dyeability.
　本発明の一態様は、染色性に優れる光学部材用ポリチオウレタン樹脂を提供する。 の 一 One embodiment of the present invention provides a polythiourethane resin for an optical member having excellent dyeability.
　ポリチオウレタン樹脂は、下記式１で表される結合：
Figure JPOXMLDOC01-appb-C000001
 を分子内に複数有する樹脂である。式１において、Ｚは酸素原子または硫黄原子である。チオール基がイソシアネート基と反応することによりＺが酸素原子の上記結合が形成され、イソチオシアネート基と反応することによりＺが硫黄原子の上記結合が形成される。本発明および本明細書における「チオウレタン結合」とは、上記の式１で表される結合をいうものとする。式１中、＊は、チオウレタン結合が、隣接する他の構造と結合する位置を示す。
　本発明者らは鋭意検討を重ねた結果、ポリチオウレタン樹脂の染色性は、チオウレタン結合の含有率を下げ、エステル結合の含有率を高めることにより改善できることを新たに見出した。 The polythiourethane resin has a bond represented by the following formula 1:
Figure JPOXMLDOC01-appb-C000001
 Is a resin having a plurality of in the molecule. In Formula 1, Z is an oxygen atom or a sulfur atom. When the thiol group reacts with the isocyanate group, Z forms the above bond of an oxygen atom, and when the thiol group reacts with the isothiocyanate group, the above bond forms a sulfur atom of Z. The “thiourethane bond” in the present invention and the present specification refers to a bond represented by the above formula 1. In Formula 1, * indicates the position where the thiourethane bond is bonded to another adjacent structure.
As a result of intensive studies, the present inventors have newly found that the dyeability of the polythiourethane resin can be improved by lowering the content of thiourethane bonds and increasing the content of ester bonds.
　即ち、本発明の一態様は、
　チオウレタン結合の含有率が３０．００質量％以下であり、かつエステル結合の含有率が１５．００質量％以上である、光学部材用ポリチオウレタン樹脂（以下、単に「ポリチオウレタン樹脂」とも記載する。）、
　に関する。 That is, one embodiment of the present invention provides:
A polythiourethane resin for optical members having a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more (hereinafter also referred to simply as "polythiourethane resin") Described).
About.
　本発明の一態様によれば、染色性に優れる光学部材用ポリチオウレタン樹脂、およびこのポリチオウレタン樹脂が染色されてなる光学部材を提供することができる。 According to one embodiment of the present invention, it is possible to provide a polythiourethane resin for an optical member having excellent dyeability, and an optical member obtained by dyeing the polythiourethane resin.
［光学部材用ポリチオウレタン樹脂］
　上記ポリチオウレタン樹脂は、チオウレタン結合の含有率が３０．００質量％以下であり、かつエステル結合の含有率が１５．００質量％以上である。以下、上記ポリチオウレタン樹脂について、更に詳細に説明する。 [Polythiourethane resin for optical members]
The polythiourethane resin has a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more. Hereinafter, the polythiourethane resin will be described in more detail.
＜チオウレタン結合の含有率＞
　上記ポリチオウレタン樹脂のチオウレタン結合の含有率は、このポリチオウレタン樹脂の質量（１００質量％）に対して、３０．００質量％以下であり、好ましくは２５．００質量％以下であり、より好ましくは２０．００質量％以下である。また、上記のチオウレタン結合の含有率は、０質量％超であり、１．００質量％以上、２．００質量％以上、３．００質量％以上、４．００質量％以上、５．００質量％以上、６．００質量％以上または７．００質量％以上であることもできる。ポリチオウレタン樹脂のチオウレタン結合の含有率を低くすることは、染色性を高めるうえで好ましい。 <Content of thiourethane bond>
The thiourethane bond content of the polythiourethane resin is 30.00% by mass or less, preferably 25.00% by mass or less, based on the mass (100% by mass) of the polythiourethane resin. It is more preferably at most 20.00% by mass. Further, the content of the thiourethane bond is more than 0% by mass, and is 1.00% by mass or more, 2.00% by mass or more, 3.00% by mass or more, 4.00% by mass or more, % Or more, 6.00% or more, or 7.00% or more. It is preferable to lower the content of thiourethane bonds in the polythiourethane resin in order to enhance dyeability.
＜エステル結合の含有率＞
　上記ポリチオウレタン樹脂のエステル結合（－Ｃ（＝Ｏ）－Ｏ－）の含有率は、このポリチオウレタン樹脂の質量（１００質量％）に対して、１５．００質量％以上であり、好ましくは１７．００質量％以上であり、より好ましくは２０．００質量％以上である。また、上記のエステル結合の含有率は、例えば３０．００質量％以下または２５．００質量％以下である。ポリチオウレタン樹脂のエステル結合の含有率が高いことは、染色性を高めるうえで好ましい。 <Content of ester bond>
The content of the ester bond (—C (＝ O) —O—) in the polythiourethane resin is 15.00% by mass or more based on the mass (100% by mass) of the polythiourethane resin, and is preferable. Is at least 17.00% by mass, more preferably at least 20.00% by mass. The content of the ester bond is, for example, 30.00% by mass or less or 25.00% by mass or less. It is preferable that the content of the ester bond in the polythiourethane resin is high in order to enhance the dyeability.
　ポリチオウレタン樹脂のチオウレタン結合の含有率およびエステル結合の含有率は、公知の方法で求めることができる。また、ポリチオウレタン樹脂を得るための重合性組成物の組成が既知な場合、この既知の組成に基づき、ポリチオウレタン樹脂のチオウレタン結合の含有率およびエステル結合の含有率を算出することができる。上記ポリチオウレタン樹脂のチオウレタン結合の含有率およびエステル結合の含有率は、ポリチオウレタン樹脂を得るために用いられる重合性組成物の組成によって調整することができる。 チ オ The content of thiourethane bonds and the content of ester bonds of the polythiourethane resin can be determined by a known method. Further, when the composition of the polymerizable composition for obtaining the polythiourethane resin is known, it is possible to calculate the content of thiourethane bonds and the content of ester bonds of the polythiourethane resin based on the known composition. it can. The thiourethane bond content and the ester bond content of the polythiourethane resin can be adjusted by the composition of the polymerizable composition used to obtain the polythiourethane resin.
　上記ポリチオウレタン樹脂は、重合性組成物を硬化させることによって製造することができる。次に、上記ポリチオウレタン樹脂を得るために使用可能な重合性組成物について、更に詳細に説明する。 The polythiourethane resin can be produced by curing a polymerizable composition. Next, the polymerizable composition that can be used to obtain the polythiourethane resin will be described in more detail.
＜重合性組成物＞
　チオウレタン結合は、ポリイソ（チオ）シアネート化合物が有するイソ（チオ）シアネート基とポリチオール化合物が有するチオール基との反応（以下、「チオウレタン化反応」とも記載する。）により形成され得る。したがって、上記ポリチオウレタン樹脂を得るための重合性組成物としては、ポリイソ（チオ）シアネート化合物およびポリチオール化合物を少なくとも含む重合性組成物を用いることができる。また、上記ポリチオウレタン樹脂へのエステル結合を導入するためには、エステル結合を有する成分を使用する方法や反応によりエステル結合をもたらすことができる成分を使用する方法を挙げることができる。一態様では、重合性組成物に含まれる重合性化合物の一種以上として、エステル結合含有化合物を使用することができる。この点については更に後述する。 <Polymerizable composition>
The thiourethane bond can be formed by a reaction between an iso (thio) cyanate group of the polyiso (thio) cyanate compound and a thiol group of the polythiol compound (hereinafter also referred to as “thiourethane-forming reaction”). Therefore, as the polymerizable composition for obtaining the above polythiourethane resin, a polymerizable composition containing at least a polyiso (thio) cyanate compound and a polythiol compound can be used. In order to introduce an ester bond into the polythiourethane resin, a method using a component having an ester bond or a method using a component capable of producing an ester bond by a reaction can be used. In one embodiment, an ester bond-containing compound can be used as one or more polymerizable compounds contained in the polymerizable composition. This point will be further described later.
　本発明および本明細書において、「ポリイソ（チオ）シアネート化合物」とは、イソ（チオ）シアネート基を１分子あたり２つ以上有する化合物をいうものとする。「イソ（チオ）シアネート」とは、イソシアネートおよび／またはイソチオシアネートを意味する。イソシアネートはイソシアナートと呼ばれることもあり、イソチオシアネートはイソチオシアナートと呼ばれることもある。「ポリチオール化合物」とは、チオール基を１分子あたり２つ以上有する化合物をいうものとする。 に お い て In the present invention and the present specification, the “polyiso (thio) cyanate compound” refers to a compound having two or more iso (thio) cyanate groups per molecule. "Iso (thio) cyanate" means isocyanate and / or isothiocyanate. Isocyanates are sometimes called isocyanates, and isothiocyanates are sometimes called isothiocyanates. “Polythiol compound” refers to a compound having two or more thiol groups per molecule.
（ポリイソ（チオ）シアネート化合物）
　ポリイソ（チオ）シアネート化合物は、脂肪族化合物、脂環式化合物、芳香族化合物、複素環式化合物等であることができる。ポリイソ（チオ）シアネート化合物が有するイソ（チオ）シアネート基の数は、１分子あたり２つ以上であり、好ましくは２～４つであり、より好ましくは２つまたは３つである。 (Polyiso (thio) cyanate compound)
The polyiso (thio) cyanate compound can be an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. The number of iso (thio) cyanate groups contained in the polyiso (thio) cyanate compound is 2 or more per molecule, preferably 2 to 4, more preferably 2 or 3.
