WO2021153632A1 - 光学材料用重合性組成物、光学材料用重合性プレポリマー組成物、硬化物及び光学材料の製造方法 - Google Patents

光学材料用重合性組成物、光学材料用重合性プレポリマー組成物、硬化物及び光学材料の製造方法 Download PDF

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WO2021153632A1
WO2021153632A1 PCT/JP2021/002900 JP2021002900W WO2021153632A1 WO 2021153632 A1 WO2021153632 A1 WO 2021153632A1 JP 2021002900 W JP2021002900 W JP 2021002900W WO 2021153632 A1 WO2021153632 A1 WO 2021153632A1
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Prior art keywords
optical material
optical
mass
polymerizable composition
optical materials
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PCT/JP2021/002900
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English (en)
French (fr)
Japanese (ja)
Inventor
幸治 末杉
伸介 伊藤
将太郎 中野
勇輔 松井
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to KR1020217029533A priority Critical patent/KR20210116710A/ko
Priority to CN202310825885.8A priority patent/CN116874734A/zh
Priority to KR1020227033177A priority patent/KR20220138004A/ko
Priority to EP25162581.0A priority patent/EP4541832A3/en
Priority to MX2021013149A priority patent/MX2021013149A/es
Priority to EP21748375.9A priority patent/EP3919967B1/en
Priority to US17/431,360 priority patent/US11542357B2/en
Priority to PH1/2021/551981A priority patent/PH12021551981B1/en
Priority to CN202310812941.4A priority patent/CN116874733A/zh
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to CN202180002443.2A priority patent/CN113557256B/zh
Priority to CN202310815368.2A priority patent/CN116891563A/zh
Priority to JP2021522555A priority patent/JP7141529B2/ja
Publication of WO2021153632A1 publication Critical patent/WO2021153632A1/ja
Priority to JP2022002564A priority patent/JP2022036209A/ja
Anticipated expiration legal-status Critical
Priority to US17/963,231 priority patent/US20230051738A1/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
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • 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
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses

Definitions

  • the present disclosure relates to a polymerizable composition for an optical material, a polymerizable prepolymer composition for an optical material, a cured product, and a method for producing an optical material.
  • Examples of a method for producing a resin used as an optical material for plastic lenses include a casting polymerization method in which a polymerizable composition containing a monomer is injected into a mold and heat-cured.
  • a polymerizable composition is prepared and degassed, then the polymerizable composition is injected into a mold (mold), and after heat curing (polymerization reaction), the product is taken out from the mold (demolding). ), Annealing is performed to obtain an optical material (for example, a lens, a semi-finished blank, etc.).
  • Patent Document 1 describes that a mold in which a polymerizable composition was injected was gradually heated to 10 ° C. to 120 ° C. and polymerized in 20 hours to obtain a molded product.
  • the mold in which the polymerizable composition was injected was gradually heated from 25 ° C. to 120 ° C. and heated to 120 ° C. and heated at 120 ° C. for 4 hours to form a molded product. It is stated that it was obtained.
  • Patent Document 1 International Publication No. 2014/027427
  • Patent Document 2 International Publication No. 2014/133111
  • An object to be solved by one embodiment of the present disclosure is to provide a method for producing an optical material, which can maintain the quality of the obtained optical material and shorten the production time of the optical material. Further, the problem to be solved by one embodiment of the present disclosure is for an optical material used in a method for producing an optical material, which can maintain the quality of the obtained optical material and shorten the production time of the optical material.
  • the purpose is to provide a polymerizable composition.
  • the first embodiment of the present disclosure includes the following aspects.
  • the polymerizable composition for an optical material according to ⁇ 1> which has a thixotropy of 1.3 or less.
  • ⁇ 3> ⁇ 1> or ⁇ which comprises two or more kinds of monomers for different optical materials, a polymerization catalyst, and a prepolymer which is a polymer of the two or more kinds of monomers for different optical materials and has a polymerizable functional group.
  • the two or more different monomers for optical materials are polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, and two or more hydroxyl groups.
  • the polymerizable composition for an optical material according to any one of ⁇ 1> to ⁇ 3> which contains at least one active hydrogen compound selected from the group consisting of a polyol compound containing a thiol compound and an amine compound.
  • ⁇ 5> The polymerizable composition for an optical material according to any one of ⁇ 1> to ⁇ 4>, wherein the polymerization catalyst satisfies the following condition 1.
  • -Ea / R is -7100 or more and -2900 or less.
  • Ea is the activation energy calculated by the Arrhenius plot from the reaction rate constants of the two or more different monomers for optical materials at two or more different temperatures
  • R is the gas constant (8.314 J / mol / K).
  • the polymerization catalyst is any one of ⁇ 1> to ⁇ 5> containing at least one selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.
  • the polymerizable composition for an optical material according to. ⁇ 6-1> The polymerizable property for an optical material according to any one of ⁇ 1> to ⁇ 6>, wherein the polymerization catalyst contains at least one selected from the group consisting of an amine-based catalyst and an organic tin-based catalyst. Composition.
  • the polymerization catalysts are 3,5-lutidine, 2,4,6-cholidine, triethylenediamine, N, N-dimethylethanolamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and
  • the polymerizable composition for an optical material according to any one of ⁇ 1> to ⁇ 6-1>, which comprises at least one selected from the group consisting of dibutyltindiacetate.
  • a composition comprising a prepolymer which is a polymer of two or more kinds of monomers for different optical materials and has a polymerizable functional group, and a polymerization catalyst, and which is a monomer for two or more different kinds of different optical materials.
  • a polymerizable prepolymer composition for optical materials wherein at least one is an isocyanate compound having no aromatic ring and the viscosity measured with a B-type viscometer at 25 ° C. and 60 rpm is 10 mPa ⁇ s to 2000 mPa ⁇ s.
  • ⁇ 8> The polymerizable prepolymer composition for an optical material according to ⁇ 7>, wherein the content of the polymerization catalyst with respect to a total of 100 parts by mass of the prepolymer is 0.1 part by mass to 4.0 parts by mass.
  • ⁇ 8-1> The polymerizable prepolymer composition for an optical material according to ⁇ 7> or ⁇ 8>, which has a thixotropy of 1.3 or less.
  • ⁇ 8-2> The polymerizable prepolymer composition for an optical material according to any one of ⁇ 7> to ⁇ 8-1>, wherein the prepolymer contains an isocyanate group.
  • the two or more different monomers for optical materials are polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, and two or more hydroxyl groups.
  • the polymerization catalyst is any one of ⁇ 7> to ⁇ 10> containing at least one selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.
  • the polymerizable prepolymer composition for an optical material according to. ⁇ 11-1> The polymerizable property for an optical material according to any one of ⁇ 7> to ⁇ 11>, wherein the polymerization catalyst contains at least one selected from the group consisting of an amine-based catalyst and an organic tin-based catalyst. Prepolymer composition.
  • ⁇ 11-2> A composition before forming the prepolymer from the refractive index A of the polymerizable prepolymer composition for optical materials, which contains the two or more different monomers for optical materials and a polymerization catalyst.
  • ⁇ 12> The polymerizable composition for optical materials according to any one of ⁇ 1> to ⁇ 6-2> or the polymerizable composition for optical materials according to any one of ⁇ 7> to ⁇ 11-2>.
  • ⁇ 12-1> A cured product of the polymerizable composition for an optical material, wherein the two or more different monomers for an optical material have two or more mercapto groups in the polymerizable composition for an optical material.
  • Polythiol compound At least one active hydrogen compound selected from the group consisting of a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound.
  • the cured product according to ⁇ 12> which comprises.
  • ⁇ 12-2> A cured product of the polymerizable composition for an optical material, wherein the polymerization catalyst is ⁇ 12> or ⁇ 12-1> satisfying the following condition 1 in the polymerizable composition for an optical material.
  • the cured product according to any one of ⁇ 12> to ⁇ 12-2> which comprises at least one selected from the group consisting of metal-based catalysts.
  • ⁇ 12-4> A cured product of the polymerizable composition for an optical material, wherein the polymerization catalyst is selected from the group consisting of an amine-based catalyst and an organotin-based catalyst in the polymerizable composition for an optical material.
  • ⁇ 12-5> A cured product of the polymerizable composition for an optical material, wherein in the polymerizable composition for an optical material, the polymerization catalyst is 3,5-lutidine, 2,4,6-colysine, or tri.
  • ⁇ 12> to ⁇ 12-4> containing at least one selected from the group consisting of ethylenediamine, N, N-dimethylethanolamine, N-ethylmorpholine, dibutyltindichloride, dimethyltindichloride, dibutyltindilaurate and dibutyltindiacetate.
  • the cured product according to any one.
  • the prepolymer is obtained by mixing a part of the material monomer and at least a part of the polymerization catalyst and polymerizing at least a part of the two or more different optical material monomers.
  • a method for producing an optical material which comprises a prepolymerization step of obtaining a mixture containing a prepolymer, and in which at least one of the two or more different monomers for an optical material is an isocyanate compound having no aromatic ring. ⁇ 15> Further, by adding at least the remainder of the two or more kinds of different optical material monomers to the mixture containing the prepolymer, the two or more kinds of different optical material monomers and the prepolymer are added.
  • the method for producing an optical material according to ⁇ 14> which comprises a curing step of obtaining an optical material which is a cured product of the polymerizable composition for an optical material by curing.
  • the two or more different monomers for optical materials are polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, and two or more hydroxyl groups.
  • the method for producing an optical material according to any one of ⁇ 13> to ⁇ 15> which contains at least one active hydrogen compound selected from the group consisting of a polyol compound containing a thiol compound and an amine compound.
  • ⁇ 17> The method for producing an optical material according to any one of ⁇ 13> to ⁇ 16>, wherein the polymerization catalyst satisfies the following condition 1.
  • -Ea / R is -7100 or more and -2900 or less.
  • Ea is the activation energy calculated by the Arrhenius plot from the reaction rate constants of the two or more different monomers for optical materials at two or more different temperatures
  • R is the gas constant (8.314 J / mol / K).
  • the polymerization catalyst is any one of ⁇ 13> to ⁇ 17> containing at least one selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.
  • the method for producing an optical material according to. ⁇ 19> The method for producing an optical material according to any one of ⁇ 13> to ⁇ 18>, wherein the polymerization catalyst contains at least one selected from the group consisting of an amine-based catalyst and an organic tin-based catalyst.
  • a cured product of two or more different optical monomers, at least one of the two or more different optical material monomers is an isocyanate compound having no aromatic ring, and a radius from the center of the cured product.
  • a cured product in which there is no pulse having a length of 1.0 mm or more within a range of 15 mm, and the amine content measured by gas chromatograph mass spectrometry is 0.03% by mass or more and 2.5% by mass or less.
  • an optical material used in a method for producing an optical material which can maintain the quality of the obtained optical material and satisfactorily shorten the production time of the optical material.
  • a polymerizable composition can be provided.
  • a method for producing an optical material capable of maintaining the quality of the obtained optical material and shortening the production time of the optical material.
  • a polymerizable composition for an optical material used in a method for producing an optical material which can maintain the quality of the obtained optical material and shorten the production time of the optical material. Can be provided.
  • a method for producing an optical material which can suppress the pulse in the obtained optical material and shorten the production time of the optical material.
  • a polymerizable composition for an optical material used in a method for producing an optical material which can suppress pulse in the obtained optical material and shorten the production time of the optical material. Can provide things.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the term "process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • the present disclosure includes a first embodiment and a second embodiment. Each embodiment will be described.
