JP2014047334A - Production method of polymerizable composition for optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a polymerizable composition for optical material in which when producing the polymerizable composition for optical material using sulfur, a compound having intramolecular episulfide group, and a compound having an intramolecular SH group, a side reaction in a preliminary polymerization reaction and viscosity increase due to excessive reaction progress can be suppressed, and productivity is favorable without generating striae.SOLUTION: A preliminary reaction temperature is made near to a room temperature that is near to a polymerization initiation temperature, in a production method of a polymerizable composition for optical material from a mixture including inorganic compound having a sulfur atom, a compound having an episulfide group, and an SH group inclusion organic compound having two intermolecular SH groups.

Description

  The present invention relates to a method for producing a highly productive composition for low-viscosity optical materials, and further relates to optical materials (optical resin materials) such as plastic lenses, prisms, optical fibers, information recording bases, and filters using the composition. The optical material of the present invention is suitably used as a plastic lens, particularly a spectacle lens.

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 the case of a product, there is a problem that it precipitates or the dissolution becomes incomplete when the concentration of the compound is high.
Therefore, a method has been proposed in which an inorganic compound having a sulfur atom and / or a selenium atom and a sulfur-containing organic compound such as a polyepisulfide compound capable of reacting with the inorganic compound are preliminarily polymerized (see Patent Document 2). . However, the preliminary polymerization reaction of the above-mentioned reference is usually carried out at 50 ° C. to 70 ° C., and it is necessary to cool the composition to about room temperature which is the polymerization starting temperature after mold injection. However, since the preliminary reaction temperature is high, there is a problem that the viscosity of the polymerizable composition increases due to the progress of side reactions or a significant temperature decrease due to cooling. There are problems such as shortening of temperature and generation of striae due to the difference between the temperature after cooling and the initial holding temperature of the polymerization process. For this reason, a production method capable of a prepolymerization reaction at a reaction temperature close to room temperature of a polymerizable composition for an optical material containing a sulfur-containing organic compound such as a polyepisulfide compound and an inorganic compound having a sulfur atom and / or a selenium atom is desired. It was.

Japanese Patent Laid-Open No. 2001-2783 JP 2004-197005 A

An object of the present invention is to perform prepolymerization without causing striae when producing a polymerizable composition for an optical material using a compound having sulfur, an episulfide group in the molecule, and a compound having an SH group in the molecule. An object of the present invention is to provide a method for producing a polymerizable composition for an optical material with good productivity capable of suppressing an increase in viscosity due to reaction side reaction or excessive reaction progress.

As a result of intensive studies in view of such circumstances, the present inventors have found that an inorganic compound having a sulfur atom, a compound having an episulfide group, and a mixture containing an SH group-containing organic compound having two SH groups in the molecule In the method for producing a polymerizable composition for optical materials from the above, by making the preliminary reaction temperature near room temperature close to the polymerization initiation temperature, side reactions during the preliminary reaction and excessive reaction progress during cooling after the preliminary reaction are suppressed. As a result, the inventors have found that the viscosity of the polymerizable composition for optical materials can be kept low without causing striae, and have reached 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（以下（ｃ）化合物）
［２］：前記混合物が、予備反応触媒として下記（ｄ）化合物を含むことを特徴とする［１］記載の光学材料用重合性組成物の製造方法。
（ｄ）下記（２）式で表される化合物（以下（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）
［３］：［１］または［２］記載の製造方法で製造された光学材料用重合性組成物を重合初期温度Ｔ３（ただし、Ｔ３はＴ２−１０℃〜Ｔ２＋１０℃であり、かつ、０〜４０℃である）として重合させることを特徴とする光学材料の製造方法。
［４］：［３］記載の方法により製造される光学材料。 [1]: A preliminary reaction solution is obtained by prereacting a mixture of the following (a) compound, the following (b) compound, and the following (c) compound at a reaction temperature T1 (T1 is 0 to 45 ° C.). Production of a polymerizable composition for an optical material, characterized in that a polymerization catalyst is added to the reaction solution and the temperature is T2 (where T2 is T1-10 ° C to T1 + 10 ° C and 0-45 ° C). Method.
(A) Sulfur (hereinafter referred to as (a) compound)
(B) Compound having two episulfide groups represented by the following formula (1) in the molecule (hereinafter referred to as 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 (hereinafter referred to as (c) compound)
[2] The method for producing a polymerizable composition for an optical material according to [1], wherein the mixture contains the following compound (d) as a pre-reaction catalyst.
(D) A compound represented by the following formula (2) (hereinafter referred to as (d) compound).

