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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/06—Polythioethers from cyclic thioethers
  • C08G75/08—Polythioethers from cyclic thioethers from thiiranes
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • 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
  • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
  • G02C7/022—Ophthalmic lenses having special refractive features achieved by special materials or material structures
• • 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
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
  • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
  • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene

Definitions

• the present invention relates to a composition for an optical material and the like, and more particularly to an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate and a filter, and particularly a composition for an optical material suitable for a plastic lens and the like.
• plastic materials are lightweight, have high toughness, and are easy to dye, they have been widely used in various optical materials, especially spectacle lenses, in recent years.
• the performances particularly required for optical materials, especially spectacle lenses are low specific gravity, high transparency and low yellowness, high heat resistance, high strength, etc. as physical properties, and high refractive index and high optical performance.
• Abbe number A high refractive index makes it possible to make the lens thinner, and a high Abbe number reduces the chromatic aberration of the lens, but as the refractive index increases, the Abbe number decreases, so studies are being conducted to improve both at the same time.
• the most representative method among these studies is a method using an episulfide compound shown in Patent Document 1.
• Patent Document 2 proposes a composition in which a thiol compound is added to an episulfide compound. Further studies aimed at achieving a high refractive index have been conducted, and the composition consisting of sulfur, episulfide and thiol shown in Patent Documents 3 and 4 and the composition consisting of a compound having a cyclic skeleton and episulfide shown in Patent Document 5 are being studied. Has been proposed.
• the episulfide compound can be polymerized alone or with many other compounds due to its high reactivity, and can be composed according to various uses.
• the viscosity of these episulfide compounds or compositions containing them may increase at the time of preparation, which makes workability difficult.
• a method of adding a halide of an element of Group 13 to 16 in the long periodic table shown in Patent Document 6 has been proposed.
• any of the coloration of the resin, the change in color tone after heating the resin, and the change in color tone after irradiation of the resin may be deteriorated, and it is difficult to maintain a good balance between these physical properties. there were.
• the problem to be solved by the present invention is optics that suppresses an increase in viscosity during compounding and maintains a good balance between coloring of the resin after curing, color tone change after heating of the resin, and color tone change after light irradiation of the resin.
• the purpose is to provide a composition for materials and the like.
• the present inventors have made a composition for an optical material containing (a) an episulfide compound, (b) a polymerization catalyst, and (c) an ester compound having a halogen at the ⁇ -position.
• This problem was solved by a compound, and the present invention was reached. That is, the present invention is as follows. 1. 1. A composition for an optical material containing (a) an episulfide compound, (b) a polymerization catalyst, and (c) an ester compound having a halogen at the ⁇ -position. 2. 2. (A) The composition for an optical material according to 1 above, wherein the episulfide compound is a compound represented by the following formula (1).
• composition for an optical material according to 1 or 2 above which further contains a polythiol compound.
• X represents S, Se or Te.
• a to f 0 to 3, 8 ⁇ (a + c + e) ⁇ 1, 8 ⁇ (b + d + f) ⁇ 2, and (b + d + f) ⁇ (a + c + e).) 5.
• composition for an optical material according to any one of 1 to 4 above, wherein the ester compound having a halogen at the ⁇ -position in (c) is a compound represented by the following formula (10).
• X represents a halogen.
• R 1 and R 2 each independently represent a hydrocarbon having 1 to 10 carbon atoms.
• Composition for materials 7. An optical material obtained by polymerizing the composition for an optical material according to any one of 1 to 6 above.
• the (a) episulfide compound used in the present invention includes all episulfide compounds, and specific examples thereof are listed separately for compounds having a chain aliphatic skeleton, an aliphatic cyclic skeleton, or an aromatic skeleton.
• Examples of the compound having a chain aliphatic skeleton include compounds represented by the following formulas (1) to (4).
• m represents an integer of 0 to 4
• n represents an integer of 0 to 2.
• n represents 0.
• Examples of the compound having an aliphatic cyclic skeleton include compounds represented by the following formula (5) or (6).
• p and q each independently represent an integer of 0 to 4.