  • the polymerizable composition for an optical material of the first embodiment is a polymerizable composition for an optical material containing two or more different monomers for an optical material and a polymerization catalyst, and the two or more different optical materials. At least one of the monomers is an isocyanate compound having no aromatic ring, and the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is more than 0.05 parts by mass and 2.0.
  • the viscosity is 10 mPa ⁇ s to 1000 mPa ⁇ s, which is less than a part by mass and is measured with a B-type viscosity meter under the conditions of 25 ° C. and 60 rpm.
  • the polymerizable composition for an optical material of the first embodiment can maintain the quality of the obtained optical material and can satisfactorily shorten the production time of the optical material.
  • the polymerizable composition for an optical material of the first embodiment is an isocyanate compound containing two or more different monomers for an optical material, and at least one of the monomers for an optical material does not have an aromatic ring.
  • the monomer for the optical material may be any monomer used for optics and is not particularly limited. For example, it may be a monomer used for producing an optical material having any of the following properties.
  • the optical material obtained by using the monomer for an optical material may have a total light transmittance of 10% or more.
  • the total light transmittance of the optical material may be measured in accordance with JIS K 7361-1 (1997).
  • the optical material obtained by using the monomer for an optical material may have a haze (that is, total haze) of 10% or less, preferably 1% or less, and more preferably 0.5% or less.
  • the haze of the optical material is a value measured at 25 ° C.
  • the optical material obtained by using the monomer for an optical material has a refractive index of preferably 1.58 or more.
  • the optical material obtained by using the monomer for an optical material may have a refractive index of 1.80 or less or 1.75 or less.
  • the refractive index of the optical material may be measured in accordance with JIS K7142 (2014).
  • the shape of the optical material obtained by using the monomer for the optical material is not particularly limited, and may be a plate shape, a columnar shape, a rectangular parallelepiped shape, or the like.
  • Examples of the monomer for optical materials include a polymerizable monomer that polymerizes when a polymerization catalyst described later is used. Specifically, an isocyanate compound, a polythiol compound having two or more mercapto groups, a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound. And so on.
  • the two or more different monomers for optical materials are polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, and polyols containing two or more hydroxyl groups. It preferably contains at least one active hydrogen compound selected from the group consisting of compounds and amine compounds.
  • isocyanate compound examples include an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, and a heterocyclic isocyanate compound, and one type or a mixture of two or more types is used. These isocyanate compounds may include dimers, trimers and prepolymers. Examples of these isocyanate compounds include the compounds exemplified in International Publication No. 2011/055540.
  • examples of the isocyanate compound include halogen-substituted products (for example, chlorine-substituted products, bromine-substituted products, etc.), alkyl-substituted products, alkoxy-substituted products, carbodiimide-modified products, urea-modified products, and burette-modified products of the above-mentioned compounds.
  • halogen-substituted products for example, chlorine-substituted products, bromine-substituted products, etc.
  • alkyl-substituted products for example, alkyl-substituted products, alkoxy-substituted products, carbodiimide-modified products, urea-modified products, and burette-modified products of the above-mentioned compounds.
  • the alicyclic isocyanate compound refers to an isocyanate compound containing an alicyclic structure and may contain a structure other than the alicyclic structure such as a heterocyclic structure.
  • the aromatic isocyanate compound refers to an isocyanate compound containing an aromatic structure and which may contain any one or a combination of an aliphatic structure, an alicyclic structure and a heterocyclic structure.
  • the heterocyclic isocyanate compound refers to an isocyanate compound containing a heterocyclic structure and not containing an alicyclic structure and an aromatic structure.
  • Aliphatic isocyanate compounds refer to isocyanate compounds that do not contain aromatic, alicyclic and heterocyclic structures.
  • the isocyanate compound preferably contains at least one selected from an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound and a heterocyclic isocyanate compound.
  • At least one of the monomers for an optical material in the first embodiment is an isocyanate compound having no aromatic ring.
  • the isocyanate compound having no aromatic ring include an alicyclic isocyanate compound having no aromatic ring, a heterocyclic isocyanate compound, and an aliphatic isocyanate compound.
  • the alicyclic isocyanate compound, the heterocyclic isocyanate compound, and the aliphatic isocyanate compound having no aromatic ring are not too fast in the polymerization reaction as compared with the isocyanate compound having an aromatic ring, and the polymerization reaction is easy to control.
  • the monomer for optical materials may contain an isocyanate compound other than the isocyanate compound having no aromatic ring.
  • the isocyanate compound having no aromatic ring and the isocyanate compound having an aromatic ring are used.
  • the ratio is preferably in the range of 7: 3 to 10: 0, and more preferably in the range of 8: 2 to 10: 0, in terms of the molar ratio of the isocyanate group.
  • the isocyanate compound other than the isocyanate compound having no aromatic ring is not particularly limited, and examples thereof include an isocyanate compound having an aromatic ring.
  • the monomer for optical material contains an isocyanate compound having no aromatic ring and an isocyanate compound having an aromatic ring
  • the number of moles of the isocyanate group in the isocyanate compound having no aromatic ring is the isocyanate group in the isocyanate compound having an aromatic ring. It is preferable that the number of moles is larger than the number of moles.
  • the isocyanate compound is isophorone diisocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2. 2.1] -Heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -Heptane, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate , Dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 1,6-hexamethylene diisocyanate, and at least 1,5-pentamethylene diisocyanate.
  • Isophorone diisocyanate 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, dicyclohexylmethane diisocyanate , And at least one selected from 1,3-bis (isocyanatomethyl) cyclohexane, more preferably.
  • active hydrogen compound examples include polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, polyol compounds containing two or more hydroxyl groups, amine compounds and the like. Can be mentioned.
  • an oligomer of the active hydrogen compound or a halogen-substituted product of the active hydrogen compound for example, a chlorine-substituted product, a bromine-substituted product, etc.
  • the active hydrogen compound may be used alone or in combination of two or more.
  • the polythiol compound having two or more mercapto groups examples include the compounds exemplified in International Publication No. 2016/125736.
  • the polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiane octane, 5 , 7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecan, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecan, 4,8 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythrito
  • polythiol compound having 3 or more mercapto groups examples include polythiol compounds having three or more mercapto groups.
  • the polymerizable composition for an optical material of the first embodiment contains a polythiol compound having three or more mercapto groups as an active hydrogen compound, the polythiol having three or more mercapto groups is considered from the viewpoint of accelerating the polymerization reaction. It is preferable that at least one mercapto group among the three or more mercapto groups contained in the compound contains a compound (also referred to as compound (N1)) in which a group represented by the following formula (N1) is substituted.
  • the polymerizable composition for an optical material of the first embodiment is a polythiol compound having three or more mercapto groups when the peak area is measured by high performance liquid chromatography from the viewpoint that the polymerization reaction can be easily adjusted.
  • the peak area of the compound (N1) is preferably 3.0 or less, more preferably 1.5 or less, with respect to the peak area of 100.
  • the peak area of the compound (N1) is relative to the peak area of 100 of the polythiol compound having three or more mercapto groups, from the viewpoint of promoting the polymerization reaction. , 0.01 or more is preferable.
  • the peak area by high performance liquid chromatography can be measured by the method described in paragraph 0146 of International Publication No. 2014/027665.
  • Hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups examples include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glucerinbis (mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol, and pentaerythritol.
  • Tris (3-mercaptopropionate), pentaerythritol tris (thioglycolate) and the like can be mentioned, but are not limited to these exemplified compounds.
  • polyxe compound containing two or more hydroxyl groups examples include one or more aliphatic or alicyclic alcohols. Specifically, linear or branched aliphatic alcohols, alicyclic alcohols, and alcohols obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, and ⁇ -caprolactone to these alcohols. And so on. More specifically, the compounds exemplified in International Publication No. 2016/125736 can be mentioned.
  • the polyol compound is preferably ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, and the like. It is at least one selected from 1,3-cyclohexanediol and 1,4-cyclohexanediol.
  • amine compound examples include ethylenediamine, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and the like.
  • the active hydrogen compound preferably contains a polythiol compound having two or more mercapto groups from the viewpoint of increasing heat resistance and refractive index.
  • the content of the polythiol compound having two or more mercapto groups is preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass or more, based on the total mass of the active hydrogen compound. Is more preferable.
  • the active hydrogen compound in the first embodiment 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9- Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithia
  • the total content of undecane and pentaerythritol tetrakis (3-mercaptopropionate) is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the active hydrogen compound. , 80% by mass or more is more preferable.
  • the polymerizable composition for an optical material of the first embodiment contains at least one polymerization catalyst.
  • the polymerization catalyst is not particularly limited, and for example, a basic catalyst, an organic metal catalyst, a zinc carbamic acid salt, an ammonium salt, a sulfonic acid, or the like can be used. Only one type of the above-mentioned polymerization catalyst may be used, or two or more types may be used in combination as appropriate.
  • Basic catalyst examples include amine-based catalysts (including imidazole-based catalysts). Specifically, tertiary amine-based catalysts such as triethylenediamine, N, N-dimethylethanolamine, triethylamine, and N-ethylmorpholin; 2-methylpyrazine, pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2 , 6-Lutidine, 3,5-Lutidine, 2,4,6-cholidine, 3-chloropyridine, N, N-diethylaniline, N, N-dimethylaniline, hexamethylenetetramine, quinoline, isoquinoline, N, N- Examples thereof include dimethyl-p-toluidine, N, N-dimethylpiperazine, quinaldine, 4-methylmorpholine, triallylamine, trioctylamine, 1.2-dimethylimidazole, 1-benzyl-2-methylimidazole and the like
  • an amine-based catalyst is preferable among the above.
  • the amine-based catalyst include 3,5-lutidine; 2,4,6-cholidine; triethylenediamine, N, N-dimethylethanolamine, triethylamine, tertiary amine-based catalysts such as N-ethylmorpholine; and the like. Be done.
  • the amine-based catalyst preferably contains at least one selected from 3,5-lutidine, 2,4,6-cholidine, triethylenediamine, N, N-dimethylethanolamine, and N-ethylmorpholine.
  • the basic catalyst preferably contains a compound represented by the following general formula (2) and / or a compound represented by the following general formula (3).
  • R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom, and there are a plurality of them. R 1 may be the same or different.
  • Q indicates a carbon atom or a nitrogen atom.
  • m represents an integer from 0 to 5.
  • R 2 , R 3 and R 4 are independently each of a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. Indicates a group, an allyl group, or a hydrocarbon group containing a hydroxyl group.
  • the pKa value is preferably 1 or more, more preferably 3 or more, and further preferably 4 or more.
  • the pKa value is preferably 9 or less, more preferably 8 or less.
  • the pKa value is, for example, (a) The Journal of Physical Chemistry vol. It can be measured by the method described in 68, number 6, page 1560 (1964), (b) a method using an automatic potential difference titrator (AT-610 (trade name), etc.) manufactured by Kyoto Denshi Kogyo Co., Ltd., and ( c) The acid dissociation index, etc. described in the Chemical Society of Japan's Chemical Handbook (Revised 3rd Edition, June 25, 1984, published by Maruzen Co., Ltd.) can be used.
  • organometallic catalyst examples include an organotin catalyst; organic acid salts such as iron, nickel, and zinc; an acetylacetonate complex; a catalyst composition composed of a metal carboxylate compound and a quaternary ammonium salt compound; Examples thereof include a catalyst composition composed of an amine compound; a metal catalyst in which an alkoxy group, a carboxy group, etc. are coordinated with titanium or aluminum; and the like.
