JP6089744B2 - Method for producing polymerizable composition for optical material - Google Patents

Description

The present invention relates to a method for producing a polymerizable composition for an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate, a filter, and an adhesive, particularly a plastic lens for eyeglasses.

In recent years, plastic materials have been widely used in various optical materials, particularly eyeglass lenses, because they are light and tough and easy to dye. The main performance required for optical materials, especially spectacle lenses, is low specific gravity, high transparency and low yellowness, high refractive index and high Abbe number as optical properties, etc. In recent years, high refractive index and high Abbe number In order to achieve this, a polymerizable composition for an optical material in which an inorganic compound having a sulfur atom and / or a selenium atom is blended with a polyepisulfide compound has been proposed (for example, Patent Document 1).
Optical materials obtained by polymerizing and curing these compositions have achieved a high refractive index, but many inorganic compounds having sulfur atoms and / or selenium atoms are solid at room temperature and have low solubility. In such a case, there is a problem that precipitation occurs or dissolution becomes incomplete when the concentration of the compound is high.
In view of this, a technique has been proposed in which an inorganic compound having a sulfur atom and / or selenium atom and a sulfur-containing organic compound such as an episulfide compound capable of reacting with the inorganic compound are preliminarily polymerized (see Patent Document 2). However, if the content of the inorganic compound having a sulfur atom and / or selenium atom increases, the viscosity of the polymerizable composition becomes too high, and normal casting polymerization operations such as filtration and mold injection become difficult. A compound having one SH group (see Patent Document 3), a compound having one or more NH groups and / or NH ₂ groups (see Patent Document 4), or one disulfide bond in order to reduce the viscosity during the polymerization reaction The manufacturing method which adds the compound (refer patent document 5) which has the above is proposed. However, in a composition having a content of an inorganic compound having a sulfur atom and / or selenium atom of 10 parts by mass or more, even when an additive that lowers these viscosities is added, the prepolymerization reaction is performed excessively and / or Or when the temperature after composition preparation is too high, the viscosity of the composition increases, or the increase in viscosity after about 3 hours, which is the injection time required for producing optical materials industrially, is large. For example, normal casting operations such as filtration and mold injection become difficult, and there is a problem that it is necessary to increase the size of the filtration and injection apparatus and shorten the injection line. Furthermore, in order to improve the productivity of optical materials, there has been a demand for a production method for obtaining a further low-viscosity polymerizable composition for optical materials that is easier to filter and inject.
In addition, the prepolymerization reaction of the above-mentioned reference is usually performed at 50 ° C. to 70 ° C., and it is necessary to cool the polymerizable composition to about room temperature which is a polymerization start temperature after production, and thus the prepolymerization reaction is completed. After or after the production of the polymerizable composition, a cooling step to room temperature is required. To increase the reaction scale, cooling is not performed unless the cooling device is enlarged or a cooling coil is introduced into the reaction device. It is also a problem that the pre-reaction time becomes longer due to the longer time required for the change, or changes every time. For this reason, development of the manufacturing method of the polymeric composition for optical materials which can complete prepolymerization reaction in reaction temperature near room temperature and a short time was desired.

Japanese Patent Laid-Open No. 2001-2783 JP 2004-197005 A JP 2006-348285 A JP 2006-348289 A JP 2006-348286 A

The subject of the present invention is the time required for cooling in the prepolymerization reaction when producing a polymerizable composition for optical materials using a compound having two sulfur and episulfide groups in the molecule and a compound having two SH groups. To develop a method for producing a polymerizable composition for optical materials having a low viscosity and a small increase in viscosity, by setting the reaction temperature to near room temperature to complete the preliminary polymerization reaction within 3 hours. Thus, the productivity of the optical material is improved.

In view of such a situation, the present inventors have conducted extensive research, and as a result, obtained a polymerizable composition for an optical material having a compound having two sulfur and episulfide groups in the molecule and a compound having two SH groups. In the prepolymerization reaction during production, a hindered amine compound having a specific structure using sulfur having a median diameter of 5 μm to 500 μm is used as a prepolymerization catalyst, and stirring during the prepolymerization reaction is performed with a Reynolds number of 1.5 ×. By controlling from 10 ³ to 1.5 × 10 ⁴ , it becomes possible to carry out the reaction temperature at the time of the prepolymerization reaction in the vicinity of room temperature and within 3 hours. Has been found to be able to be produced, leading to the present invention. That is, the present invention is as follows.

