polymerizable composition for optical material, method for producing the composition, method for pro

专利摘要:
POLYMERZABLE COMPOSITION FOR OPTICAL MATERIAL, METHOD FOR PRODUCING IT, AND METHOD FOR PRODUCING OPTICAL MATERIAL. Using a method to produce a composition for an optical material using (a) sulfur, (b) a compound having two intramolecular episulfide groups, (c) a compound having one or more (preferably two) SH groups, and (d) an amine compound having a specific structure, wherein compound (a) and compound (c) are prepolymerized in the presence of compound (b) using compound (d) as the prepolymerization catalyst, the present invention provides a polymerisable composition for an optical material in which the rate of viscosity increase during prepolymerization is slow and the reaction temperature is approximately room temperature, and which has a low viscosity and shows little increase in viscosity. By means of another embodiment of the present invention, it is possible to produce an optical material that has excellent mold release characteristics, but substantially does not have streaks when polymerizing (a) sulfur, (b) a compound having two intramolecular episulfide groups, and (c) a compound having one or more SH groups in the presence of (d) a hindered amine catalyst having a specific structure.
公开号:BR112014020099B1
申请号:R112014020099-8
申请日:2013-02-13
公开日:2020-12-01
发明作者:Teruo Kamura；Naotsugu Shimoda；Yoshihiko Nishimori；Eiji Koshiishi；Motoharu Takeuchi
申请人:Mitsubishi Gas Chemical Company, Inc.；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to an optical component for a plastic lens, a prism, an optical fiber, an information recording substrate, a filter, an adhesive or others, in particular, an optical lens such as contact lenses. plastic for glasses. The present invention also concerns an optical material that has excellent mold release characteristics and substantially no streaks and a method for producing the same, in which a polymerizable composition, comprising: a preliminary reaction solution obtained by subjecting the sulfur, a compound having two intramolecular episulfide groups and a compound having one or more intramolecular SH groups to a prepolymerization reaction using a hindered amine having a specific structure as a prepolymerization catalyst; and a polymerization catalyst, is polymerized and cured. The present invention also concerns a method for producing a composition for optical materials having high productivity and low viscosity, and an optical material (optical resin material) for a plastic lens, a prism, an optical fiber, a registration substrate. information, a filter or others using it. TECHNICAL FUNDAMENTALS
[0002] [0002] Plastic materials are light in weight, highly flexible and easy to dye, and therefore are widely used in recent times for various types of optical materials, particularly eyeglass lenses. Optical materials, particularly spectacle lenses, are specifically required to have, as main properties, low specific gravity, high transparency and low yellowing, and as optical properties, high refractive index and high Abbe number. Recently, a polymerizable composition for optical materials, in which an inorganic compound having a sulfur atom and / or a selenium atom is mixed with a polysulfide compound for the purpose of obtaining a high refractive index and a high Abbe number, proposal (for example, Patent Document 1).
[0003] [0003] If a high refractive index can be obtained by an optical material obtained through the polymerization and curing of such a composition, in many cases, an inorganic compound having a sulfur atom and / or a selenium atom is solid at normal temperature and it has low solubility, and therefore there are problems where precipitation can occur when providing a composition and the compound can be insufficiently dissolved when the concentration is high.
[0004] [0004] For this reason, a technique in which an inorganic compound having a sulfur atom and / or a selenium atom and a sulfur-containing organic compound such as a polysulfide compound, which can react with the inorganic compound, is subjected to a prepolymerization reaction has previously been proposed (see Patent Document 2). However, when the content of the inorganic compound having a sulfur atom and / or a selenium atom is increased, the viscosity of a polymerizable composition becomes very high, and it is difficult to perform usual injection and polymerization operations such as filtration and mold injection. Therefore, for the purpose of reducing viscosity at the time of the prepolymerization reaction, the addition of a compound having an SH group (see Patent Document 3), a compound having one or more NH groups and / or NH2 groups ( see Patent Document 4) or a compound having one or more disulfide bonds (see Patent Document 5) has been proposed. However, in the case of a composition in which the content of an inorganic compound having a sulfur atom and / or a selenium atom is 10 parts by weight or more, even when an additive to reduce the viscosity of the composition is added, the viscosity can be increased, for example, in the case where a prepolymerization reaction is excessively carried out and / or the temperature after preparation of the composition is very high, or the viscosity after about 3 hours, which is the injection time generally required to produce an optical material industrially, can be significantly increased. As a result, it becomes difficult to perform the usual injection operations such as filtration and mold injection, and there are problems in which the increase in the size of the filter and injection apparatus and the shortening of the injection line are required. In addition, for the purpose of improving the productivity of optical materials, a polymerizable composition for optical materials having a lower viscosity, which makes it easier to perform the filtration and injection operations, has been desired.
[0005] [0005] Furthermore, since the prepolymerization reaction of the aforementioned reference is generally carried out from 50 ° C to 70 ° C, it is necessary to cool the composition to about room temperature, which is the temperature at which polymerization starts after application. mold injection, and the cooling step is necessary after the end of the prepolymerization reaction. To increase a reaction scale, unless increasing the size of a cooling device, the introduction of a cooling coil in a reaction device, etc. carried out, the time required for cooling increases or changes in each case. This is also the problem. For this reason, a method for producing a polymerizable composition for optical materials that can be subjected to a prepolymerization reaction at a reaction temperature close to room temperature is desired.
[0006] [0006] In Patent Documents 1 and 2, an optical material having a high refractive index can be obtained, but the mold release characteristics when releasing it from a mold after polymerization and curing may be insufficient. In the case of optical materials having a complicated shape, in particular, an optical lens, the smaller the radius of curvature of the lens, the more insufficient the mold release characteristics tend to be, and it is extremely difficult to improve the mold release characteristics of minus power lenses of -15.0D or more. In case of insufficient mold release characteristics, production time may be increased, a defect in an optical material and / or a mold may be generated, and it may become impossible to use the optical material and / or the mold. In this way, production can be affected in this way. In order to improve the mold release characteristics of optical materials, a mold release agent is generally used, and external mold release agents, which are applied to a mold and used, and / or mold release agents internals, which are added to a monomer and used, are known (see Patent Document 6).
[0007] [0007] However, the method of applying a mold release agent to a mold is very complicated, and there are problems where the surface of an optical material becomes uneven due to an external mold release agent and turbidity is generated in an optical material. In addition, also in the case of internal mold release agents, there are problems in which the addition of only a small amount of an internal mold release agent generates turbidity in an optical material and a prepolymerization reaction rate and / or polymerization reaction is affected in this way generating many streaks in the optical material. Therefore, an optical material that has good mold release characteristics and substantially has no streaks without the aforementioned influences and a method for producing the same has been desired.
[0008] [0008] In addition, the prepolymerization reaction of Patent Documents 1 and 2 is generally carried out from 50 ° C to 70 ° C, and it is necessary to cool the composition to about room temperature which is the starting temperature of the polymerization after injection of mold. However, since the preliminary reaction temperature is high, there is a problem in which the viscosity of the polymerizable composition is increased by the progress of the secondary reaction, the significant reduction in temperature due to cooling or others. When the temperature after cooling is adjusted to a high temperature to prevent the viscosity from rising, there are problems in which the pot life is shortened and streaks are generated due to the difference between the temperature after cooling and the holding temperature in a stage prior to the polymerization stage. Therefore, a production method in which a polymerizable composition for optical materials comprising a sulfur-containing organic compound such as a polysulfide compound and an inorganic compound having a sulfur atom and / or a selenium atom that can be subjected to a reaction of prepolymerization at a reaction temperature close to room temperature has been desired. PREVIOUS TECHNICAL DOCUMENTS PATENT DOCUMENTS
[0009] [0009] Patent Document 1: Japanese Patent Publication Open to the Public No. 2001-2783
[0010] [0010] Patent Document 2: Japanese Patent Publication Open to the Public No. 2004-197005
[0011] [0011] Patent Document 3: Japanese Patent Publication Open to the Public No. 2006-348285
[0012] [0012] Patent Document 4: Japanese Patent Publication Open to the Public No. 2006-348289
[0013] [0013] Patent Document 5: Japanese Patent Publication Open to the Public No. 2006-348286
[0014] [0014] Patent Document 6: International Publication Pamphlet W089 / 10575 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[0015] [0015] The problems to be solved by the present invention are to make it easy to control the end point of a prepolymerization reaction when producing a polymerizable composition for optical materials using sulfur, a compound having two groups of intramolecular episulfide and one compound having one or more (preferably two) SH groups, and to reduce the time required to cool by adjusting the reaction temperature to approximately room temperature. In addition, another problem is to develop a polymerizable composition for optical materials having a low viscosity, which is easily subjected to filtration and the injection operation, in order to improve the productivity of optical materials.