  • the organometallic catalyst is preferable as the organometallic catalyst.
  • the organotin catalyst include dibutyltin dichloride (DBC), dimethyltin dichloride (DMC), dibutyltin dilaurate (DBTDL), and dibutyltin diacetate.
  • the organotin catalyst contains at least one selected from dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate.
  • the polymerization catalyst preferably contains at least one selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst.
  • the polymerization catalyst contains at least one selected from the group consisting of amine-based catalysts and organic tin-based catalysts.
  • polymerization catalyst examples include 3,5-lutidine, 2,4,6-cholidine, triethylenediamine, N, N-dimethylethanolamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin dilaurate and dibutyltin diacetate. It is preferable to include at least one selected from the group.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is more than 0.05 parts by mass and 2.0 parts by mass or less.
  • the content of the polymerization catalyst in the first embodiment is large as compared with the conventional method for producing an optical material.
  • the polymerization reaction can be promoted satisfactorily, and as will be described later, the viscosity of the polymerizable composition is increased, and heat convection, which is presumed to be a cause of optics, is suppressed, while being high in a shorter time than before. A high quality optical material can be obtained.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is more than 0.05 parts by mass, the polymerization reaction can be satisfactorily promoted, so that the polymerization reaction can be promoted satisfactorily in a short time. High quality optical materials can be obtained. Further, by satisfactorily promoting the polymerization reaction, it is possible to improve the releasability when the cured product is taken out from the mold. From the above viewpoint, the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is preferably 0.08 parts by mass or more, and is preferably 0.10 parts by mass or more. Is more preferable, and it is more preferably 0.13 parts by mass or more, and further preferably 0.17 parts by mass or more.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is 2.0 parts by mass or less, for example, when a polymerizable composition for optical materials is injected into a mold. Handleability can be improved.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is preferably 1.8 parts by mass or less, and preferably 1.5 parts by mass or less. Is more preferably 1.0 part by mass or less, particularly preferably 0.5 part by mass or less, and even more preferably 0.3 part by mass or less.
  • the content of the polymerization catalyst may be appropriately set according to the type of the polymerization catalyst, the type and amount of the monomers (isocyanate compound, active hydrogen compound, other components, etc.) used, and the desired shape of the molded product. can.
  • the range of the content of the polymerization catalyst described above may be appropriately changed depending on the type of the monomer for the optical material and the polymerization catalyst.
  • the monomers for optical materials are dicyclohexylmethanediisocyanate and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiawndecane and 4,7-dimercaptomethyl-1,11-dimercapto.
  • the polymerization catalyst is 3,5-lutidin.
  • the polymerization catalyst preferably uses 1.0 part by mass or more, more preferably 1.5 parts by mass or more, with respect to 100 parts by mass of two or more different monomers for optical materials.
  • the monomer for optical materials contains 1,3-bis (isocyanatomethyl) cyclohexane, pentaerythritol tetrakis (2-mercaptoacetate) and 2,5-bis (mercaptomethyl) -1,4-dithian, and is a polymerization catalyst.
  • the polymerization catalyst preferably uses 0.03 parts by mass or more, and 0.07 parts by mass or more with respect to 100 parts by mass of two or more different monomers for optical materials. Is more preferable.
  • the polymerization catalyst preferably satisfies the following condition 1.
  • -Ea / R is -7100 or more and -2900 or less.
  • Ea is the activation energy calculated by the Arrhenius plot from the reaction rate constants of two or more different monomers for optical materials at two or more different temperatures
  • R is the gas constant (8.314 J / mol / K). Is.
  • the polymerization catalyst satisfies the condition 1
  • the variation in the polymerization rate can be suppressed in the process of the polymerization effect of the polymerizable composition, and as a result, the occurrence of optical strain and pulsation is suppressed, and the appearance is excellent.
  • Optical materials can be obtained.
  • the value of Ea is calculated by the following method.
  • the composition 1 containing the polymerization-reactive compound and a predetermined amount of the polymerization catalyst is heated and kept at a plurality of temperatures, the physical property values 1a derived from the functional group before heating of the polymerization-reactive compound and A physical property acquisition step of acquiring a physical property value 1b derived from a residual functional group after heat retention for a predetermined time, and a physical property acquisition step.
  • the specific embodiment of the method for calculating the value of Ea and the method for determining whether or not the polymerization catalyst satisfies the condition 1 is the same as the specific embodiment described in International Publication No. 2020/256057.
  • the polymerizable composition for an optical material of the first embodiment may contain any additive.
  • Optional additives include photochromic compounds, internal mold release agents, brewing agents, UV absorbers and the like.
  • a photochromic compound is a compound in which the molecular structure is reversibly changed by irradiation with light of a specific wavelength, and the absorption characteristics (absorption spectrum) are changed accordingly.
  • Examples of the photochromic compound used in the first embodiment include compounds whose absorption characteristics (absorption spectrum) change with respect to light of a specific wavelength.
  • the photochromic compound is not particularly limited, and any conventionally known compound that can be used for a photochromic lens can be appropriately selected and used.
  • any conventionally known compound that can be used for a photochromic lens can be appropriately selected and used.
  • one or more of spiropyran compounds, spirooxazine compounds, flugide compounds, naphthopirane compounds, bisimidazole compounds and the like can be used depending on the desired coloring.
  • Examples of the internal mold release agent include acidic phosphoric acid esters.
  • Examples of the acidic phosphoric acid ester include phosphoric acid monoester and phosphoric acid diester, which can be used alone or in combination of two or more.
  • the bluing agent examples include those having an absorption band in the orange to yellow wavelength region of the visible light region and having a function of adjusting the hue of an optical material made of a resin. More specifically, the bluing agent contains a substance showing a blue to purple color.
  • UV absorber examples include benzophenon-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, and 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxy.
  • Triazine-based ultraviolet absorbers such as 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2H-benzotriazole-2-yl) -4-methylphenol, 2 -(2H-benzotriazole-2-yl) -4-tert-benzotriazole-based ultraviolet absorbers such as octylphenol can be mentioned, but 2- (2H-benzotriazole-2-yl) -4-tert- Examples thereof include octylphenol and benzotriazole-based ultraviolet absorbers of 2- (5-chloro-2H-benzotriazole-2-yl) -4-methyl-6-tert-butylphenol. These UV absorbers can be used alone or in combination of two or more.
  • the polymerizable composition for an optical material of the first embodiment has a viscosity of 10 mPa ⁇ s or more and 40 mPa ⁇ s or more measured under the condition of 25 ° C. and 60 rpm with a B-type viscometer from the viewpoint of suppressing pulse. It is preferably 70 mPa ⁇ s or more, more preferably 80 mPa ⁇ s or more, particularly preferably 100 mPa ⁇ s or more, and even more preferably 120 mPa ⁇ s or more.
  • the polymerizable composition for an optical material of the first embodiment has a viscosity of 1000 mPa measured at 25 ° C.
  • -S or less preferably 700 mPa ⁇ s or less, and more preferably 400 mPa ⁇ s or less.
  • the viscosity of the polymerizable composition for optical materials of the first embodiment may be adjusted depending on the intended use of the obtained cured product. For example, when a cured product is obtained by using a mold for a plus lens, the edge (that is, the injection port) is narrow (for example, 1 mm to 3 mm), so that the polymerizable composition for an optical material of the first embodiment has a viscous structure. From the viewpoint of suppression, the viscosity is preferably 10 mPa ⁇ s to 100 mPa ⁇ s.
  • the edge that is, the injection port
  • the edge is wide (for example, 5 mm to 15 mm), so that the polymerizable composition for an optical material of the first embodiment
  • the viscosity is preferably 10 mPa ⁇ s to 1000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 1000 mPa ⁇ s, from the viewpoint of suppressing pulse.
  • the viscosity of the polymerizable composition for optical materials By increasing the viscosity of the polymerizable composition for optical materials, it is possible to suppress heat convection due to the temperature difference between the inside and outside of the composition when heat is applied to the composition from the outside, and it is derived from heat convection. Convection can be reduced. However, if the amount of catalyst is small, the thickening rate at the time of polymerization is not sufficient, so that the maximum temperature difference does not become large enough to suppress heat convection, and the temperature cannot be raised rapidly in a short time. In addition, the time required to complete the polymerization also increases.
  • the viscosity of the entire composition can be increased more quickly by increasing the amount of catalyst within the optimum range in consideration of the reactivity of the isocyanate compound having no aromatic ring. As a result, it is possible to suppress thermal convection due to a rapid temperature rise while suppressing uneven polymerization, and the polymerization can proceed in a short time.
  • the polymerizable composition for optical materials of the first embodiment preferably has a thixotropy ratio of 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.
  • the polymerizable composition for an optical material of the first embodiment has a thixotropy ratio of 1.3 or less, so that the composition can be quickly filled in a polymerization container such as a mold described later, and is being polymerized.
  • the thermal convection can be suppressed and the monomer for optical material can further prevent the occurrence of veins and the like. As a result, it is possible to suppress the occurrence of veins and the like in the obtained optical material and maintain good quality.
  • the polymerizable composition for optical materials of the first embodiment preferably has a thixotropy ratio of 0.9 or more, more preferably 0.95 or more, and further preferably 1.0 or more.
  • the thixotropy is calculated by dividing the viscosity ⁇ 1 measured with a B-type viscometer at 25 ° C. and a rotation speed of 6 rpm by the viscosity ⁇ 2 measured at a rotation speed of 60 rpm.
  • the thixotropy is reduced, for example, by reducing the molecular weight of two or more types of monomers for optical materials, suppressing the degree of polymerization of the prepolymer below a certain level, or reducing the ratio of structures that give elasticity to the monomers. be able to.
  • the polymerizable composition for an optical material of the first embodiment is a polymer of two or more different monomers for an optical material, a polymerization catalyst, and two or more different monomers for an optical material, and has a polymerizable functional group. It is preferable to include a polymer.
  • the prepolymer is a polymer of two or more different monomers for optical materials and has a polymerizable functional group.
  • a cured product obtained by polymerizing a prepolymer and two or more different monomers for an optical material can be used as an optical material.
  • the prepolymer examples include a polymer in which the polymerizable functional groups of two types of the monomer for the optical material are not polymerized at an equivalent ratio of 1: 1 among the monomers for the optical material, and two types of optics among the monomers for the optical material. Examples thereof include polymers in which material monomers are polymerized at an unbalanced equivalent ratio.
  • the polymerizable functional group is a functional group that can be polymerized with another polymerizable functional group, and specific examples thereof include functional groups having an active hydrogen such as an isocyanate group and a mercapto group, which will be described later. ..
  • Polymerizing at an equivalent ratio of 1: 1 means that, for example, when polymerizing using an isocyanate compound and a polythiol compound, the isocyanate group contained in the isocyanate compound and the mercapto group contained in the polythiol compound become 1: 1 in molar ratio. It is to polymerize in an amount.
  • the polymerizable prepolymer composition for optical materials of the first embodiment is a composition containing a polymer of two or more different monomers for optical materials, a prepolymer having a polymerizable functional group, and a polymerization catalyst. At least one of the two or more different monomers for optical materials is an isocyanate compound having no aromatic ring, and the viscosity measured with a B-type viscometer at 25 ° C. and 60 rpm is 10 mPa ⁇ s to 2000 mPa ⁇ s. Is. It is preferable that the viscosity of the prepolymer composition does not change with time (that is, it is stable).