　ポリイソ（チオ）シアネート化合物は、例えば、脂肪族化合物、脂環式化合物、芳香族化合物、複素環式化合物等であることができる。ポリイソ（チオ）シアネート化合物の具体例としては、ヘキサメチレンジイソシアネート、１，５－ペンタンジイソシアネート、イソホロンジイソシアネート、ビス（イソシアナトメチル）シクロヘキサン、ジシクロヘキシルメタンジイソシアネート、２，５－ビス（イソシアナトメチル）－ビシクロ[２．２．１]ヘプタン、２，６－ビス（イソシアナトメチル）－ビシクロ[２．２．１]ヘプタン、ビス（４－イソシアナトシクロへキシル）メタン、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，４－ビス（イソシアナトメチル）シクロヘキサン等の脂肪族ポリイソシアネート化合物；キシリレンジイソシアネート、１，３－ジイソシアナトベンゼン、トリレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族ポリイソシアネート化合物等を挙げることができる。更に、上記ポリイソ（チオ）シアネート化合物の塩素置換体、臭素置換体等のハロゲン置換体、アルキル置換体、アルコキシ置換体、ニトロ置換体や多価アルコールとのプレポリマー型変性体、カルボジイミド変性体、ウレア変性体、ビュレット変性体、ダイマー化またはトリマー化反応生成物等も使用できる。ポリイソ（チオ）シアネート化合物としては、一種のポリイソ（チオ）シアネート化合物のみ使用してもよく、二種以上のポリイソ（チオ）シアネート化合物を混合して使用してもよい。一態様では、上記重合性組成物は、ポリイソ（チオ）シアネート化合物として、環状構造含有化合物を含むことができる。環状構造含有化合物は、炭素環式化合物であってもよく、複素環式化合物であってもよく、また単環式化合物であってもよく、二環式以上の多環式化合物であってもよい。また、ポリイソ（チオ）シアネート化合物は、環状構造を複数含むものであってもよい。一態様では、ポリイソ（チオ）シアネート化合物は、芳香族化合物（芳香族ポリイソ（チオ）シアネート化合物）であることができる。 The polyiso (thio) cyanate compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. Specific examples of the polyiso (thio) cyanate compound include hexamethylene diisocyanate, 1,5-pentane diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, and 2,5-bis (isocyanatomethyl) -bicyclo. [2.2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanato) Aliphatic polyisocyanate compounds such as methyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane; aromatic polyisocyanates such as xylylene diisocyanate, 1,3-diisocyanatobenzene, tolylene diisocyanate and diphenylmethane diisocyanate Lithocyanate compounds and the like can be mentioned. Further, the polyiso (thio) cyanate compound may be a chlorine-substituted product, a halogen-substituted product such as a bromine-substituted product, an alkyl-substituted product, an alkoxy-substituted product, a nitro-substituted product, a modified prepolymer with a polyhydric alcohol, a carbodiimide-modified product, Urea modified products, buret modified products, dimerization or trimerization reaction products, and the like can also be used. As the polyiso (thio) cyanate compound, only one kind of polyiso (thio) cyanate compound may be used, or a mixture of two or more kinds of polyiso (thio) cyanate compounds may be used. In one aspect, the polymerizable composition can include a cyclic structure-containing compound as the polyiso (thio) cyanate compound. The cyclic structure-containing compound may be a carbocyclic compound, a heterocyclic compound, a monocyclic compound, or a bicyclic or higher polycyclic compound. Good. Further, the polyiso (thio) cyanate compound may include a plurality of cyclic structures. In one aspect, the polyiso (thio) cyanate compound can be an aromatic compound (aromatic polyiso (thio) cyanate compound).
　一態様では、ポリイソ（チオ）シアネート化合物は、エステル結合含有化合物であることができる。エステル結合を含有するポリイソ（チオ）シアネート化合物は、例えば、エステル結合を１分子あたり２つ以上含むことができ、例えば２～５つ含むことができる。 In one aspect, the polyiso (thio) cyanate compound can be an ester bond-containing compound. The polyiso (thio) cyanate compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, two to five ester bonds.
　上記重合性組成物におけるポリイソ（チオ）シアネート化合物の含有率は、上記重合性組成物の質量（１００質量％）に対して、例えば０質量％超５０．００質量％以下、好ましくは１０．００～３５．００質量％の範囲であることができる。本発明および本明細書において、重合性組成物の質量とは、重合性組成物が溶媒を含む場合には溶媒を除く質量をいうものとする。 The content of the polyiso (thio) cyanate compound in the polymerizable composition is, for example, more than 0% by mass and 50.00% by mass or less, preferably 10.00% by mass, based on the mass (100% by mass) of the polymerizable composition. It can be in the range of ～ 35.00% by mass. In the present invention and the present specification, the mass of the polymerizable composition means the mass excluding the solvent when the polymerizable composition contains a solvent.
（ポリチオール化合物）
　ポリチオール化合物は、脂肪族化合物、脂環式化合物、芳香族化合物、複素環式化合物等であることができる。ポリチオール化合物が有するチオール基の数は、１分子あたり２つ以上であり、好ましくは２～４つである。また、ポリチオール化合物が有するチオール基の数が１分子あたり３つ以上であることも好ましい。 (Polythiol compound)
The polythiol compound can be an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. The number of thiol groups contained in the polythiol compound is two or more per molecule, preferably 2 to 4. Further, the number of thiol groups contained in the polythiol compound is preferably 3 or more per molecule.
　ポリチオール化合物としては、例えば、メタンジチオール、１，２－エタンジチオール、１，１－プロパンジチオール、１，２－プロパンジチオール、１，３－プロパンジチオール、２，２－プロパンジチオール、１，６－ヘキサンジチオール、１，２，３－プロパントリチオール、テトラキス（メルカプトメチル）メタン、１，１－シクロヘキサンジチオール、１，２－シクロヘキサンジチオール、２，２－ジメチルプロパン－１，３－ジチオール、３，４－ジメトキシブタン－１，２－ジチオール、２－メチルシクロヘキサン－２，３－ジチオール、１，１－ビス（メルカプトメチル）シクロヘキサン、チオリンゴ酸ビス（２－メルカプトエチルエステル）、２，３－ジメルカプトコハク酸（２－メルカプトエチルエステル）、２，３－ジメルカプト－１－プロパノール（２－メルカプトアセテート）、２，３－ジメルカプト－１－プロパノール（３－メルカプトアセテート）、ジエチレングリコールビス（２－メルカプトアセテート）、ジエチレングリコールビス（３－メルカプトプロピオネート）、１，２－ジメルカプトプロピルメチルエーテル、２，３－ジメルカプトプロピルメチルエーテル、２，２－ビス（メルカプトメチル）－１，３－プロパンジチオール、ビス（２－メルカプトエチル）エーテル、エチレングリコールビス（２－メルカプトアセテート）、エチレングリコールビス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（２－メルカプトアセテート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（２－メルカプトアセテート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、１，２－ビス（２－メルカプトエチルチオ）－３－メルカプトプロパン等の脂肪族ポリチオール化合物；１，２－ジメルカプトベンゼン、１，３－ジメルカプトベンゼン、１，４－ジメルカプトベンゼン、１，２－ビス（メルカプトメチル）ベンゼン、１，３－ビス（メルカプトメチル）ベンゼン、１，４－ビス（メルカプトメチル）ベンゼン、１，３－ビス（メルカプトエチル）ベンゼン、１，４－ビス（メルカプトエチル）ベンゼン、１，２－ビス（メルカプトメトキシ）ベンゼン、１，３－ビス（メルカプトメトキシ）ベンゼン、１，４－ビス（メルカプトメトキシ）ベンゼン、１，２－ビス（メルカプトエトキシ）ベンゼン、１，３－ビス（メルカプトエトキシ）ベンゼン、１，４－ビス（メルカプトエトキシ）ベンゼン、１，２，３－トリメルカプトベンゼン、１，２，４－トリメルカプトベンゼン、１，３，５－トリメルカプトベンゼン、１，２，３－トリス（メルカプトメチル）ベンゼン、１，２，４－トリス（メルカプトメチル）ベンゼン、１，３，５－トリス（メルカプトメチル）ベンゼン、１，２，３－トリス（メルカプトエチル）ベンゼン、１，２，４－トリス（メルカプトエチル）ベンゼン、１，３，５－トリス（メルカプトエチル）ベンゼン、１，２，３－トリス（メルカプトメトキシ）ベンゼン、１，２，４－トリス（メルカプトメトキシ）ベンゼン、１，３，５－トリス（メルカプトメトキシ）ベンゼン、１，２，３－トリス（メルカプトエトキシ）ベンゼン、１，２，４－トリス（メルカプトエトキシ）ベンゼン、１，３，５－トリス（メルカプトエトキシ）ベンゼン、１，２，３，４－テトラメルカプトベンゼン、１，２，３，５－テトラメルカプトベンゼン、１，２，４，５－テトラメルカプトベンゼン、１，２，３，４－テトラキス（メルカプトメチル）ベンゼン、１，２，３，５－テトラキス（メルカプトメチル）ベンゼン、１，２，４，５－テトラキス（メルカプトメチル）ベンゼン、１，２，３，４－テトラキス（メルカプトエチル）ベンゼン、１，２，３，５－テトラキス（メルカプトエチル）ベンゼン、１，２，４，５－テトラキス（メルカプトエチル）ベンゼン、１，２，３，４－テトラキス（メルカプトエチル）ベンゼン、１，２，３，５－テトラキス（メルカプトメトキシ）ベンゼン、１，２，４，５－テトラキス（メルカプトメトキシ）ベンゼン、１，２，３，４－テトラキス（メルカプトエトキシ）ベンゼン、１，２，３，５－テトラキス（メルカプトエトキシ）ベンゼン、１，２，４，５－テトラキス（メルカプトエトキシ）ベンゼン、２，２'－ジメルカプトビフェニル、４，４' －ジメルカプトビフェニル、４，４' －ジメルカプトビベンジル、２，５－トルエンジチオール、３，４－トルエンジチオール、１，４－ナフタレンジチオール、１，５－ナフタレンジチオール、２，６－ナフタレンジチオール、２，７－ナフタレンジチオール、２，４－ジメチルベンゼン－１，３－ジチオール、４，５－ジメチルベンゼン－１，３－ジチオール、９，１０－アントラセンジメタンチオール、１，３－ジ（ｐ－メトキシフェニル）プロパン－２，２－ジチオール、１，３－ジフェニルプロパン－２，２－ジチオール、フェニルメタン－１，１－ジチオール、２，４－ジ（ｐ－メルカプトフェニル）ペンタン等の芳香族ポリチオール化合物；２，５－ジクロロベンゼン－１，３－ジチオール、１，３－ジ（ｐ－クロロフェニル）プロパン－２，２－ジチオール、３，４，５－トリブロム－１，２－ジメルカプトベンゼン、２，３，４，６－テトラクロル－１，５－ビス（メルカプトメチル）ベンゼン等の塩素置換体、臭素置換体等のハロゲン置換芳香族ポリチオール化合物；１，２－ビス（メルカプトメチルチオ）ベンゼン、１，３－ビス（メルカプトメチルチオ）ベンゼン、１，４－ビス（メルカプトメチルチオ）ベンゼン、１，２－ビス（メルカプトエチルチオ）ベンゼン、１，３－ビス（メルカプトエチルチオ）ベンゼン、１，４－ビス（メルカプトエチルチオ）ベンゼン、１，２，３－トリス（メルカプトメチルチオ）ベンゼン、１，２，４－トリス（メルカプトメチルチオ）ベンゼン、１，３，５－トリス（メルカプトメチルチオ）ベンゼン、１，２，３－トリス（メルカプトエチルチオ）ベンゼン、１，２，４－トリス（メルカプトエチルチオ）ベンゼン、１，３，５－トリス（メルカプトエチルチオ）ベンゼン、１，２，３，４－テトラキス（メルカプトメチルチオ）ベンゼン、１，２，３，５－テトラキス（メルカプトメチルチオ）ベンゼン、１，２，４，５－テトラキス（メルカプトメチルチオ）ベンゼン、１，２，３，４－テトラキス（メルカプトエチルチオ）ベンゼン、１，２，３，５－テトラキス（メルカプトエチルチオ）ベンゼン、１，２，４，５－テトラキス（メルカプトエチルチオ）ベンゼン等、およびこれらの核アルキル化物等のチオール基（メルカプト基とも呼ばれる。）