（ここで、ｍは０〜４の整数、ｎは０〜１の整数を表す。）
（ｃ）ＳＨ基を２個有する化合物（（ｃ）化合物）
（ｄ）下記（２）式で表される化合物（（ｄ）化合物）。

（Ｒは炭素数１〜４のアルキル基、
Ｘはビニル基、ビニリデン基またはビニレン基のいずれかを有する炭素数２〜１１の有機基）
［２］：［１］記載の方法により得られる光学材料用重合性組成物を重合硬化した光学材料。
［３］：［２］記載の光学材料からなる光学レンズ。 [1]: 10 to 50 parts by mass of the following (a) compound having a median diameter of 5 to 500 μm, 50 to 90 parts by mass of the following (b) compound (however, the total of the (a) compound and the (b) compound is 100 masses) And (c) 1 to 20 parts by mass of the following compound and (d) 0.001 to 3 parts by mass of the following compound (d) as a prepolymerization catalyst to obtain a prepolymerization reaction solution, and It is a method for producing a polymerizable composition for an optical material having a step of adding a polymerization catalyst to a prepolymerization reaction solution, and the prepolymerization reaction is carried out at a reaction temperature of 0 ° C to 45 ° C and a Reynolds number of 1.5 × 10 ³ to 5. A method for producing a polymerizable composition for an optical material, which is performed under 5 × 10 ⁴ stirring.
(A) Sulfur ((a) compound)
(B) Compound having two episulfide groups represented by the following formula (1) in the molecule (compound (b))

(Here, m represents an integer of 0 to 4, and n represents an integer of 0 to 1.)
(C) Compound having two SH groups ((c) compound)
(D) A compound represented by the following formula (2) (compound (d)).

(R is an alkyl group having 1 to 4 carbon atoms,
X is a C2-C11 organic group having any of a vinyl group, vinylidene group or vinylene group)
[2]: An optical material obtained by polymerizing and curing a polymerizable composition for an optical material obtained by the method described in [1].
[3]: An optical lens made of the optical material according to [2].

According to the present invention, in the prepolymerization reaction for producing a polymerizable composition for an optical material using a compound having two sulfur and episulfide groups in the molecule and a compound having two SH groups, the prereaction temperature is about room temperature. After the prepolymerization reaction is completed or after the production of the polymerizable composition for optical materials, the cooling process to room temperature is no longer necessary or unnecessary, and the polymerizable composition for optical materials in a short time. In addition, it has become possible to produce a polymerizable composition for optical materials with low viscosity and small increase in viscosity with high productivity.

The purity of sulfur as the compound (a) used in the present invention is 98% or more. If the purity is less than 98%, the phenomenon that spiders are easily generated in the optical material due to the influence of impurities is likely to occur. The purity of sulfur is preferably 99.0% or more, more preferably 99.5% or more, and further preferably 99.9% or more. Generally available sulfur includes finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur, etc. depending on the shape and purification method. In the present invention, any sulfur having a purity of 98% or more can be used. But it doesn't matter. In the present invention, the prepolymerization reaction is a solid-liquid reaction of the solid (a) compound with the liquid (b) compound and (c) compound. Therefore, in order to complete the prepolymerization reaction in a short time, the median diameter of the compound (a) needs to be 500 μm or less in order to increase the contact area between the solid (a) compound and the reaction solution. However, if the median diameter is too small, the risk of dust explosion increases, so it is better not to use sulfur whose median diameter of the compound (a) is too small. That is, the particle diameter of sulfur is important, and the median diameter is 5 μm to 500 μm, more preferably the median diameter is 50 μm to 400 μm, and still more preferably the median diameter is 100 μm to 300 μm. A method for producing sulfur having a necessary median diameter can be obtained by mechanically pulverizing the above-described sulfur and then selecting it with a sieve.
(A) As for the addition amount of the compound, the higher the sulfur atom content in the optical material polymerizable composition, the higher the refractive index of the optical material is obtained. However, if the addition amount is too large, the composition may remain undissolved. Since the viscosity of the composition is remarkably increased, when the total mass of the compounds (a) and (b) is 100 parts by mass, 10 to 50 parts by mass is used, preferably 10 to 45 parts by mass, more preferably 15 to 40 parts by mass.