  • the polymerizable prepolymer composition for an optical material does not contain a component having another polymerizable functional group that easily polymerizes with the polymerizable functional group contained in the prepolymer as described later.
  • the stable viscosity of the prepolymer composition means that when the prepolymer composition is stored at 20 ° C. for 24 hours, the change in viscosity before and after storage is 10% or less.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is 0.1 parts by mass to 4.0 parts by mass. It is preferably a part.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is 0.1 parts by mass or more, the polymerization reaction can be satisfactorily promoted, so that the polymerization reaction can be promoted satisfactorily in a short time. High quality optical materials can be obtained. Further, by satisfactorily promoting the polymerization reaction, it is possible to improve the releasability when the cured product is taken out from the mold. From the above viewpoint, the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is preferably 0.15 parts by mass or more, preferably 0.20 parts by mass or more. Is more preferable.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is 4.0 parts by mass or less, for example, when a polymerizable composition for optical materials is injected into a mold. Handleability can be improved.
  • the content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials is preferably 3.0 parts by mass or less, and preferably 2.0 parts by mass or less. Is more preferable, and 1.0 part by mass or less is further preferable.
  • the polymerizable prepolymer composition for optical materials of the first embodiment preferably has a thixotropy ratio of 1.3 or less, more preferably 1.2 or less, and further preferably 1.1 or less. ..
  • the polymerizable prepolymer composition for an optical material of the first embodiment has a thiox ratio of 1.3 or less, so that the composition can be quickly filled in a polymerization container such as a mold described later and polymerized.
  • the heat convection inside can be suppressed and the monomer for optical material can further prevent the occurrence of veins and the like. As a result, it is possible to suppress the occurrence of veins and the like in the obtained optical material and maintain good quality.
  • the polymerizable composition for optical materials of the first embodiment preferably has a thixotropy ratio of 0.9 or more, more preferably 0.95 or more, and further preferably 1.0 or more.
  • the method for measuring the thixotropy is as described above.
  • the prepolymer contains an isocyanate group from the viewpoint of handleability of the composition. That is, it is preferable that all the isocyanate groups contained in the prepolymer are not polymerized and only a part thereof is polymerized, and the isocyanate groups contained in the isocyanate compound used in the production of the prepolymer composition. It is preferable that 85% or more remains unpolymerized.
  • the prepolymer contains an isocyanate group, that is, the isocyanate compound is contained in a larger amount than the monomer for other optical materials capable of polymerizing with the isocyanate compound, so that the monomer for other optical materials has a high viscosity.
  • the viscosity of the polymerizable prepolymer composition for materials can be kept low, and the handling of the composition becomes easy.
  • the prepolymer is substantially free of isocyanate groups.
  • the prepolymer is substantially free of isocyanate groups means that almost all the isocyanate groups are polymerized. Specifically, “the prepolymer is substantially free of isocyanate groups” means that the content of the isocyanate groups in the prepolymer is below the detection limit when measured by an IR spectrometer. .. Since the prepolymer is substantially free of isocyanate groups, the stability of the polymerizable prepolymer composition for optical materials can be improved because the highly reactive isocyanate groups are substantially absent.
  • the polymerizable prepolymer composition for an optical material of the first embodiment is a composition before forming a prepolymer from the refractive index A of the polymerizable prepolymer composition for an optical material, and the two or more different types of optics are described above.
  • the value obtained by subtracting the refractive index B of the prepolymer raw material composition which is a composition containing the monomer for materials and the polymerization catalyst (also referred to as “refractive index A-refractive index B”), is preferably more than 0, preferably 0. It is more preferably .003 or more, and even more preferably 0.010 or more.
  • the refractive index A is the refractive index of the polymerizable prepolymer composition for optical materials after polymerizing the monomer for optical materials and the polymerization catalyst to obtain a prepolymer
  • the refractive index B is the polymerization of the monomer for optical materials and the polymerization catalyst. It is the refractive index of the prepolymer raw material composition before the prepolymer is obtained.
  • the refractive index A-refractive index B When the refractive index A-refractive index B is within the above range, it becomes easy to adjust the polymerizable composition for an optical material to a predetermined viscosity. In addition, it becomes easy to stabilize the quality (for example, refractive index, appearance, etc.) of the cured product of the polymerizable composition for optical materials.
  • the refractive index A-refractive index B may be 0.020 or less, or 0.018 or less.
  • the refractive index A-refractive index B is preferably 0.005 or more, and more preferably 0.010 or more. Further, it is preferably 0.030 or less, and more preferably 0.020 or less.
  • the refractive index A-refractive index B is preferably 0.003 or more, and more preferably 0.005 or more. Further, it is preferably 0.020 or less, and more preferably 0.015 or less.
  • the cured product of the first embodiment is a cured product of the polymerizable composition for optical materials of the first embodiment or the polymerizable prepolymer composition for optical materials of the first embodiment.
  • the cured product of the first embodiment preferably has an amine content of 0.03% by mass or more, preferably 0.05% by mass, when an amine-based catalyst is used as the polymerization catalyst.
  • the above is more preferable, and 0.07% by mass or more is further preferable.
  • the cured product of the first embodiment preferably has an amine content of 2.5% by mass or less, preferably 2.0% by mass or less, from the viewpoint of improving the handleability of the polymerizable composition for optical materials. Is more preferable, and 1.5% by mass or less is further preferable.
  • the amine content is the amine content measured by gas chromatograph mass spectrometry from the dichloromethane composition obtained by dispersing the cured product in dichloromethane and ultrasonically extracting it.
  • the cured product of the first embodiment preferably has a tin content of 0.05% by mass or more, preferably 0.1% by mass or more, when an organotin catalyst is used. More preferably, it is more preferably 0.2% by mass or more. Further, the cured product of the first embodiment preferably has a tin content of 2.5% by mass or less, preferably 2.0% by mass or less, from the viewpoint of improving the handleability of the polymerizable composition for optical materials. Is more preferable, and 1.5% by mass or less is further preferable.
  • the method for measuring the amine content in the cured product is as follows. 200 mg of the cured product powdered with a metal file and 3 mL of dichloromethane are placed in a centrifuge tube (volume 10 mL), ultrasonically extracted for 10 minutes at room temperature using an ultrasonic cleaner (manufactured by IUCHI, US-4), and centrifuged. Centrifuge is performed at 4000 rpm for 10 minutes using a separator (KUBOTA, desktop small centrifuge 2410).
  • KUBOTA desktop small centrifuge 2410
  • the supernatant is collected, the residue is dispersed again in 3 mL of dichloromethane, and the above ultrasonic extraction and centrifugation are performed to collect the supernatant (hereinafter, also referred to as “residue extraction”).
  • dichloromethane was added to the obtained supernatant so that the total amount was 10 mL.
  • the obtained 10 mL supernatant was filtered, and gas chromatograph mass spectrometry (also referred to as GC-MS) (GC-MS apparatus: manufactured by Agent, 6890GC / 5973N MSD, column: CP-Sil 8 CB for Amine (0.
  • the amine compound means an amine compound that can be used as a polymerization catalyst, or an amine compound derived from the amine compound.
  • the cured product of the first embodiment preferably has a devitrification of less than 50, more preferably less than 35.
  • the devitrification is measured by the following method. Light from a light source (for example, Luminar Ace LA-150A manufactured by Hayashi Repic Co., Ltd.) is transmitted to the cured product in a dark place. The image of the light transmitted through the cured product is captured in an image processing device (for example, an image processing device manufactured by Ube Information Systems Inc.), the captured image is subjected to shading processing, and the degree of shading of the processed image is determined pixel by pixel.
  • the devitrification is defined as the value calculated as the average value of the degree of shading of each pixel.
  • the cured product of the first embodiment preferably has no veins having a length of 1.0 mm or more within a radius of 15 mm from the center of the cured product, and is within or outside the range of a radius of 15 mm from the center of the cured product. It is more preferable that there is no radius of 1.0 mm or more.
  • the cured product of the first embodiment is a cured product of two or more different optical monomer types, and at least one of the two or more different optical material monomers has an aromatic ring. It is an isocyanate compound that does not exist, there is no vein with a length of 1.0 mm or more within a radius of 15 mm from the center of the cured product, and the amine content measured by gas chromatograph mass spectrometry is 0.03% by mass or more. It may be a cured product having an amount of 2.5% by mass or less.
  • the two or more different optical monomers and isocyanate compounds having no aromatic ring are as described above.
  • two or more different optical monomers may contain an isocyanate compound other than the isocyanate compound having no aromatic ring.
  • the isocyanate compound having no aromatic ring and the isocyanate having an aromatic ring from the viewpoint of controlling the polymerization reaction, the isocyanate compound having no aromatic ring and the isocyanate having an aromatic ring
  • the ratio with the compound is preferably in the range of 7: 3 to 10: 0, and more preferably in the range of 8: 2 to 10: 0, in terms of the molar ratio of the isocyanate group.
  • the method for producing the optical material of the first embodiment includes the following production method A and production method B.
  • the production method A is an isocyanate compound containing two or more different monomers for optical materials and a polymerization catalyst, and at least one of the two or more different monomers for optical materials does not have an aromatic ring.
  • a curing step of curing the polymerizable composition for optical materials comprises a curing step of curing the polymerizable composition for optical materials by polymerizing two or more different monomers for optical materials in the polymerizable composition for optical materials.
  • the manufacturing method A can maintain the quality of the obtained optical material and shorten the manufacturing time of the optical material.
  • the manufacturing method A may include the preparation step, the viscosity adjusting step, and the curing step in this order.
  • the polymerizable composition for optical materials prepared in the preparation step in the production method A has a polymerization catalyst content of more than 0.05 parts by mass and 2.0 parts by mass with respect to a total of 100 parts by mass of the two or more different monomers for optical materials. It is less than a part by mass.
  • the content of this polymerization catalyst is large as compared with the conventional method for producing an optical material.
  • the heat of reaction can be used to accelerate the polymerization reaction of the monomer for optical material in the polymerizable composition for optical material, a high-quality optical material can be obtained in a shorter time than before.
  • the polymerizable composition for optical materials is mainly heated to generate the polymerization reaction.
  • heating of the polymerizable composition for optical materials is not always necessary.
  • the production method A also utilizes the self-heating of the composition, the polymerization can proceed without being excessively dependent on the heat supply from the outside.
  • the refractive index is a state in which the refractive index of a specific portion is different from the normal refractive index of the surroundings. It can also be expressed as a state in which a disadvantage occurs in the desired use of the optical material. Pulsation is a type of defect in optical materials.
  • the production method A is an isocyanate compound containing two or more different monomers for optical materials and a polymerization catalyst, and at least one of the two or more different monomers for optical materials does not have an aromatic ring.
  • the preparatory step of preparing a polymerizable composition for an optical material in which the content of the polymerization catalyst is more than 0.05 parts by mass and 2.0 parts by mass or less with respect to a total of 100 parts by mass of different monomers for optical materials of more than one kind is included.
  • the preparation step may be a step of simply preparing a prefabricated polymerizable composition for an optical material, or a step of producing a polymerizable composition for an optical material.
  • the polymerizable composition for an optical material is not particularly limited as long as it contains two or more different monomers for an optical material and a polymerization catalyst.
  • the polymerizable composition for an optical material an off-the-shelf product may be used, or at least two or more different monomers for an optical material and a polymerization catalyst may be mixed and prepared.