[0016] [0016] In addition, the problem to be solved by the present invention is the improvement of the mold release characteristics and the reduction of the streaks in an optical material having a high refractive index obtained through the polymerization and curing of a polymerizable composition, comprising: a preliminary reaction solution obtained through a sulfur prepolymerization reaction, a compound having two intramolecular episulfide groups and a compound having one or more intramolecular SH groups; and a polymerization catalyst.
[0017] [0017] Streaks as used here refer to cotton-like or layered portions of a material component having a different refractive index than that of the base material in an optical material, and such streaks are generated, for example, by the slight sparsity / optical density caused by the convection of a polymerizable composition caused by the generation of heat during polymerization and curing, and the non-uniform progress of a polymerization reaction. Therefore, in the case of optical lenses, the greater the minus power is, the greater the thickness of the peripheral portion of the optical lens is, and this often causes streaks. For this reason, it is difficult to reduce the streaks of optical lenses with more than -12.5D, and in addition, it is extremely difficult to reduce the streaks of optical lenses with more than -15.0D.
[0018] [0018] Furthermore, the problem to be solved by the present invention is to provide a method for producing a polymerizable composition for optical materials having good productivity, which allows the inhibition of the increase in viscosity due to a secondary reaction of the prepolymerization reaction or excessive progress of the reaction without the generation of stretch marks when producing the polymerizable composition for optical materials using sulfur, a compound having intramolecular episulfide groups and a compound having intramolecular SH groups. MEANS TO SOLVE PROBLEMS
[0019] [0019] The present inventors diligently did research to solve the problems and found that at least one of the problems described above can be solved by the present invention described below. Specifically, the present invention is as follows:
[0020] [0020] <1> A polymerizable composition for optical materials, comprising: a preliminary reaction solution obtained by subjecting 10 to 50 parts by weight of the compound (a) described below and from 1 to 20 parts by weight of the compound ( c) described below to a prepolymerization reaction in the presence of 50 to 90 parts by mass of the compound (b) described below (with the proviso that the total amount of compound (a) and compound (b) is 100 parts by mass), using from 0.001 to 10 parts by mass (the upper limit is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less) of the compound (d) described below as a pre catalyst -polymerization; and a polymerization catalyst: (a) sulfur (compound (a)); (b) a compound having two intramolecular episulfide groups represented by the following formula (1) (compound (b)):
[0021] [0021] <2> A method for producing a polymerizable composition for optical materials, which comprises adding a polymerization catalyst to the preliminary reaction solution obtained by subjecting 10 to 50 parts by mass of the compound (a) described below and 1 to 20 parts by mass of the compound (c) described below to the prepolymerization reaction in the presence of 50 to 90 parts by mass of the compound (b) described below (with the proviso that the total amount of the compound (a) and the compound (b) is 100 parts by weight), using from 0.001 to 10 parts by weight (the upper limit is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less) of compound (d) described below as a prepolymerization catalyst: (a) sulfur (compound (a)); (b) a compound having two intramolecular episulfide groups represented by the following formula (I) (compound (b)):
[0022] [0022] <3> The polymerizable composition for optical materials according to <1> above, wherein the polymerizable composition for optical materials is also obtained by adding the polymerization catalyst and compound (c) to the preliminary reaction solution.
[0023] [0023] <4> A method for producing an optical material, which comprises polymerizing and curing the polymerizable composition for optical materials according to <1> above.
[0024] [0024] <5> An optical material obtained using the production method according to <4> above.
[0025] [0025] <6> An optical lens comprising the optical material according to <5> above.
[0026] [0026] <7> A method for producing a polymerizable composition for optical materials, which comprises the steps of: subject 10 to 50 parts by mass of the compound (a) described below and 1 to 20 parts by mass of the compound (c) described below to a prepolymerization reaction at a reaction temperature T1 (where T1 is 0 at 45 ° C) in the presence of 50 to 90 parts by mass of compound (b) described below (with the proviso that the total amount of compound (a) and compound (b) is 100 parts by mass), using from 0.001 to 5 parts by mass of the compound (d) described below as a prepolymerization catalyst, to obtain a preliminary reaction solution; and add a polymerization catalyst to the preliminary reaction solution with the temperature being adjusted to T2 (with the proviso that T2 is T1 -15 ° C to T1 + 10 ° C and 0 to 45 ° C): (a) sulfur (compound (a)); (b) a compound having two intramolecular episulfide groups represented by the following formula (1) (compound (b)):
[0027] [0027] <8> A method for producing an optical material, which comprises copolymerizing the copolymerizable composition for optical materials produced from the production method according to <7> above with the initial polymerization temperature being adjusted to T3 (with the condition that T3 is T2 - 10 ° C to T2 + 10 ° C and 0 to 40 ° C). ADVANTAGE EFFECTS OF THE INVENTION
[0028] [0028] According to the present invention, in a prepolymerization reaction when producing a polymerizable composition for optical materials using sulfur, a compound having two groups of intramolecular episulfide and a compound having one or more (preferably two) groups SH, the speed of viscosity increase during the reaction is reduced, and it is easy to control the end point of the reaction. In addition, by adjusting the reaction temperature to approximately room temperature, the time required for cooling can be reduced. In addition, using the polymerizable composition for optical materials having a low viscosity according to the present invention, it is easy to carry out the filtration and injection operation, and the productivity of the optical materials can be improved.
[0029] [0029] Furthermore, according to the present invention, an optical material, which is obtained through the polymerization and curing of a preliminary reaction solution obtained by subjecting sulfur, a compound having two groups of intramolecular episulfide and a compound having a or more SH groups to a prepolymerization reaction and a polymerization catalyst, can be easily released from a mold. In addition, when compared to conventional production methods, particularly when producing optical lenses, it is possible to reduce optical lenses that substantially have no streaks to a higher quality level even in the case of powerful lenses, and the productivity of optical materials can be improved.
[0030] [0030] Furthermore, according to the present invention, in a prepolymerization reaction when producing a polymerizable composition for optical materials using sulfur, a compound having two groups of intramolecular episulfide and a compound having one or more (preferably two) SH groups, the reaction temperature is adjusted to a temperature close to room temperature, and as a result, in the production process, the temperature of the composition does not become 50 ° C or higher as in conventional techniques. Therefore, a secondary reaction is inhibited, the increase in viscosity of the polymerizable composition is inhibited, and productivity can be improved. CARRYING OUT WAYS TO CARRY OUT THE INVENTION
[0031] [0031] The polymerizable composition for optical materials having a low viscosity, which is the objective of the present invention, has a viscosity that makes it possible to easily perform filtration and operation and in the mold and allows for improved productivity. The viscosity at 20 ° C is preferably 150 mPa.s or less, and more preferably 100 mPa.s or less.
[0032] [0032] The purity of the sulfur which is the compound (a) to be used in the present invention is 98% or more. When the purity is less than 98%, the phenomenon in which the turbidity is generated in the optical material under the influence of impurities tends to occur easily, but when the purity is 98% or more, the phenomenon in which the turbidity is generated does not occur. The purity of the sulfur is preferably 99.0% or greater, more preferably 99.5% or greater, and even more preferably 99.9% or greater. Generally, the available sulfur is classified into finely pulverized sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur and others depending on the form and method of purification thereof, but in the present invention, any sulfur can be used as long as the purity of it is 98% or greater. Preferably, the finely pulverized sulfur having fine particles, which is easily dissolved when producing the polymerizable composition for optical materials, is used. The higher the sulfur atom content in the polymerizable composition for optical materials, the greater the refractive index of the obtained optical material, but when the amount of addition is much higher, some of the sulfur may remain undissolved in the composition and the viscosity of the composition will makes it significantly high. Therefore, when the total amount of compound (a) and compound (b) is 100 parts by weight, the amount of compound (a) to be added is 10 to 50 parts by weight, preferably 10 to 45 parts by weight. dough, more preferably 15 to 40 parts by weight, still more preferably 15 to 35 parts by weight, and much more preferably 15 to 30 parts by weight.
[0033] [0033] When the total amount of compound (a) and compound (b) is 100 parts by weight, the amount of compound (b) to be added in the present invention is 50 to 90 parts by weight, preferably 55 to 90 parts by mass, more preferably from 60 to 85 parts by mass, and much more preferably from 70 to 85 parts by mass.