The addition amount of the compound (b) used in the present invention is 50 to 90 parts by mass, preferably 55 to 90 parts by mass, when the total of the compounds (a) and (b) is 100 parts by mass. Preferably it is 60-85 mass parts.
Specific examples of the compound (b) include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, 1,2-bis (β-epi It is an episulfide compound having two episulfide groups in the molecule, such as thiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,4-bis (β-epithiopropylthio) butane. . (A) The compounds may be used alone or in combination of two or more. Among them, preferred specific examples are bis (β-epithiopropyl) sulfide (formula (3)) and / or bis (β-epithiopropyl) disulfide (formula (4)), and the most preferred specific example is bis ( β-epithiopropyl) sulfide.

The compound (c) used in the present invention is a compound having two SH groups. When the number of SH groups is 1, the viscosity increase rate during the prepolymerization reaction decreases, but the Tg and The refractive index tends to decrease. On the other hand, when the number of SH groups is 3 or more, the increase in viscosity during the preliminary polymerization reaction is remarkably increased.
The addition amount of the compound (c) used in the present invention is 1 to 20 parts by mass, preferably 2 to 18 parts by mass, when the total of the compounds (a) and (b) is 100 parts by mass. Preferably it is 3-15 mass parts, Most preferably, it is 4-12 mass parts, Most preferably, it is 5-10 mass parts. When the amount is larger than the above range, problems such as a decrease in heat resistance of the obtained optical material may occur.
(C) Specific examples of the compound include methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimer. Mercaptobutane, 1,6-dimercaptohexane, 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-mercaptoethylthio) ethane, 2,3-dimercapto-1-propanol, 1,3-dimercapto-2-propanol, Ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis 3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis ( 3-mercaptopropionate), 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 1,4-bis (mercapto) Methyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethylthiomethyl) ) -1,4-dithiane, 2,5-bis (mercaptome) L) -1-thian, 2,5-bis (2-mercaptoethyl) -1-thian, 2,5-bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 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, bis (4-mercaptomethylphenyl) sulfide, and the like. Among them, preferred specific examples include methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, bis (mercaptomethyl) ether, Bis (mercaptomethyl) sulfide, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercapto) Ethyl) -1,4-dithiane, 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-mercapto) Eniru) methane, bis (4-mercapto-phenyl) sulfide. More preferably methanedithiol, 1,2-dimercaptoethane, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2, 5-bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis ( Mercaptomethyl) benzene, particularly preferably 1,2-dimercaptoethane, bis (2-mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,3-bis (mercaptomethyl) Benzene, 1,4-bis (mercaptomethyl) benzene. These compounds having two SH groups may be used alone or in combination of two or more.

The compound (d) used in the present invention includes all the compounds represented by the above formula (2), but is obtained after polymerization and curing with a compatibility with other composition components and a polymerizable composition for optical materials. A low molecular weight compound is preferable so as not to lower the refractive index of the cured product, and specifically, a compound in which X in the formula (2) is the following structural formula (5). Among these compounds, 1,2,2,6,6-pentamethylpiperidyl methacrylate (the following structural formula (6)), 1,2,2,6,6-pentamethylpiperidyl acrylate are preferable. (The following structural formula (7)) and / or 1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate (the following structural formula (8)). Is easy 1,2,2,6,6-pentamethylpiperidyl methacrylate.

(D) The addition amount of a compound is 0.001-3 mass parts with respect to a total of 100 mass parts of (a) and (b) compound, Preferably it is 0.002-1 mass parts, More preferably Is 0.003 to 0.5 parts by mass.