  • the mixing method is not particularly limited, and a known method can be used.
  • the temperature at which each of the above components is mixed is not particularly limited, but is preferably 30 ° C. or lower, and more preferably room temperature (25 ° C.) or lower. From the viewpoint of the pot life of the prepared polymerizable composition for optical materials, it may be preferable to lower the temperature further than 25 ° C. However, if the solubility of the additive such as an internal mold release agent and each of the above components is not good, the temperature of each of the above components may be raised in advance to dissolve the additive in each of the above components. ..
  • the polymerization catalyst is mixed in advance with a part of the two or more kinds of monomers for different optical materials, and then the rest of the two or more kinds of monomers for different optical materials are further mixed for the optical material. It is preferably a step of producing a polymerizable composition. As a result, a mixture containing a part of the above-mentioned two or more kinds of different monomer for optical material and the above-mentioned polymerization catalyst, and a mixture containing the above-mentioned polymerization catalyst and containing the rest of the above-mentioned two or more kinds of different kinds of monomer for optical material.
  • the polymerization catalyst is mixed in advance with a part of the two or more kinds of monomers for different optical materials, and then the rest of the two or more kinds of monomers for different optical materials are mixed once. It may be mixed in a plurality of times.
  • Specific aspects of the preparation step include, for example, the following aspects.
  • a part of the monomer for optical material and an additive are charged to prepare a mixed solution.
  • This mixed solution is stirred at 25 ° C. for 1 hour to completely dissolve each component, and then a part of the rest of the monomer for optical material is further charged, and this is stirred to obtain a uniform solution. Defoaming is performed on this solution to obtain a first mixed solution.
  • the rest of the monomer for the optical material and the catalyst are stirred at 25 ° C. for 30 minutes to completely dissolve them to obtain a second mixture.
  • the first mixture and the second mixture are mixed to obtain a polymerizable composition for an optical material as a uniform solution.
  • the production method B includes a casting step of adjusting the viscosity of the polymerizable composition for an optical material measured at 25 ° C. and 60 rpm with a B-type viscometer to 10 mPa ⁇ s to 1000 mPa ⁇ s and casting it into a mold.
  • the viscosity of the polymerizable composition for materials can be within an appropriate range.
  • the viscosity of the polymerizable composition for optical materials is 10 mPa ⁇ s or more, preferably 40 mPa ⁇ s or more, more preferably 70 mPa ⁇ s or more, and 80 mPa ⁇ s or more. More preferably, it is particularly preferably 100 mPa ⁇ s or more, and even more preferably 120 mPa ⁇ s or more.
  • the viscosity of the polymerizable composition for an optical material is 1000 mPa ⁇ s or less, preferably 700 mPa ⁇ s or less, preferably 400 mPa ⁇ s, from the viewpoint of maintaining good handleability when molding the optical material into a desired shape. It is more preferably s or less.
  • the method for adjusting the viscosity of the polymerizable composition for an optical material is not particularly limited.
  • the viscosity of the polymerizable composition for an optical material may be adjusted by adding a highly viscous compound, heating, stirring, or the like.
  • the production method A includes a curing step of curing the polymerizable composition for optical materials by polymerizing two or more different monomers for optical materials in the polymerizable composition for optical materials in a mold.
  • the production method A includes a curing step, the polymerizable composition for an optical material can be polymerized, and an optical material can be produced.
  • the polymerizable composition for optical materials is heated to generate the polymerization reaction.
  • the polymerizable composition for optical materials in the production method A has the heat of reaction (that is, self) associated with the polymerization reaction.
  • the polymerizable composition for optical materials can be cured by polymerization by allowing the polymerizable composition for optical materials to stand.
  • the environment in which the curing step is performed is not particularly limited, and the mold can be cured by heating from the outside of the mold. It is preferable that the step is to cure the polymerizable composition for optical materials by allowing the polymerizable composition for materials to stand in a closed space.
  • the step is to cure the polymerizable composition for optical materials by allowing the polymerizable composition for materials to stand in a closed space.
  • the adiabatic environment refers to an environment in which heat is retained inside and heat conduction between the inside and the outside is suppressed.
  • An environment in which heat conduction between the inside and the outside is suppressed means that when the polymerizable composition for an optical material is allowed to stand in the closed system space, the heat conduction between the inside and the outside of the closed system space is increased. It means an environment in which the polymerizable composition for an optical material can be cured.
  • the adiabatic environment can be formed, for example, using an adiabatic material. That is, by allowing the polymerizable composition for an optical material to stand in a heat insulating container made of a heat insulating material, heat can be retained inside the heat insulating container and heat conduction between the inside and the outside can be suppressed. ..
  • the thermal conductivity of the heat insulating material is preferably 0.50 W / mK or less, more preferably 0.10 W / mK or less, and even more preferably 0.05 W / mK or less.
  • the density of the heat insulating material is preferably 10 kg / m 3 or more, more preferably 15 kg / m 3 or more, and even more preferably 20 kg / m 3 or more.
  • the polymerization reaction of the polymerizable composition for optical materials is hindered by the reaction heat, or the polymerization reaction of the polymerizable composition for optical materials is excessively promoted by heating from the outside. It is preferable to heat the adiabatic reaction tank so that it is in a constant temperature state (constant temperature reaction tank) within a range that does not cause the reaction. As a result, the environmental temperature in the reaction vessel (constant temperature reaction vessel) in which the mold is placed can be kept warm or constant temperature according to the temperature rise state due to the self-heating of the monomer for optical material. The polymerization reaction can be promoted satisfactorily.
  • the adiabatic reaction tank or the constant temperature reaction tank as described above can be used.
  • adiabatic polymerization in an adiabatic environment using an adiabatic reaction vessel can be performed by the following procedure. can.
  • the inner surface of the vacuum container is covered with a member having heat insulating and heat-retaining properties such as urethane foam and cork, and the mold in which the monomer is injected is wrapped with a member such as a waste cloth as necessary. Then, the mold in which the monomer is injected is allowed to stand in the vacuum container.
  • the curing step may be a step of curing the polymerizable composition for optical materials by allowing the polymerizable composition for optical materials to stand without being heated from the outside.
  • heating of the polymerizable composition for an optical material is not always necessary.
  • an apparatus may be used, which may increase the burden economically. If the manufacturing method A is used, the optical material can be manufactured by a simple method, so that the economic burden can be reduced.
  • the curing step is preferably a step of curing the polymerizable composition for optical materials by allowing the polymerizable composition for optical materials to stand for 2 to 10 hours.
  • the polymerization reaction is carried out over several hours to several tens of hours (for example, about 20 hours to 48 hours) while gradually raising the temperature by heating.
  • the time for carrying out the polymerization reaction is short, the polymerizable composition for an optical material is not completely cured, so that the optical material cannot be obtained, or the quality of the optical material is deteriorated.
  • the optical material can be produced in a short time while maintaining the quality of the obtained optical material.
  • the optical material can be produced by allowing the polymerizable composition for an optical material to stand for 10 hours or less. From the above viewpoint, it is more preferable that the polymerizable composition for an optical material is allowed to stand for 8 hours or less in the curing step. Further, from the viewpoint of obtaining a satisfactorily cured optical material by carrying out a polymerization reaction, the polymerizable composition for an optical material is preferably allowed to stand for 2 hours or more, and more preferably for 5 hours or more.
  • a microwave irradiation step of irradiating the polymerizable composition for an optical material with microwaves for a predetermined time may be provided.
  • Step a The polymerizable composition for an optical material is injected (cast) into a mold (inside the cavity of the mold).
  • Step b A mold in which the polymerizable composition for an optical material is injected is allowed to stand in a closed system space for a predetermined time for adiabatic polymerization.
  • Step a First, the polymerizable composition is injected into a molding mold held by a gasket, tape or the like. At this time, depending on the physical characteristics required for the obtained optical material, it is preferable to perform a defoaming treatment under reduced pressure, a filtration treatment under pressure, a reduced pressure, or the like, if necessary.
  • the polymerization conditions are not limited, but are preferably adjusted appropriately depending on the composition of the polymerizable composition for optical materials, the type and amount of catalyst used, the shape of the mold, and the like.
  • the mold in which the polymerizable composition for an optical material is injected may be allowed to stand in an adiabatic environment for 2 to 4 hours for polymerization.
  • a heating step may be added after the adiabatic polymerization process in which the mold in which the polymerizable composition for optical materials is injected is allowed to stand in an adiabatic environment for a certain period of time.
  • step b in the adiabatic polymerization process continuously or intermittently in parallel with the step of allowing the mold infused with the polymerizable composition for optical materials to stand in an adiabatic environment (adiabatic polymerization).
  • the mold in which the polymerizable composition for optical materials is injected is heated at a temperature not exceeding the self-heating generated by the polymerizable composition for optical materials, or the inside of the adiabatic reaction tank is heated to keep the environmental temperature in the adiabatic reaction tank warm. You may do it.
  • the production method A may include an annealing step of annealing the cured polymerizable composition for an optical material, if necessary.
  • the temperature at which the annealing treatment is performed is usually 50 to 150 ° C., but is preferably 90 to 140 ° C., and more preferably 100 to 130 ° C.
  • the production method A may be provided with another step if necessary.
  • another step for example, in the case of manufacturing an optical material using a mold, an injection step of injecting a polymerizable composition for an optical material into a mold can be mentioned.
  • the optical material in the manufacturing method A can be used for a plastic lens, a prism, an optical fiber, an information recording substrate, a filter, a light emitting diode and the like.
  • the optical material in the first embodiment can be preferably used for a plastic lens, and can be more preferably used for a plastic lens for spectacles.
  • the production method B includes a preparatory step of preparing 100 parts by mass of two or more different monomers for optical materials and a polymerization catalyst of 0.010 parts by mass to 2.0 parts by mass. A part of the two or more different monomers for optical materials and at least a part of the polymerization catalyst are mixed, and at least a part of the two or more different monomers for optical materials is polymerized to prepolymerize.
  • the manufacturing method B can suppress the veins in the obtained optical material and shorten the manufacturing time of the optical material.
  • At least the remainder of the two or more different monomers for optical materials is added to the mixture containing the prepolymer.
  • a step of producing a polymerizable composition for an optical material which comprises a monomer for an optical material containing more than one kind, the prepolymer, and the polymerization catalyst.
  • the production method B includes, in addition to the preparation step and the prepolymerization step, a step of manufacturing a polymerizable composition for an optical material and a curing step, thereby better suppressing the veins in the obtained optical material. Moreover, the manufacturing time of the optical material can be shortened more satisfactorily.
  • the polymerizable composition for optical materials prepared in the preparation step in Production Method B has a polymerization catalyst content of 0.010 parts by mass to 2.0 parts by mass with respect to a total of 100 parts by mass of two or more different monomers for optical materials. It is a department.
  • the content of this polymerization catalyst is large as compared with the conventional method for producing an optical material. Therefore, as in the case of the production method A, it is possible to obtain a high-quality optical material in which the pulse is suppressed in a shorter time than before.
  • heating of the polymerizable composition for an optical material is not always necessary.
  • the production method B includes a preparation step, a prepolymerization step, a step of producing a polymerizable composition for an optical material, and a curing step, so that convection in the mold where the polymerization reaction is performed can be suppressed. It is possible to suppress the occurrence of pulsation in the obtained cured product.
