Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • 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
  • C08G18/08—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
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
  • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
  • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
• • 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

Definitions

• This disclosure relates to a polymerizable composition and a method for producing the same, a resin, a molded article, an optical material, and a lens.
• a polymerizable composition containing an active hydrogen compound (e.g., a polythiol compound) and a polyiso(thio)cyanate compound may be used as a polymerizable composition for producing a resin optical material (e.g., a lens).
• a resin optical material e.g., a lens.
• Patent Document 1 discloses a polymerizable composition capable of producing a resin molded product in which opacity and striae are suppressed, which is: A di- or higher functional iso(thio)cyanate compound, A di- or higher functional active hydrogen compound (e.g., a polythiol compound), a non-tin catalyst consisting of a compound having a specific chemical structure and a pKa of 1 to 9 (e.g., 2-methylpyrazine, ⁇ -picoline, ⁇ -picoline, 2,6-lutidine, 3,5-lutidine, 3-chloropyridine, triallylamine, and trioctylamine); A polymerizable composition comprising:
• Patent document 1 International Publication No. 2018-079829
• An object of one aspect of the present disclosure is to provide a polymerizable composition capable of producing a resin in which opacity, air bubbles, and devitrification are suppressed, the polymerizable composition comprising a polyiso(thio)cyanate compound (A), an active hydrogen compound (B), a nitrogen-containing compound (C) which is at least one of a nitrogen-containing aromatic heterocyclic compound and a tertiary amine compound, and water, and a method for producing the polymerizable composition; and a resin, a molded body, and a lens in which opacity, air bubbles, and devitrification are suppressed.
• Means for solving the above problems include the following aspects. ⁇ 1> A polyiso(thio)cyanate compound (A), An active hydrogen compound (B); a nitrogen-containing compound (C) which is at least one of a nitrogen-containing aromatic heterocyclic compound and a tertiary amine compound; Water, Including, The water content is 1900 ppm by mass or less based on the total amount of the polymerizable composition. Polymerizable compositions.
• m R 1s each independently represent 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;
• Q represents a carbon atom or a nitrogen atom;
• m represents an integer of 0 to 5.
• R 2 , R 3 , and R 4 each independently represent a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an allyl group.
• R 2 and R 3 may be bonded to each other to form a ring.
• the compound represented by the formula (1) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine,
• the compound represented by formula (2) is at least one selected from the group consisting of triallylamine and trioctylamine.
• polyiso(thio)cyanate compound (A) includes at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.
• the polyiso(thio)cyanate compound (A) includes at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diis
• the polythiol compound (B1) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithia
• the polymerizable composition according to claim 4 further comprising at least one selected from the group consisting of 1,2-dimercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,4-dithiane, bis(2-mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.
• ⁇ 7> The polymerizable composition according to any one of ⁇ 1> to ⁇ 6>, wherein the water content is 100 ppm by mass or more based on the total amount of the polymerizable composition.
• ⁇ 8> A method for producing the polymerizable composition according to any one of ⁇ 1> to ⁇ 6>, a raw material composition (BX) containing the active hydrogen compound (B) and water, the water content being 3800 ppm by mass or less based on the total amount of the raw material composition (BX); The polyiso(thio)cyanate compound (A), The nitrogen-containing compound (C); Mixing the A method for producing a polymerizable composition.
• ⁇ 9> A resin that is a cured product of the polymerizable composition according to any one of ⁇ 1> to ⁇ 7>.
• ⁇ 10> A molded product comprising the resin according to ⁇ 9>.
• ⁇ 11> An optical material comprising the resin according to ⁇ 9>.
• ⁇ 12> A lens comprising the resin according to ⁇ 9>.
• a polymerizable composition capable of producing a resin in which opacity, air bubbles, and devitrification are suppressed
• the polymerizable composition comprising a polyiso(thio)cyanate compound (A), an active hydrogen compound (B), a nitrogen-containing compound (C) which is at least one of a nitrogen-containing aromatic heterocyclic compound and a tertiary amine compound, and water, and a method for producing the polymerizable composition; and a resin, a molded body, and a lens in which opacity, air bubbles, and devitrification are suppressed.
• a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• the polymerizable composition of the present disclosure comprises: A polyiso(thio)cyanate compound (A), An active hydrogen compound (B); a nitrogen-containing compound (C) which is at least one of a nitrogen-containing aromatic heterocyclic compound and a tertiary amine compound; Water, Including, The water content is 1900 ppm by mass or less based on the total amount of the polymerizable composition. It is a polymerizable composition.