The prepolymerization reaction, which is important in the method for producing the polymerizable composition for an optical material of the present invention, will be described in detail below. In the present invention, (a) a sulfur compound, (b) a compound having two episulfide groups in the molecule and (c) a compound having two SH groups, (d) a compound It has the process of obtaining a prepolymerization reaction liquid by carrying out a prepolymerization reaction as a prepolymerization catalyst. The reaction between sulfur and thiol is usually accelerated by heating regardless of the presence or absence of a catalyst, but the method of using a basic compound as a catalyst greatly improves the reaction rate and greatly increases the reaction time. This is preferable because it can be shortened. However, since the basic compound preferably acts as a polymerization catalyst for the episulfide group of the episulfide compound, the compound (a) and the compound (c) are used as a catalyst for the prepolymerization reaction in the presence of the compound (b). When a basic compound such as a metal alkoxide, an organic metal, or an amine compound is used, a prepolymerization reaction liquid (prepolymer) and / or a prepolymerization reaction liquid (prepolymer) and a polymerizable composition for an optical material comprising a polymerization catalyst There is a problem that the viscosity of the liquid becomes high or the pot life necessary for the pouring operation becomes short because the speed of increasing the viscosity is high. As a result of intensive studies, when a prepolymerization reaction was performed using the compound (d), which is a specific basic compound, as a prepolymerization catalyst, the compound (d) was episulfide due to steric hindrance due to substituents at both ends of the amino group. Since the activity of the compound as a polymerization catalyst is remarkably low, it has been found that the (a) compound and the (c) compound can be prepolymerized with high selectivity. Further, when the compound (d) was used as a prepolymerization catalyst, it was found that a prepolymerization reaction liquid (prepolymer) having no precipitation of sulfur as the compound (a) was obtained even at a reaction temperature near room temperature.

(A) 10-50 parts by mass of compound and (c) 1-20 parts by mass of compound (b) in the presence of 50-90 parts by mass of compound, (d) 0.001-3 parts by mass of compound as a preliminary polymerization catalyst A specific method for the polymerization reaction is that the compounds (a), (b), (c) and (d) are at 0 ° C to 45 ° C, preferably 5 ° C to 40 ° C, more preferably 10 ° C to 40 ° C. Stir and mix. At this time, all the components may be mixed in the same container under stirring at the same time, or may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container. The Reynolds number in mixing and stirring is important, and the Reynolds number represented by ρ × ω × d ² / μ needs to be 1.5 × 10 ³ to 1.5 × 10 ⁴ . However, ρ = liquid density (kg / m ³ ), ω = blade rotation speed (/ s), d = blade diameter (m), and μ = liquid viscosity (Pa · s).
The prepolymerization reaction in the present invention is a solid-liquid reaction of the solid (a) compound with the liquid (b) compound and (c) compound. Therefore, in order to complete the prepolymerization reaction in a short time, it is necessary to sufficiently renew the surface of the compound (a) which is a solid, but when the Reynolds number is smaller than 1.5 × 10 ³ , the surface renewal is sufficiently performed. It does not occur and the reaction rate is significantly slowed down. On the other hand, when the Reynolds number is larger than 1.5 × 10 ⁴ , the prepolymerization reaction proceeds rapidly, and it may be difficult to control the progress of the reaction. When the reaction proceeds rapidly, the viscosity of the prepolymerization reaction solution becomes very high, and the resulting polymerizable composition for optical materials is filtered and casting into a mold becomes difficult, so the workability is greatly reduced. To do. The viscosity at 20 ° C., which is a general casting temperature, is preferably 200 mPa · s or less, more preferably 100 mPa · s or less even after 3 hours required for normal casting operation. The stirring blade used for stirring may be a stirring blade such as a pitch paddle blade, a propeller blade, a pitched turbine blade, an anchor blade, a ribbon blade, and a portal blade, which are generally used. Preferably, the pitch paddle blade and the propeller blade are used. The pitched turbine blade.

The prepolymerization reaction may be carried out in the presence of a gas such as nitrogen, oxygen, hydrogen, hydrogen sulfide, etc., in any atmosphere such as sealed under normal pressure or increased or reduced pressure, or under reduced pressure. In order to maintain physical properties such as property and light resistance, it is preferable to reduce the partial pressure of oxidizing gas such as oxygen as much as possible.

Measuring the liquid chromatography, viscosity, specific gravity, refractive index and / or amount of gas generated during the prepolymerization reaction is necessary to produce a certain optical material by detecting the reaction progress and controlling the reaction. Is preferable. The stopping point of the prepolymerization reaction is appropriately set in consideration of the reprecipitation and viscosity of the compound (a) in the prepolymerization reaction liquid (prepolymer) to be obtained, but 50% or more of the compound (a) It is preferable to react.