[0034] [0034] Specific examples of compound (b) include an episulfide compound having two intramolecular episulfide groups such as bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, 1, 2-bis (β-epithiopropylthio) ethane 1,3-bis (β-epithiopropylthio) propane and 1,4-bis (β-epithiopropylthio) butane. Like compound (b), such compounds can be used alone, or two or more of these can be used in combination. Among these, specific preferred examples are bis (β-epithiopropyl) sulfide (formula (3)) and / or bis (β-epithiopropyl) disulfide (formula (4)), and bis (β-epithiopropyl) sulfide is more preferred:
[0035] [0035] bis (β-epithiopropyl) sulfide
[0036] [0036] bis (β-epithiopropyl) disulfide
[0037] [0037] The compound (c) to be used in the present invention is a compound having one or more SH groups, and examples of which include: a mercaptan derivative; a thiophenol derivative; and a mercaptan derivative and a thiophenol derivative, which have an unsaturated group such as vinyl, aromatic vinyl, methacryl, acrylic and allyl. More specifically, examples of the mercaptan derivative include: a monomercaptan derivative such as methyl mercaptan, ethyl mercaptan, n-propyl mereaptane, n-butyl mercaptan, ally mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan , n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, tert-dodecyl mercaptan, benzyl mercaptan, 4-chlorobenzyl methylthioglycolate, ethylthioglycolate, n-butyl thioglycolate, n-octyl thioglycolate, methyl (3-mercaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropylate), 2 3-mercaptopropionate) and n-octyl (3-mercaptopropionate); and a polymeric derivative such as methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6 -dimercaptoexane, 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-mercaptomethyl-1,4-dimercaptobutane, 2- (2-mercaptoethylthio) -1,3 - dimercaptopropane, 2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane, tetracis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate ), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercapto-propionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetracis (2-mercaptoacetate ), pentaerythritol tetracis (3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4 -ditian, 2,5-bis (2-mercaptoethyl) -1,4-dithian, 2,5-bis (mercaptomethyl) -1 -thian, 2,5-bis (2-mercaptoethyl) -1 -thian, 1, 4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercapto-phenyl) ether, 2,2-bis (4-mercaptophenyl) propane, bis ( 4-mercaptomethyl-phenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, 2,5-dimercapto-1, 3, 4-thiadiazole and 3,4-thiofeditian. Examples of the thiophenol derivative include thiophenol, 4-ter-butylthiophenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene and 1,4-dimercaptobenzene. The mercaptan derivative having an unsaturated group and the thiophenol derivative having an unsaturated group will be specifically described below. Examples of the mercaptan derivative having an unsaturated group include allyl mercaptan, 2-vinyl benzyl mercaptan, 3-vinyl benzyl mercaptan and 4-vinyl benzyl mercaptan. Examples of the thiophenol derivative having an unsaturated group include a thiol compound containing, as the main component, one or two more types of substances selected from the group consisting of 2-vinylthiophenol, 3-vinylthiophenol, 4-vinylthiophenol, etc. , but are not imitated to these. In the case of having an SH group, the speed of viscosity increase during the prepolymerization reaction is reduced, but Tg, heat resistance and refractive index of the obtained optical material tend to be reduced.
[0038] [0038] However, in the case of having 3 or more SH groups, the increase in viscosity during the prepolymerization reaction can be significantly increased. Therefore, the compound having two SH groups in a molecule is preferred. Specific examples of these include methanedithiol, 1,2-dimereaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptoexane, bis (mercaptomethyl) ether, bis (2-mercaptoethyl) ether, bis (mercaptomethyl) sulfide, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 1,2-bis (2-mercaptoethyloxy) ethane, 1,2-bis (2 -mercapto-ethylthio) ethane, 2,3-dimercapto-1-propanol, 1,3-dimercapto-2-propanol, ethylene glycol (2-mercaptoacetate), ethylene glycol (3-mercaptopropionate), diethylene glycol (2-mercaptoacetate), diethylene glycolbis (3-mercaptopropionate), 1,4-butanediolbis (2-mercaptoacetate), 1,4-butanediolbis (3-mercaptopropionate), 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3 -bis (mercapto-methyl) cyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithian, 2,5-bis (2-mercaptoethyl) -1,4-dithian , 2,5-bis (2-mereaptoethylthiomethyl) -1,4-dithian, 2,5-bis (mereaptomethyl) -1 -thian, 2,5-bis (2-mercapto ethyl) -1-thian, 2,5-bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercapto-benzene, 1,3-bis (mercaptomethyl) benzene, 1,4 -bis (mercaptomethyl) -benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, 2,2-bis (4-mercaptophenyl) propane, bis (4-mercaptophenyl) ether, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4-mercaptomethylphenyl) propane, bis (4-mercaptomethylphenyl) ether and bis (4-mercaptomethylphenyl) sulfide. Among these, specific preferred examples are methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, bis (mercapto-methyl) ether, bis (mercaptomethyl) sulfide, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 2,5-bis (mercaptomethyl) -1,4-dithian, 2,5-bis (2-mercaptoethyl) -1,4-dithian, 2, 5-bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, bis (4- mercaptophenyl) methane and bis (4-mercaptophenyl) sulfide. More preferred are methanedithiol, 1,2-dimercaptoethane, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 2,5-bis (mercaptomethyl) -1,4-dithian, 2,5-bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis (mercaptomethyl) benzene and 1,4-bis (mercaptomethyl) benzene, and 1,2- dimercaptoethane, bis (2-mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl) -1,4-dithian, 1,3-bis (mercaptomethyl) benzene (also known as m-xylylenedithiol) and 1,4-bis (mercaptomethyl) ) benzene (also known as p-xylylenedithiol). Note that these compounds having one or more SH groups can be used alone, or two or more of these can be used in combination.
[0039] [0039] When the total amount of compound (a) and compound (b) is 100 parts by weight, the amount of compound (c) to be added in the present invention is 1 to 20 parts by weight, preferably 2 to 18 parts by weight, more preferably from 3 to 15 parts by weight, particularly preferably from 4 to 12 parts by weight, and even more preferably from 5 to 10 parts by weight. When the ratio of compound (c) is less than the ranges described above, the viscosity of the preliminary reaction solution during the prepolymerization reaction can be rapidly increased. However, when the ratio is greater than the ranges described above, problems such as reduced Tg and heat resistance of the obtained optical material are caused.
[0040] [0040] The compound (d) to be used in the present invention includes all compounds represented by the formula (2) mentioned above, but is preferably a low molecular weight compound so as not to reduce compatibility with other components of the composition and the refractive index of a cured product obtained after polymerization and curing of the polymerizable composition for optical materials, and specifically, it is a compound represented by formula (2), where X is the structural formula (5) mentioned above. Among such compounds, methacrylate and 1,2,2,6,6-pentamethylpiperidyl (structural formula (6) described below), 1,2,2,6,6-pentamethylpiperidyl acrylate (structural formula (7) described below) and / or 1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate (structural formula (8) described below) are preferred, and the most preferred specific example of the compound is 1,2,2,6 methacrylate, 6-pentamethylpiperidyl, which is readily available in the industry.
[0041] [0041] When the total amount of compound (a) and compound (b) is 100 parts by weight, the amount of compound (d) to be added is preferably from 0.001 to 5 parts by weight, more preferably from 0.002 to 3 parts by weight, and particularly preferably from 0.003 to 1 part by weight.
[0042] [0042] In addition, in one embodiment, when the total amount of compound (a) and compound (b) is 100 parts by weight, the amount of compound (d) to be added is preferably from 0.001 to 3 parts by mass, more preferably from 0.002 to 1 part by mass, and particularly preferably from 0.003 to 0.5 part by mass.