以外に硫黄原子を含有する芳香族ポリチオール化合物；ビス（メルカプトメチル）スルフィド、ビス（メルカプトエチル）スルフィド、ビス（メルカプトプロピル）スルフィド、ビス（メルカプトメチルチオ）メタン、ビス（２－メルカプトエチルチオ）メタン、ビス（３－メルカプトプロピルチオ）メタン、１，２－ビス（メルカプトメチルチオ）エタン、１，２－ビス（２－メルカプトエチルチオ）エタン、１，２－ビス（３－メルカプトプロピルチオ）エタン、１，３－ビス（メルカプトメチルチオ）プロパン、１，３－ビス（２－メルカプトエチルチオ）プロパン、１，３－ビス（３－メルカプトプロピルチオ）プロパン、１，２－ビス（２－メルカプトエチルチオ）－３－メルカプトプロパン、２－メルカプトエチルチオ－１，３－プロパンジチオール、１，２，３－トリス（メルカプトメチルチオ）プロパン、１，２，３－トリス（２－メルカプトエチルチオ）プロパン、１，２，３－トリス（３－メルカプトプロピルチオ）プロパン、テトラキス（メルカプトメチルチオメチル）メタン、テトラキス（２－メルカプトエチルチオメチル）メタン、テトラキス（３－メルカプトプロピルチオメチル）メタン、ビス（２，３－ジメルカプトプロピル）スルフィド、２，５－ジメルカプト－１，４－ジチアン、ビス（メルカプトメチル）ジスルフィド、ビス（メルカプトエチル）ジスルフィド、ビス（メルカプトプロピル）ジスルフィド等、およびこれらのチオグリコール酸およびメルカプトプロピオン酸のエステル、ヒドロキシメチルスルフィドビス（２－メルカプトアセテート）、ヒドロキシメチルスルフィドビス（３－メルカプトプロピオネート）、ヒドロキシエチルスルフィドビス（２－メルカプトアセテート）、ヒドロキシエチルスルフィドビス（３－メルカプトプロピオネート）、ヒドロキシプロピルスルフィドビス（２－メルカプトアセテート）、ヒドロキシプロピルスルフィドビス（３－メルカプトプロピオネート）、ヒドロキシメチルジスルフィドビス（２－メルカプトアセテート）、ヒドロキシメチルジスルフィドビス（３－メルカプトプロピオネート）、ヒドロキシエチルジスルフィドビス（２－メルカプトアセテート）、ヒドロキシエチルジスルフィドビス（３－メルカプトプロピオネート）、ヒドロキシプロピルジスルフィドビス（２－メルカプトアセテート）、ヒドロキシプロピルジスルフィドビス（３－メルカプトプロピオネート）、２－メルカプトエチルエーテルビス（２－メルカプトアセテート）、２－メルカプトエチルエーテルビス（３－メルカプトプロピオネート）、１，４－ジチアン－２，５－ジオールビス（２－メルカプトアセテート）、１，４－ジチアン－２，５－ジオールビス（３－メルカプトプロピオネート）、チオグリコール酸（２－メルカプトエチルエステル）、チオジプロピオン酸ビス（２－メルカプトエチルエステル）、４，４' －チオジブチル酸ビス（２－メルカプトエチルエステル）、ジチオジグリコール酸ビス（２－メルカプトエチルエステル）、ジチオジプロピオン酸ビス（２－メルカプトエチルエステル）、４，４' －ジチオジブチル酸ビス（２－メルカプトエチルエステル）、チオジグリコール酸ビス（２，３－ジメルカプトプロピルエステル）、チオジプロピオン酸ビス（２，３－ジメルカプトプロピルエステル）、ジチオジグリコール酸ビス（２，３－ジメルカプトプロピルエステル）、ジチオジプロピオン酸ビス（２，３－ジメルカプトプロピルエステル）、４－メルカプトメチル－３，６－ジチアオクタン－１，８－ジチオール、ビス（１，３－ジメルカプト－２－プロピル）スルフィド、ビス（メルカプトメチル）－３，６，９－トリチアウンデカン－１，１１－ジチオール（「ビス（メルカプトメチル）－３，６，９－トリチア－１，１１－ウンデカンジチオール」とも呼ばれる；４，７－ビス（メルカプトメチル）－３，６，９－トリチアウンデカン－１，１１－ジチオール、４，８－ビス（メルカプトメチル）－３，６，９－トリチアウンデカン－１，１１－ジチオールおよび５，７－ビス（メルカプトメチル）－３，６，９－トリチアウンデカン－１，１１－ジチオールからなる群から選択される異性体の一種またはこれら異性体の二種もしくは三種の混合物）等のチオール基以外に硫黄原子を含有する脂肪族ポリチオール化合物；３，４－チオフェンジチオール、テトラヒドロチオフェン－２，５－ジメルカプトメチル、２，５－ジメルカプト－１，３，４－チアジアゾール、２，５－ジメルカプト－１，４－ジチアン、２，５－ジメルカプトメチル－１，４－ジチアン等のチオール基以外に硫黄原子を含有する複素環化合物等が挙げられる。 Examples of the polythiol compound include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, and 1,6-hexane Dithiol, 1,2,3-propanetrithiol, tetrakis (mercaptomethyl) methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4- Dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl thiomalate), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3 Dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethyleneglycol bis (3-mercaptopropionate), 1, 2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2- Mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropanetris (3-mercaptopropionate), pentae Aliphatic polythiol compounds such as thritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; Dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl ) Benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethoxy) benzene, 1,3-bis (mercaptomethoxy) benzene, 1,4 -Bis (mercaptomethoxy) benzene, 1,2-bis (mercaptoe Toxi) benzene, 1,3-bis (mercaptoethoxy) benzene, 1,4-bis (mercaptoethoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3 5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3 -Tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethoxy) benzene, 1,2 1,4-tris (mercaptomethoxy) benzene, 1,3,5-tris (mercaptomethoxy) benzene, 1,2,3-to (Mercaptoethoxy) benzene, 1,2,4-tris (mercaptoethoxy) benzene, 1,3,5-tris (mercaptoethoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3 1,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1 , 2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4 5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3 -Tetrakis (mercaptomethoxy) benzene, 1,2,4,5-tetrakis (mercaptomethoxy) benzene, 1,2,3,4-tetrakis (mercaptoethoxy) benzene, 1,2,3,5-tetrakis (mercaptoethoxy) ) Benzene, 1,2,4,5-tetrakis (mercaptoethoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4 ′ -dimercaptobiphenyl, 4,4 ′ -dimercaptobibenzyl, 2,5- Toluene dithiol, 3,4-toluene dithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol , 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthrace Dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-dithiol Aromatic polythiol compounds such as (p-mercaptophenyl) pentane; 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5 Halogen-substituted aromatic polythiol compounds such as chlorine-substituted products such as -tribromo-1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene, and bromine-substituted products; 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene ) Benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) Benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris ( Mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetraki Thiol groups such as (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, and their alkylated nuclei (Also called a mercapto group. ), Aromatic polythiol compounds containing a sulfur atom in addition to bis) (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane , Bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) ) -3-Mercaptopropane, 2-mercaptoethylthio-1, -Propanedithiol, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (Mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4 Dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and the like, and esters of thioglycolic acid and mercaptopropionic acid; hydroxymethylsulfide bis (2-mercapto Acetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate) , Hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyldisulfidebis (2-mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxy Ethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfidebis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3-mercaptopropionate), thioglycolic acid (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester) Bis (2-mercaptoethyl ester), 4,4 '}-thiodibutylate, bis (2-mercaptoethyl ester) dithiodiglycolate, bis (2-mercaptoethyl ester) dithiodipropionate, 4,4'}-dithiodibutyl Acid bis (2-mercaptoethyl ester), Bis (2,3-dimercaptopropyl ester) odiglycolate, bis (2,3-dimercaptopropyl ester) thiodipropionate, bis (2,3-dimercaptopropyl ester) dithiodiglycolate, dithiodipropion (2,3-dimercaptopropyl ester) acid, 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, bis (1,3-dimercapto-2-propyl) sulfide, bis (mercaptomethyl)- 3,6,9-trithiaundecane-1,11-dithiol (also called "bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol"; 4,7-bis (mercaptomethyl) -3,6,9-Trithiaundecane-1,11-dithiol, 4,8-bis (mercap Methyl) -3,6,9-trithiaundecane-1,11-dithiol and 5,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol. Polythiol compounds containing a sulfur atom in addition to a thiol group, such as one of the isomers or a mixture of two or three of these isomers); 3,4-thiophenedithiol, tetrahydrothiophene-2,5-dimercaptomethyl Containing a sulfur atom in addition to thiol groups such as 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,4-dithiane and 2,5-dimercaptomethyl-1,4-dithiane And the like.