  • the production method B includes a prepolymerization step, the storage stability of the mixture containing the prepolymer (for example, the polymerizable composition for an optical material) is improved as compared with the case without the prepolymerization. Can be maintained. For example, when the mixture containing the prepolymer is stored for a certain period of time, the polymerization reaction in the mixture can be suppressed. That is, a longer pot life can be secured.
  • the production method B includes a preparatory step of preparing 100 parts by mass in total of two or more different monomers for optical materials and 0.010 parts by mass to 2.0 parts by mass of a polymerization catalyst.
  • a total of 100 parts by mass of two or more different monomers for optical materials and 0.010 parts by mass to 2.0 parts by mass of a polymerization catalyst are prepared. That is, in the production method B, a polymerization catalyst of 0.010 parts by mass to 2.0 parts by mass is used with respect to a total of 100 parts by mass of two or more different monomers for optical materials.
  • the polymerization catalyst By using a polymerization catalyst of 0.010 parts by mass or more with respect to 100 parts by mass of two or more different monomers for optical materials, the polymerization reaction can be satisfactorily promoted, so that the pulse is suppressed in a short time. High quality optical material can be obtained. Further, by satisfactorily promoting the polymerization reaction, it is possible to improve the releasability when the cured product is taken out from the mold. From the above viewpoint, the polymerization catalyst preferably uses 0.015 parts by mass or more, more preferably 0.038 parts by mass or more, based on 100 parts by mass of two or more different monomers for optical materials. It is more preferable to use 0.10 parts by mass or more, and it is particularly preferable to use 0.17 parts by mass or more.
  • the range of the content of the polymerization catalyst described above may be appropriately changed depending on the type of the monomer for the optical material and the polymerization catalyst.
  • the monomers for optical materials are 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane, pentaerythritol tetrakis (3-mercaptopropionate), and 4-mercaptomethyl.
  • the polymerization catalyst is 0.10 with respect to 100 parts by mass of two or more different monomers for optical materials. It is preferable to use parts by mass or more, and more preferably 0.17 parts by mass or more.
  • the handleability when injecting a polymerizable composition for optical materials into a mold is improved. be able to.
  • the polymerization catalyst may be used in an amount of 1.0 part by mass or less and 0.3 part by mass or less with respect to 100 parts by mass of two or more different monomers for optical material. It may be used, and may be used in an amount of 0.15 parts by mass or less.
  • the amount of the polymerization catalyst can be appropriately set depending on the type of the polymerization catalyst, the type and amount of the monomers (isocyanate compound, active hydrogen compound, other components, etc.) used, and the desired shape of the molded product. ..
  • a part of two or more different monomers for optical materials and at least a part of the polymerization catalyst are mixed, and at least a part of two or more different monomers for optical materials is polymerized. It comprises a prepolymerization step of obtaining a mixture containing the prepolymer by obtaining the prepolymer.
  • the present inventors considered that the occurrence of convection due to the non-uniform temperature distribution in the mold in which the polymerization reaction is carried out is one of the causes of generating veins in the obtained cured product. Therefore, the present inventors produce a prepolymer by prepolymerizing a part of the monomer for the optical material, and the polymerizable composition for the optical material contains the prepolymer, so that the viscosity of the polymerizable composition for the optical material is high. Focused on increasing. This makes it possible to suppress convection in the mold. Further, in the manufacturing method B, the temperature difference between the inside and the outside of the mold can be made less likely to occur by preventing the self-heating from escaping to the outside. Combined with the above viewpoints, it is presumed that the production method B can suppress the veining of the obtained cured product.
  • the prepolymerization step in the prepolymerization step, all of the monomers for one type of optical material among two or more different monomers for optical material and the monomers for optical material other than the one type of monomer for optical material are used. By including a part and all or a part of the polymerization catalyst, a prepolymer having excellent pot life can be obtained.
  • a part of two or more kinds of monomers for different optical materials is not particularly limited.
  • a part of two or more kinds of monomers for different optical materials may be an amount of a part of each of two or more kinds of monomers for different optical materials.
  • a part of two or more kinds of monomers for different optical materials may be all of one or more kinds of monomers for optical materials among two or more kinds of monomers for different optical materials.
  • a part of the polymerization catalyst may be used or the whole may be used.
  • a part is used as the polymerization catalyst, there is no particular limitation on the mode of "a part of the polymerization catalyst" as well as "a part of two or more kinds of monomers for different optical materials".
  • a part of the polymerization catalyst may be a part of the amount of the polymerization catalyst.
  • a part of the polymerization catalyst is preferably 5 parts by mass to 80 parts by mass out of 100 parts by mass of the polymerization catalyst from the viewpoint of ensuring a long-term pot life, and is preferably 10 parts by mass. It is more preferably parts to 60 parts by mass, and further preferably 15 parts to 50 parts by mass.
  • a part of two or more kinds of monomers for different optical materials shall be 5 parts by mass to 95 parts by mass out of 100 parts by mass of two or more kinds of monomers for different optical materials from the viewpoint of ensuring a long-term pot life. Is more preferable, and it is more preferably 20 parts by mass to 80 parts by mass, and further preferably 30 parts by mass to 70 parts by mass.
  • prepolymerization step in the production method B is not limited to the following aspects.
  • some of the two or more different optical material monomers are all of one optical material monomer among the two or more different optical material monomers, and other than one optical material monomer. It is preferably composed of a part of a monomer for other optical materials.
  • the prepolymerization step of embodiment b is a mixture of a part of two or more different monomers for optical materials and a part of a polymerization catalyst, and at least a part of two or more different monomers for optical materials.
  • the step of producing a polymerizable composition for an optical material is carried out with respect to the mixture containing the prepolymer with the balance and polymerization of at least two or more different monomers for the optical material.
  • This is a step of obtaining a polymerizable composition for an optical material containing two or more different monomers for an optical material, a prepolymer, and a polymerization catalyst by adding the remainder of the catalyst.
  • two or more different monomers for optical materials contain an isocyanate compound, some of two or more different monomers for optical materials contain a part of an isocyanate compound, and two or more different monomers for optical materials.
  • the balance preferably contains the balance of the isocyanate compound.
  • Production method B further includes a viscosity adjusting step of adjusting the viscosity of the mixture containing the prepolymer to 30 mPa ⁇ s to 2000 mPa ⁇ s after the prepolymerization step and before the step of manufacturing the polymerizable composition for optical materials. It is preferable to include it.
  • the viscosity of the mixture containing the prepolymer is within the above range, the polymerizable composition for optical materials produced in the process for producing the polymerizable composition for optical materials is produced from the viewpoint of suppressing the veins in the obtained optical material.
  • the viscosity can be within an appropriate range. As a result, the pulse in the obtained optical material can be suppressed.
  • the viscosity of the mixture containing the prepolymer is preferably 40 mPa ⁇ s to 2000 mPa ⁇ s, and more preferably 50 mPa ⁇ s to 1800 mPa ⁇ s.
  • the viscosity is measured using a B-type viscometer under the conditions of 25 ° C. and 60 rpm (revolutions per minute).
  • the method for adjusting the viscosity of the mixture containing the prepolymer is not particularly limited.
  • the viscosity of the mixture containing the prepolymer may be adjusted by adding a highly viscous compound, heating, stirring or the like.
  • the temperature at which the mixture containing the prepolymer is prepared is not particularly limited as long as the temperature at which the prepolymer can be obtained by the polymerization reaction.
  • it may be 20 ° C. to 50 ° C. or 25 ° C. to 45 ° C.
  • the stirring time for preparing the mixture containing the prepolymer is not particularly limited as long as the stirring time is such that the prepolymer can be obtained by the polymerization reaction. For example, it may be 30 minutes to 5 hours, or 1 hour to 5 hours.
  • a method for preparing a mixture containing a prepolymer specifically, a method for preparing a mixture containing a prepolymer while adjusting the viscosity by stirring at 40 ° C. for 3 hours may be used.
  • a mixture containing a prepolymer is prepared with two or more different monomers for an optical material by adding at least the remainder of two or more different monomers for the optical material.
  • This is a step of obtaining a polymerizable composition for an optical material containing a polymer and a polymerization catalyst.
  • the process for producing the polymerizable composition for optical materials at an appropriate time, it is possible to improve the handleability when, for example, the polymerizable composition for optical materials is injected into the mold.
  • the process of producing a polymerizable composition for an optical material when the remainder of at least two or more different monomers for an optical material is added to a mixture containing a prepolymer, the remainder of two or more different monomers for an optical material is simply added. It may be mixed in multiple times, or may be mixed in a plurality of times.
  • the remainder of two or more kinds of monomers for different optical materials refers to "a part of two or more kinds of monomers for different optical materials" in the prepolymerization step among two or more kinds of monomers for different optical materials. Means the rest.
  • the "remaining of two or more different monomers for optical materials” has a functional group that polymerizes with respect to the polymerizable functional group of the prepolymer, and polymerizes with respect to the polymerizable functional group of the prepolymer. It may be a monomer for an optical material in which the amount of the functional group is an amount (that is, an equivalent amount) capable of substantially polymerizing with all of the polymerizable functional groups of the prepolymer. From the viewpoint of enhancing the optical uniformity of the composition for optical materials, it is preferable that the balance of two or more different monomers for optical materials contains the same type of monomers as the monomers for optical materials constituting the prepolymer.
  • the temperature at which each of the above components is mixed is not particularly limited, but is preferably 30 ° C. or lower, and more preferably room temperature (25 ° C.) or lower. It may be preferable that the temperature at which each component is mixed is lower than 25 ° C. However, if the solubility of the additive such as an internal mold release agent and each of the above components is not good, the temperature of each of the above components may be raised in advance to dissolve the additive in each of the above components. ..
  • an additive for example, an internal mold release agent
  • an additive for example, an internal mold release agent
  • This mixed solution is stirred at 25 ° C. for 1 hour to completely dissolve each component, and then degassed to obtain a first mixed solution.
  • the balance of the monomer for the optical material and the balance of the polymerization catalyst, if necessary, are stirred at 25 ° C. for 30 minutes to completely dissolve the mixture to obtain a second mixture.
  • the first mixture and the second mixture are mixed, stirred and then degassed to obtain a polymerizable composition for an optical material as a uniform solution.
  • the production method B may further include a liquid feeding step of feeding the polymerizable composition for optical materials into a casting mold after the step of manufacturing the polymerizable composition for optical materials and before the curing step.
  • the liquid feeding step may be a step of feeding the polymerizable composition for an optical material to a casting mold while remixing it in a static mixer.
  • the liquid feeding step may be a step of feeding the polymerizable composition for an optical material to a casting mold while remixing it with a dynamic mixer.
  • the production method B includes a curing step of obtaining an optical material which is a cured product of the polymerizable composition for optical materials by curing two or more different monomers for optical materials in the polymerizable composition for optical materials.
  • the specific mode, preferred mode, etc. of the curing step in the production method B are the same as the details of the specific mode, preferred mode, etc. described in the section ⁇ Curing step> in the above-mentioned manufacturing method A.
  • ⁇ Second prepolymerization process> In the production method B, in addition to the above-mentioned preparation step and prepolymerization step, the balance of the two or more different monomers for optical materials and the balance of the polymerization catalyst are further mixed, and the two or more different types are different.
  • a polymerizable composition for an optical material containing the prepolymer, the second prepolymer, and the polymerization catalyst by adding the mixture containing the second prepolymer to the mixture containing the prepolymer.
  • the production method B can obtain a mixture containing the prepolymer obtained by the prepolymerization step and a mixture containing the second prepolymer obtained by the second prepolymerization step.
