Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
  • C07D331/02—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero 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
  • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

• the present invention relates to a 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 base, and a filter, and particularly suitable for a plastic lens.
• an optical material such as a plastic lens, a prism, an optical fiber, an information recording base, and a filter, and particularly suitable for a plastic lens.
• Patent Document 2 a composition comprising one or more inorganic compounds selected from inorganic compounds having a sulfur atom and / or selenium atom shown in Patent Document 2 and an episulfide compound is proposed.
• Patent Documents 3 to 5 have been proposed in order to improve transparency.
• white turbidity has not been solved in a lens having a thick center called a plus power lens.
• the plus power lens concentrates the transmitted light, it can be said that the plus power lens is easily visible with the naked eye even if it has a slight decrease in transparency, and is easily clouded. Moreover, since it is an optical material use, when white turbidity arises after hardening, it will become all bad and a huge loss will arise. Therefore, there has been a demand for a method that predicts whether or not white turbidity is generated after curing in a stage before curing, and enables determination of quality.
• the problem to be solved by the present invention is to suppress white turbidity of a cured product obtained by polymerizing and curing a composition containing sulfur and an episulfide compound, and in particular, to generate white turbidity in a lens having a thick center thickness called a plus power lens. It is to suppress. Furthermore, an object of the present invention is to provide an optical material composition capable of predicting and discriminating the occurrence of white turbidity after curing at the stage before polymerization and curing, and determining the quality.
• the present inventors have found that a composition for optical materials containing sulfur having an turbidity value of 10 ppm or less and an episulfide compound in a 30% by mass carbon disulfide solution, etc. This has solved the problem and has led to the present invention. That is, the present invention is as follows. ⁇ 1> A composition for an optical material, characterized by containing sulfur having an turbidity value of 10 ppm or less and an episulfide compound when a 30% by mass carbon disulfide solution is prepared. ⁇ 2> The composition for optical materials according to ⁇ 1>, further containing a polythiol compound.
• composition for optical materials according to ⁇ 1> wherein the sulfur and the episulfide compound are preliminarily polymerized.
• composition for optical materials according to ⁇ 1> wherein 10% by mass or more of the sulfur is preliminarily polymerized with an episulfide compound.
• composition for optical materials according to ⁇ 3> or ⁇ 4> wherein the composition is subjected to deaeration treatment after preliminary polymerization.
• ⁇ 6> An optical material obtained by polymerizing the composition for optical materials according to any one of ⁇ 1> to ⁇ 5>.
• a method for producing a composition for optical materials comprising a step of preliminarily polymerizing sulfur having an turbidity value of 10 ppm or less and an episulfide compound when a 30% by mass carbon disulfide solution is prepared. is there.
• the method for producing a composition for optical materials according to ⁇ 7> further including a step of adding a polythiol compound.
• white turbidity of a cured product obtained by polymerizing and curing a composition containing sulfur and an episulfide compound, which has been difficult in the prior art, is suppressed, particularly in a lens having a thick center thickness called a plus power lens. It became possible to suppress the occurrence. Furthermore, it has become possible to provide a composition for optical materials capable of predicting and determining the occurrence of white turbidity after curing at the stage before polymerization and curing, and determining whether the product is good or bad.
• the turbidity is measured using a turbidimeter according to JIS K0101, using a kaolin standard solution as a standard. These measurements are performed, and sulfur having a turbidity value of 10 ppm or less when used as a 30% by mass carbon disulfide solution is used. Preferably it is 6 ppm or less, More preferably, it is 3 ppm or less, Most preferably, it is 2 ppm or less.
• the turbidity value exceeds 10 ppm, a large amount of white turbidity occurs after curing of the composition when forming a lens having a thick center called a plus power lens.
• the 30% carbon disulfide solution is obtained by weighing 9.0 g of sulfur in a vial, adding 21.0 g of carbon disulfide, adding a stir bar and stirring at room temperature for 30 minutes using a stirrer. Prepare.