(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)
[3]: The polymerizable composition for an optical material produced by the production method described in [1] or [2] is subjected to polymerization initial temperature T3 (where T3 is T2-10 ° C. to T2 + 10 ° C., and 40.degree. C.), and a method for producing an optical material.
[4]: An optical material produced by the method according to [3].

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 reaction temperature is set to about room temperature. Thus, the temperature of the composition does not exceed 50 ° C. in the manufacturing process unlike the conventional method. For this reason, side reactions are suppressed, and an increase in the viscosity of the polymerizable composition is suppressed, and productivity can be improved.

In view of productivity, it is desirable that the polymerizable composition for an optical material has a low viscosity that facilitates filtration and injection into a mold, and preferably has a viscosity of 200 mPa · s or less at the temperature at the time of casting. Preferably, the viscosity at the casting temperature is 100 mPa · s or less. In view of industrial mass production, it takes about 3 hours as the time required to inject the total amount of the prepared composition into the mold. During this time, the viscosity of the polymerizable composition may not exceed the above viscosity. preferable.

The purity of sulfur as the compound (a) used in the present invention is 98% or more. If the purity is less than 98%, a phenomenon in which the optical material is spoiled easily due to the influence of impurities is likely to occur. However, if the purity is 98% or more, the phenomenon in which the spider is generated is eliminated. 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. Preferably, it is finely divided finely divided sulfur that is easily dissolved during the production of the polymerizable composition for an optical material. (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 35 parts by mass.

ビス（β−エピチオプロピル）スルフィド 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.

Bis (β-epithiopropyl) sulfide

ビス（β−エピチオプロピル）ジスルフィド

Bis (β-epithiopropyl) disulfide

The compound (c) used in the present invention is a compound having two SH groups. When the number of SH groups is 1, the rate of increase in viscosity during the prepolymerization reaction is reduced, but the heat resistance and refractive index of the obtained optical material are likely to decrease. When the number of SH groups is 3 or more, prepolymerization is performed. This is not preferable because the increase in viscosity during the 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. (C) When the ratio of a compound is smaller than the said range, the effect which suppresses the viscosity increase rate at the time of prepolymerization reaction will become small. On the other hand, when the amount is larger than the above range, there arises a problem that the heat resistance of the obtained optical material is lowered.
(C) Specific examples of the compound include methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimercapto Butane, 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 ( -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 (mercaptomethyl) ) 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 (mercaptomethi ) -1-thian, 2,5-bis (2-mercaptoethyl) -1-thian, 2,5-bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, , 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- Mercaptoethyloleates methylphenyl) 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.

１，２，２，６，６−ペンタメチルピペリジルメタクリレ−ト

１，２，２，６，６−ペンタメチルピペリジルアクリレ−ト

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 In the present invention, the compound (d) can be used as a preliminary reaction catalyst. (D) The compound includes all the compounds represented by the formula (2), but is compatible with other composition components and the refractive index of the cured product obtained after polymerization and curing of the polymerizable composition for optical materials. Is a compound having a low molecular weight, in particular, 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.