• a resin in which opacity, bubbles, and devitrification are suppressed can be produced.
• the effect of suppressing clouding and bubbles is an effect obtained by the nitrogen-containing compound (C) serving as a curing catalyst.
• the effect of suppressing devitrification is obtained by controlling the water content to 1,900 ppm by mass or less based on the total amount of the polymerizable composition.
• the nitrogen-containing compound (C) when used as a curing catalyst, opacity and striae can be suppressed, but devitrification (that is, devitrification evaluated by the degree of devitrification) may not be suppressed.
• the water content is 1,900 ppm by mass or less relative to the total amount of the polymerizable composition, so that the effect of suppressing opacity and striae can be obtained while also suppressing devitrification.
• the polymerizable composition of the present disclosure contains at least one polyiso(thio)cyanate compound (A).
• the polyiso(thio)cyanate compound (A) is not particularly limited as long as it is a compound having at least two iso(thio)cyanate groups in one molecule.
• polyiso(thio)cyanate compound (A) examples include: Aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, and xylylene diisocyanate; Alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, dicyclohexyldimethylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,5-
• the polyiso(thio)cyanate compound (A) may also be a halogen-substituted compound such as a chlorine-substituted compound or a bromine-substituted compound, an alkyl-substituted compound, an alkoxy-substituted compound, a nitro-substituted compound, a prepolymer-type modified compound with a polyhydric alcohol, a carbodiimide-modified compound, a urea-modified compound, a biuret-modified compound, a dimerization or trimerization reaction product, or the like.
• a halogen-substituted compound such as a chlorine-substituted compound or a bromine-substituted compound, an alkyl-substituted compound, an alkoxy-substituted compound, a nitro-substituted compound, a prepolymer-type modified compound with a polyhydric alcohol, a carbodi
• the polyiso(thio)cyanate compound (A) is It is preferable that the composition contains a polyisocyanate compound. It is preferable that the isocyanate-containing copolymer contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.
• pentamethylene diisocyanate hexamethylene diisocyanate
• the polyiso(thio)cyanate compound (A) may further contain at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).
• the peak area of the compound (N1) measured by gas chromatography under the following GC condition 1 is preferably 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• -GC condition 1- Filler: DB-1 (film thickness) 1.5 ⁇ m
• the peak area of the compound (N1) is more preferably 5.0 ppm or more, further preferably 50 ppm or more, and further preferably 100 ppm or more, relative to the peak area of xylylene diisocyanate.
• the peak area of the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, relative to the peak area of xylylene diisocyanate.
• the peak area of the compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6,373,536.
• the peak area of the compound (N2) measured by gas chromatography under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• -GC condition 2- Column: HP-50+, inner diameter 0.25 mm ⁇ length 30 m ⁇ film thickness 0.25 ⁇ m (manufactured by Hewlett-Packard) Oven temperature: heated from 50° C. to 280° C. at a rate of 10° C./min, and held at 280° C. for 6 min.
• the peak area of the compound (N2) is more preferably 0.1 ppm or more, further preferably 0.3 ppm or more, and further preferably 0.6 ppm or more, relative to the peak area of xylylene diisocyanate.
• the peak area of the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and even more preferably 60 ppm or less, relative to the peak area of xylylene diisocyanate.
• the peak area of the compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6,373,536.
• the peak area of the compound (N3) measured by gas chromatography under the above-mentioned GC condition 1 is preferably 0.10 ppm or more relative to the peak area 1 of xylylene diisocyanate.
• the peak area of the compound (N3) is more preferably 0.1 ppm or more, further preferably 3.0 ppm or more, and further preferably 5.0 ppm or more, relative to the peak area of xylylene diisocyanate.
• the peak area of the compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, even more preferably 100 ppm or less, and even more preferably 75 ppm or less, relative to the peak area of xylylene diisocyanate.
• the peak area of the compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6,373,536.
• the acid content of the polyiso(thio)cyanate compound (A) is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm.
• the lower limit of the acid content of the polyiso(thio)cyanate compound (A) is not particularly limited, but the lower limit is, for example, 1 ppm.
• the acid content of the polyiso(thio)cyanate compound (A) can be measured in accordance with the method described in paragraph 0091 of WO 2021/256417.
• the polyiso(thio)cyanate compound (A) may contain a stabilizer.