• Sulfur production methods include sublimation purification from natural sulfur ore, mining by melting sulfur buried underground, recovery methods using hydrogen sulfide obtained from oil and natural gas desulfurization processes, etc.
• the sulfur used in the present invention may be sulfur obtained by any manufacturing method as long as the turbidity value when it is a 30% by mass carbon disulfide solution is 10 ppm or less.
• a recovery method using hydrogen sulfide obtained from the destillation step as a raw material is preferable.
• commercially available sulfur includes finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur and the like depending on the shape and purification method, but the sulfur used in the present invention is 30% by mass.
• the turbidity value in the case of a carbon sulfide solution is 10 ppm or less
• sulfur obtained by any shape or purification method may be used.
• it is preferably finer than 10 mesh, more preferably finer than 30 mesh, and most preferably finer than 60 mesh.
• the episulfide compounds used in the present invention include all episulfide compounds, but as specific examples, they are listed separately as compounds having a chain aliphatic skeleton, an aliphatic cyclic skeleton, and an aromatic skeleton.
• Examples of the compound having a chain aliphatic skeleton include compounds represented by the following formula (1). (However, m represents an integer from 0 to 4, and n represents an integer from 0 to 2.)
• Examples of the compound having an aliphatic cyclic skeleton include compounds represented by the following formula (2) or (3). (P and q each represents an integer of 0 to 4) (P and q each represents an integer of 0 to 4) Examples of the compound having an aromatic skeleton include compounds represented by the following formula (4). (P and q each represents an integer of 0 to 4)
• specific examples of the compound represented by the above formula (1) having a chain aliphatic skeleton include bis ( ⁇ -epithiopropyl) sulfide, bis ( ⁇ -epithiopropyl) disulfide, bis ( ⁇ -epithiopropylthio) methane, 1,2-bis ( ⁇ -epithiopropylthio) ethane, 1,3-bis ( ⁇ -epithiopropylthio) propane, 1,4-bis ( ⁇ -epithio) Propylthio) butane, bis ( ⁇ -epithiopropylthioethyl) sulfide.
• Examples of episulfide compounds having an aliphatic cyclic skeleton include 1,3 and 1,4-bis ( ⁇ -epithiopropylthio) cyclohexane, 1,3 and 1,4-bis ( ⁇ -epithiopropylthiomethyl).
• Preferred examples include cyclohexane, 2,5-bis ( ⁇ -epithiopropylthio) -1,4-dithiane, and 2,6-bis ( ⁇ -epithiopropylthioethylthiomethyl) -1,4-dithiane.
• episulfide compounds having an aromatic skeleton include 1,3 and 1,4-bis ( ⁇ -epithiopropylthio) benzene, 1,3 and 1,4-bis ( ⁇ -epithiopropylthiomethyl) benzene. Is preferred.
• preferred compounds are those represented by the formula (1) having a chain aliphatic skeleton, specifically, bis ( ⁇ -epoxypropyl) sulfide, bis ( ⁇ -epoxypropyl) disulfide, bis ( ⁇ -epoxy).
• Propylthio) methane 1,2-bis ( ⁇ -epoxypropylthio) ethane, 1,3-bis ( ⁇ -epoxypropylthio) propane, 1,4-bis ( ⁇ -epoxypropylthio) butane, bis ( ⁇ -Epoxypropylthioethyl) sulfide.
• the sulfur used in the composition for optical materials of the present invention is usually 0.1 to 40 parts by mass, preferably 0.5 to 30 parts by mass, when the total of sulfur and episulfide compound is 100 parts by mass. Parts, particularly preferably 5 to 25 parts by weight.
• composition for optical materials of the present invention is preferably preliminarily reacted with an episulfide compound and sulfur.
• the conditions for this preliminary polymerization reaction are preferably from ⁇ 10 ° C. to 120 ° C. for 0.1 to 240 hours, more preferably from 0 to 100 ° C. for 0.1 to 120 hours, particularly preferably from 20 to 80 ° C. 1 to 60 hours.