　上記重合性組成物に含まれるポリチオール化合物は、一態様では、脂肪族化合物であることができる。また、一態様では、ポリチオール化合物は、エステル結合含有化合物であることができる。エステル結合を含有するポリチオール化合物は、例えば、エステル結合を１分子あたり２つ以上含むことができ、例えば２～５つ含むことができる。ポリチオール化合物は、一態様では、エステル結合含有脂肪族化合物であることができる。 ポ リ In one embodiment, the polythiol compound contained in the polymerizable composition can be an aliphatic compound. In one embodiment, the polythiol compound can be an ester bond-containing compound. The polythiol compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, 2 to 5 ester bonds. The polythiol compound, in one aspect, can be an ester bond-containing aliphatic compound.
　上記重合性組成物におけるポリチオール化合物の含有率は、上記重合性組成物の質量（１００質量％）に対して、例えば２０．００～８０．００質量％、好ましくは３０．００～７０．００質量％であることができる。 The content of the polythiol compound in the polymerizable composition is, for example, 20.00 to 80.00% by mass, preferably 30.00 to 70.00% by mass with respect to the mass (100% by mass) of the polymerizable composition. %.
（その他の成分）
　上記重合性組成物は、ポリイソ（チオ）シアネート化合物およびポリチオール化合物に加えて、一種以上の他の重合性化合物を含んでもよい。そのような重合性化合物としては、例えばポリエン化合物を挙げることができる。本発明および本明細書において、「ポリエン化合物」とは、炭素－炭素二重結合を１分子あたり２つ以上有する化合物をいうものとする。ポリエン化合物およびポリチオール化合物を含む重合性組成物の硬化物は、ポリエン化合物が有する炭素－炭素二重結合とポリチオール化合物が有するチオール基との反応（以下、「チオール－エン反応」と記載する。）により形成される結合を有することができる。 (Other components)
The polymerizable composition may include one or more other polymerizable compounds in addition to the polyiso (thio) cyanate compound and the polythiol compound. Examples of such a polymerizable compound include a polyene compound. In the present invention and the present specification, “polyene compound” refers to a compound having two or more carbon-carbon double bonds per molecule. A cured product of the polymerizable composition containing a polyene compound and a polythiol compound reacts with a carbon-carbon double bond of the polyene compound and a thiol group of the polythiol compound (hereinafter referred to as a “thiol-ene reaction”). Can have a bond formed by
　ポリエン化合物が有する炭素－炭素二重結合の数は、１分子あたり２つ以上であり、３つ以上であることが好ましく、例えば３～５つであることができる。ポリエン化合物は、炭素－炭素二重結合を、（メタ）アクリル基、ビニル基、アリル基等の炭素－炭素二重結合含有基中に含むことができる。ポリエン化合物に複数含まれる炭素－炭素二重結合含有基の種類は、同一であってもよく異なっていてもよい。 数 The number of carbon-carbon double bonds of the polyene compound is 2 or more, preferably 3 or more, for example, 3 to 5 per molecule. The polyene compound can include a carbon-carbon double bond in a carbon-carbon double bond-containing group such as a (meth) acryl group, a vinyl group, and an allyl group. The types of the carbon-carbon double bond-containing groups contained in the polyene compound may be the same or different.
　ポリエン化合物の具体例としては、ジビニルベンゼン、ジビニルトルエン等のビニル化合物、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキシド変性トリ（メタ）アクリレート等の（メタ）アクリレート、ジアリルフタレート、ジアリルマレエート、トリアリルシアヌレート、トリアリルイソシアヌレート、トリアリルトリメリテート、テトラアリロキシエタン等のアリル化合物等が挙げられる。ポリエン化合物としては、一種のポリエン化合物のみ使用してもよく、二種以上を混合して使用してもよい。 Specific examples of the polyene compound include vinyl compounds such as divinylbenzene and divinyltoluene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. (Meth) acrylates such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide-modified tri (meth) acrylate , Diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyl Allyl compounds such as Kishietan like. As the polyene compound, only one kind of polyene compound may be used, or two or more kinds may be used as a mixture.
　ポリエン化合物は、例えば、脂肪族化合物、脂環式化合物、芳香族化合物、複素環式化合物等であることができる。一態様では、ポリエン化合物は、環状構造含有化合物であることができる。環状構造含有化合物は、炭素環式化合物であってもよく、複素環式化合物であってもよく、また単環式化合物であってもよく、二環式以上の多環式化合物であってもよい。また、ポリエン化合物は、環状構造を複数含むものであってもよい。一態様では、ポリエン化合物は、複素脂環式化合物または複素芳香族化合物であることができ、具体的にはイソシアヌル環含有化合物またはシアヌル環含有化合物であることができる。 The polyene compound can be, for example, an aliphatic compound, an alicyclic compound, an aromatic compound, a heterocyclic compound, or the like. In one aspect, the polyene compound can be a cyclic structure containing compound. The cyclic structure-containing compound may be a carbocyclic compound, a heterocyclic compound, a monocyclic compound, or a bicyclic or higher polycyclic compound. Good. Further, the polyene compound may include a plurality of cyclic structures. In one aspect, the polyene compound can be a heteroalicyclic or heteroaromatic compound, and specifically can be an isocyanuric ring-containing compound or a cyanuric ring-containing compound.
　一態様では、ポリエン化合物は、エステル結合含有化合物であることができる。エステル結合を含有するポリエン化合物は、例えば、エステル結合を１分子あたり２つ以上含むことができ、例えば２～５つ含むことができる。 で は In one embodiment, the polyene compound can be an ester bond-containing compound. The polyene compound containing an ester bond can contain, for example, two or more ester bonds per molecule, for example, two to five ester bonds.
　上記重合性組成物におけるポリエン化合物の含有率は、上記重合性組成物の質量（１００質量％）に対して、例えば０質量％超５０．００質量％以下、好ましくは１０．００～３５．００質量％の範囲であることができる。 The content of the polyene compound in the polymerizable composition is, for example, more than 0% by mass and 50.00% by mass or less, preferably 10.00 to 35.00, based on the mass (100% by mass) of the polymerizable composition. % By weight.
　上記重合性組成物は、必要に応じて、光学部材の製造のために一般に用いられる添加剤、重合触媒等の公知の成分の一種以上を任意に含むことができる。添加剤としては、例えば、紫外線吸収剤、酸化防止剤、離型剤等の各種添加剤を挙げることができる。また、添加剤として、ホスフィン誘導体等の有機リン化合物を用いることもできる。添加剤の使用量は適宜設定することができる。 The polymerizable composition may optionally contain one or more known components such as additives and polymerization catalysts generally used for the production of optical members. Examples of the additive include various additives such as an ultraviolet absorber, an antioxidant, and a release agent. Also, an organic phosphorus compound such as a phosphine derivative can be used as an additive. The amount of the additive used can be appropriately set.
　また、上記重合性組成物は、重合触媒として、ポリイソ（チオ）シアネート化合物とポリチオール化合物とのチオウレタン化反応を触媒する重合触媒（以下、「第１の重合触媒」とも記載する。）を含むことが好ましい。
　また、上記重合性組成物がポリエン化合物を含む場合、重合触媒として、ポリエン化合物とポリイソ（チオ）シアネート化合物とのチオール－エン反応を触媒する重合触媒（以下、「第２の重合触媒」とも記載する。）を第１の重合触媒と併用することが好ましい。
　チオウレタン化反応を触媒する第１の重合触媒およびチオール－エン反応を触媒する第２の重合触媒としては、公知の重合触媒を用いることができる。
　チオウレタン化反応を触媒する第１の重合触媒としては、ジブチル錫ジアセテ－ト、ジブチル錫ジラウレ－ト、ジブチル錫ジクロライド、ジメチル錫ジクロライド、モノメチル錫トリクロライド、トリメチル錫クロライド、トリブチル錫クロライド、トリブチル錫フロライド、ジメチル錫ジブロマイド等の有機錫系化合物を挙げることができる。上記重合性組成物は、例えば、第１の重合触媒を、上記重合性組成物の質量（１００質量％）に対して、０．０１～０．５０質量％含むことができる。
　チオール－エン反応を触媒する第２の重合触媒としては、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビス－２，４－ジメチルバレロニトリル、ジメチル－２，２’－アゾビスイソオブチレート、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、１，１’－アゾビス（１－アセトキシ１－フェニルエタン）、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）等のアゾビス系化合物、過酸化ベンゾイル、過酸化アセチル、過酸化ｔｅｒｔ－ブチル、過酸化プロピオニル、過酸化ラウロイル、過酢酸ｔｅｒｔ－ブチル、過安息香酸ｔｅｒｔ－ブチル、ｔｅｒｔ－ブチルヒドロペルオキシド、ｔｅｒｔ－ブチルペルオキシピバレート、１，１－ビス（ｔ－ブチルパーオキシ）－３， ３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－アミルパーオキシ－２－エチルヘキサノエート、ｔ－アミルパーイソノナノエート、ｔ－アミルパーオキシアセテート、ｔ－アミルパーオキシベンゾエート等の過酸化物系化合物等を挙げることができる。上記重合性組成物は、例えば、第２の重合触媒を、上記重合性組成物の質量（１００質量％）に対して、０．０１～０．１０質量％含むことができる。 Further, the polymerizable composition includes, as a polymerization catalyst, a polymerization catalyst that catalyzes a thiourethanation reaction between a polyiso (thio) cyanate compound and a polythiol compound (hereinafter, also referred to as “first polymerization catalyst”). Is preferred.