• the mixing ratio of the polythiol compound (B1) to the polyiso(thio)cyanate compound (A) is preferably such that the molar ratio of the mercapto groups contained in the polythiol compound (B1) to the iso(thio)cyanate groups of the polyiso(thio)cyanate compound (A) (mercapto groups/iso(thio)cyanate groups) is 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3.
• the polymerizable composition of the present disclosure contains at least one active hydrogen compound (B).
• active hydrogen compound means a compound that contains an active hydrogen group.
• active hydrogen group means a hydroxyl group, a mercapto group (ie, a thiol group), a primary amino group, or a secondary amino group.
• Examples of the active hydrogen compound (B) include Polythiol compounds (B1) (i.e., compounds containing two or more mercapto groups (i.e., thiol groups)), Polyol compound (B2) (i.e., a compound containing two or more hydroxyl groups), Hydroxythiol compounds (B3) (i.e., compounds containing one or more hydroxyl groups and one or more mercapto groups); Polyamine compounds (B4) (i.e. compounds containing two or more amino groups), etc.
• Polythiol compounds (B1) i.e., compounds containing two or more mercapto groups (i.e., thiol groups)
• Polyol compound (B2) i.e., a compound containing two or more hydroxyl groups
• Hydroxythiol compounds (B3) i.e., compounds containing one or more hydroxyl groups and one or more mercapto groups
• Polyamine compounds (B4) i.e. compounds containing two or more amino groups
• polythiol compound (B1) As the active hydrogen compound (B), a polythiol compound (B1) is preferred.
• the polythiol compound (B1) is not particularly limited as long as it is a compound containing two or more mercapto groups.
• the polythiol compound (B1) that can be contained in the polymerizable composition of the present disclosure may be one type of compound, or two or more types of compounds.
• the polythiol compound (B1) is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, Pentaerythritol tetrakis(2-mercaptoacetate), Pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dit
• the polythiol compound (B1) contains polythiol T as a main component
• the total content of polythiol T relative to the total amount of the polythiol compound (B1) is 50% or more.
• the total content of polythiol T relative to the total amount of polythiol compounds (B1) is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.
• the term “%” used herein means the ratio (area %) of the total area of all peaks of polythiol T to the total area of all peaks of polythiol compound (B1) determined by high performance liquid chromatography.
• the polythiol compound (B1) may contain a compound in which at least one of the three or more mercapto groups contained in the compound containing three or more mercapto groups is substituted with a group represented by the following formula (S1) (hereinafter also referred to as compound (S1)). This can further promote the polymerization reaction.
• the peak area of the compound (S1) is preferably 0.01 to 3.0, and more preferably 0.01 to 1.5, relative to 100 of the peak area of the compound containing three or more mercapto groups.
• the peak area of the compound (S1) is 0.01 or more relative to 100 of the peak area of the compound containing three or more mercapto groups, the polymerization reaction is further promoted.
• the peak area of the compound (S1) is 3.0 or less relative to 100 of the peak area of the compound containing three or more mercapto groups, the controllability of the polymerization reaction is excellent.
• the total content of the polyiso(thio)cyanate compound (A) and the active hydrogen compound (B) is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, based on the total amount of the polymerizable composition.
• the upper limit of the total content of the polyiso(thio)cyanate compound (A) and the active hydrogen compound (B) is, for example, 98 mass % or less based on the total amount of the polymerizable composition.
• the nitrogen-containing compound (C) preferably contains at least one of a compound represented by the following formula (1) and a compound represented by the following formula (2).
• m R 1s each independently represent 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;
• Q represents a carbon atom or a nitrogen atom; and
• m represents an integer of 0 to 5.
• m R 1s each independently represent 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;
• Q represents a carbon atom, a nitrogen atom, or an oxygen atom; and
• m represents an integer of 0 to 5.
• m is preferably an integer from 0 to 3, and more preferably an integer from 1 to 3.
• examples of the linear alkyl group having 1 to 20 carbon atoms represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an n-octyl group, a nonyl group, a decyl group, and a dodecyl group.
• examples of the branched alkyl group having 3 to 20 carbon atoms represented by R 1 include an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, an isooctyl group, a 2-ethylhexyl group, a 2-propylpentyl group, and an isodecyl group.
• examples of the cycloalkyl group having 3 to 20 carbon atoms represented by R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
• R 1 is preferably a linear alkyl group having 1 to 20 carbon atoms or a halogen atom, and more preferably a linear alkyl group having 1 to 3 carbon atoms or a chlorine atom.