The production method of the present invention includes a step of obtaining a polymerizable composition for an optical material by adding a polymerization catalyst to the prepolymerization reaction solution obtained as described above. At this time, a polymerization regulator may be added as necessary. In addition, the polymerizable composition for an optical material of the present invention is subjected to a composition component and / or a prepolymerization reaction of the present invention for the purpose of improving various performances such as oxidation resistance, weather resistance, dyeability, strength, and refractive index. It is also possible to add a compound capable of reacting with a part or all of the prepolymerization reaction solution obtained in this manner. Compounds having an SH group, epoxy compounds, iso (thio) cyanate compounds, carboxylic acid derivatives, carboxylic acid anhydride derivatives, phenol derivatives, amine compounds, vinyl compounds, allyl compounds that can react with some or all of the composition components Examples thereof include compounds, acrylic compounds, and methacrylic compounds.
Polymerization catalysts include amine compounds, phosphine compounds, quaternary ammonium salts, quaternary phosphonium salts, condensates of aldehydes and amine compounds, salts of carboxylic acids and ammonia, urethane derivatives, thiourethane derivatives, guanidine derivatives, Thiourea derivative, thiazole derivative, sulfenamide derivative, thiuram derivative, dithiocarbamate, xanthate, tertiary sulfonium salt, secondary iodonium salt, mineral acid, Lewis acid, organic acid, silicic acid, tetrafluoride Examples thereof include boric acid, peroxides, azo compounds, and acidic phosphate ester derivatives. These polymerization catalysts may be used alone or in combination of two or more. Among these, preferred specific examples include tetra-n-butylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, quaternary ammonium salts such as 1-n-dodecylpyridinium chloride, tetra-n-butylphosphonium bromide, Quaternary phosphonium salts such as tetraphenylphosphonium bromide can be mentioned. Among these, more preferred specific examples are triethylbenzylammonium chloride and / or tetra-n-butylphosphonium bromide. Examples of the polymerization regulator include halides of Group 13 to 16 elements in the long-term periodic table. These polymerization regulators may be used alone or in combination of two or more. Of these, preferred are halides of silicon, germanium, tin and antimony. More preferred are chlorides of silicon, germanium, tin and antimony, and further preferred are chlorides of germanium, tin and antimony having an alkyl group. Specific examples of the most preferred are dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyltin trichloride, dibutyldichlorogermanium, butyltrichlorogermanium, diphenyldichlorogermanium, phenyltrichlorogermanium, triphenylantimony dichloride.

It is preferable to perform a deaeration treatment before injecting the polymerizable composition for an optical material into a mold from the viewpoint of achieving high transparency of the optical material. The deaeration treatment is preferably performed during the preliminary polymerization reaction or when the polymerization catalyst is mixed in order to improve productivity. Deaeration is performed under reduced pressure. The deaeration process is performed under a reduced pressure of 0.001 to 100 torr for 1 minute to 24 hours at 0 ° C. to 45 ° C. The degree of vacuum is preferably 0.005 to 50 torr, more preferably 0.01 to 30 torr, and the degree of vacuum may be varied within these ranges. The deaeration time is preferably 5 minutes to 8 hours, more preferably 10 minutes to 4 hours. The temperature at the time of deaeration is preferably 5 ° C. to 40 ° C., more preferably 10 ° C. to 40 ° C., and the temperature may be varied within these ranges. In the deaeration treatment, renewing the interface of the polymerizable composition for an optical material by stirring, blowing of gas, vibration by ultrasonic waves, or the like is a preferable operation for enhancing the deaeration 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 mercaptans, but the types are particularly limited as long as the effects of the degassing treatment are expressed. Not.

In the optical material manufacturing method of the present invention, various additives such as known antioxidants, bluing agents, ultraviolet absorbers, deodorants and the like are added to the polymerizable composition for optical materials, and the practicality of the resulting material is obtained. Of course, it is possible to improve further. Further, when the optical material of the present invention is easily peeled off from the mold during polymerization, a known external and / or internal adhesion improver is added, or when it is difficult to peel off from the mold, a known external and / or internal mold release is added. It is also effective to add a property improver to improve the adhesiveness or releasability between the resulting optical material and the mold.