• a catalyst it is effective to use a catalyst to proceed the preliminary reaction, and preferred examples include 2-mercapto-1-methylimidazole, triphenylphosphine, 3,5-dimethylpyrazole, N-cyclohexyl-2-benzothia Zolylsulfinamide, dipentamethylene thiuram tetrasulfide, tetrabutyl thiuram disulfide, tetraethyl thiuram disulfide, 1,2,3-triphenylguanidine, 1,3-diphenylguanidine, 1,1,3,3-tetramethyleneguanidine , Aminoguanidine urea, trimethylthiourea, tetraethylthiourea, dimethylethylthiourea, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, Cho
• the preliminary reaction may be performed under any atmosphere such as air, inert gas such as nitrogen, sealed under normal pressure or pressure reduction. It is also possible to use liquid chromatography or a refractometer to detect the progress of the preliminary reaction.
• polythiol compounds that can be used in the present invention include all polythiol compounds, and specifically include methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercapto.
• preferred compounds among the above include bis (2-mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 2,5-bis (mercapto).
• Benzene, 1,4-bis (mercaptomethyl) include benzene. More specific examples of the compound are bis (2-mercaptoethyl) sulfide and 1,3-bis (mercaptomethyl) benzene.
• the polythiol compound used in the present invention is usually used in an amount of 1 to 30 parts by mass, preferably 2 to 20 parts by mass, particularly preferably 3 to 15 parts by mass, when the total amount of sulfur and episulfide compound is 100 parts by mass. It is.
• the deaeration treatment is performed under reduced pressure before, during or after mixing the compound capable of reacting with some or all of the composition components, the polymerization catalyst, and the additive. Preferably, it is performed under reduced pressure during or after mixing.
• the treatment conditions are 0 to 100 ° C. for 1 minute to 24 hours under a reduced pressure of 0.001 to 50 torr.
• the degree of vacuum is preferably 0.005 to 25 torr, more preferably 0.01 to 10 torr, and the degree of vacuum may be varied within these ranges.
• the deaeration time is preferably 5 minutes to 18 hours, more preferably 10 minutes to 12 hours.
• the temperature at the time of deaeration 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 of gas, vibration by ultrasonic waves, etc. is a preferable operation for enhancing the degassing effect.
• the components removed by the degassing treatment are mainly dissolved gases such as hydrogen sulfide and low-boiling substances such as low molecular weight thiols. The kind of component is not limited.
• amines, onium salts and phosphine compounds are used as the catalyst for polymerizing and curing the composition for optical materials of the present invention.
• Specific examples include amines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds.
• quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds having good compatibility with the composition are more preferable, and quaternary phosphonium salts are 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, tetra- Examples thereof include quaternary phosphonium salts such as n-butylphosphonium bromide and tetraphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine.
• quaternary ammonium salts such as tetra-n-butylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride, tetra- Examples thereof include
• the polymerization catalyst may be used alone or in combination of two or more.
• the addition amount of the polymerization catalyst varies depending on the components of the composition, the mixing ratio and the polymerization curing method, but is not generally determined, but is usually 0.001% by mass to 5% by mass with respect to the total amount of the optical material composition. In the following, preferably, 0.01% by mass or more and 1% by mass or less, and most preferably 0.01% by mass or more and 0.5% by mass or less are used.
• the addition amount of the polymerization catalyst is more than 5% by mass, the refractive index and heat resistance of the cured product may be lowered and coloring may occur. On the other hand, if it is less than 0.001% by mass, it may not be sufficiently cured and the heat resistance may be insufficient.
• a polymerization regulator can be added as necessary for the purpose of extending the pot life or dispersing the polymerization heat.
• the polymerization regulator include group 13-16 halides in the long-term periodic table. Of these, preferred compounds are halides of silicon, germanium, tin and antimony, and more preferred compounds are chlorides of germanium, tin and antimony having an alkyl group.
• More preferred compounds are specifically dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyltin trichloride, dibutyldichlorogermanium, butyltrichlorogermanium, diphenyldichlorogermanium, phenyltrichlorogermanium, triphenylantimony dichloride, and most preferred.
• a specific example of the compound is dibutyltin dichloride.