1,2,2,6,6-pentamethylpiperidyl methacrylate

1,2,2,6,6-pentamethylpiperidyl acrylate

1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate

Details of the prepolymerization reaction for obtaining the polymerizable composition for an optical material of the present invention will be described below. The present invention is characterized in that a prepolymerization reaction is performed in the presence of the compound (b) with a compound (a) having two sulfur groups as the compound (a) and two SH groups as the compound (c). The reaction between sulfur and thiol is usually accelerated by heating in the presence or absence of a basic compound, but this is preferable because the reaction time can be greatly shortened by a method using a basic compound. However, since the basic compound preferably acts as a polymerization catalyst for the episulfide compound, when a normal basic compound is used as the catalyst for the prepolymerization reaction in the presence of the compound (a) and the compound (c), There are problems such that the viscosity of the pre-reacted product (prepolymer) and / or the polymerizable composition comprising the pre-reacted product (prepolymer) is increased, the speed of increasing the viscosity is high, and the pot life is shortened. As a result of intensive studies, when a prepolymerization reaction was performed using 0.001 to 3 parts by mass of the compound (d), which is a specific basic compound, as a prepolymerization catalyst, the compound (d) depends on substituents at both ends of the amino group. Due to the steric hindrance, the activity as a polymerization catalyst for the episulfide compound is remarkably low, and it has been found that the (a) compound and the (c) compound can be prepolymerized with high selectivity. Furthermore, when the compound (d) was used as a prepolymerization catalyst, it was found that a prereacted product (prepolymer) without precipitation of sulfur as the compound (a) was obtained even at a reaction temperature near room temperature.

That is, in the present invention, the specific method of prepolymerizing the compound (a) and the compound (c) in the presence of the compound (b) is preferably the compounds (a), (b) and (c). (D) A compound is added and stirred and mixed at 0 ° C to 45 ° C, preferably 5 ° C to 40 ° C, more preferably 10 ° C to 40 ° C. In this case, the addition method (a) and (b) is carried out while controlling the temperature of the compound to the reaction temperature, and even if the compounds (c) and (d) are added after mixing, the compounds (a) and (b) (C) Even if a part of the compound is mixed while controlling the temperature to the reaction temperature, and the remainder of the compound (c) and the compound (d) are added after mixing, the compounds (a), (b) and (c) are added. The compound (d) may be added after mixing while controlling the reaction temperature.
The 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, but the color tone, heat resistance, In order to maintain physical properties such as light resistance, it is preferable to reduce the partial pressure of oxidizing gas such as oxygen as much as possible.
In the prepolymerization reaction, liquid chromatography and / or measuring the viscosity and / or specific gravity and / or refractive index and / or the amount of gas generated can be determined by detecting the degree of reaction progress and controlling the reaction. It is preferable when manufacturing an optical material. The stopping point of the prepolymerization reaction is appropriately set in consideration of the reprecipitation and viscosity of the compound (a) in the prereacted product (prepolymer) to be obtained, but 50% or more of the compound (a) is reacted. It is preferable to make it. The prepolymerization reaction time can be controlled by the amount of the compound (d) added and the reaction temperature. However, if the reaction time is too short, it is difficult to control the stopping point, and if it is too long, the productivity will be poor, and therefore, from 10 minutes. 5 hours, preferably 10 minutes to 3 hours, more preferably 10 minutes to 2 hours.
Furthermore, if necessary, various additives that can improve the performance of the obtained optical material such as an antioxidant, bluing agent, ultraviolet absorber, deodorant, etc. may be added as appropriate during the prepolymerization reaction. I do not care.

A specific method for preparing a polymerizable composition using the obtained preliminary reaction liquid (prepolymer) is to mix a polymerization catalyst necessary for polymerization and curing with the preliminary reaction liquid. At this time, the polymerization catalyst can be added in advance dissolved in a compound capable of reacting with at least one component of the component (b), the compound (c) or the prepolymerization reaction product. A method of adding it by dissolving in is preferable. In mixing the polymerization catalyst, the set temperature, the time required for this, etc. may be basically the conditions that each component is sufficiently mixed, but the excessive temperature and time are not preferable between the respective raw materials and additives. This is not appropriate, for example, when a reaction occurs and the viscosity is increased to make the casting operation difficult. 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. Further, if necessary, it can be mixed under reduced pressure, and the reduced pressure condition is 0.001 to 100 torr, preferably 0.005 to 50 torr, more preferably 0.01 to 30 torr. The degree of decompression may be varied within the range.
Further, if necessary, it is preferable to add a polymerization regulator in order to appropriately control the polymerization reaction for obtaining the optical material when mixing the polymerization catalyst.
Further, if necessary, when mixing the polymerization catalyst, such as a compound capable of reacting with at least one of the components of the prepolymerization reaction product, antioxidant, bluing agent, ultraviolet absorber, deodorant, etc. Various additives and the like may be added as appropriate.