When the polymerizable composition contains a polyene compound, a polymerization catalyst that catalyzes a thiol-ene reaction between the polyene compound and the polyiso (thio) cyanate compound (hereinafter also referred to as a “second polymerization catalyst”) Is preferably used in combination with the first polymerization catalyst.
As the first polymerization catalyst that catalyzes the thiourethane reaction and the second polymerization catalyst that catalyzes the thiol-ene reaction, known polymerization catalysts can be used.
Examples of the first polymerization catalyst that catalyzes the thiourethanation reaction include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, and tributyltin. Organic tin compounds such as fluoride and dimethyltin dibromide can be mentioned. The polymerizable composition can contain, for example, the first polymerization catalyst in an amount of 0.01 to 0.50% by mass based on the mass (100% by mass) of the polymerizable composition.
Examples of the second polymerization catalyst that catalyzes the thiol-ene reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis-2. , 4-Dimethylvaleronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (cyclohexane-1-carbonitrile), 1,1'-azobis (1-acetoxy-1-phenylethane) , Azobis compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauroyl peroxide, peracetic acid tert-butyl, tert-butyl perbenzoate, tert-butyl hydroperoxide, tert-butylperoxypivalate, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-amylperisononanoate, t Peroxide compounds such as -amylperoxyacetate and t-amylperoxybenzoate. The polymerizable composition may contain, for example, the second polymerization catalyst in an amount of 0.01 to 0.10% by mass based on the mass (100% by mass) of the polymerizable composition.
　上記重合性組成物は、以上説明した各種成分を同時に、または任意の順序で順次、混合することにより調製することができる。調製方法は特に限定されるものではなく、重合性組成物の調製方法として公知の方法を採用することができる。また、重合性組成物は、溶媒を添加せずに調製してもよく、任意の量の溶媒を添加して調製してもよい。溶媒としては、重合性組成物に使用可能な溶媒として公知の溶媒の一種以上を用いることができる。 The polymerizable composition can be prepared by mixing the various components described above simultaneously or sequentially in an arbitrary order. The preparation method is not particularly limited, and a known method for preparing a polymerizable composition can be employed. Further, the polymerizable composition may be prepared without adding a solvent, or may be prepared by adding an arbitrary amount of a solvent. As the solvent, one or more known solvents that can be used for the polymerizable composition can be used.
＜ポリチオウレタン樹脂の製造方法＞
　先に説明したポリイソ（チオ）シアネート化合物、ポリチオール化合物およびポリエン化合物は、いずれも重合性化合物であり、これら化合物を重合させることにより、上記重合性組成物を硬化させて硬化物（ポリチオウレタン樹脂）を得ることができる。こうして得られるポリチオウレタン樹脂は、各種光学部材として用いることができる。例えば、光学部材としては、眼鏡レンズ、望遠鏡レンズ、双眼鏡レンズ、顕微鏡レンズ、内視鏡レンズ、各種カメラの撮像系レンズ等の各種レンズを挙げることができる。本発明および本明細書における「レンズ」には、一層以上の層が任意に積層される「レンズ基材」が包含されるものとする。 <Method for producing polythiourethane resin>
The polyiso (thio) cyanate compound, polythiol compound, and polyene compound described above are all polymerizable compounds, and the above polymerizable composition is cured by polymerizing these compounds to obtain a cured product (polythiourethane resin). ) Can be obtained. The polythiourethane resin thus obtained can be used as various optical members. For example, examples of the optical member include various lenses such as a spectacle lens, a telescope lens, a binocular lens, a microscope lens, an endoscope lens, and an imaging system lens of various cameras. The “lens” in the present invention and the present specification includes a “lens substrate” in which one or more layers are arbitrarily laminated.
　例えば、レンズ形状を有する硬化物（「プラスチックレンズ」とも呼ばれる。）を製造するためには、注型重合が好ましい。注型重合では、所定の間隔をもって対向する２つのモールドと、上記間隔を閉塞することにより形成されたキャビティを有する成形型のキャビティへ重合性組成物を注入し、このキャビティ内で重合性組成物に含まれる重合性化合物の重合（硬化反応）を行い硬化物を得ることができる。注型重合に使用可能な成形型の詳細については、例えば特開２００９－２６２４８０号公報の段落００１２～００１４および同公報の図１を参照できる。上記公報では、２つのモールドの間隔を、封止部材としてガスケットにより閉塞した成形型が示されているが、封止部材としてはテープを用いることもできる。 For example, in order to produce a cured product having a lens shape (also referred to as “plastic lens”), cast polymerization is preferable. In the casting polymerization, the polymerizable composition is injected into a cavity of a mold having two cavities facing each other at a predetermined interval and a cavity formed by closing the space, and the polymerizable composition is injected into the cavity. The polymerization (curing reaction) of the polymerizable compound contained in the above can be performed to obtain a cured product. For details of molds usable for casting polymerization, refer to, for example, paragraphs 0012 to 0014 of JP-A-2009-262480 and FIG. 1 of the same. In the above publication, a molding die in which a gap between two molds is closed by a gasket as a sealing member is shown, but a tape may be used as the sealing member.
　一態様では、注型重合は、次のように行うことができる。重合性組成物を、成形型側面に設けた注入口から成形型キャビティに注入する。注入後、重合性組成物に含まれる重合性化合物を、好ましくは加熱により重合（硬化反応）させることで、重合性組成物が硬化し、キャビティの内部形状が転写された硬化物を得ることができる。重合条件は、特に限定されるものではなく、重合性組成物の組成等に応じて適宜設定することができる。一例として、重合性組成物をキャビティに注入した成形型を、加熱温度２０～１５０℃で１～７２時間程度加熱することができるが、この条件に限定されるものではない。本発明および本明細書において、注型重合に関する加熱温度等の温度とは、成形型が配置される雰囲気温度をいう。また、加熱中に、任意の昇温速度で昇温することができ、任意の降温速度で降温（冷却）することができる。重合（硬化反応）終了後、キャビティ内部の硬化物を成形型から離型する。注型重合において通常行われているように、キャビティを形成している上下モールドとガスケットまたはテープを任意の順序で取り外すことにより、硬化物を成形型から離型することができる。成形型から離型された硬化物（ポリチオウレタン樹脂）は、必要に応じて後処理を行った後、光学部材として用いることができ、例えば各種レンズ（例えばレンズ基材）として用いることができる。一例として、眼鏡レンズのレンズ基材として用いられる硬化物は、通常、離型後に、アニーリング、染色処理、丸め工程等の研削工程、研磨工程、耐衝撃性を向上させるためのプライマーコート層、表面硬度を上げるためのハードコート層等のコート層形成工程等の後工程に付され得る。更に、反射防止層、撥水層等の各種機能性層を、レンズ基材上に形成することができる。これらの工程については、いずれも公知技術を適用することができる。こうして、レンズ基材が上記ポリチオウレタン樹脂である眼鏡レンズを得ることができる。更に、この眼鏡レンズをフレームに取り付けることにより、眼鏡を得ることができる。 で は In one embodiment, the casting polymerization can be performed as follows. The polymerizable composition is injected into the mold cavity from an injection port provided on the side surface of the mold. After the injection, the polymerizable compound contained in the polymerizable composition is preferably polymerized (cured reaction) by heating, whereby the polymerizable composition is cured, and a cured product in which the internal shape of the cavity is transferred can be obtained. it can. The polymerization conditions are not particularly limited, and can be appropriately set according to the composition of the polymerizable composition and the like. As an example, the mold in which the polymerizable composition has been injected into the cavity can be heated at a heating temperature of 20 to 150 ° C. for about 1 to 72 hours, but is not limited to this condition. In the present invention and the present specification, the temperature such as a heating temperature for casting polymerization refers to an ambient temperature at which a mold is placed. In addition, during heating, the temperature can be increased at an arbitrary rate, and the temperature can be decreased (cooled) at an arbitrary rate. After the completion of the polymerization (curing reaction), the cured product inside the cavity is released from the mold. As is usually done in casting polymerization, the cured product can be released from the mold by removing the upper and lower molds and the gasket or tape forming the cavity in any order. The cured product (polythiourethane resin) released from the mold can be used as an optical member after post-processing as necessary, and can be used as, for example, various lenses (for example, a lens substrate). . As an example, a cured product used as a lens base material for an eyeglass lens is usually, after release, annealing, dyeing, a grinding process such as a rounding process, a polishing process, a primer coat layer for improving impact resistance, and a surface. It can be applied to a post-process such as a process of forming a coat layer such as a hard coat layer for increasing hardness. Further, various functional layers such as an antireflection layer and a water-repellent layer can be formed on the lens substrate. For each of these steps, a known technique can be applied. Thus, an eyeglass lens in which the lens substrate is the above polythiourethane resin can be obtained. Furthermore, spectacles can be obtained by attaching this spectacle lens to a frame.