[0043] [0043] X =
[0044] [0044] 1,2,2,6,6-pentamethylpiperidyl methacrylate
[0045] [0045] 1,2,2,6,6-pentamethylpiperidyl acrylate
[0046] [0046] 1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate
[0047] [0047] The prepolymerization reaction to obtain the polymerizable composition for optical materials of the present invention will be described in detail below. The present invention is characterized in that the sulfur which is compound (a) and a compound having one or more (preferably two) SH groups which is compound (c) are subjected to a prepolymerization reaction in the presence of compound ( B). The reaction between sulfur and thiol is generally promoted by heating in the presence or absence of a basic compound, and is preferred because the reaction time can be significantly reduced through a method using a basic compound. However, since the basic compound suitably acts as a polymerisation catalyst for episulfide compounds, when using a common base compound as a catalyst for a prepolymerization reaction of compound (a) and compound (c) in the presence of the compound (b), there are problems in which the viscosity of a preliminarily reacted product (prepolymer) and / or a polymerizable composition comprising the preliminary reacted product (prepolymer) is increased and the rate of viscosity rise is increased and pot life is shortened. Under such circumstances, the present inventors diligently did research and found that when a prepolymerization reaction is carried out using from 0.001 to 10 parts by mass (the upper limit is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less) of compound (d), which is a specific basic compound, such as a prepolymerization catalyst, compound (a) and compound (c) can be subjected to the highly selective prepolymerization reaction, because compound (d) has significantly low activity as a polymerization catalyst for episulfide compounds due to the sterile impairment caused by the compound's amino group substituents. Furthermore, it has been found that when using compound (d) as a prepolymerization catalyst, a preliminarily reacted product (prepolymer) can be obtained without precipitation of the sulfur which is compound (a) even at a temperature of reaction at approximately room temperature.
[0048] [0048] Specifically, in the method of subjecting 10 to 50 parts by weight of compound (a) and 1 to 20 parts by weight of compound (c) to a prepolymerization reaction in the presence of 50 to 90 parts by mass of compound (b), using from 0.001 to 10 parts by weight (the upper limit is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less) of compound (d) as a prepolymerization catalyst , compounds (a), (b), (c) and (d) are stirred and mixed from 0 ° C to 45 ° C, preferably from 5 ° C to 40 ° C, and more preferably from 10 ° C to 40 ° C. In this regard, all components can be mixed together simultaneously in the same container with agitation. Alternatively, the components can be added and mixed in a step-wise manner. Alternatively, the respective various components can be mixed separately and then mixed again in the same container.
[0049] [0049] The reaction can be carried out in any atmosphere, for example, in the presence of a gas, such as nitrogen, oxygen, hydrogen and hydrogen sulfide, in an atmosphere sealed under normal pressure or increased / reduced pressure, or under pressure reduced, but to maintain the physical properties of the obtained optical material, such as color tone, heat resistance and light resistance, it is preferred to reduce the partial pressure of an oxidation gas such as oxygen as much as possible.
[0050] [0050] In order to detect how much of the reaction has occurred and control the reaction to produce a certain amount of the optical material, it is preferred to perform liquid chromatography and / or the measurement of viscosity and / or specific gravity and / or refractive index and / or the amount of gas generated at the time of the prepolymerization reaction. Note that the completion point of the prepolymerization reaction is appropriately adjusted taking into account the reprecipitation of compound (a), viscosity, etc. In the product obtained preliminarily reacted (prepolymer), but it is preferred to allow 50% or more of compound (a) to be reacted.
[0051] [0051] For the purpose of improving characteristics such as oxidation resistance, weather resistance, dye affinity, resistance and refractive index, it is possible to carry out polymerization and curing with the addition of a compound that can react with a part or all of the components of the composition of the present invention and / or the polymerizable composition obtained by carrying out the prepolymerization reaction. Examples of the compound that can react with some or all of the components of the composition include compounds having SH groups, epoxy compounds, iso (thio) cyanates, carboxylic acids, carboxylic acid anhydrides, phenols, amines, vinyl compounds, compounds of allyl, acrylic compounds and methacrylic compounds.
[0052] [0052] In addition, for polymerization and curing, a publicly known polymerization catalyst and / or polymerization modifier can be added as needed. Examples of the polymerization catalyst include amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, an aldehyde condensation product with an amine-based compound, a carboxylic acid and ammonium salt, urethanes, thiourethanes, guanidines, thioureas , thiazoles, sulfonamides, thiurans, dithiocarbamates, xanthogenates, ternary sulfonium salts, secondary iodine salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroborates, peroxides, compounds based on azo and acidic phosphoric acid esters. These polymerization catalysts can be used alone, or two or more of these can be used in combination. Among these, specific preferred examples include quaternary ammonium salts such as tetra-n-butylammonium bromide, triethylbenzyl ammonium chloride, cetyldimethylbenzyl ammonium chloride and 1-n-dodecyl pyridinium chloride and quaternary phosphonium salts such as bromide bromide tetra-n-butylphosphonium and tetrafenyl phosphonium bromide. Among these, the most specific preferred examples are triethylbenzyl ammonium chloride and / or tetra-n-butylphosphonium bromide. Examples of the polymerization modifier include halides of elements belonging to Groups 13 to 16 of the long form of the periodic table. These polymerization modifiers can be used alone, or two or more of these can be used in combination. Among these, silicon, germanium, tin and antimony halides are preferred, silicon, germanium, tin and antimony chlorides are more preferred, and germanium, tin and antimony chlorides, which have an even more preferred alkyl group. Specifically, dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, dibutyldichlorogermanium octyltin trichloride, butyltrichlorogermanium, diphenyl dichlorogermanium, phenyl trichlorogermanium and dichloride and are more preferred antiphenyl.
[0053] [0053] It is preferred to carry out the aeration treatment before injecting the polymerizable composition for optical materials into the mold to obtain the reduction in the speed of raising the viscosity of the polymerizable composition and high transparency of the optical material. Deaeration treatment is carried out under reduced pressure before, during or after mixing a reaction product obtained by subjecting compound (a), compound (b), compound (c) and compound (d) to the reaction prepolymerization with a compound that can react with part or all of the components of the composition, additives, polymerization catalyst, polymerization modifier, etc. Preferably, the aeration treatment is carried out under reduced pressure during or after mixing. The deaeration treatment conditions are as follows: under reduced pressure from 0.001 to 100 torr; 1 minute to 24 hours; and 0 ° C to 45 ° C. The degree of pressure reduction is preferably from 0.005 to 50 torr, and more preferably from 0.01 to 30 torr. The degree of pressure reduction can be varied within these ranges. The deaeration time is preferably 5 minutes to 8 hours, and more preferably 10 minutes to 4 hours. The temperature at the time of deaeration is preferably 5 to 40 ° C, more preferably 10 to 40 ° C, and the temperature can be varied within these ranges. The operation of renewing the surface of the polymerizable composition for optical materials by means of agitation, gas blowing, vibration caused by ultrasonic waves or others during the deaeration treatment is preferable in terms of improving the deaeration effect. Components removed by deaeration treatment are mainly dissolved gases such as hydrogen sulfide, low-boiling substances such as low molecular weight mercaptan, etc., but the type of components is not particularly imitated as long as the effects of deaeration treatment are exercised.
[0054] [0054] In the method of producing an optical material of the present invention, it is certainly possible to add publicly known additives, such as an antioxidant, a blue dyeing agent, an ultraviolet absorbent and a deodorant to the polymerizable composition for optical materials to improve the practicality of the material obtained. In addition, when the optical material of the present invention is easily released from the mold during polymerization, it is possible to add a publicly known external and / or internal adhesion enhancing agent, and when the optical material is not easily released from the mold, it is possible to add a publicly known external and / or internal mold release improving agent. It is effective to add such an agent to improve the adhesiveness or mold release characteristics between the obtained optical material and the mold.
[0055] [0055] Next, the method for producing the optical material will be described in detail. The prepolymerization reaction composition obtained by subjecting compound (a), compound (b), compound (c) and compound (d) to a prepolymerization reaction is mixed with a compound that can react with some or all of the components of the prepolymerization reaction composition. During this, various additives such as a tackifier or mold release agent, an antioxidant, a blue tinting agent, an ultraviolet absorbent, a deodorant and others can be suitably added. At the time of mixing, the temperature to be adjusted, the time required for mixing, etc. are basically not limited as long as the components can be mixed sufficiently, but the excessive temperature and time cause an undesirable reaction between the raw materials and the additives and also cause the viscosity to rise to make it difficult to perform the melt-molding operation, and therefore are inappropriate. The mixing temperature should be in the range of about 5 ° C to about 40 ° C, and preferably in the range of 10 ° C to 40 ° C. The mixing time is about 1 minute to 12 hours, preferably from 5 minutes to 8 hours, and even more preferably 5 minutes to 4 hours. As needed, mixing can be performed with active energy radius being blocked. After that, it is preferred to carry out the aeration treatment according to the method mentioned above. It is necessary to filter the impurities and others of the polymerizable composition for optical materials to be purified using a filter just before the melt molding operation to improve the quality of the optical material of the present invention. The pore diameter of the filter to be used here is about 0.05 to 10 pm, and generally 0.1 to 5.0 pm. The filter material is preferably PTFE, PET, PP or others. If filtration is not carried out or if filtration is carried out using a filter having a pore diameter of more than 10 pm, foreign matter can be mixed in the optical material or the transparency can be reduced, and therefore the product generally obtained it cannot be used as optical material. The polymerizable composition for optical materials thus obtained, is injected into a mold made of glass or metal, and then subjected to polymerization and curing using an electric oven, an active energy ray generating apparatus or others. The polymerization time is 0.1 to 100 hours, and generally 1 to 48 hours. The polymerization temperature is from -10 to 160 ° C, and generally from 0 to 140 ° C, and in particular, the temperature of initiation of polymerization is generally from 0 to 40 ° C. Polymerization can be carried out by carrying out a a step of maintaining the composition at a predetermined polymerization temperature for a predetermined amount of time, a step of increasing the temperature at a rate of 0.1 ° C to 100 ° C / h and a step of decreasing the temperature by a rate of 0.1 ° C to 100 ° C / h, or a combination of these steps. In addition, it is preferred to anneal the material at a temperature of 40 to 150 ° C for about 5 minutes to 5 hours after the end of the polymerization in terms of the distortion of elimination of the optical material. In addition, a surface treatment such as coloring, hard coating, anti-reflective treatment, properties that provide anti-tarnish, anti-cloud properties, impact resistance or others can be carried out as needed.