As the polymerization catalyst in the present invention, amine compounds, phosphine compounds, quaternary ammonium salt derivatives, quaternary phosphonium salt derivatives, condensates of aldehyde and amine compounds, salts of carboxylic acid and ammonia, urethane compounds, thiourethanes Compound, guanidine compound, thiourea compound, thiazole compound, sulfenamide compound, thiuram compound, dithiocarbamate derivative, xanthate, tertiary sulfonium salt derivative, secondary iodonium salt derivative, mineral acid, Lewis acid, organic Examples thereof include acids, silicic acid, tetrafluoroboric acid, peroxides, azo compounds, and acidic phosphate 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.

As a polymerization regulator in this invention, the halide of the 13th-16th group element in a long-term periodic table can be mentioned. 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.

The compound capable of reacting with at least one component of the prepolymerization reaction product in the present invention can be added for the purpose of improving various performances such as oxidation resistance, weather resistance, dyeability, strength, refractive index, Examples of the compound include an SH group, an epoxy compound, an iso (thio) cyanate compound, a carboxylic acid derivative, a carboxylic acid anhydride, a phenol derivative, an amine compound, a vinyl compound, an allyl compound, an acrylic compound, and a methacrylic compound.

It is preferable to perform a degassing treatment before injecting the polymerizable composition for an optical material prepared by the above method into a mold from the viewpoint of reducing the rate of increase in the viscosity of the polymerizable composition and the high transparency of the optical material. . The deaeration treatment includes a reaction product obtained by prepolymerizing (a) compound, (b) compound, (c) compound and (d) compound, a compound capable of reacting with some or all of the composition components, It is carried out under reduced pressure before, during or after mixing of the additive, polymerization catalyst, polymerization regulator and the like. Preferably, it is performed under reduced pressure during or after mixing. The deaeration process is performed under a reduced pressure of 0.001 to 100 torr for 1 minute to 24 hours at 0 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, which accelerate the increase in viscosity of the polymerizable composition for optical materials. The type is not particularly limited as long as the above effect is exhibited.

Controlling the temperature of the casting liquid before pouring the polymerizable composition for optical materials into the mold is important for improving workability. It is not desirable to greatly change the temperature from the pre-reaction temperature due to the effect of viscosity increase due to reaction progress or temperature decrease, preferably from + 10 ° C. to −10 ° C., more preferably from + 5 ° C. to −5 ° C. from the pre-reaction temperature. . In addition, it is effective to obtain a good optical material by keeping the casting solution temperature close to the initial polymerization temperature. This temperature control has the effect of preventing striae due to convection due to the difference between the casting liquid temperature and the temperature of the polymerization furnace. This striae prevention effect is maximized when the composition temperature is equal to the furnace temperature, but when the casting liquid temperature is too low, problems such as condensation and (a) compound precipitation cause the casting liquid temperature to be too high. In this case, since the problem that the rate of increase in viscosity is increased, the casting liquid temperature is preferably + 10 ° C. to −10 ° C., more preferably + 5 ° C. to −5 ° C. with respect to the initial polymerization temperature, And it is 0 degreeC-45 degreeC, Preferably it is 10 degreeC-40 degreeC, More preferably, it is 15 degreeC-35 degreeC.

Immediately before injection into the mold, it is preferable to purify these polymerizable compositions by filtering impurities and the like with a filter 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 thus obtained is injected into a glass or metal mold and then polymerized and cured by an electric furnace or an active energy ray generator. The polymerization time is usually 0.1 to 100 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.

The striae of the optical material obtained in the present invention is a portion in which the material component having a refractive index different from that of the base material in the optical material is formed in a cotton-like or layered form, and the polymerizability due to polymerization heat generation during polymerization curing It is caused by minute density in the optical material due to the convection of the composition, non-uniform progression of the polymerization reaction, or the like. Usually, when performing striae evaluation of an optical material, it is transmitted through the optical material (optical lens) from which the mercury lamp light source is manufactured, and the transmitted light is projected onto a white plate, and the appearance striae level is evaluated according to the following criteria. That is, if no striae are visually confirmed, the striae is 1st grade, and if the striae of visible limit are confirmed by thin and dispersed striae, the striae is 2nd grade, and the striae is 2nd grade or higher. When confirmed, it is classified as striae class 3, and 90% or more and less than 95% of the manufactured optical material is preferably striae class 1 and striae class 3 is less than 5%. % Or more and less than 95% is more preferably free of striae 1 and striae 3 optical materials, and 95% or more of the manufactured optical material is free of striae 1 and striae 3 optical materials. Further preferred.