• p represents 1 and q represents 2.
• p represents 1 and q represents 2.
• Examples of the compound having an aromatic skeleton include compounds represented by the following formula (7) or (8).
• p represents an integer of 0 to 4 and q represents an integer of 1 to 3.
• p represents 1 and q represents 2.
• p and q independently represent an integer of 0 or 1, respectively.
• p represents 1 and q represents 1.
• the preferable compound is a compound having a chain aliphatic skeleton and represented by the above formulas (1) and (2), specifically, bis ( ⁇ -epithiopropyl) sulfide and bis ( ⁇ -epithiopropyl) sulfide.
• Disulfide Bis ( ⁇ -Epithiopropyl) Trisulfide, Bis ( ⁇ -Epithiopropylthio) Methan, 1,2-Bis ( ⁇ -Epithiopropylthio) Etan, 1,3-Bis ( ⁇ -Epithio) Propylthio) propane, 1,4-bis ( ⁇ -epithiopropylthio) butane, bis ( ⁇ -epithiopropylthioethyl) sulfide, and the compound of formula (2).
• amines, onium salts, phosphine compounds and the like are used as the (b) polymerization catalyst for polymerizing and curing the composition used in the present invention.
• Specific examples include amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, phosphine compounds and the like.
• a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound having good compatibility with the composition are more preferable, and a quaternary phosphonium salt is more preferable.
• more preferable compounds include quaternary ammonium salts such as tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride, and tetra-.
• quaternary phosphonium salts such as n-butylphosphonium bromide and tetraphenylphosphonium bromide
• phosphine compounds such as triphenylphosphine.
• the polymerization catalyst may be used alone or in combination of two or more.
• the amount of the polymerization catalyst added varies depending on the composition, the mixing ratio and the polymerization curing method, and therefore cannot be unconditionally determined, but is usually 0.001 mass with respect to the total amount of the composition for optical materials. % Or more and 5% by mass or less, preferably 0.01% by mass or more and 1% by mass or less, most preferably 0.01% by mass or more and 0.5% by mass or less.
• the amount of the polymerization catalyst added is more than 5% by mass, the refractive index and heat resistance of the cured product are lowered, and the cured product may be colored. Further, if it is less than 0.001% by mass, it may not be sufficiently cured and the heat resistance may be insufficient.
• the ester compound (c) having a halogen at the ⁇ -position used in the present invention includes all ester compounds having a halogen at the ⁇ -position, but is preferably a compound represented by the following formula (10).
• X represents a halogen, preferably Cl, Br, or I.
• R 1 and R 2 each independently represent a hydrocarbon having 1 to 10 carbon atoms, preferably a hydrocarbon having 1 to 4 carbon atoms, and more preferably methyl, ethyl, or propyl.
• halogenated malonic acid ester more preferably a diester compound having a halogen at the ⁇ -position, and specifically, dimethyl chloromalonate, diethyl chloromalonate, dimethyl bromomalonate, and diethyl bromomalonate. be. Of these, dimethyl chloromalonate and diethyl chloromalonate are preferable.
• the amount of the compound (c) added is usually 0.0001 to 5.0% by mass, preferably 0.0005 to 3.0% by mass, more preferably 0.0005 to 3.0% by mass, based on the total amount of the composition for optical materials. It is 0.001 to 2.0% by mass.
• a polythiol compound may be added to the composition for optical materials of the present invention.
• the polythiol compound includes all polythiol compounds, and specifically, methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2, 3-Trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane, 1,5-dimercapto -3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl -1,3-dimercaptopropane, 2-mercap
• more preferable compounds are bis (2-mercaptoethyl) sulfide and 1,3-bis (mercaptomethyl) benzene, and the most preferable compound is bis (2-mercaptoethyl) sulfide.
• the amount of the polythiol compound added is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and further preferably 3 to 20% by mass with respect to the total amount of the composition for optical materials.
• Sulfur or the compound represented by the formula (9) may be added to the composition for optical materials of the present invention.
• X represents S, Se or Te, and preferably S.