[0056] [0056] In the specific method of subjecting compound (a) and compound (c) to a prepolymerization reaction in the presence of compound (b) in the present invention, compound (d) is preferably added to compounds (a) , (b) and (c) and stirred and mixed from 0 ° C to 45 ° C, preferably from 5 ° C to 40 ° C, and more preferably from 10 ° C to 40 ° C. With respect to the addition method in this time, compounds (a) and (b) are mixed together with the temperature being controlled to the reaction temperature, and then compounds (c) and (d) are mixed together and then added to the mixture. Alternatively, compounds (a) and (b) and a part of compound (e) are mixed together with the temperature being controlled to the reaction temperature, and then the rest of compound (c) and compound (d) are mixed together and then added to the mix. Alternatively, compounds (a), (b) and (c) are mixed together with the temperature being controlled to the reaction temperature, and then compound (d) is added to the mixture.
[0057] [0057] The reaction can be carried out in any atmosphere, for example, in the presence of a gas such as nitrogen, oxygen, hydrogen and hydrogen sulfide, in a sealed atmosphere under normal pressure or increased / reduced pressure, or under reduced pressure, but in order to maintain the physical properties of the obtained optical material such as color tone, heat resistance and light resistance, it is preferred to reduce the partial pressure of an oxidation gas such as oxygen as much as possible.
[0058] [0058] In order to detect how much of the reaction went and control the reaction to produce a certain amount of the optical material, it is preferred to perform liquid chromatography and / or the measurement of specific viscosity and / or gravity and / or refractive index and / or amount of gas generated at the time of the prepolymerization reaction. Note that the completion point of the prepolymerization reaction is appropriately adjusted taking into account the reprecipitation of compound (a), viscosity, etc. In the product obtained preliminarily reacted (prepolymer), but it is preferred to allow 50% or more of compound (a) to be reacted. The prepolymerization reaction time can be controlled by the amount of compound (d) to be added and the reaction temperature. However, when the reaction time is very short, it is difficult to control the completion point, and when the reaction time is very long, productivity is reduced. Therefore, the reaction time is 10 minutes to 5 hours, preferably 10 minutes to 3 hours, and more preferably 10 minutes to 2 hours.
[0059] [0059] For the purpose of improving workability, it is important to control the temperature of a melt molding solution before injecting the polymerizable composition for optical materials into the mold. It is undesirable to allow the temperature to change significantly from the preliminary reaction temperature in terms of the progress of the reaction and the effect of increasing viscosity due to the reduction in temperature. The temperature is preferably equal to the preliminary reaction temperature of + 10 ° C to -15 ° C, more preferably equal to the preliminary reaction temperature of + 10 ° C to -10 ° C, even more preferably equal to the preliminary reaction temperature of + 5 ° C to -10 ° C, and particularly preferably equal to the preliminary reaction temperature of + 5 ° C to -5 ° C. In addition, it is effective to adjust the temperature of the melt molding solution to close to the temperature of initial polymerization to obtain good optical materials. This temperature control has the effect of preserving the generation of stretch marks due to the convection caused by the difference between the temperature of the melt molding solution and the temperature of the polymerization oven. This effect of preserving the striations becomes as high as the temperature of the composition is equal to the temperature of the oven. However, when the temperature of the melt molding solution is very low, there are problems such as dew condensation and precipitation of compound (a), and when the temperature of the melt molding solution is very high, there is a problem where the viscosity rise speed becomes higher. Therefore, the temperature of the melt molding solution is preferably equal to the initial polymerization temperature of + 10 ° C to -10 ° C, and more preferably equal to the initial polymerization temperature of + 5 ° C to -5 ° C, and at the same time, the temperature of the melt molding solution is 0 ° C to 45 ° C, preferably 10 ° C to 40 ° C, and even more preferably 15 ° C to 35 ° C.
[0060] [0060] Streaks of the optical material obtained by the present invention refer to cotton-like portions or layered portions of a material component having a refractive index different from that of the base material in the optical material, and such streaks are generated, for example, the slight sparse / density in the optical material caused by the convection of the polymerizable composition caused by the generation of heat during polymerization and curing, and the irregular progress of the polymerization reaction. Generally, when the streaks of the optical material are evaluated, a light source from a mercury lamp is transmitted through the prepared optical material (optical lens), the transmitted light is projected onto a white board, and the level of streaks of the external appearance is assessed based on the criteria described below. Specifically, the case where no streak is visually confirmed is classified in the first degree of streak, the case where thin and dispersed streaks that are visible are confirmed is classified in the second degree of streak, and in the case where streak thicker than in the second degree stretch marks are confirmed is classified into the third degree of stretch marks. Preferably, 90% or more and less than 95% of the optical materials produced are classified in the first degree of streaks less than 5% of optical materials are classified in the third degree of streaks. More preferably, 90% or more and less than 95% of the optical materials produced are classified in the first grade and streaks and no optical material is classified in the third grade of streaks. Even more preferably, 95% or more of the optical materials produced are classified in the first grade and streaks and no optical material is classified in the third grade of streaks.
[0061] [0061] EXAMPLES
[0062] [0062] In the following, the present invention will be specifically described by way of working examples, but the present invention is not limited to these. The analysis of polymerizable compositions for optical materials and optical materials obtained through polymerization was conducted in the ways described below.
[0063] [0063] [Viscosity of polymerizable compositions]
[0064] [0064] The viscosity of the prepolymerization solution at 20 ° C was measured using a type B viscometer (manufactured by Toki Sangyo Co., Ltd., TV10M).
[0065] [0065] [Measurement of heat resistance of optical materials]
[0066] [0066] An optical material was cut to a thickness of 3 mm, and the measurement of TMA (Seiko Instruments Inc., TMA / SS6100) was performed by adding 10 g of weight to a pin (φ: 0.5 mm ) and raising the temperature at a rate of 30 ° C to 10 ° C / minutes to measure the temperature of the softening point (Tg).
[0067] [0067] [Refractive index and Abbe number of optical materials]
[0068] [0068] Regarding the refractive index and the Abbe number of the optical materials, the refractive index on the e line (ne) and the Abbe number on the d line (vd) at 25 ° C were measured using a precision digital refractometer ( Shimadzu Corporation, KPR-200).
[0069] [0069] [Evaluation of streaks of optical materials (optical lenses)]
[0070] A: 95 ou mais das 100 lentes óticas estão classificadas no primeiro grau de estrias e não há lente ótica classificada no terceiro grau de estrias. B: 90 ou mais e menos do que 95 das 100 lentes óticas estão classificadas no primeiro grau de estrias e não há lente ótica classificada no terceiro grau de estrias. C: 90 ou mais e menos do que 95 das 100 lentes óticas estão classificadas no primeiro grau de estrias e menos do que 5 lentes óticas estão classificadas no terceiro grau de estrias. D: 80 ou mais e menos do que 90 das 100 lentes óticas estão classificadas no primeiro grau de estrias e 5 ou mais e menos do que 10 lentes óticas estão classificadas no terceiro grau de estrias. E: 10 ou mais das 100 lentes óticas estão classificadas no terceiro grau de estrias. [0070] A light source from a mercury lamp was transmitted through the prepared optical material (optical lens), the transmitted light was projected on a white board, and the level of streaks of the external appearance was assessed based on the criterion described below . The case where no streak was visually confirmed was classified in the first degree of streak, the case where thin and dispersed streaks that were visible were classified was in the second degree and streak, and the case where streak thicker than in the second degree of stretch were confirmed was classified in the third degree of stretch marks. In addition, 100 optical lenses were produced and evaluated on the 5-point scale described below. A: 95 or more of the 100 optical lenses are classified in the first streak grade and there is no optical lens classified in the third streak grade. B: 90 or more and less than 95 of the 100 optical lenses are classified in the first degree of streaks and there is no optical lens classified in the third degree of streaks. C: 90 or more and less than 95 of the 100 optical lenses are classified in the first degree of streaks and less than 5 optical lenses are classified in the third degree of streaks. D: 80 or more and less than 90 of the 100 optical lenses are classified in the first degree of streaks and 5 or more and less than 10 optical lenses are classified in the third degree of streaks. E: 10 or more of the 100 optical lenses are classified in the third degree of stretch marks.