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]
Using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV10M type), the viscosity at each casting liquid temperature was measured.
[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.
[Strategic evaluation of optical materials (optical lenses)]
The mercury lamp light source was transmitted through the optical material (optical lens), the transmitted light was projected onto a white plate, and the appearance striae level was evaluated according to the following criteria. If no striae are confirmed by visual inspection, the striae is grade 1; if striations that are visible in the thin and dispersed striae are confirmed, striae 2 is confirmed; In the case of struggle, it was classified as third grade. In addition, 100 optical lenses were prepared and evaluated according to the following five levels.
A: There are 95 or more striae class 1 optical lenses out of 100, and there are no striae class 3 optical lenses.
B: The number of striae class 1 optical lenses is 90 or more and less than 95 out of 100, and there is no striae class 3 optical lens.
C: The number of striae class 1 optical lenses is 90 or more and less than 95 out of 100 sheets, and the number of striae class 3 optical lenses is less than 5.
D: The number of striae class 1 optical lenses is 80 or more and less than 90 out of 100 sheets, and the number of striae class 3 optical lenses is 5 or more and less than 10.
E: 10 or more striae grade 3 optical lenses out of 100.

Example 1
(A) 15.5 parts by mass of sulfur as a compound, (b) 84.5 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) 7.7 parts by mass, (d) 1,2,2,6,6-pentamethylpiperidyl methacrylate (hereinafter referred to as d-1 compound) as compound ) 0.016 parts by mass were added and reacted at 30 ° C. for 1.0 hour under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. The composition was cooled to 25 ° C., the hourly temperature, to obtain a polymerizable composition for an optical material without turbidity. The viscosity of the obtained composition at 25 ° C., which is the casting temperature, was 40 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 82 mPa · s.
(Plastic lens manufacturing method)
The obtained polymerizable composition was filtered through a 1.0 μm PTFE membrane filter to obtain a 300 mold set composed of a glass mold (design power (S / C) -10.0D / 0.0D) and a gasket. Injected. These molds are set in an oven in an oven at an initial holding temperature of 5, 20, 35 ° C. to 100 ° C. over 22 hours. I got a lens. Table 1 shows the results of the optical lens striae, refractive index, Abbe number, and heat resistant softening point (Tg).