• the polymerization regulator may be used alone or in combination of two or more.
• the addition amount of the polymerization regulator is usually 0.0001 to 5.0% by mass, preferably 0.0005 to 3.0% by mass, and more preferably 0 to the total amount of the optical material composition. 0.001 to 2.0% by mass.
• additives such as known antioxidants, ultraviolet absorbers and bluing agents are added to make the resulting material more practical.
• the antioxidant include phenol derivatives.
• preferred compounds are polyhydric phenols and halogen-substituted phenols, more preferred compounds are catechol, pyrogallol, and alkyl-substituted catechols, and most preferred compounds are catechol and pyrogallol.
• the ultraviolet light inhibitor include benzotriazole compounds.
• preferred compounds include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 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-ethoxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-butoxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyloxy) Phenyl) -2H- benzotriazole, 2- (2-hydroxy -5-tert-octylphenyl)
• a known external and / or internal adhesion improver is used or added to control the adhesion between the obtained cured product and the mold. It is also possible to improve.
• the adhesion improving agent include known silane coupling agents and titanate compounds, and these 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 optical material composition.
• a known external and / or internal mold release agent may be used or added to improve the mold release properties of the resulting cured product. Is also possible.
• Release agents include fluorine-based nonionic surfactants, silicon-based nonionic surfactants, phosphate esters, acidic phosphate esters, oxyalkylene-type acidic phosphate esters, alkali metal salts of acidic phosphate esters, and alkalis of oxyalkylene-type acidic phosphate esters.
• Examples include metal salts, 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. May be mixed and used. The addition amount is usually 0.0001 to 5% by mass with respect to the total amount of 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 in detail.
• Additives such as the above-mentioned composition components, antioxidants, ultraviolet absorbers, polymerization catalysts, radical polymerization initiators, adhesion improvers, mold release agents, etc., all mixed together in the same container under stirring,
• Each raw material may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container.
• Each raw material and auxiliary raw material may be mixed in any order.
• the set temperature, the time required for this, and the like may basically be the conditions under which each component is sufficiently mixed.
• the optical material composition thus obtained may be filtered in order to eliminate contamination of foreign matters and improve the quality of the lens. Filtration is usually performed using a filter having a pore size of 0.05 to 3 ⁇ m.
• the composition for optical material subjected to the above reaction and treatment is poured into a glass or metal mold, and after the polymerization and curing reaction is advanced by irradiation with active energy rays such as heating or ultraviolet rays, the composition is removed from the mold. . In this way, an optical material is manufactured.
• the composition for 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 performed by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature by 0.1 ° C.
• an optical material of the present invention it is preferable to anneal the cured product at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours after the polymerization is completed in order to remove distortion of the optical material. It is processing. Furthermore, surface treatments such as dyeing, hard coating, impact resistant coating, antireflection and imparting antifogging properties can be performed as necessary.
• 10 lenses having a lens diameter of 75 mm and a power of plus 10D are prepared, and A in which no cloudiness is observed, 9 in which no cloudiness is observed, B, 7 or 8 in which cloudiness is not observed. C was not observed, D was not observed for 6 sheets, and E was 5 or less for which no cloudiness was observed. A to D pass.
• Example 1 85 parts by mass of bis ( ⁇ -epithiopropyl) sulfide and 0.5 parts by mass of 2-mercapto-1-methylimidazole are added to 15 parts by mass of sulfur with a turbidity of 1.8 ppm, and the sulfur consumption rate is 50% ( Preliminary reaction was performed at 60 ° C. until HPLC measurement by GPC mode. After cooling to 20 ° C., 0.2 parts by mass of dibutyltin dichloride and 0.03 parts by mass of triethylbenzylammonium chloride as a polymerization catalyst were added and mixed uniformly, then degassed for 10 hours at 10 Torr and 20 ° C.
• Example 2 The same operation as in Example 1 was performed except that sulfur having a turbidity of 2.7 ppm was used. The results are shown in Table 1.
• Example 3 The same operation as in Example 1 was performed except that sulfur having a turbidity of 5.6 ppm was used. The results are shown in Table 1.