  • the viscosities of the mixture containing the prepolymer and the mixture containing the second prepolymer can be brought close to each other, so that both can be mixed more easily.
  • two or more different monomers for optical materials, polymerization catalysts, specific embodiments, preferred embodiments and the like are described as two or more different monomers for optical materials, polymerization catalysts, specific embodiments in the prepolymerization step. It is the same as the embodiment, the preferred embodiment and the like.
  • the prepolymerization step is performed by adding the mixture containing the second prepolymer to the mixture containing the prepolymer.
  • This is a step of obtaining a polymerizable composition for an optical material containing a polymer, the second prepolymer, and the polymerization catalyst.
  • the mixture containing the prepolymer, specific embodiments, preferred embodiments and the like are the same as the above-mentioned specific embodiments and preferred embodiments in the above-mentioned ⁇ process for producing a polymerizable composition for optical materials>. Is.
  • the curing step cures the prepolymer and the second prepolymer in the polymerizable composition for an optical material, whereby the polymerizable composition for the optical material is cured.
  • This is the process of obtaining an optical material that is a cured product of a product.
  • the prepolymer, specific embodiments, preferred embodiments, etc. are the same as the specific embodiments, preferred embodiments, etc. in the above-mentioned ⁇ curing step>.
  • the production method B may include an annealing step of annealing the cured polymerizable composition for an optical material, if necessary.
  • the preferred embodiment of the annealing step in the production method B is the same as the preferred embodiment of the annealing step in the production method A.
  • the production method B may be provided with another step if necessary.
  • the specific aspects, preferred embodiments, etc. of the other steps in the production method B are the same as the specific embodiments, preferred embodiments, etc. of the other steps in the production method A.
  • the method for producing an optical material according to the second embodiment includes two or more different monomers for optical materials and a polymerization catalyst, and the polymerization of the two or more different monomers for optical materials with respect to a total of 100 parts by mass.
  • the method for producing an optical material according to the second embodiment is other than that the content of the polymerization catalyst with respect to a total of 100 parts by mass of two or more different monomers for optical materials is 0.1 part by mass to 0.3 part by mass. Is the same as the method for producing the optical material of the first embodiment.
  • the method for producing the optical material of the second embodiment details of specific examples, preferable specific examples, specific embodiments, preferred embodiments, etc. of the respective components are described in the specific examples of each component in the method for producing the optical material of the first embodiment. It is the same as the details of a preferable specific example, a specific embodiment, a preferred embodiment and the like.
  • the second embodiment of the present disclosure includes the following aspects. ⁇ 2-1> The content of the polymerization catalyst with respect to a total of 100 parts by mass of the two or more different monomers for optical materials and the polymerization catalyst, and the two or more different monomers for optical materials is 0.
  • a method for producing an optical material which comprises a curing step of curing the polymerizable composition for an optical material.
  • the polymerization catalyst is mixed in advance with a part of the two or more kinds of monomers for different optical materials, and then the rest of the two or more kinds of monomers for different optical materials are further mixed.
  • the method for producing an optical material according to ⁇ 2-1> which is a step of producing the polymerizable composition for an optical material.
  • the curing step is a step of curing the polymerizable composition for optical materials by allowing the polymerizable composition for optical materials to stand in a closed system space.
  • the method for producing an optical material according to ⁇ 2-2> is a step of curing the polymerizable composition for optical materials by allowing the polymerizable composition for optical materials to stand in a closed system space.
  • the curing step is a step of curing the polymerizable composition for optical materials by allowing the polymerizable composition for optical materials to stand without being heated from the outside.
  • the curing step is a step of curing the polymerizable composition for an optical material by allowing the polymerizable composition for an optical material to stand for 2 to 10 hours.
  • the two or more different monomers for optical materials are an isocyanate compound, a polythiol compound having two or more mercapto groups, and a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups.
  • a polyol compound containing two or more hydroxyl groups containing, a polyol compound containing two or more hydroxyl groups, and at least one active hydrogen compound selected from the group consisting of amine compounds.
  • ⁇ 2-7> The method for producing an optical material according to ⁇ 2-6>, wherein the isocyanate compound contains an isocyanate compound having no aromatic ring.
  • the polymerization catalyst contains at least one selected from the group consisting of a basic catalyst having a pKa value of 4 to 8 and an organometallic catalyst ⁇ 2-1> to ⁇ 2-7.
  • the method for producing an optical material according to any one of. ⁇ 2-9> The optical device according to any one of ⁇ 2-1> to ⁇ 2-8>, wherein the polymerization catalyst contains at least one selected from the group consisting of an amine-based catalyst and an organic tin-based catalyst. Material manufacturing method.
  • the polymerization catalyst is 3,5-lutidine, 2,4,6-cholidine, triethylenediamine, N, N-dimethylethanolamine, triethylamine, N-ethylmorpholine, dibutyltin dichloride, dimethyltin dichloride, dibutyltin.
  • the method for producing an optical material according to any one of ⁇ 2-1> to ⁇ 2-9>, which comprises at least one selected from the group consisting of dilaurate and dibutyltindiacetate.
  • the content of the polymerization catalyst is 0 with respect to a total of 100 parts by mass of the two or more different monomers for optical materials and the polymerization catalyst, and the two or more different monomers for optical materials are included. .
  • a polymerizable composition for an optical material which is 1 part by mass to 0.3 part by mass.
  • the polythiol compound used in this example can be produced by the method described in International Publication No. 2014/027665.
  • Example A ⁇ Example A>
  • the method for measuring the viscosity in Example A is the same as the method described above.
  • the molded article obtained in each Example or Comparative Example was evaluated as follows.
  • (Breakthrough) Light from a light source (Luminar Ace LA-150A manufactured by Hayashi Repic Co., Ltd.) was transmitted to the produced molded product in a dark place.
  • the image of the light transmitted through the molded body was captured in an image processing device (manufactured by Ube Information Systems Inc.), and the captured image was subjected to shading processing.
  • the degree of shading of the processed image was quantified for each pixel, the average value of the degree of shading of each pixel was obtained, and the devitrification of the molded product was obtained.
  • the obtained devitrification was evaluated according to the following criteria.
  • C The devitrification was 50 or more and less than 100.
  • D The devitrification was 100 or more.
  • a molded body having a center thickness of 8 mm and a diameter of 78 mm was projected with an ultra-high pressure mercury lamp (light source model OPM-252HEG: manufactured by Ushio, Inc.), and the transmitted image was visually observed and evaluated according to the following criteria.
  • B Although pulse was observed, it was generally acceptable as a product.
  • a vein with a length of 1.0 mm or more is visually observed outside the range of a radius of 15 mm from the center of the molded body, 1.0 mm is visually observed within a range of a radius of 15 mm from the center of the molded body. No radius of the above length was observed, and the product was generally acceptable.
  • C The pulse was observed and it was unacceptable as a product.
  • veins having a length of 1.0 mm or more were visually observed within and outside a radius of 15 mm from the center of the molded body.
  • each polymerization catalyst is as follows. Dibutyl Tin (II) Dichloride-5737 3,5-lutidine-3397 2,4,6-coridine-4483
  • Example 1A ZelekUN [internal mold release agent] manufactured by Stepan, 0.1 parts by mass, 2- (2H-benzotriazole-2-yl) -4-tert-octylphenol [ultraviolet absorber] 1.5 parts by mass, and 2,5 ( 6) -Bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane [monomer for optical material] 40.6 parts by mass was charged to prepare a mixed solution. The mixture was stirred at 25 ° C. for 1 hour to completely dissolve.
  • this solution While filtering this solution with a 1 ⁇ m PTFE filter, it is composed of a 4-curve glass mold (upper mold) with a diameter of 78 mm and a 4-curve glass mold (lower mold) with a diameter of 78 mm. It was injected at a rate of 10 g / sec into a molded cavity having a cavity for use. This cast product was placed in a heat insulating container at 25 ° C. and allowed to stand for 4 hours for adiabatic polymerization. I got a body (lens).
  • Example 2A A molded product was obtained in the same manner as in Example 1A except that the amount of the catalyst was as shown in Table 1. Moreover, when the properties of the obtained molded product were measured, good physical properties were shown at a refractive index (ne) of 1.598, an Abbe number ( ⁇ e) of 39, and a glass transition temperature (Tg) of 114 ° C. The results of devitrification, pulse and releasability are shown in Table 1.
  • Example 4A A molded product was obtained in the same manner as in Example 3A except that the amount of the catalyst was as shown in Table 1. Moreover, when the properties of the obtained molded product were measured, good physical properties were shown at a refractive index (ne) of 1.598, an Abbe number ( ⁇ e) of 39, and a glass transition temperature (Tg) of 113 ° C. The results of devitrification, pulse and releasability are shown in Table 1.
  • Example 5A A molded product was obtained by the same method as in Example 3A except that the amount of the catalyst was as shown in Table 1. Moreover, when the properties of the obtained molded product were measured, good physical properties were shown at a refractive index (ne) of 1.597, an Abbe number ( ⁇ e) of 39, and a glass transition temperature (Tg) of 109 ° C. The results of devitrification, pulse and releasability are shown in Table 1.
  • Example 7A A molded product was obtained in the same manner as in Example 1A except that the type and amount of the catalyst were as shown in Table 1. Moreover, when the properties of the obtained molded product were measured, good physical properties were shown at a refractive index (ne) of 1.598, an Abbe number ( ⁇ e) of 39, and a glass transition temperature (Tg) of 108 ° C. The results of devitrification, pulse and releasability are shown in Table 1.
  • Example 1A The same polymerizable composition as in Example 1A was prepared except that the amount of the catalyst was as shown in Table 1, and the mixture was injected into the mold cavity.
  • the mold in which the polymerizable composition was injected was put into a polymerization oven, and the temperature was gradually raised from 20 ° C. to 130 ° C. over 20 hours for polymerization. After completion of the polymerization, the mold was taken out from the oven, the molded product was released from the cavity, and further annealed at 120 ° C. for 2 hours to obtain a molded product.
  • Example 3A Polymerization was carried out in the same manner as in Example 1A except that the type and amount of the catalyst were as shown in Table 1, but the catalyst was not cured. Since it did not cure, the devitrification and the like were not evaluated.
  • Example 8A In Example 1A Changing the first mixture to the mixture prepared as follows, Changed 0.3 parts by mass of dibutyl tin (II) dichloride to 0.15 parts by mass of dimethyl tin (II) dichloride (DMC), and When the cast product was placed in a heat insulating container at 25 ° C. and allowed to stand for 5 hours for adiabatic polymerization, the molded product was subjected to additional heating at 120 ° C. for 1 hour in the same manner as in Example 1A. (Lens) was produced.
  • FIG. 1 shows a graph showing the relationship between the elapsed time of the polymerization reaction and the temperature inside the heat insulating container in the production of the molded product.
  • Example 8A- Method for producing the first mixed solution in Example 8A- First, a composition (9.8 parts by mass) containing 2,5 (6) -bis (isocyanatomethyl) -bicyclo- [2.2.1] -heptane was added as a photochromic compound to Revisacol Weekley Gray (manufactured by Vivimed). 0.036 parts by mass), Revisacol Heat Green (0.060 parts by mass) manufactured by Vivimed, Peacock Blue (0.030 parts by mass) manufactured by Vivimed, Jalapeno Red (0.024 parts by mass) manufactured by Vivimed, and HOSTAVIN PR-25 (0.075 parts by mass) was dissolved as an ultraviolet absorber to prepare a master solution.