• a to f independently represent an integer of 0 to 3, and 8 ⁇ (a + c + e) ⁇ 1, 8 ⁇ (b + d + f) ⁇ 2, and (b + d + f) ⁇ (a + c + e).
• the compound represented by the formula (9) includes all compounds, and specifically, dithiane, 1,2-dithiane, 1,3-dithiane, trithietan, 1,2-dithiolane, 1,3-.
• the conditions for this preliminary polymerization reaction are preferably ⁇ 10 ° C. to 120 ° C. for 0.1 to 240 hours, more preferably 0 to 100 ° C. for 0.1 to 120 hours, and particularly preferably 20 to 80 ° C. for 0. . 1-60 hours.
• the use of catalysts to facilitate the preliminary reaction is effective and preferred examples are 2-mercapto-1-methylimidazole, triphenylphosphine, 3,5-dimethylpyrazole, N-cyclohexyl-2-benzothia.
• Zoryl sulfin amide dipentamethylene thiuram tetrasulfide, tetrabutyl thiuram disulfide, tetraethyl thiuram disulfide, 1,2,3-triphenylguanidine, 1,3-diphenylguadinin, 1,1,3,3-tetramethyleneguanidine , Aminoguanidine urea, trimethylthiourea, tetraethylthiourea, dimethylethylthiourea, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, pipecorium pipecoryldithiocarbamate and the like.
• sulfur and the compound represented by the formula (9) are consumed by 10% or more (100% before the reaction) by this preliminary polymerization reaction, and 20% or more should be consumed. Is more preferable.
• the preliminary reaction may be carried out in any atmosphere, such as in the atmosphere, under an inert gas such as nitrogen, or under normal pressure or hermetically sealed by pressurization or depressurization. It is also possible to use liquid chromatography or a refractive index meter to detect the progress of the preliminary reaction.
• the amount of sulfur or the compound represented by the formula (9) added is usually 0.01 to 40% by mass, preferably 0.1 to 30% by mass, based on the total amount of the composition for optical materials. , More preferably 0.5 to 25% by mass.
• the degassing treatment is carried out under reduced pressure before, during or after mixing the compound, the polymerization catalyst, and the additive capable of reacting with a part or all of the composition components.
• the treatment conditions are 0 ° C. to 100 ° C. for 1 minute to 24 hours under a reduced pressure of 0.001 to 50 torr.
• the degree of decompression is preferably 0.005 to 25 torr, more preferably 0.01 to 10 torr, and the degree of decompression may be varied within these ranges.
• the degassing time is preferably 5 minutes to 18 hours, more preferably 10 minutes to 12 hours.
• the temperature at the time of degassing is preferably 5 ° C to 80 ° C, more preferably 10 ° C to 60 ° C, and the temperature may be varied within these ranges.
• renewing the interface of the composition for optical materials by stirring, blowing gas, vibration by ultrasonic waves, or the like is a preferable operation for enhancing the degassing effect.
• the components removed by the degassing treatment are mainly dissolved gas such as hydrogen sulfide and low boiling point substances such as low molecular weight thiol, but if the effect of the present invention is exhibited, the target of removal is particularly high.
• the type of ingredient is not limited. Furthermore, purifying these compositions for optical materials and / or each raw material before mixing by filtering impurities and the like with a filter having a pore size of about 0.05 to 10 ⁇ m further improves the quality of the optical materials of the present invention. It is also preferable from the viewpoint of enhancing.
• additives such as known antioxidants, ultraviolet absorbers and bluing agents are added to further improve the practicality of the obtained material.
• the antioxidant include phenol derivatives.
• preferred compounds are polyhydric phenols and halogen-substituted phenols, more preferred compounds are catechols, pyrogallols, and alkyl-substituted catechols, and the most preferred compounds are catechols and pyrogallols.
• Preferred examples of the UV protection agent include benzotriazole compounds.
• the most preferable compounds are 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 5-chloro-2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H.
• -Benzotriazole 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, and 2- (2-Hydroxy-5-tert-octylphenyl) -2H-benzotriazole.
• Preferred examples of the bluing agent include anthraquinone compounds.