The manufacturing method of the optical material will be described in detail as follows. (A) Compound, (b) Compound, (c) Compound and (d) Polymerization for optical materials by adding a polymerization catalyst and, if necessary, a polymerization regulator to a prepolymerization reaction solution obtained by prepolymerization reaction A composition is obtained, and if necessary, a compound capable of reacting with some or all of the components of the prepolymerization reaction solution is mixed. At this time, various additives such as an adhesion improver or a releasability improver, an antioxidant, a bluing agent, an ultraviolet absorber, and a deodorant may be appropriately added. In mixing, the set temperature, the time required for this, etc., basically need only be the conditions that each component is sufficiently mixed, but the excessive temperature, time is an undesirable reaction between each raw material and additive, Furthermore, the viscosity is increased, making the casting operation difficult, and so on. The mixing temperature should be in the range of about 5 ° C to 40 ° C, and the preferred temperature range is 10 ° C to 40 ° C. The mixing time is 1 minute to 12 hours, preferably 5 minutes to 8 hours, and most preferably about 5 minutes to 4 hours. If necessary, the active energy ray may be blocked and mixed. Then, it is preferable to perform a deaeration process by the above-mentioned method. Immediately before the casting operation, it is necessary to purify these polymerizable compositions for optical materials by filtering impurities and the like in order to further improve the quality of the optical material of the present invention. The pore diameter of the filter used here is about 0.05 to 10 μm, and generally 0.1 to 5.0 μm is used. As the material of the filter, PTFE, PET, PP or the like is preferably used. The When filtration is not performed, or when filtration is performed with a filter having a pore diameter exceeding 10 μm, foreign materials are mixed in the optical material or transparency is lowered, so that it is usually unusable as an optical material. The polymerizable composition for optical material thus obtained is polymerized and cured by an electric furnace, an active energy ray generator or the like after being poured into a glass or metal mold, and the polymerization time is 0.1 to 100. The time is usually 1 to 48 hours, the polymerization temperature is -10 to 160 ° C, usually 0 to 140 ° C, and the polymerization initiation temperature is generally 0 to 40 ° C. The polymerization can be carried out by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature from 0.1 ° C. to 100 ° C./h, lowering the temperature from 0.1 ° C. to 100 ° C./h, and a combination thereof. Further, after the polymerization is completed, annealing the material at a temperature of 40 to 150 ° C. for about 5 minutes to 5 hours is a preferable treatment for removing distortion of the optical material. Furthermore, surface treatments such as dyeing, hard coating, antireflection, antifogging, antifouling and impact resistance can be performed as necessary.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Analysis of the polymerizable composition for optical material and the optical material obtained by polymerization were carried out by the following methods.
[viscosity]
The viscosity was measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV10M type).
[Measurement of heat resistance of optical materials]
Cut the sample to 3mm thickness, give 10g weight to the 0.5mmφ pin, raise the temperature from 30 ° C to 10 ° C / min, perform TMA measurement (Seiko Instruments, TMA / SS6100), and measure the softening point did.
[Refractive index of optical material, Abbe number]
The refractive index and Abbe number of the optical material were measured using a digital precision refractometer (manufactured by Shimadzu Corporation, KPR-200), and the refractive index at the e-line at 25 ° C. and the Abbe number at the d-line.
[(A) Measurement of Compound Particle Size]
The median diameter was measured for the sample using the particle size distribution meter (the product made from HORIBA, LA-300).