  • Revisacol Weekley Gray manufactured by Vivimed
  • Revisacol Heat Green 0.060 parts by mass
  • Peacock Blue 0.030 parts by mass
  • Jalapeno Red 0.024 parts by mass
  • HOSTAVIN PR-25 0.075 parts by mass
  • the maximum heat generation temperature in the polymerization process was 132 ° C., and the maximum heat generation duration was 65 minutes. No white turbidity could be observed in the produced molded product, and the transparency was good. In addition, no voids were generated due to bubbles, cracks, etc.
  • Example B the production method B of the first embodiment will be specifically described with reference to Example B, but the production method B of the first embodiment is not limited to these examples.
  • the method for measuring the viscosity in Example B is the same as the method described above.
  • the molded article obtained in each Example or Comparative Example was evaluated as follows.
  • the molded product was projected with an ultra-high pressure mercury lamp (light source model OPM-252HEG: manufactured by Ushio, Inc.), and the transmitted image was visually observed and evaluated according to the following criteria.
  • Example 1B Mitsui Chemicals, Inc.
  • MR internal mold release agent 0.1 parts by mass
  • Tinuvin 329 0.1 parts by mass
  • 2,5 (6) -bis (isocyanatomethyl) -bicyclo -[2.2.1] -Heptane 40.6 parts by mass was charged to prepare a mixed solution. The mixture was stirred at 25 ° C. for 1 hour to completely dissolve.
  • a prepolymer raw material composition that is a composition before forming a prepolymer from the refractive index A of the polymerizable prepolymer composition for optical materials, and is a composition containing two or more different monomers for optical materials and a polymerization catalyst.
  • Table 2 shows the value obtained by subtracting the refractive index B of the object (also referred to as “refractive index A-refractive index B”).
  • the obtained polymerizable composition for optical materials was remixed in a static mixer and sent to a casting mold (that is, a mold).
  • the viscosity (also referred to as casting viscosity) of the polymerizable composition for an optical material when the liquid was sent to a mold and cast was adjusted to the value shown in Table 2.
  • a 4-curve or 6-curve glass mold (upper mold) having a diameter of 78 mm and a glass mold having a diameter of 78 mm (upper mold) and a diameter of 78 mm are used while filtering the polymerizable composition for optical materials with a 1 ⁇ m PTFE filter.
  • Example 2B to Example 4B Except for changing the polymerization catalyst amount and stirring time of the first mixed solution in the prepolymerization step to the values shown in Table 2 and adjusting the casting viscosity of the polymerizable composition for optical materials to the values shown in Table 2.
  • a molded body (lens) was obtained by the same method as in Example 1B.
  • Example 5B Mitsui Chemicals, Inc.
  • MR internal mold release agent 0.1 parts by mass
  • Tinuvin 329 0.1 parts by mass
  • 2,5 (6) -bis (isocyanatomethyl) -bicyclo -[2.2.1] -Heptane 50.6 parts by mass was charged to prepare a mixed solution. The mixture was stirred at 25 ° C. for 1 hour to completely dissolve.
  • the viscosities of the mixture containing the prepolymer are shown in Table 2. Then, the mixture containing the prepolymer was degassed at 400 Pa and 25 ° C. for 1 hour to obtain a first mixed solution. Pentaerythritol tetrakis (3-mercaptopropionate) [monomer for optical material] 22.2 parts by mass, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane [monomer for optical material] 23.7% by mass After the parts were charged to prepare a mixed solution, the obtained mixed solution was degassed at 400 Pa and 25 ° C. for 1 hour to obtain a second mixed solution.
  • the first mixed solution and the second mixed solution were mixed at 20 ° C. to obtain a polymerizable composition for an optical material.
  • the liquid was sent to a casting mold by the same method as in Example 1B, and the casting viscosity was adjusted to the values shown in Table 2.
  • the cast material was placed in a heat insulating container at 25 ° C. and allowed to stand for 2 hours for adiabatic polymerization. Then, the cast material was taken out from the heat insulating container and further subjected to heat polymerization at 120 ° C. for 1 hour. The cured molded body was released from the mold and further annealed at 120 ° C. for 2 hours to obtain a molded body (lens).
  • Example 6B to Example 7B The contents of pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane in the prepolymerization step were changed to the values shown in Table 2 and polymerized for optical materials.
  • a molded product (lens) was obtained by the same method as in Example 5B except that the casting viscosity of the sex composition was adjusted to the values shown in Table 2.
  • Example 8B The cast material was placed in a heat insulating container at 25 ° C. and allowed to stand for 3 hours for adiabatic polymerization, and then the cast material was taken out from the heat insulating container and released by the same method as in Example 7B. I got a body (lens).
  • Example 9B A molded body (lens) was obtained by the same method as in Example 7B except that the cast product was heated from 30 ° C. to 120 ° C. over time without adiabatic polymerization and heat polymerization was carried out over 3 hours.
  • Example 10B to Example 11B The contents of pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane in the prepolymerization step were changed to the values shown in Table 2 and polymerized for optical materials.
  • a molded product (lens) was obtained by the same method as in Example 5B except that the casting viscosity of the sex composition was adjusted to the values shown in Table 2.
  • Example 12B The polymerization catalyst was changed from 3,5-lutidine to dibutyltin (II) dichloride, and pentaerythritol tetrakis (3-mercaptopropionate) and 4-mercaptomethyl-1,8-dimercapto-3,6 in the prepolymerization step.
  • a molded body (lens) was obtained.
  • Example 13B A molded body (lens) was obtained by the same method as in Example 12B except that the cast product was heated from 30 ° C. to 120 ° C. over time without adiabatic polymerization and heat polymerization was carried out over 3 hours.
  • a1 A mixture of 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane a2: Dicyclohexylmethane diisocyanate a3: 1,3-bis (isocyanatomethyl) cyclohexane b1: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane b2: pentaerythritol tetrakis (3-mercaptopropionate) b3: 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecan and 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecan B4: Pentaerythritol tetrakis (2-mer
  • a preparatory step for preparing a total of 100 parts by mass of two or more different monomers for optical materials and 0.010 parts by mass to 2.0 parts by mass of a polymerization catalyst A part of two or more different monomers for optical materials and at least a part of a polymerization catalyst are mixed, and at least a part of two or more different monomers for optical materials is polymerized to obtain a prepolymer.
  • a prepolymerization step of obtaining a mixture containing a prepolymer, and Optical containing at least two or more different monomers for optical materials, a prepolymer, and a polymerization catalyst by adding the remainder of two or more different monomers for optical materials to the mixture containing the prepolymer.
  • a process for producing a polymerizable composition for an optical material to obtain a polymerizable composition for a material A curing step of obtaining an optical material which is a cured product of a polymerizable composition for an optical material by curing two or more different monomers for an optical material in the polymerizable composition for an optical material.
  • Examples 2B to 4B and Examples 6B to 11B have a viscosity (that is, casting viscosity) of the polymerizable composition for an optical material at the time of casting of 70 mPa ⁇ s or more. The optics could be suppressed better.
  • Example 14B Dicyclohexylmethane diisocyanate [monomer for optical material] 58.9 parts by mass, Tinuvin 329 [ultraviolet absorber] 1.5 parts by mass, Mitsui Chemicals, Inc.
  • MR internal mold release agent Internal mold release agent 0.1 parts by mass A mixed solution was prepared in. The mixture was stirred at 25 ° C. for 1 hour to completely dissolve.
  • the liquid was sent to a casting mold by the same method as in Example 1, and the casting viscosity was adjusted to the value shown in Table 3.
  • the cast material was placed in a heat insulating container at 25 ° C. and allowed to stand for 3 hours for adiabatic polymerization. Then, the cast material was taken out from the heat insulating container and further subjected to heat polymerization at 130 ° C. for 2 hours. The cured molded body was released from the mold and further annealed at 120 ° C. for 2 hours to obtain a molded body (lens).
  • a preparatory step for preparing a total of 100 parts by mass of two or more different monomers for optical materials and 0.010 parts by mass to 2.0 parts by mass of a polymerization catalyst A part of two or more different monomers for optical materials and at least a part of a polymerization catalyst are mixed, and at least a part of two or more different monomers for optical materials is polymerized to obtain a prepolymer.
  • a prepolymerization step of obtaining a mixture containing a prepolymer, and Optical containing at least two or more different monomers for optical materials, a prepolymer, and a polymerization catalyst by adding the remainder of two or more different monomers for optical materials to the mixture containing the prepolymer.
  • a process for producing a polymerizable composition for an optical material to obtain a polymerizable composition for a material A curing step of obtaining an optical material which is a cured product of a polymerizable composition for an optical material by curing two or more different monomers for an optical material in the polymerizable composition for an optical material.
  • Example 15B 1,3-Bis (isocyanatomethyl) cyclohexane [monomer for optical material] 48 parts by mass, Tinuvin 329 [ultraviolet absorber] 1.5 parts by mass, JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.) 0.18 parts by mass It was charged to prepare a mixed solution. The mixture was stirred at 25 ° C. for 1 hour to completely dissolve. Then, 4.0 parts by mass of pentaerythritol tetrakis (2-mercaptoacetate) and 3.9 parts by weight of 2,5-bis (mercaptomethyl) -1,4-dithiane were added to this mixed solution, and 25 parts by weight was charged.
  • the mixture was stirred at ° C. for 5 minutes to obtain a uniform solution. Further, 0.1 part by mass of 3,5-lutidine [polymerization catalyst] was added to the obtained uniform solution, and the mixture was stirred at 40 ° C. for 3 hours to polymerize the monomer for optical material while adjusting the viscosity. A mixture containing the polymer was obtained. The viscosities of the mixture containing the prepolymer are shown in Table 5. Then, the mixture containing the prepolymer was degassed at 400 Pa and 25 ° C. for 1 hour to obtain a first mixture.
  • the cast material was taken out from the heat insulating container and further subjected to heat polymerization at 120 ° C. for 1 hour.
  • the cured molded body was released from the mold and further annealed at 120 ° C. for 2 hours to obtain a molded body (lens).
  • a preparatory step for preparing a total of 100 parts by mass of two or more different monomers for optical materials and 0.010 parts by mass to 2.0 parts by mass of a polymerization catalyst A part of two or more different monomers for optical materials and at least a part of a polymerization catalyst are mixed, and at least a part of two or more different monomers for optical materials is polymerized to obtain a prepolymer.
  • a prepolymerization step of obtaining a mixture containing a prepolymer, and Optical containing at least two or more different monomers for optical materials, a prepolymer, and a polymerization catalyst by adding the remainder of two or more different monomers for optical materials to the mixture containing the prepolymer.
  • a process for producing a polymerizable composition for an optical material to obtain a polymerizable composition for a material A curing step of obtaining an optical material which is a cured product of a polymerizable composition for an optical material by curing two or more different monomers for an optical material in the polymerizable composition for an optical material.

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JPWO2023145685A1 (https=) * 2022-01-27 2023-08-03
WO2025023323A1 (ja) 2023-07-27 2025-01-30 三井化学株式会社 重合性組成物及びその製造方法、樹脂、成形体、光学材料、並びにレンズ
WO2025041800A1 (ja) * 2023-08-23 2025-02-27 三井化学株式会社 光学材料用重合性組成物、光学材料用重合性プレポリマー組成物、硬化物及び光学材料の製造方法

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