[0071] [0071] [Evaluation of the mold release characteristics of optical materials (optical lenses)]
[0072] [0072] After a polymerizable composition was polymerized and cured, when the prepared optical material (optical lens) was released from a mold made of glass, the states of the optical lens and the mold and the mold release workability were evaluated on the scale of 4 points described below. Very good: When an optical lens is released from a mold made of glass, the optical lens can be easily released in a short time without breaking the optical lens and the mold. Good: When an optical lens is released from a mold made of glass, the optical lens can be released without breaking the optical lens and the mold. Weak: When an optical lens is released from a mold made of glass, the optical lens and mold are not broken, but a part of the mold made of glass adheres to the optical lens or a part of the optical lens adheres to mold made of glass, and the mold release workability is significantly low and takes a long time. Very weak: An optical lens cannot be released, or the optical lens and / or a mold made of glass is broken.
[0073] [0073] [Color tone of optical materials (YI value)]
[0074] [0074] The Y1 value of a circular flat plate of a cured and cured product (thickness: 2.5 mm, φ: 60 mm) was measured using a spectroscopic colorimeter (Color Techno System Corporation, JS555).
[0075] [0075] Example 1
[0076] [0076] (Method for prepolymerization reaction and method for producing a polymerizable composition)
[0077] [0077] To 16.0 parts by mass of sulfur as compound (a), 84.0 parts by mass of bis (13-epithiopropyl) sulfide as compound (b) (hereinafter referred to as compound (b-1 )) and 8.6 parts by mass of bis (2-mercaptoethyl) sulfide as compound (c) (hereinafter referred to as compound (e-1)), 0.020 part by mass of 1,2,2,6, 6-pentamethylpiperidyl-4-methacrylate as compound (d) (hereinafter referred to as compound (d-1)) were added, and the mixture was subjected to a prepolymerization reaction in an atmosphere of nitrogen under normal pressure at 30 ° C. The preliminary reaction solution 0.5 hour after the start of the reaction was yellow and clear, and it was a homogeneous precipitation without precipitation of a solid such as sulfur. In addition, the preliminary reaction solution was cooled to 20 ° C for 0.1 hour. The preliminary reaction solution after cooling was yellow and clear, no solid such as sulfur was precipitated, and the viscosity at 20 ° C was 30 mPa.s. To these preliminary reaction solution obtained, 0.10 part by mass of triethylbenzyl ammonium chloride as a polymerization catalyst and 0.25 part by mass of dibutyltin dichloride as a polymerization modifier were added, and the mixture was stirred and mixed while undergoing deaeration treatment under 10 Torr to provide a polymerizable composition. The viscosity of the polymerizable composition obtained was 30 mPa.s, and the viscosity of the polymerizable composition after being maintained at 20 ° C for 3 hours was 35 mPa.s. The results are shown in table 1.
[0078] [0078] (Method for producing a plastic lens)
[0079] [0079] The polymerizable composition obtained was filtered using a 1.0 µm PTFE membrane filter, which was injected into 100 sets of each of the 3 types of molds, which were composed of a glass mold (power indicated ( S / C) -4,0D / 0,0D) and a gasket, a glass mold (indicated power (S / C) -12,5D / 0,0D) and a gasket, and a glass mold (indicated power (S / C) -15.0D / 0.0D) and a gasket, respectively. These molds were heated in an oven with the temperature being slowly raised from 20 ° C to 100 ° C over 22 hours to be polymerized and cured, and then the molds were cooled to room temperature, and the optical lenses were obtained by releasing the molds. The results with respect to the mold release characteristics at this time, and streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 1.
[0080] [0080] Example 2
[0081] [0081] (Method for prepolymerization reaction and method for producing a polymerizable composition)
[0082] [0082] At 16.0 parts by weight of sulfur which is the compound (a), 84.0 parts by weight of bis (13-epithiopropyl) sulfide which is the compound (b-1) and 7.8 parts by weight bis (2-mercaptoethyl) sulfide which is compound (c-1), 0.020 part by mass of 1,2,2,6,6-pentamethylpiperidyl-4-methacrylate which is compound (d-1) was added, and the mixture was subjected to a prepolymerization reaction in a nitrogen atmosphere under normal pressure at 30 ° C. The preliminary reaction solution 0.5 hour after the start of the reaction was yellow and clear, and it was a homogeneous precipitation without precipitation of a solid such as sulfur. In addition, the preliminary reaction solution was cooled to 20 ° C for 0.1 hour while being subjected to deaeration treatment under 10 Torr. The preliminary reaction solution after cooling was yellow and clear, no solid such as sulfur was precipitated, and the viscosity at 20 ° C was 35 mPa.s. 0.10 part by mass of triethylbenzyl ammonium chloride as a polymerization catalyst and 0.25 part by mass of dibutyltin dichloride as a polymerization modifier were dissolved in 0.80 part by mass of bis (2-mercaptoethyl) sulfide which is the compound (c-1) previously, and the mixture was added to the obtained preliminary reaction solution. In addition, the obtained mixture was stirred and mixed while being subjected to the aeration treatment under 10 Torr to provide a polymerizable composition. The viscosity of the polymerizable composition obtained was 33 mPa.s, and the viscosity of the polymerizable composition after being maintained at 20 ° C for 3 hours was 38 mPa.s. The results are shown in table 1.
[0083] [0083] (Method to produce a plastic lens)
[0084] [0084] The polymerizable composition obtained was filtered using a 1.0 µm PTFE membrane filter, and this was injected into 100 sets of each of the 3 types of molds, which were composed of a glass mold (power indicated ( S / C) -4,0D / 0,0D) and a gasket, a glass mold (indicated power (S / C) -12,5D / 0,0D) and a gasket, and a glass mold (indicated power (S / C) -15.0D / 0.0D) and a gasket, respectively. These molds were heated in an oven with the temperature being slowly raised from 20 ° C to 100 ° C over 22 hours to be polymerized and cured, and then the molds were cooled to room temperature, and the optical lenses were obtained by releasing the molds. The results with respect to the mold release characteristics at this time, and the streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 1.
[0085] [0085] Examples 3 to 6
[0086] [0086] The process was carried out in a manner similar to that of Example 1, except that the respective compounds and amounts were used for those described in table 1. In addition, the results with respect to the viscosity of the obtained polymerizable composition, and the characteristics of mold release, streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 1.
[0087] [0087] Examples from 7 to 10
[0088] [0088] The process was carried out in a manner similar to that of Example 2, except that the respective compounds and amounts were changed to those described in table 1. In addition, the results with respect to the viscosity of the polymerizable composition obtained, and the characteristics of mold release, streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 1.
[0089] [0089] Example 11
[0090] [0090] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) as the compound (c) and 0.016 part by mass of the compound (d-1) as the compound (d) were added and the mixture was reacted in a nitrogen atmosphere under normal pressure at 30 ° C for 1.0 hour . To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was cooled up to 25 ° C which is the temperature at the time of the melt molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 25 ° C which is the temperature at the time of melting molding was 40 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 82 mPa. s.
[0091] [0091] Subsequently, the optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0092] [0092] Example 12
[0093] [0093] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) and 0.005 part by mass of the compound (d-1) as the compound (d) were added, and the mixture was reacted in an atmosphere of nitrogen under normal pressure at 40 ° C for 1.5 hours. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added and the mixture was cooled to 30 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 30 ° C which is the temperature at the time of melting molding was 36 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 110 mPa. s.