　上記ポリチオウレタン樹脂は、好ましくは染色処理に付すことができる。上記ポリチオウレタン樹脂は、優れた染色性を示すことができる。染色処理は、例えば、染料を含む染色浴に上記硬化物を浸漬することにより行うことができる。染色浴は、例えば、市販の染料を、必要に応じて溶媒により希釈することにより調製することができる。また、染色浴には、必要に応じて界面活性剤等の公知の添加剤を添加することもできる。染色浴の温度は、例えば３０～１００℃の範囲であることができる。染色浴への硬化物の浸漬時間は、特に限定されるものではないが、例えば１分～１時間程度である。また、  上記染色処理後、染料を定着させるために加熱処理を行ってもよい。この加熱処理における加熱温度（例えば加熱処理を行う加熱炉の炉内の雰囲気温度）は、例えば３０℃～１２０℃、加熱処理時間は例えば１５分～２時間であるが、特に制限はない。また、染色処理後、必要に応じて、洗浄や先に例示した後工程の１つ以上を行うことができる。 The above polythiourethane resin can be preferably subjected to a dyeing treatment. The polythiourethane resin can exhibit excellent dyeability. The dyeing treatment can be performed, for example, by immersing the cured product in a dyeing bath containing a dye. The dyeing bath can be prepared, for example, by diluting a commercially available dye with a solvent as necessary. In addition, known additives such as a surfactant can be added to the dyeing bath as needed. The temperature of the dye bath can be, for example, in the range from 30 to 100 ° C. The immersion time of the cured product in the dyeing bath is not particularly limited, but is, for example, about 1 minute to 1 hour. Further, (1) After the dyeing treatment, a heat treatment may be performed to fix the dye. The heating temperature in this heat treatment (for example, the ambient temperature in the furnace of the heating furnace for performing the heat treatment) is, for example, 30 ° C. to 120 ° C., and the heat treatment time is, for example, 15 minutes to 2 hours, but is not particularly limited. After the dyeing treatment, if necessary, washing and one or more of the post-processes exemplified above can be performed.
［光学部材］
　本発明の一態様は、上記ポリチオウレタン樹脂が染色されてなる光学部材に関する。上記ポリチオウレタン樹脂および染色処理等の光学部材に関する詳細については、先の記載を参照できる。 [Optical members]
One embodiment of the present invention relates to an optical member obtained by dyeing the polythiourethane resin. The above description can be referred to for details regarding the above-mentioned polythiourethane resin and optical members such as dyeing treatment.
　以下、本発明を実施例により更に詳細に説明するが、本発明は実施例に示す態様に限定されるものではない。以下に記載の操作および評価は、特記しない限り、大気中室温下（２０～２５℃程度）で行った。また、以下に記載の％は、特記しない限り質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the embodiments shown in the examples. The operations and evaluations described below were performed in the air at room temperature (about 20 to 25 ° C.) unless otherwise specified. The percentages described below are based on mass unless otherwise specified.
［比較例１］
　３００ｍｌナス型フラスコに、ポリイソシアネート化合物として２，４－トリレンジイソシアネート（ＴＤＩ）４４．６ｇを仕込み、有機リン化合物としてトリフェニルホスフィン（ＴＰＰ）０．３０ｇ、離型剤としてブトキシエチルアシッドホスフェート（城北化学株式会社製ＪＰ－５０６Ｈ）０．１５ｇ、重合触媒としてジメチル錫ジクロライド０．０４ｇを添加し、２０℃窒素パージ下で１時間撹拌を続けた。これらが完全に溶解したところで、ポリチオール化合物としてぺンタエリスリトールテトラキス（２－メルカプトアセテート）（ＰＥＴＭＡ）５５．４ｇを配合し、０．１３ｋＰａ（１．０Ｔｏｒｒ）で２０分減圧撹拌を行い、ポリイソシアネート化合物およびポリチオール化合物を含み、ポリエン化合物を含まない重合性組成物１を調製した。
　この重合性組成物１を、孔径１．０μｍのポリテトラフルオロエチレンメンブランフィルターを通して成形型のキャビティに注入し、初期温度２５℃から最終温度１２０℃の温度プログラムにて２４時間注型重合を行い、中心肉厚２ｍｍのプラスチックレンズを作製した。
　こうして作製されたプラスチックレンズのチオウレタン結合の含有率は３８．４２質量％、エステル結合の含有率は２２．５４質量％である。
　作製されたプラスチックレンズを、成形型から離型した後、下記条件による染色処理に付した。染色処理後のプラスチックレンズの染色濃度を、カラー濃度試験機を使用して以下の条件で測定した。
（染色条件）
染料：茶色系染料水溶液
染色浴の温度：８１℃
染色時間（染色浴への浸漬時間）：１０分間
（染色濃度の測定条件）
測定波長：５５０ｎｍ
染色濃度：１００－透過率［％Ｔ］(５５０ｎｍ) [Comparative Example 1]
In a 300 ml eggplant type flask, 44.6 g of 2,4-tolylene diisocyanate (TDI) was charged as a polyisocyanate compound, 0.30 g of triphenylphosphine (TPP) as an organic phosphorus compound, and butoxyethyl acid phosphate (Johoku) as a release agent. 0.15 g of JP-506H manufactured by Chemical Co., Ltd.) and 0.04 g of dimethyltin dichloride as a polymerization catalyst were added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C. When these were completely dissolved, 55.4 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was blended as a polythiol compound, and the mixture was stirred under reduced pressure at 0.13 kPa (1.0 Torr) for 20 minutes to obtain a polyisocyanate compound. And a polymerizable composition 1 containing a polythiol compound and no polyene compound.
This polymerizable composition 1 was poured into a cavity of a mold through a polytetrafluoroethylene membrane filter having a pore size of 1.0 μm, and cast polymerization was performed for 24 hours by a temperature program at an initial temperature of 25 ° C. to a final temperature of 120 ° C., A plastic lens having a center thickness of 2 mm was produced.
The plastic lens thus produced has a thiourethane bond content of 38.42% by mass and an ester bond content of 22.54% by mass.
After the produced plastic lens was released from the mold, it was subjected to a dyeing treatment under the following conditions. The dyeing density of the plastic lens after the dyeing treatment was measured using a color density tester under the following conditions.
(Staining conditions)
Dye: Brown dye aqueous solution Dyeing bath temperature: 81 ° C
Dyeing time (immersion time in dyeing bath): 10 minutes (measuring conditions of dyeing concentration)
Measurement wavelength: 550 nm
Staining concentration: 100-transmittance [% T] (550 nm)
［実施例１］
　３００ｍｌナス型フラスコに、ポリイソ（チオ）シアネート化合物として２，４－トリレンジイソシアネート（ＴＤＩ）１０．９ｇ、ポリエン化合物としてトリアリルイソシアヌレート（ＴＡＩＣ）３２．８ｇを仕込み、有機リン化合物としてトリフェニルホスフィン（ＴＰＰ）０．３０ｇ、離型剤としてブトキシエチルアシッドホスフェート（城北化学株式会社製ＪＰ－５０６Ｈ）０．１５ｇ、重合触媒としてジメチル錫ジクロライド０．０１ｇおよび２，２’―アゾビスー２，４－ジメチルバレロニトリル０．０２ｇを添加し、２０℃窒素パージ下で１時間撹拌を続けた。これらが完全に溶解したところで、ポリチオール化合物としてぺンタエリスリトールテトラキス（２－メルカプトアセテート）（ＰＥＴＭＡ）５６．３ｇを配合し、０．１３ｋＰａ（１．０Ｔｏｒｒ）で２０分減圧撹拌を行い、ポリエン化合物、ポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物２を調製した。
　この重合性組成物２を、孔径１．０μｍのポリテトラフルオロエチレンメンブランフィルターを通して成形型のキャビティに注入し、初期温度２５℃から最終温度１２０℃の温度プログラムにて２４時間注型重合を行い、中心肉厚２ｍｍのプラスチックレンズを作製した。
　こうして作製されたプラスチックレンズのチオウレタン結合の含有率は９．４１質量％、エステル結合の含有率は２２．８９質量％である。
　作製されたプラスチックレンズを、成形型から離型した後、上記条件による染色処理に付した。染色処理後のプラスチックレンズの染色濃度を上記方法により測定した。 [Example 1]
A 300 ml eggplant-shaped flask was charged with 10.9 g of 2,4-tolylene diisocyanate (TDI) as a polyiso (thio) cyanate compound and 32.8 g of triallyl isocyanurate (TAIC) as a polyene compound, and triphenylphosphine as an organic phosphorus compound. (TPP) 0.30 g, butoxyethyl acid phosphate (JP-506H manufactured by Johoku Chemical Co., Ltd.) 0.15 g as a release agent, dimethyltin dichloride 0.01 g and 2,2′-azobis-2,4-dimethyl as a polymerization catalyst 0.02 g of valeronitrile was added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C. When these were completely dissolved, 56.3 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was blended as a polythiol compound, and the mixture was stirred under reduced pressure at 0.13 kPa (1.0 Torr) for 20 minutes to obtain a polyene compound, Polymerizable composition 2 containing a polyiso (thio) cyanate compound and a polythiol compound was prepared.
This polymerizable composition 2 was injected into a cavity of a mold through a polytetrafluoroethylene membrane filter having a pore size of 1.0 μm, and cast polymerization was performed for 24 hours by a temperature program at an initial temperature of 25 ° C. to a final temperature of 120 ° C., A plastic lens having a center thickness of 2 mm was produced.
The plastic lens thus manufactured has a thiourethane bond content of 9.41% by mass and an ester bond content of 22.89% by mass.
After the produced plastic lens was released from the mold, it was subjected to a dyeing treatment under the above conditions. The staining density of the plastic lens after the staining treatment was measured by the above method.