Example 1
(A) 16.8 parts by mass of sulfur as a compound having a median diameter of 100 μm, (b) 83.2 parts by mass of bis (β-epithiopropyl) sulfide (hereinafter referred to as b-1 compound) as the compound, (c ) Bis (2-mercaptoethyl) sulfide (hereinafter referred to as “c-1 compound”) as 8.8 parts by mass as compound (d) 1,2,2,6,6-pentamethylpiperidyl methacrylate (hereinafter referred to as “compound”) (referred to as d-1 compound) 0.02 parts by mass, and using a 4-blade 45 ° C. inclined pitch paddle blade with a blade diameter of 0.078 m under normal pressure in a nitrogen atmosphere, the stirring speed is 5 / s. The mixture was stirred and reacted. The viscosity at the start of the reaction was 15 mPa · s, the liquid density was 1253 Kg / m ³ , and the Reynolds number was 2.5 × 10 ³ . The preliminary reaction product 1.2 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 48 mPa · s. 0.75 part by mass of bis (2-mercaptoethyl) sulfide, 0.25 part by mass of di-n-butyltin dichloride, and 0.10 part by mass of tetrabutylammonium bromide were added to the obtained reaction solution. Therefore, the preliminary reaction time was 1.2 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The resulting composition had a viscosity at 20 ° C. of 50 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 54 mPa · s. The obtained polymerizable composition for an optical material was degassed at 10 Torr, filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 2
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Example 2 of Table 1. The preliminary reaction product after 0.75 hour from the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 40 mPa · s. After adding 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride, and 0.10 parts by mass of tetrabutylammonium bromide to the obtained reaction solution, desorption at 10 Torr. While cooling, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 0.85 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 50 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 62 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 3
Preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were as shown in Example 3 in Table 1. The preliminary reaction product 1.5 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 62 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 1.6 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 64 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 82 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 4
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were as shown in Example 4 in Table 1. The preliminary reaction product 0.4 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 38 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 0.5 hour. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 40 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 47 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 5
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Example 5 of Table 1. The preliminary reaction product 0.35 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 86 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 0.45 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 82 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 96 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 6
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were as shown in Example 6 in Table 1. The preliminary reaction product 1.8 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 52 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 1.9 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 55 mPa · s, and the viscosity after being held at 20 ° C. for 3 hours was 59 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 7
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were as shown in Example 7 in Table 1. The preliminary reaction product 1.5 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 88 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 1.6 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 84 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 95 mPa · s. The obtained polymerizable composition for an optical material was filtered with a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 8
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Example 8 in Table 1. The preliminary reaction product 1.2 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 80 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 0.9 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 76 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 86 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 9
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Example 9 in Table 1. The preliminary reaction product 1.5 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 88 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 1.6 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 84 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 95 mPa · s. The obtained polymerizable composition for an optical material was filtered through a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Example 10
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Example 10 of Table 1. The preliminary reaction product after 2.0 hours from the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 96 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.5 hours to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 2.5 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 92 mPa · s, and the viscosity after holding at 20 ° C. for 3 hours was 108 mPa · s. The obtained polymerizable composition for an optical material was filtered with a 1 μm PTFE membrane filter, and poured into a mold having a thickness of 2.5 mm composed of a glass plate and a gasket. The molding mold was gradually heated from 20 ° C. to 100 ° C. over 21 hours to be polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical material. The evaluation results of the refractive index, Abbe number, heat resistance and appearance of the obtained optical material are shown together in Table 1.

Comparative Example 1
A preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 1 in Table 2. The viscosity at the start of the reaction was 10 mPa · s, and the Reynolds number was 1.3 × 10 ³ . Residual sulfur was observed in the preliminary reaction product after 3.0 hours from the start of the reaction. The results are shown in Table 2.

Comparative Example 2
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 2 in Table 2. Residual sulfur was observed in the preliminary reaction product after 3.0 hours from the start of the reaction. The results are shown in Table 2.

Comparative Example 3
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 3 in Table 2. Residual sulfur was observed in the preliminary reaction product after 3.0 hours from the start of the reaction. The results are shown in Table 2.

Comparative Example 4
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 4 in Table 2. Residual sulfur was observed in the preliminary reaction product after 3.0 hours from the start of the reaction. The results are shown in Table 2.

Comparative Example 5
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 5 in Table 2. The pre-reacted material 0.1 hours after the start of the reaction was yellow and transparent, no precipitation of solids such as sulfur was observed, and the viscosity at 20 ° C. was 325 mPa · s. 0.75 parts by mass of bis (2-mercaptoethyl) sulfide, 0.25 parts by mass of di-n-butyltin dichloride and 0.10 parts by mass of tetrabutylammonium bromide are added to the resulting reaction solution, and degassed at 10 Torr. However, it took 0.1 hour to cool to 20 ° C. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 1.6 hours. The obtained reaction liquid was yellow and transparent, and precipitation of solids, such as sulfur, was not seen. The viscosity of the obtained composition at 20 ° C. was 420 mPa · s, and the viscosity after being held at 20 ° C. for 3 hours was 860 mPa · s.