• the compound represented by formula (1) is preferably at least one selected from the group consisting of 2-methylpyrazine, pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine.
• R 2 , R 3 , and R 4 each independently represent a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an allyl group.
• R 2 and R 3 may be bonded to each other to form a ring.
• R 2 , R 3 , and R 4 are each independently preferably a linear alkyl group having 3 to 20 carbon atoms, more preferably a linear alkyl group having 3 to 10 carbon atoms, and particularly preferably a linear alkyl group having 5 to 10 carbon atoms.
• Examples of the linear alkyl group having 3 to 20 carbon atoms represented by R 2 , R 3 , or R 4 include an n-propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an n-octyl group, a nonyl group, a decyl group, and a dodecyl group.
• R2 and R3 may be bonded to each other to form a ring. That is, the compound represented by formula (2) may be a cyclic amine compound having a structure in which R2 and R3 are bonded to each other to form a ring.
• the cyclic amine compound include 1-propylpiperidine, 1-butylpiperidine, 1-cyclohexylpiperidine, 1-butylpyrrolidine, and 1-cyclohexylpyrrolidine.
• the compound represented by formula (2) is preferably at least one selected from the group consisting of triallylamine and trioctylamine.
• the content of the nitrogen-containing compound (C) in the polymerizable composition i.e., the total content of the nitrogen-containing aromatic heterocyclic compound and tertiary amine compound; for example, the total content of the compound represented by formula (1) and the compound represented by formula (2)
• the content of the nitrogen-containing compound (C) in the polymerizable composition is preferably 0.01% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass, based on the total content of the polyiso(thio)cyanate compound (A) and the active hydrogen compound (B).
• the content of the nitrogen-containing compound (C) in the polymerizable composition i.e., the total content of the nitrogen-containing aromatic heterocyclic compound and tertiary amine compound; for example, the total content of the compound represented by formula (1) and the compound represented by formula (2)) is preferably 0.01% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass, based on the total amount of the polymerizable composition.
• the polymerizable composition of the present disclosure may contain, as a curing catalyst, a compound other than the nitrogen-containing compound (C) described above.
• the proportion of the nitrogen-containing compound (C) in the curing catalyst is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.
• the polymerizable composition of the present disclosure contains water.
• the water content is 1,900 ppm by mass or less based on the total amount of the polymerizable composition.
• the water content is 1,900 ppm by mass or less relative to the total amount of the polymerizable composition, so that devitrification of the obtained resin is suppressed.
• the water content is preferably 1500 ppm by mass or less, and more preferably 1100 ppm by mass or less, based on the total amount of the polymerizable composition.
• the polymerizable composition of the present disclosure may contain other components in addition to the components described above.
• Other components include internal release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, and blue ink agents such as inorganic pigments.
• an acidic phosphate ester can be used as the internal mold release agent.
• acidic phosphate esters include monophosphate esters and diphosphate esters, and each can be used alone or in a mixture of two or more types.
• the method for producing the above-mentioned polymerizable composition of the present disclosure is not particularly limited, and any known method for mixing the above-mentioned components can be appropriately applied.
• An example of a method for producing the polymerizable composition of the present disclosure (hereinafter also referred to as Production Method A) is as follows, but the method for producing the polymerizable composition of the present disclosure is not limited to Production Method A.
• Manufacturing method A is a raw material composition (BX) containing an active hydrogen compound (B) and water, the water content of which is 3800 ppm by mass or less based on the total amount of the raw material composition (BX); A polyiso(thio)cyanate compound (A), a nitrogen-containing compound (C); (hereinafter also referred to as the mixing step).
• BX raw material composition
• the mixing step in addition to the above-mentioned components, components other than the above-mentioned components may be mixed.
• the preparation method A may include other steps in addition to the mixing step.
• a raw material composition (BX) is used.
• the raw material composition (BX) is a composition containing an active hydrogen compound (B) and water, and the water content is 3800 ppm by mass or less based on the total amount of the raw material composition (BX).
• the water content in raw material composition (BX) is preferably 2200 ppm by mass or less, and more preferably 1000 ppm by mass or less.
• the water content in raw material composition (BX) is preferably 10 ppm by mass or more, more preferably 100 ppm by mass or more, even more preferably 200 ppm by mass or more, even more preferably 300 ppm by mass or more, and even more preferably 400 ppm by mass or more. It is.
• the order in which the raw materials i.e., the raw material composition (BX), the polyiso(thio)cyanate compound (A), and the nitrogen-containing compound (C)) are mixed (i.e., the order in which they are charged into a container used for mixing) is not particularly limited.