[0094] [0094] Subsequently, the optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0095] [0095] Example 13
[0096] [0096] 15.5 parts by weight of sulfur which is compound (a), 84.5 parts by weight of compound (b-1) as compound (b), 8.6 parts by weight of compound (c- 1) and 0.016 part by mass of 1,2,2,6,6-pentamethylpiperidyl acrylate (hereinafter referred to as compound (d-2)) as compound (d) were added, and the mixture was reacted in a nitrogen atmosphere under normal pressure at 25 ° C for 1.5 hours. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was maintained at 25 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 25 ° C, which is the temperature at the time of melting molding, was 42 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 85 mPa. s.
[0097] [0097] Subsequently, the optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0098] [0098] Example 14
[0099] [0099] 10.0 parts by weight of sulfur which is compound (a), 90.0 parts by weight of bis ^ -epithiopropyl) disulfide as compound (b) (hereinafter referred to as compound (b-2) ), 5.0 parts by mass of the compound (c-1) as the compound (c) and 0.1 parts by mass of the compound (d-1) were added, and the mixture was reacted in an atmosphere of nitrogen under pressure normal at 5 ° C for 1.2 hours. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was heated up to 15 ° C which is the temperature at the time of melting molding while being subjected to the aeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 15 ° C which is the temperature at the time of melting molding was 90 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 103 mPa. s.
[0100] [00100] Subsequently, optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0101] [00101] Example 15
[0102] [00102] 20.0 parts by weight of sulfur which is the compound (a), 80.0 parts by weight of the compound (b-1) as the compound (b), 10.0 parts by weight of the compound (c- 1) and 0.016 part by mass of the compound (d-1) as the compound (d) were added, and the mixture was reacted in an atmosphere of nitrogen under normal pressure at 30 ° C for 1.5 hours. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was cooled up to 20 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 20 ° C which is the temperature at the time of melt molding was 82 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melt molding for 3 hours was 115 mPa. s.
[0103] [00103] Subsequently, the optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0104] [00104] Example 16
[0105] [00105] 30.0 parts by weight of sulfur which is the compound (a), 70.0 parts by weight of the compound (b-1) as the compound (b), 15.0 parts by weight of the compound (c- 1) and 0.033 part by mass of the compound (d-1) as the compound (d) were added, and the mixture was reacted in an atmosphere of nitrogen under normal pressure at 30 ° C for 1.0 hour. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was cooled up to 25 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 25 ° C which is the temperature at the time of melting molding was 55 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 96 mPa. s.
[0106] [00106] Subsequently, optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0107] [00107] Comparative Example 1
[0108] [00108] (Method for prepolymerization reaction and method for producing a polymerizable composition)
[0109] [00109] 16.0 parts by weight of sulfur which is the compound (a) and 84.0 parts by weight of bis (β-epithiopropyl) sulfide which is the compound (b-1) were mixed well at 60 ° C to provide a homogeneous solution. Subsequently, 0.50 part by mass of 2-mercapto-1-methylimidazole (indicated as MMI) as a prepolymerization catalyst was added to it, and the mixture was subjected to a prepolymerization reaction at 60 ° C. The preliminary reaction solution obtained was cooled to 20 ° C. The preliminary reaction solution after cooling was yellow and clear, no solid such as sulfur was precipitated, and the viscosity at 20 ° C was 70 mPa.s. 0.03 part by mass of triethylbenzyl ammonium chloride as a polymerization catalyst and 0.20 part by mass of dibutyltin dichloride as a polymerization modifier were dissolved in 8.6 parts by mass of bis (2-mercaptoethyl) sulfide which is the compound (c-1) in advance, and the mixture was added to the obtained preliminary reaction solution. In addition, the obtained mixture was stirred and mixed while being subjected to the aeration treatment under 10 Torr to provide a polymerizable composition. The viscosity of the polymerizable composition obtained was 80 mPa.s, and the viscosity of the polymerizable composition after being maintained at 20 ° C for 3 hours was 130 mPa.s. The results are shown in table 2.
[0110] [00110] (Method to produce a plastic lens)
[0111] [00111] The polymerizable composition obtained was filtered using a 1.0 µm PTFE membrane filter, and this was injected into 100 sets of each of the 3 types of molds, which were composed of a glass mold (power indicated ( S / C) -4,0D / 0,0D) and a gasket, a glass mold (indicated power (S / C) -12,5D / 0,0D) and a gasket, and a glass mold (indicated power (S / C) -15.0D / 0.0D) and a gasket, respectively. These molds were heated in an oven with the temperature being slowly raised from 20 ° C to 100 ° C over 22 hours to be polymerized and cured, and then the molds were cooled to room temperature, and the optical lenses were obtained by releasing the molds. The results with respect to the mold release characteristics at this time, and streaks, heat resistance (Tg), Y1 value, refractive index and Abbe number of the optical lenses are shown in table 2.
[0112] [00112] Comparative Example 2
[0113] [00113] (Method for prepolymerization reaction and method for producing a polymerizable composition)
[0114] [00114] 16.0 parts by weight of sulfur which is compound (a), 84.0 parts by weight of bis (β-epithiopropyl) sulfide which is compound (b-1) and 7.8 parts by weight of bis (2-mercaptoethyl) sulfide which is the compound (c-1) were mixed well at 60 ° C to provide a homogeneous solution. Subsequently, 0.50 part by mass of 2-mercapto-1-methylimidazole (indicated as MMI) as a prepolymerization catalyst was added to it, and the mixture was subjected to a prepolymerization reaction at 60 ° C. The preliminary reaction solution obtained was cooled to 20 ° C. The preliminary reaction solution after cooling was yellow and clear, no solid such as sulfur was precipitated, and the viscosity at 20 ° C was 50 mPa.s. 0.03 part by mass of triethylbenzyl ammonium chloride as a polymerization catalyst and 0.20 part by mass of dibutyltin dichloride as a polymerization modifier were dissolved in 0.8 part by mass of bis (2-mercaptoethyl) sulfide which is the compound (c-1) in advance, and the mixture was added to the obtained preliminary reaction solution. In addition, the obtained mixture was stirred and mixed while being subjected to the aeration treatment under 10 Torr to provide a polymerizable composition. The viscosity of the polymerizable composition obtained was 55 mPa.s, and the viscosity of the polymerizable composition after being maintained at 20 ° C for 3 hours was 115 mPa.s. The results are shown in table 2.
[0115] [00115] (Method for producing a plastic lens)
[0116] [00116] The polymerizable composition obtained was filtered using a 1.0 µm PTFE membrane filter, and this was injected into 100 sets of each of the 3 types of molds, which were composed of a glass mold (power indicated ( S / C) -4.0D / 0.0D) and a gasket, a glass mold (indicated power (S / C) -12.5D / 0.0D) and a gasket, and a glass mold (indicated power (S / C) -15.0D / 0.0D) and a gasket, respectively. These molds were heated in an oven with the temperature being slowly raised from 20 ° C to 100 ° C over 22 hours to be polymerized and cured, and then the molds were cooled to room temperature, and the optical lenses were obtained by releasing of the molds. The results with respect to the mold release characteristics at this time, and streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 2.
[0117] [00117] Comparative Example 3
[0118] [00118] The process was carried out in a manner similar to that of Example 1, except that the amount of compound (d) was changed. Nevertheless, rapid polymerization occurred, and no optical material was obtained.
[0119] [00119] Comparative Example 4
[0120] [00120] The process was carried out in a manner similar to that of Example 1, except that the amount of compound (d) was changed. However, sulfur remained partially undissolved, and no homogeneous optical material was obtained.
[0121] [00121] Comparative Example 5
[0122] [00122] The process was carried out in a manner similar to that of Comparative Example 1, except that 0.01 part by mass of dioctylic acid phosphate as an internal mold release agent was added in order to obtain a homogeneous solution at 60 ° Ç.
[0123] [00123] The results regarding the viscosity of the polymerizable composition obtained at this moment, and the characteristics of mold release, streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 2 However, a fine turbidity was generated in all optical lenses obtained.
[0124] [00124] Comparative Example 6
[0125] [00125] The process was carried out in a similar manner to that of Comparative Example 5, except that 0.01 part by mass of DS-401 (Daikin Industries, Ltd.) was used instead of dioctyl acid phosphate as a release agent of internal mold. The results regarding the viscosity of the polymerizable composition obtained at this moment, and the characteristics of mold release, streaks, heat resistance (Tg), YI value, refractive index and Abbe number of the optical lenses are shown in table 2. Notwithstanding , a fine turbidity was generated in all obtained optical lenses.