Comparative Example 6
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 6 in Table 2. D-2 did not dissolve in the pre-reacted material after 1 hour from the start of the reaction. In addition, residual sulfur was also confirmed. The results are shown in Table 2.

Comparative Example 7
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 7 in Table 2. 0.3 hours after the start of the reaction, the preliminary reaction product rapidly polymerized, and no preliminary reaction solution was obtained. The results are shown in Table 2.

Comparative Example 8
The preliminary reaction was performed in the same procedure as in Example 1, and the reaction conditions were the same as those shown in Comparative Example 8 in Table 2. The preliminary reaction product 0.2 hours after the start of the reaction polymerized rapidly, and no preliminary reaction product was obtained. The results are shown in Table 2.

Comparative Example 9
(A) 20 parts by mass of sulfur having a median diameter of 300 μm as the compound, and (b) 80 parts by mass of bis (β-epithiopropyl) sulfide as the compound were heated to 65 ° C. and mixed well until 1.8%. It took time. Subsequently, 0.5 part by mass of 2-mercapto-1-methylimidazole was added and reacted at 60 ° C. for 0.9 hours. Thereafter, the obtained resin composition was cooled to 20 ° C. This took 2 hours. Thereto, 5 parts by mass of benzyl mercaptan, 0.03 parts by mass of triethylbenzylammonium chloride and 0.2 parts by mass of di-n-butyltin dichloride were added and mixed well, and a uniform solution was added. It was. Therefore, the preliminary reaction time combining the reaction time and the cooling time was 4.7 hours.

ｂ−１：ビス（β−エピチオプロピル）スルフィド
ｂ−２：ビス（β−エピチオプロピル）ジスルフィド
ｃ−１：ビス（２−メルカプトエチル）スルフィド
ｃ−２：１，３ビス（メルカプトメチル）ベンゼン
ｄ−１：１，２，２，６，６−ペンタメチルピペリジルメタクリレ−ト
ｄ−２：１，２，２，６，６−ペンタメチルピペリジルアクリレ−ト
ｄ−３：１，２，２，６，６−ペンタメチルピペリジル−４−ビニルベンゾエート

b-1: bis (β-epithiopropyl) sulfide b-2: bis (β-epithiopropyl) disulfide c-1: bis (2-mercaptoethyl) sulfide c-2: 1,3 bis (mercaptomethyl) Benzene d-1: 1,2,2,6,6-pentamethylpiperidyl methacrylate d-2: 1,2,2,6,6-pentamethylpiperidyl acrylate d-3: 1,2 , 2,6,6-Pentamethylpiperidyl-4-vinylbenzoate

ＭＭＩ：１−メチル−２−メルカプトイミダゾール
ＴＭＰＭ：２，２，６，６−テトラメチルピペリジルメタクリレ−ト

MMI: 1-methyl-2-mercaptoimidazole TMPM: 2,2,6,6-tetramethylpiperidyl methacrylate

Claims (1)

10 to 50 parts by mass of the following (a) compound having a median diameter of 5 to 500 μm, 50 to 90 parts by mass of the following (b) compound (provided that the total of the (a) compound and the (b) compound is 100 parts by mass) And (c) 1-20 parts by mass of the following compound, and (d) 0.001-3 parts by mass of the following compound as a prepolymerization catalyst for prepolymerization reaction to obtain a prepolymerization reaction liquid, and the prepolymerization reaction liquid The method for producing a polymerizable composition for an optical material comprising a step of adding a polymerization catalyst to a reaction temperature of 0 ° C. to 45 ° C. and a Reynolds number of 1.5 × 10 ^{3 to} 1.5 ×. method for producing an optical material for the polymerizable composition, which comprises carrying out the stirring of 10 ^4.
(A) Sulfur ((a) compound)
(B) Compound having two episulfide groups represented by the following formula (1) in the molecule (compound (b))

(Here, m represents an integer of 0 to 4, and n represents an integer of 0 to 1.)
(C) Compound having two SH groups ((c) compound)
(D) A compound represented by the following formula (2) (compound (d)).

(R is an alkyl group having 1 to 4 carbon atoms, X is an organic group having 2 to 11 carbon atoms having either a vinyl group, a vinylidene group or a vinylene group)