• the polymerizable composition may be obtained by adding all the raw materials to a container at once and mixing them, or by adding the raw materials little by little to a container and mixing them.
• a part of the total amount of raw materials may be charged into a container to form a prepolymer having a polymerizable functional group as a polymer of the polyiso(thio)cyanate compound (A) and the active hydrogen compound (B), and then the rest of the raw materials may be added to obtain a polymerizable composition containing the polyiso(thio)cyanate compound (A), the active hydrogen compound (B), the nitrogen-containing compound (C), the prepolymer having a polymerizable functional group, and water.
• the resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure described above.
• the molded article of the present disclosure contains the resin of the present disclosure.
• the resin of the present disclosure can be produced by curing the polymerizable composition of the present disclosure described above, specifically, by polymerizing and curing the monomers in the polymerizable composition of the present disclosure.
• Cast polymerization can produce a molded article of the present disclosure that contains the resin of the present disclosure (i.e., the cured product of the polymerizable composition of the present disclosure).
• the polymerizable composition according to one example of the present disclosure is injected between a pair of molds held by a gasket, a tape, etc. At this time, degassing treatment, filtration treatment, etc. may be performed as necessary.
• the monomer in the composition injected between the molds is polymerized to cure the composition between the molds, and the cured product is then removed from the molds to obtain the cured product.
• Polymerization of the monomer may be carried out by heating the polymerizable composition of the present disclosure, for example, using a heating device equipped with a mechanism for heating an object to be heated in an oven, water, etc.
• the polymerization conditions e.g., polymerization temperature, polymerization time, etc.
• the polymerization temperature may be, for example, from -50°C to 150°C, or from 10°C to 150°C.
• the polymerization time may be, for example, 1 hour to 200 hours, or 1 hour to 80 hours.
• the resin or a molded article containing the resin according to the present disclosure may be obtained by carrying out a treatment such as annealing after polymerization of a monomer.
• the annealing temperature may be 50°C to 150°C, 90°C to 140°C, 100°C to 130°C, or the like.
• optical material of the present disclosure contains the resin of the present disclosure described above.
• the optical material of the present disclosure can be produced, for example, by the above-mentioned cast polymerization.
• the optical material of the present disclosure may be made of the resin of the present disclosure, or may contain the resin of the present disclosure and other elements.
• the other elements include other members, a coating layer provided on the resin of the present disclosure, and the like.
• Optical materials disclosed herein include lenses (e.g., eyeglass lenses, camera lenses, polarized lenses, etc.), light-emitting diodes (LEDs), etc.
• lenses e.g., eyeglass lenses, camera lenses, polarized lenses, etc.
• LEDs light-emitting diodes
• the lens of the present disclosure is an example of the optical material of the present disclosure, and contains the resin of the present disclosure described above. Lenses of the present disclosure may be manufactured, for example, by cast polymerization as described above.
• the lens of the present disclosure may be made of the resin of the present disclosure, or may contain the resin of the present disclosure and other elements.
• the other elements include other members, a coating layer provided on the resin of the present disclosure, and the like.
• Lenses of the present disclosure include eyeglass lenses, camera lenses, polarized lenses, and the like. Below, a spectacle lens will be described as an example of the lens of the present disclosure.
• the eyeglass lenses include a resin of the present disclosure molded into a desired lens shape.
• the eyeglass lens preferably further comprises a coating layer provided on one or both sides of the resin.
• the coating layer include a primer layer, a hard coat layer, an anti-reflection layer, an anti-fogging coating layer, an anti-fouling layer, a water-repellent layer, etc.
• Each of these coating layers can be used alone or in combination of a plurality of coating layers. When coating layers are applied to both sides of the cured product, the same coating layer may be applied to each side, or different coating layers may be applied to each side.
• the components of the coating layer can be appropriately selected depending on the purpose.
• components of the coating layer include resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, and antistatic agents.
• polythiol compound (B1-1) containing polythiol T1 as a main component was produced.
• the polythiol compound (B1-1) is an example of the active hydrogen compound (B). Details are shown below. 124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water were charged into the reactor.
• a toluene solution of polythiol compound (B1-1) mainly composed of polythiol T1 (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane) was obtained.
• This toluene solution was acid washed with 162.8 parts by mass of 35.5% by mass hydrochloric acid at 35°C to 43°C for 1 hour.