[0126] [00126] Comparative Example 7
[0127] [00127] The process was carried out in a manner similar to that of Comparative Example 1, except that YSR-6209 (Toshiba Silicone Co., Ltd.) as an external mold release agent was applied to the molds. However, turbidity was generated in all optical lenses obtained, and the surfaces of the optical lenses became rough.
[0128] [00128] Comparative Example 8
[0129] [00129] The process was carried out in a manner similar to that of Example 1, except that 2,2,6,6-tetramethylpiperidyl-4-methacrylate (indicated as TMPM) was used instead of compound (d). Nevertheless, rapid polymerization occurred, and no optical material was obtained.
[0130] [00130] Comparative Example 9
[0131] [00131] The process was carried out in a manner similar to that of Example 1, except that 1,2,2,6,6-tetramethylpiperidine (indicated as PMP) was used instead of compound (d). Nevertheless, rapid polymerization occurred, and no optical material was obtained.
[0132] [00132] Comparative Example 10
[0133] [00133] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b) and 8.6 parts by weight of the compound (c- 1) were reacted in a nitrogen atmosphere under normal pressure at 60 ° C for 24 hours without the addition of compound (d), but the sulfur remained.
[0134] [00134] Comparative Example 11
[0135] [00135] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) and 0.016 part by mass of the compound (d-1) as the compound (d) were added, and the mixture was reacted in an atmosphere of nitrogen under normal pressure at 50 ° C for 1.0 hour. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was cooled up to 40 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 40 ° C which is the temperature at the time of melting molding was 160 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 820 mPa. s.
[0136] [00136] Subsequently, the optical lenses were obtained according to the method described in Example 1. The results are shown in table 3.
[0137] [00137] Comparative Example 12
[0138] [00138] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) and 0.2 mass parts of the compound (d-1) as the compound (d) were reacted in a nitrogen atmosphere under normal pressure at -5 ° C for 1.0 hour, but the sulfur remained.
[0139] [00139] Comparative Example 13
[0140] [00140] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) and 0.016 part by mass of the compound (d-1) as the compound (d) were added, and the mixture was reacted in an atmosphere of nitrogen under normal pressure at 45 ° C for 1.0 hour. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was cooled up to 25 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 25 ° C which is the temperature at the time of melting molding was 210 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 450 mPa. s.
[0141] [00141] Subsequently, the optical lenses were obtained according to the method described in Example 2. The results are shown in table 3.
[0142] [00142] Comparative Example 14
[0143] [00143] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) and 0.016 part by mass of the compound (d-1) as the compound (d) were added, and the mixture was reacted in an atmosphere of nitrogen under normal pressure at 25 ° C for 1.5 hours. To the reaction solution obtained, 0.9 part by mass of the compound (c-1), 0.37 part by mass of dibutyltin dichloride and 0.16 part by mass of triethylbenzyl ammonium chloride were added, and the mixture was heated up to 40 ° C which is the temperature at the time of melting molding while being subjected to the deaeration treatment under 10 Torr, thus obtaining a polymerizable composition for optical materials without turbidity. The viscosity of the composition obtained at 40 ° C which is the temperature at the time of melting molding was 30 mPa.s, and the viscosity of the composition after being maintained at the temperature at the time of melting molding for 3 hours was 260 mPa. s.
[0144] [00144] Subsequently, optical lenses were obtained according to the method described in Example 2. The results are shown in table 3.
[0145] [00145] Comparative Example 15
[0146] [00146] 15.5 parts by weight of sulfur which is the compound (a), 84.5 parts by weight of the compound (b-1) as the compound (b), 8.6 parts by weight of the compound (c- 1) and 0.05 part by mass of MMI as compound (d) was reacted in a nitrogen atmosphere under normal pressure at 30 ° C for 24 hours, but the sulfur remained
[0147] [00147] Note that the letters and numerals in Tables 1 to 3 above describe the substances described below. (a) sulfur (b-1) bis (β-epithiopropyl) sulfide (b-2) bis (β-epithiopropyl) disulfide (c-1) bis (2-mercaptoethyl) sulfide (c-2) m-xylylenedithiol (c-3) 2,5-bis (mercaptomethyl) -1,4-dithian (c-4) p-xylylenedithiol (c-5) 1,2-dimercaptoethane (c-6) thiophole (d-1) 1,2,2,6,6-pentamethylpiperidyl-4-methacrylate (d-2) 1,2,2,6,6-pentamethylpiperidyl-4-acrylate (d-3) 1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate MMI: 2-mercapto-1-methylimidazole TMPM: 2,2,6,6-tetramethylpiperidyl-4-methacrylate PMP: 1,2,2,6,6-pentamethylpiperidine TEBAC: triethyl benzyl ammonium chloride DBTC: dibutyltin dichloride

权利要求:
Claims (9)
[0001]
Polymerizable composition for optical materials, characterized by the fact that it comprises: a preliminary reaction solution obtained by subjecting 10 to 50 parts by weight of the compound (a) described below and from 1 to 20 parts by weight of the compound (c) described below to a prepolymerization reaction in the presence of 50 to 90 parts by mass of compound (b) described below with the proviso that the total amount of compound (a) and compound (b) is 100 parts by mass, using from 0.001 to 5 parts by mass of the compound (d) described below as a prepolymerization catalyst; and a polymerization catalyst: (a) sulfur (compound (a)); (b) a compound having two intramolecular episulfide groups represented by the following formula (1) (compound (b)):
[0002]
Method for producing a polymerizable composition for optical materials, as defined in claim 1, characterized by the fact that it comprises the steps of: subjecting 10 to 50 parts by weight of the compound (a) described below and 1 to 20 parts by weight of the compound (c) described below to a prepolymerization reaction in the presence of 50 to 90 parts by weight of the compound (b ) described below with the proviso that the total amount of compound (a) and compound (b) is 100 parts by mass, using from 0.001 to 5 parts by mass of compound (d) described below as a pre-catalyst polymerization, to obtain a preliminary reaction solution; and add a polymerization catalyst to the preliminary reaction solution: (a) sulfur (compound (a)); (b) a compound having two intramolecular episulfide groups represented by the following formula (1) (compound (b)):
[0003]
Polymerizable composition for optical materials, according to claim 1, characterized by the fact that the polymerizable composition for optical materials is obtained by the addition of the polymerization catalyst and compound (c) to the preliminary reaction solution.
[0004]
Method for producing an optical material, characterized in that it comprises polymerizing and curing the polymerizable composition for optical materials as defined in claim 1.
[0005]
Optical material characterized by the fact that it is obtained through the production method as defined in claim 4.
[0006]
Optical lens characterized by the fact that it comprises the optical material as defined in claim 5.
[0007]
Method for producing a polymerizable composition for optical materials, as defined in claim 1, characterized by the fact that it comprises the steps of: subject 10 to 50 parts by mass of the compound (a) described below and 1 to 20 parts by mass of the compound (c) described below to a prepolymerization reaction at a reaction temperature T1 (where T1 is 0 at 45 ° C) in the presence of 50 to 90 parts by mass of compound (b) described below with the proviso that the total amount of compound (a) and compound (b) is 100 parts by mass, using 0.001 to 5 parts by weight of compound (d) described below as a prepolymerization catalyst, to obtain a preliminary reaction solution; and add a polymerization catalyst to the preliminary reaction solution with the temperature being adjusted to T2 with the proviso that T2 is from T1 - 15 ° C to T1 + 10 ° C and from 0 to 45 ° C: (a) sulfur (compound (a)); (b) a compound having two intramolecular episulfide groups represented by the following formula (I) (compound (b)):
[0008]
Method for producing an optical material, characterized by the fact that it comprises polymerizing the polymerizable composition for optical materials produced by the production method as defined in claim 7 with the initial polymerization temperature being adjusted to T3 with the proviso that T3 is T2 - 10 ° C to T2 + 10 ° C and from 0 to 40 ° C.
[0009]
Optical material characterized by the fact that it is produced using the method as defined in claim 8.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-03-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-09-15| B09A| Decision: intention to grant|

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2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012-029700|2012-02-14|

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JP2012029700|2012-02-14|

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JP2012193832A|JP6048012B2|2012-09-04|2012-09-04|Manufacturing method of optical material|

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JP2012-193832|2012-09-04|

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JP2012193833A|JP6048013B2|2012-09-04|2012-09-04|Method for producing polymerizable composition for optical material|

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JP2012-193833|2012-09-04|

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PCT/JP2013/053306|WO2013122068A1|2012-02-14|2013-02-13|Polymerizable composition for optical material, method for producing same, and method for producing optical material|

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