［実施例２］
　３００ｍｌナス型フラスコに、ポリイソ（チオ）シアネート化合物として２，４－トリレンジイソシアネート（ＴＤＩ）２２．０ｇ、ポリエン化合物としてトリアリルイソシアヌレート（ＴＡＩＣ）２２．０ｇを仕込み、有機リン化合物としてトリフェニルホスフィン（ＴＰＰ）０．３０ｇ、離型剤としてブトキシエチルアシッドホスフェート（城北化学株式会社製ＪＰ－５０６Ｈ）０．１５ｇ、重合触媒としてジメチル錫ジクロライド０．０２ｇおよび２，２’―アゾビスー２，４－ジメチルバレロニトリル０．０２ｇを添加し、２０℃窒素パージ下で１時間撹拌を続けた。これらが完全に溶解したところで、ポリチオール化合物としてぺンタエリスリトールテトラキス（２－メルカプトアセテート）（ＰＥＴＭＡ）５６．０ｇを配合し、０．１３ｋＰａ（１．０Ｔｏｒｒ）で２０分減圧撹拌を行い、ポリエン化合物、ポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物３を調製した。
　この重合性組成物３を、孔径１．０μｍのポリテトラフルオロエチレンメンブランフィルターを通して成形型のキャビティに注入し、初期温度２５℃から最終温度１２０℃の温度プログラムにて２４時間注型重合を行い、中心肉厚２ｍｍのプラスチックレンズを作製した。
　こうして作製されたプラスチックレンズのチオウレタン結合の含有率は１８．９８質量％、エステル結合の含有率は２２．７８質量％である。
　作製されたプラスチックレンズを、成形型から離型した後、上記条件による染色処理に付した。染色処理後のプラスチックレンズの染色濃度を上記方法により測定した。 [Example 2]
In a 300 ml eggplant-shaped flask, 22.0 g of 2,4-tolylene diisocyanate (TDI) as a polyiso (thio) cyanate compound and 22.0 g of triallyl isocyanurate (TAIC) as a polyene compound were charged, and triphenylphosphine was used as an organic phosphorus compound. (TPP) 0.30 g, butoxyethyl acid phosphate (JP-506H manufactured by Johoku Chemical Co., Ltd.) 0.15 g as a release agent, dimethyltin dichloride 0.02 g and 2,2′-azobis-2,4-dimethyl as a polymerization catalyst 0.02 g of valeronitrile was added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C. When these were completely dissolved, 56.0 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was blended as a polythiol compound, and the mixture was stirred under reduced pressure at 0.13 kPa (1.0 Torr) for 20 minutes to obtain a polyene compound, Polymerizable composition 3 containing a polyiso (thio) cyanate compound and a polythiol compound was prepared.
The polymerizable composition 3 was injected into a cavity of a mold through a polytetrafluoroethylene membrane filter having a pore size of 1.0 μm, and cast polymerization was performed for 24 hours by a temperature program at an initial temperature of 25 ° C. to a final temperature of 120 ° C., A plastic lens having a center thickness of 2 mm was produced.
The plastic lens thus manufactured has a thiourethane bond content of 18.98% by mass and an ester bond content of 22.78% by mass.
After the produced plastic lens was released from the mold, it was subjected to a dyeing treatment under the above conditions. The staining density of the plastic lens after the staining treatment was measured by the above method.
［実施例３］
　３００ｍｌナス型フラスコに、ポリイソ（チオ）シアネート化合物として２，４－トリレンジイソシアネート（ＴＤＩ）３３．２ｇ、ポリエン化合物としてトリアリルイソシアヌレート（ＴＡＩＣ）１１．１ｇを仕込み、有機リン化合物としてトリフェニルホスフィン（ＴＰＰ）０．３０ｇ、離型剤としてブトキシエチルアシッドホスフェート（城北化学株式会社製ＪＰ－５０６Ｈ）０．１５ｇ、重合触媒としてジメチル錫ジクロライド０．０３ｇおよび２，２’―アゾビスー２，４－ジメチルバレロニトリル０．０２ｇを添加し、２０℃窒素パージ下で１時間撹拌を続けた。これらが完全に溶解したところで、ポリチオール化合物としてぺンタエリスリトールテトラキス（２－メルカプトアセテート）（ＰＥＴＭＡ）５５．７ｇを配合し、０．１３ｋＰａ（１．０Ｔｏｒｒ）で２０分減圧撹拌を行い、ポリエン化合物、ポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物４を調製した。
　この重合性組成物４を、孔径１．０μｍのポリテトラフルオロエチレンメンブランフィルターを通して成形型のキャビティに注入し、初期温度２５℃から最終温度１２０℃の温度プログラムにて２４時間注型重合を行い、中心肉厚２ｍｍのプラスチックレンズを作製した。
　こうして作製されたプラスチックレンズのチオウレタン結合の含有率は、２８．７４質量％、エステル結合の含有率は２２．６６質量％である。
　作製されたプラスチックレンズを、成形型から離型した後、上記条件による染色処理に付した。染色処理後のプラスチックレンズの染色濃度を上記方法により測定した。 [Example 3]
A 300 ml eggplant-shaped flask was charged with 33.2 g of 2,4-tolylene diisocyanate (TDI) as a polyiso (thio) cyanate compound and 11.1 g of triallyl isocyanurate (TAIC) as a polyene compound, and triphenylphosphine as an organic phosphorus compound. (TPP) 0.30 g, butoxyethyl acid phosphate (JP-506H manufactured by Johoku Chemical Co., Ltd.) 0.15 g as a release agent, dimethyltin dichloride 0.03 g and 2,2′-azobis-2,4-dimethyl as a polymerization catalyst 0.02 g of valeronitrile was added, and stirring was continued for 1 hour under a nitrogen purge at 20 ° C. When these were completely dissolved, 55.7 g of pentaerythritol tetrakis (2-mercaptoacetate) (PETMA) was blended as a polythiol compound, and the mixture was stirred under reduced pressure at 0.13 kPa (1.0 Torr) for 20 minutes to obtain a polyene compound, Polymerizable composition 4 containing a polyiso (thio) cyanate compound and a polythiol compound was prepared.
This polymerizable composition 4 was injected into a cavity of a mold through a polytetrafluoroethylene membrane filter having a pore size of 1.0 μm, and cast polymerization was performed for 24 hours by a temperature program at an initial temperature of 25 ° C. to a final temperature of 120 ° C., A plastic lens having a center thickness of 2 mm was produced.
The plastic lens thus produced has a thiourethane bond content of 28.74% by mass and an ester bond content of 22.66% by mass.
After the produced plastic lens was released from the mold, it was subjected to a dyeing treatment under the above conditions. The staining density of the plastic lens after the staining treatment was measured by the above method.
　実施例１～３のプラスチックレンズと比較例１のプラスチックレンズは、いずれもポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物から作製されたポリチオウレタン樹脂であるが、チオウレタン結合の含有率が３０．００質量％以下でありエステル結合含有率が１５．００質量％以上である実施例１～３のプラスチックレンズは、比較例１のプラスチックレンズよりも優れた染色性（高い染色濃度）を示した。このような実施例１～３のプラスチックレンズは、優れた染色性を有することが望まれる眼鏡レンズ等の各種光学部材として好適である。例えば、実施例１～３の染色後のプラスチックレンズをレンズ基材として用いることにより、ファッション性、遮光性等の点から眼鏡レンズとして好ましい色調を呈する眼鏡レンズを製造することができる。また、染色濃度は、「実施例３＜実施例２＜実施例１」の順に高かった。 Each of the plastic lenses of Examples 1 to 3 and the plastic lens of Comparative Example 1 is a polythiourethane resin prepared from a polymerizable composition containing a polyiso (thio) cyanate compound and a polythiol compound. The plastic lenses of Examples 1 to 3 having a content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more had better dyeability (higher dyeing density) than the plastic lens of Comparative Example 1. )showed that. Such plastic lenses of Examples 1 to 3 are suitable as various optical members such as spectacle lenses which are desired to have excellent dyeability. For example, by using the dyed plastic lenses of Examples 1 to 3 as a lens substrate, it is possible to produce spectacle lenses exhibiting a favorable color tone as spectacle lenses in terms of fashionability, light shielding properties, and the like. The staining density was higher in the order of “Example 3 <Example 2 <Example 1”.
　重合性組成物１～４は、ポリイソ（チオ）シアネート化合物が有するイソシアネート基の全量がポリチオール化合物に含まれるチオール基と反応可能なモル比で各種重合性化合物を含む。上記のチオウレタン結合の含有率は、ポリイソ（チオ）シアネート化合物が有するイソシアネート基の全量が反応してチオウレタン結合が生成されるものとして、下記式により算出した値である。
　チオウレタン結合の含有率＝（生成されるチオウレタン結合の質量／重合性組成物の総質量）×１００
　また、重合性組成物１～４に含まれるポリチオール化合物であるＰＥＴＭＡは、エステル結合を含む。上記のエステル結合の含有率は、下記式により算出した値である。
　エステル結合の含有率＝（使用したＰＥＴＭＡに含まれるエステル結合の総質量／重合性組成物の総質量）×１００ The polymerizable compositions 1 to 4 contain various polymerizable compounds in a molar ratio such that the total amount of the isocyanate groups of the polyiso (thio) cyanate compound can react with the thiol groups contained in the polythiol compound. The thiourethane bond content is a value calculated by the following formula, assuming that all the isocyanate groups of the polyiso (thio) cyanate compound react to form a thiourethane bond.
Thiourethane bond content = (mass of thiourethane bond formed / total weight of polymerizable composition) × 100
PETMA, which is a polythiol compound contained in the polymerizable compositions 1 to 4, contains an ester bond. The content of the above ester bond is a value calculated by the following equation.