• the toluene solution after acid washing was washed twice with 174.1 parts by mass of degassed water at 35°C to 45°C for 30 minutes.
• the toluene solution after the second washing with degassed water was washed with 162.1 parts by mass of 0.1% by mass ammonia water for 30 minutes.
• m-Xylylene diisocyanate (hereinafter also referred to as "NCO1") (52 parts by mass) as the polyiso(thio)cyanate compound (A) and an ultraviolet absorber VIOSORB583 (manufactured by Kyodo Pharmaceutical Co., Ltd.) (1.0 part by mass) were mixed, and then, 3,5-lutidine (0.03 parts by mass) as a nitrogen-containing compound (C); JP-506H (Johoku Chemical Industry Co., Ltd.; acidic phosphate ester) (0.075 parts by mass) as an internal release agent; The above ingredients were mixed at 20° C.
• NCO1 m-Xylylene diisocyanate
• raw material composition (BX) that had been degassed in advance at 600 Pa for 1 hour was added thereto in an amount of 47 mass % based on the total amount of the resulting composition, and mixed at 20°C to obtain a polymerizable composition.
• the water content (ppm by mass) relative to the total amount of the obtained polymerizable composition was measured using a Karl Fischer moisture meter (MKC-710, manufactured by Kyoto Electronics Manufacturing Co., Ltd.), and the value was as shown in Table 1.
• the polymerizable composition was subjected to degassing at 600 Pa for 10 minutes.
• the defoamed polymerizable composition was filtered with a 1 ⁇ m Teflon (registered trademark) filter, and the filtrate was poured between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven, and the temperature inside the oven was set to 30° C.
• the temperature inside the oven was raised from 30° C. to 70° C. over 1.5 hours, then raised from 70° C. to 120° C. over 0.5 hours, then maintained at 120° C. for 1 hour, and then lowered from 120° C. to 70° C. over 1 hour.
• the monomers in the polymerizable composition i.e., NCO1 and polythiol compound (B1-1)
• a molded body containing a resin i.e., a cured product of the polymerizable composition
• the inside of the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and then the molded body containing the resin (hereinafter, referred to as a resin molded body) was removed from the pair of glass molds.
• the obtained resin molded body was annealed at 120° C. for 1 hour to obtain a circular flat lens having a thickness of 9.0 mm and a diameter of 75 mm.
• Example 4 Comparative Example 3 and Comparative Example 4
• ⁇ Production of polythiol compound (B1-1)> In the same manner as in Example 1, a polythiol compound (B1-1) was produced.
• polythiol compound (B1-2) containing polythiol T3 (i.e., pentaerythritol tetrakis(3-mercaptopropionate)) as a main component was produced.
• polythiol compound (B1-2) is an example of the active hydrogen compound (B). Details are shown below.
• reaction solution was cooled, and then washed with a base and then with water in this order. From the reaction solution after washing with water, toluene and a trace amount of water were removed under reduced pressure under heating. The remaining reaction solution was filtered through a PTFE type membrane filter to obtain 462.3 parts by mass of a polythiol compound (B1-2) containing polythiol T3 as a main component.
• ⁇ Preparation of Raw Material Composition (BX)> The polythiol compound (B1-1) and the polythiol compound (B1-2) obtained as described above were mixed with water to obtain a raw material composition (BX).
• the water content relative to the total amount of the raw material composition (BX) was measured using a Karl Fischer moisture meter (MKC-710, manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
• raw material composition (BX) that had been degassed in advance at 600 Pa for 1 hour was added thereto in an amount of 49 mass % based on the total amount of the resulting composition, and mixed at 20°C to obtain a polymerizable composition.
• the water content (ppm by mass) relative to the total amount of the obtained polymerizable composition was measured using a Karl Fischer moisture meter (MKC-710, manufactured by Kyoto Electronics Manufacturing Co., Ltd.), and the value was as shown in Table 1.
• a resin molded article was obtained in the same manner as in Example 1 except that the polymerizable composition was used.
• the obtained resin molded body was annealed at 120° C. for 1 hour to obtain a circular flat lens having a thickness of 9.0 mm and a diameter of 75 mm.
• Comparative Example 1 which used a polymerizable composition containing a polyiso(thio)cyanate compound (A), an active hydrogen compound (B), a nitrogen-containing compound (C), and water, where the water content was more than 1,900 ppm by mass based on the total amount of the polymerizable composition, the resulting lens (i.e., resin molded product) had reduced bubbles and striae, but devitrification could not be suppressed.

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