• a known external and / or internal adhesion improving agent is used or added to control the adhesion between the obtained cured product and the mold.
• the adhesion improving agent include known silane coupling agents and titanate compounds, which may be used alone or in combination of two or more.
• the addition amount is usually 0.0001 to 5% by mass with respect to the total amount of the composition for optical materials.
• a known external and / or internal mold release agent is used or added to obtain the mold release property of the obtained cured product.
• the release agent is a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, a phosphoric acid ester, an acidic phosphoric acid ester, an oxyalkylene type acidic phosphoric acid ester, an alkali metal salt of an acidic phosphoric acid ester, and an alkali of an oxyalkylene type acidic phosphoric acid ester.
• examples include metal salts, alkali metal salts of higher fatty acids, higher fatty acid esters, paraffins, waxes, higher aliphatic amides, higher aliphatic alcohols, polysiloxanes, and aliphatic amine ethylene oxide adducts.
• the above may be mixed and used.
• the amount added is usually 0.0001 to 5% by mass with respect to the optical material composition.
• the method for producing an optical material by polymerizing and curing the composition for an optical material of the present invention is as follows if it is described in more detail.
• Additives such as the above-mentioned composition components, antioxidants, UV absorbers, polymerization catalysts, radical polymerization initiators, adhesion improvers, and mold release agents can all be mixed in the same container at the same time with stirring.
• Each raw material may be added and mixed stepwise, or several components may be mixed separately and then remixed in the same container.
• the raw materials and auxiliary materials may be mixed in any order. In mixing, the set temperature, the time required for this, and the like are basically sufficient as long as each component is sufficiently mixed.
• the composition for optical materials that has been subjected to the above-mentioned reaction and treatment is injected into a glass or metal mold, and the polymerization curing reaction is promoted by heating or irradiation with active energy rays such as ultraviolet rays, and then the composition is removed from the mold. .. In this way, the optical material is manufactured.
• the composition for an optical material is preferably polymerized and cured by heating to produce an optical material.
• the curing time is 0.1 to 200 hours, usually 1 to 100 hours
• the curing temperature is ⁇ 10 to 160 ° C., usually ⁇ 10 to 140 ° C.
• the polymerization can be carried out by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature by 0.1 ° C. to 100 ° C./hour, lowering the temperature by 0.1 ° C. to 100 ° C./hour, or a combination thereof.
• surface treatment such as dyeing, hard coat, impact resistant coat, antireflection, and anti-fog property can be performed.
• each component is uniformly stirred and then kept at 20 ° C. for 3 hours, and the viscosity measured by a vibration viscometer is preferably less than 450 cp, more preferably less than 350 cp. .. Further, when the composition for an optical material of the present invention was polymerized and cured, a weather resistance test was conducted for 48 hours, and a change in color tone was measured, ⁇ Y. I. Is preferably less than 3.5, more preferably less than 2.5.
• the compounds shown in Tables 3 and 4 below ((a) compounds, sulfur and polythiol compounds) were mixed with (b) triethylbenzylammonium chloride as a polymerization catalyst in an amount of 0.03% by mass based on the total amount of the composition for optical materials.
• the stabilizers shown in 3 and 4 were added in an amount of 0.3% by mass based on the total amount of the composition for optical materials, and the mixture was polymerized and cured.
• a weather resistance test device (Weatherometer Ci4000 manufactured by Atlas)
• a weather resistance test was conducted for 48 hours under the condition of a black panel temperature of 60 ° C. and a humidity of 50%, and the change in color tone before and after the weather resistance test (yellowing degree ( ⁇ Y.I)).
• BES Bis ( ⁇ -epithiopropyl) sulfide S: Sulfur
• BMES Bis (2-mercaptoethyl) sulfide
• BES Bis ( ⁇ -epithiopropyl) sulfide S: Sulfur
• BMES Bis (2-mercaptoethyl) sulfide

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• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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• 2021
  • 2021-05-21 CN CN202180037472.2A patent/CN115667369B/zh active Active
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  • 2021-05-21 WO PCT/JP2021/019376 patent/WO2021241441A1/ja not_active Ceased
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