Ester bond content = (total weight of ester bonds contained in PETMA used / total weight of polymerizable composition) × 100
　最後に、前述の各態様を総括する。 Lastly, the above-mentioned aspects are summarized.
　一態様によれば、チオウレタン結合の含有率が３０．００質量％以下であり、かつエステル結合の含有率が１５．００質量％以上である、光学部材用ポリチオウレタン樹脂が提供される。 According to one embodiment, there is provided a polythiourethane resin for an optical member having a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more.
　上記ポリチオウレタン樹脂は、高い染色性を示すことができる。 The polythiourethane resin can exhibit high dyeability.
　一態様では、上記ポリチオウレタン樹脂のエステル結合の含有率は、１５．００～３０．００質量％の範囲であることができる。 In one embodiment, the content of the ester bond in the polythiourethane resin can be in the range of 15.00 to 30.00% by mass.
　一態様では、上記ポリチオウレタン樹脂は、ポリエン化合物、ポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物を硬化した硬化物であることができる。 In one aspect, the polythiourethane resin can be a cured product obtained by curing a polymerizable composition containing a polyene compound, a polyiso (thio) cyanate compound, and a polythiol compound.
　一態様では、上記ポリエン化合物は、環状構造含有化合物であることができる。 In one aspect, the polyene compound may be a cyclic structure-containing compound.
　一態様では、上記環状構造は、イソシアヌル環であることができる。 In one aspect, the cyclic structure can be an isocyanuric ring.
　一態様では、上記ポリエン化合物は、アリル化合物であることができる。 In one aspect, the polyene compound can be an allyl compound.
　一態様では、上記ポリエン化合物は、炭素－炭素二重結合を１分子あたり３つ以上含有する化合物であることができる。 In one embodiment, the polyene compound may be a compound containing three or more carbon-carbon double bonds per molecule.
　一態様では、上記ポリチオール化合物は、脂肪族化合物であることができる。 In one aspect, the polythiol compound can be an aliphatic compound.
　一態様では、上記ポリチオール化合物は、エステル結合含有化合物であることができる。 In one aspect, the polythiol compound can be an ester bond-containing compound.
　一態様では、上記ポリチオール化合物は、チオール基を１分子あたり３つ以上含有する化合物であることができる。 In one aspect, the polythiol compound may be a compound containing three or more thiol groups per molecule.
　一態様では、上記ポリイソ（チオ）シアネート化合物は、芳香族化合物であることができる。 In one aspect, the polyiso (thio) cyanate compound can be an aromatic compound.
　一態様では、上記光学部材は、レンズであることができる。 In one aspect, the optical member may be a lens.
　一態様では、上記レンズは、眼鏡レンズであることができる。 In one aspect, the lens may be a spectacle lens.
　一態様によれば、上記ポリチオウレタン樹脂が染色されてなる光学部材が提供される。 According to one aspect, there is provided an optical member obtained by dyeing the polythiourethane resin.
　本明細書に記載の各種態様は、任意の組み合わせで２つ以上を組み合わせることができる。 各種 The various aspects described in this specification can be combined in any combination of two or more.
　今回開示された実施の形態はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて請求の範囲によって示され、請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 The embodiments disclosed this time are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
　本発明の一態様は、眼鏡レンズ等の各種光学部材の製造分野において有用である。 の 一 One embodiment of the present invention is useful in the field of manufacturing various optical members such as spectacle lenses.

Claims (14)

  1. チオウレタン結合の含有率が３０．００質量％以下であり、かつエステル結合の含有率が１５．００質量％以上である、光学部材用ポリチオウレタン樹脂。 A polythiourethane resin for an optical member having a thiourethane bond content of 30.00% by mass or less and an ester bond content of 15.00% by mass or more.
  2. エステル結合の含有率が、１５．００～３０．００質量％の範囲である、請求項１に記載の光学部材用ポリチオウレタン樹脂。 2. The polythiourethane resin for an optical member according to claim 1, wherein the content of the ester bond is in the range of 15.00 to 30.00% by mass.
  3. ポリエン化合物、ポリイソ（チオ）シアネート化合物およびポリチオール化合物を含む重合性組成物を硬化した硬化物である、請求項１または２に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to claim 1 or 2, which is a cured product obtained by curing a polymerizable composition containing a polyene compound, a polyiso (thio) cyanate compound, and a polythiol compound.
  4. 前記ポリエン化合物は、環状構造含有化合物である、請求項３に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to claim 3, wherein the polyene compound is a compound having a cyclic structure.
  5. 前記環状構造は、イソシアヌル環である、請求項４に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to claim 4, wherein the cyclic structure is an isocyanuric ring.
  6. 前記ポリエン化合物は、アリル化合物である、請求項３～５のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to any one of claims 3 to 5, wherein the polyene compound is an allyl compound.
  7. 前記ポリエン化合物は、炭素－炭素二重結合を１分子あたり３つ以上含有する化合物である、請求項３～６のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 7. The polythiourethane resin for an optical member according to claim 3, wherein the polyene compound is a compound containing three or more carbon-carbon double bonds per molecule.
  8. 前記ポリチオール化合物は、脂肪族化合物である、請求項３～７のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 8. The polythiourethane resin for an optical member according to claim 3, wherein the polythiol compound is an aliphatic compound.
  9. 前記ポリチオール化合物は、エステル結合含有化合物である、請求項３～８のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 9. The polythiourethane resin for an optical member according to claim 3, wherein the polythiol compound is an ester bond-containing compound.
  10. 前記ポリチオール化合物は、チオール基を１分子あたり３つ以上含有する化合物である、請求項３～９のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to any one of claims 3 to 9, wherein the polythiol compound is a compound containing three or more thiol groups per molecule.
  11. 前記ポリイソ（チオ）シアネート化合物は、芳香族化合物である、請求項３～１０のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 11. The polythiourethane resin for an optical member according to claim 3, wherein the polyiso (thio) cyanate compound is an aromatic compound.
  12. 前記光学部材はレンズである、請求項１～１１のいずれか１項に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to any one of claims 1 to 11, wherein the optical member is a lens.
  13. 前記レンズは眼鏡レンズである、請求項１２に記載の光学部材用ポリチオウレタン樹脂。 The polythiourethane resin for an optical member according to claim 12, wherein the lens is a spectacle lens.
  14. 請求項１～１３のいずれか１項に記載のポリチオウレタン樹脂が染色されてなる光学部材。 An optical member obtained by dyeing the polythiourethane resin according to any one of claims 1 to 13.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020004534A1 (en) * 2018-06-29 2021-06-24 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ Hardened product for optical member and optical member
JPWO2020004532A1 (en) * 2018-06-29 2021-06-24 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ Polymerizable compositions for optical members and optical members
JPWO2020004531A1 (en) * 2018-06-29 2021-07-08 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ A polymerizable composition for an optical member, an optical member, and a method for manufacturing the optical member.

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5780428A (en) * 1980-11-10 1982-05-20 Sumitomo Bakelite Co Ltd Curable composition
JPS61159462A (en) * 1984-12-21 1986-07-19 ロクタイト．（アイルランド）．リミテツド Coating composition
JPH0379614A (en) * 1989-08-22 1991-04-04 Kureha Chem Ind Co Ltd Plastic lens material having high refractive index and low specific gravity
JPH0525240A (en) * 1991-07-19 1993-02-02 Mitsubishi Rayon Co Ltd Composition for plastic lens
JPH05287050A (en) * 1992-04-13 1993-11-02 Mitsubishi Petrochem Co Ltd High refractive index optical material and its production
JPH0971625A (en) * 1995-06-30 1997-03-18 Mitsui Toatsu Chem Inc Sulfur-containing urethane resin composition, the resin, and optical element and lens comprising the resin
JPH10114825A (en) * 1996-04-19 1998-05-06 Mitsui Chem Inc Composition for optical resin and its use

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3816202A4 (en) * 2018-06-29 2022-03-16 Hoya Lens Thailand Ltd. Cured object for optical member and optical member
WO2020004531A1 (en) * 2018-06-29 2020-01-02 ホヤ レンズ タイランド リミテッド Polymerizable composition for optical member, optical member, and method for producing optical member
EP3816201A4 (en) * 2018-06-29 2022-04-20 Hoya Lens Thailand Ltd. Polymerizable composition for optical member, and optical member

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5780428A (en) * 1980-11-10 1982-05-20 Sumitomo Bakelite Co Ltd Curable composition
JPS61159462A (en) * 1984-12-21 1986-07-19 ロクタイト．（アイルランド）．リミテツド Coating composition
JPH0379614A (en) * 1989-08-22 1991-04-04 Kureha Chem Ind Co Ltd Plastic lens material having high refractive index and low specific gravity
JPH0525240A (en) * 1991-07-19 1993-02-02 Mitsubishi Rayon Co Ltd Composition for plastic lens
JPH05287050A (en) * 1992-04-13 1993-11-02 Mitsubishi Petrochem Co Ltd High refractive index optical material and its production
JPH0971625A (en) * 1995-06-30 1997-03-18 Mitsui Toatsu Chem Inc Sulfur-containing urethane resin composition, the resin, and optical element and lens comprising the resin
JPH10114825A (en) * 1996-04-19 1998-05-06 Mitsui Chem Inc Composition for optical resin and its use

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020004534A1 (en) * 2018-06-29 2021-06-24 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ Hardened product for optical member and optical member
JPWO2020004532A1 (en) * 2018-06-29 2021-06-24 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ Polymerizable compositions for optical members and optical members
JPWO2020004531A1 (en) * 2018-06-29 2021-07-08 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ A polymerizable composition for an optical member, an optical member, and a method for manufacturing the optical member.
EP3816201A4 (en) * 2018-06-29 2022-04-20 Hoya Lens Thailand Ltd. Polymerizable composition for optical member, and optical member

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