• Example 4 The same operation as in Example 1 was performed except that sulfur having a turbidity of 10.0 ppm was used. The results are shown in Table 1.
• Comparative Example 1 The same operation as in Example 1 was performed except that sulfur having a turbidity of 12.3 ppm was used. The results are shown in Table 1.
• Example 5 To 14 parts by mass of sulfur with a turbidity of 1.8 ppm, 79 parts by mass of bis ( ⁇ -epithiopropyl) sulfide and 0.5 parts by mass of 2-mercapto-1-methylimidazole were added, and the sulfur consumption rate was 50% ( Preliminary reaction was performed at 60 ° C. until HPLC measurement by GPC mode. After cooling to 20 ° C., a mixture of 7 parts by mass of bis (2-mercaptoethyl) sulfide, 0.2 parts by mass of dibutyltin dichloride and 0.03 parts by mass of triethylbenzylammonium chloride as a polymerization catalyst was added and mixed uniformly.
• the mixture was deaerated for 1 hour at 10 Torr and 20 ° C., filtered through a PTFE membrane filter having a pore size of 3.0 ⁇ m, and injected into a mold for a plus power lens. In an oven, the temperature was raised from 20 ° C. to 100 ° C. over 22 hours, polymerized and cured, and demolded to obtain an optical material. The results are shown in Table 2.
• Example 6 The same operation as in Example 5 was performed except that sulfur having a turbidity of 2.7 ppm was used. The results are shown in Table 2.
• Example 7 The same operation as in Example 5 was performed except that sulfur having a turbidity of 5.6 ppm was used. The results are shown in Table 2.
• Example 8 The same operation as in Example 5 was performed except that sulfur having a turbidity of 10.0 ppm was used. The results are shown in Table 2.
• Comparative Example 2 The same operation as in Example 5 was performed except that sulfur having a turbidity of 12.3 ppm was used. The results are shown in Table 2.
• Example 9 To 11 parts by mass of sulfur having a turbidity of 1.8 ppm, 79 parts by mass of 2,5-bis ( ⁇ -epithiopropylthio) -1,4-dithiane, 0.2 parts by mass of 2-mercapto-1-methylimidazole, 5 parts by mass of bis (2-mercaptoethyl) sulfide was added, and the mixture was preliminarily reacted at 60 ° C. until the sulfur consumption rate reached 50% (HPLC measurement by GPC mode).
• Example 10 The same operation as in Example 9 was performed except that sulfur having a turbidity of 2.7 ppm was used. The results are shown in Table 3.
• Example 11 The same operation as in Example 9 was performed except that sulfur having a turbidity of 5.6 ppm was used. The results are shown in Table 3.
• Example 12 The same operation as in Example 9 was performed except that sulfur having a turbidity of 10.0 ppm was used. The results are shown in Table 3.
• Comparative Example 3 The same operation as in Example 9 was performed except that sulfur having a turbidity of 12.3 ppm was used. The results are shown in Table 3.
• Example 13 14 parts by mass of sulfur with a turbidity of 1.8 ppm, 79 parts by mass of bis ( ⁇ -epithiopropyl) sulfide, 0.2 parts by mass of 2-mercapto-1-methylimidazole, 1,3-bis (mercaptomethyl) benzene 2 parts by mass were added, and the mixture was preliminarily reacted at 60 ° C. until the sulfur consumption rate reached 50% (HPLC measurement by GPC mode).
• Example 14 The same operation as in Example 13 was performed except that sulfur having a turbidity of 2.7 ppm was used. The results are shown in Table 4.
• Example 15 The same operation as in Example 13 was performed except that sulfur having a turbidity of 5.6 ppm was used. The results are shown in Table 4.
• Example 16 The same operation as in Example 13 was performed except that sulfur having a turbidity of 10.0 ppm was used. The results are shown in Table 4.
• Comparative Example 4 The same operation as in Example 13 was performed except that sulfur having a turbidity of 12.3 ppm was used. The results are shown in Table 4.

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