Example 2
(A) 15.5 parts by mass of sulfur as the compound, 84.5 parts by mass of b-1 compound as compound (b), 7.7 parts by mass of c-1 compound, and 0.005 of d-1 compound as (d) compound Mass parts were added and reacted at 40 ° C. for 1.5 hours under normal pressure of nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. The composition was cooled to 30 ° C., the hourly temperature, to obtain a polymerizable composition for an optical material without turbidity. The viscosity of the obtained composition at 30 ° C., which is the casting temperature, was 36 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 110 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Example 3
(A) 15.5 parts by mass of sulfur as a compound, (b) 84.5 parts by mass of a b-1 compound, 7.7 parts by mass of a c-1 compound, (d) 1, 2, 2, 6 as a compound , 6-Pentamethylpiperidyl acrylate (hereinafter referred to as d-2 compound) (0.016 parts by mass) was added and reacted at 25 ° C. for 1.5 hours under normal pressure of nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. A polymerizable composition for optical materials was obtained which was kept at 25 ° C. which is the hourly temperature and was not turbid. The viscosity at 25 ° C., which is the casting temperature of the obtained composition, was 42 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 85 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Example 4
(A) 16.0 parts by mass of sulfur as a compound, 84.0 parts by mass of b-1 compound as (b) compound, 1,3-bis (mercaptomethyl) benzene (hereinafter referred to as c-2 compound) as (c) compound 8.7 parts by mass) and 0.3 part by mass of the d-1 compound were added, and the reaction was carried out at 5 ° C. for 0.8 hours under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-2 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added, and cast while degassing at 10 Torr. It heated to 15 degreeC which is hour temperature, and the polymeric composition for optical materials without a turbidity was obtained. The viscosity of the obtained composition at 15 ° C., which is the casting temperature, was 160 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 180 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Example 5
(A) 10.0 parts by mass of sulfur as a compound, (b) 90.0 parts by mass of bis (β-epithiopropyl) disulfide (hereinafter referred to as b-2 compound) as the compound, (c) c-1 as the compound 4.1 parts by mass of the compound and 0.1 parts by mass of the d-1 compound were added and reacted at 5 ° C. for 1.2 hours under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. It heated to 15 degreeC which is hour temperature, and the polymeric composition for optical materials without a turbidity was obtained. The viscosity of the obtained composition at 15 ° C., which is the casting temperature, was 90 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 103 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Example 6
(A) 20.0 parts by mass of sulfur as a compound, (b) 80.0 parts by mass of a b-1 compound, 9.1 parts by mass of a c-1 compound, (d) 0.016 parts of a d-1 compound as a compound A part by mass was added, and the mixture was reacted at 30 ° C. under a nitrogen atmosphere and normal pressure for 1.5 hours. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. The composition was cooled to 20 ° C., which is an hourly temperature, to obtain a polymerizable composition for an optical material without turbidity. The viscosity of the obtained composition at a casting temperature of 20 ° C. was 82 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 115 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Example 7
(A) 30.0 parts by mass of sulfur as a compound, 70.0 parts by mass of b-1 compound as compound (b), 14.1 parts by mass of c-1 compound, and 0.033 of d-1 compound as (d) compound Mass parts were added and reacted at 30 ° C. for 1.0 hour under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. The composition was cooled to 25 ° C., the hourly temperature, to obtain a polymerizable composition for an optical material without turbidity. The viscosity of the obtained composition at 25 ° C., which is the temperature at the time of casting, was 55 mPa · s, and the viscosity after holding at the temperature at the time of casting for 3 hours was 96 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Comparative Example 1
(A) 15.5 parts by mass of sulfur as a compound, (b) 84.5 parts by mass of a b-1 compound, 8.6 parts by mass of a c-1 compound, (d) without adding a compound, and under a nitrogen atmosphere and normal pressure The reaction was continued at 60 ° C. for 24 hours, but sulfur remained.

Comparative Example 2
(A) 15.5 parts by mass of sulfur as the compound, 84.5 parts by mass of b-1 compound as compound (b), 7.7 parts by mass of c-1 compound, and 0.016 of d-1 compound as compound (d) Mass parts were added and reacted at 50 ° C. for 1.0 hour under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. The composition was cooled to 40 ° C., the hourly temperature, to obtain a polymerizable composition for an optical material having no turbidity. The viscosity of the obtained composition at 40 ° C., which is the casting temperature, was 160 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 820 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Comparative Example 3
(A) 15.5 parts by mass of sulfur as a compound, 84.5 parts by mass of b-1 compound as compound (b), 8.6 parts by mass of c-1 compound, 0.2 d-1 compound as compound (d) Part by mass was added and reacted at −5 ° C. under a nitrogen atmosphere and normal pressure for 1.0 hour, but sulfur remained.

Comparative Example 4
(A) 15.5 parts by mass of sulfur as the compound, 84.5 parts by mass of b-1 compound as compound (b), 7.7 parts by mass of c-1 compound, and 0.016 of d-1 compound as compound (d) Mass parts were added and reacted at 45 ° C. for 1.0 hour under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. The composition was cooled to 25 ° C., the hourly temperature, to obtain a polymerizable composition for an optical material without turbidity. The viscosity at 25 ° C., which is the casting temperature of the obtained composition, was 210 mPa · s, and the viscosity after holding at the casting temperature for 3 hours was 450 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Comparative Example 5
(A) 15.5 parts by mass of sulfur as the compound, 84.5 parts by mass of b-1 compound as compound (b), 7.7 parts by mass of c-1 compound, and 0.016 of d-1 compound as compound (d) A part by mass was added, and the mixture was reacted at 25 ° C. for 1.5 hours under normal pressure in a nitrogen atmosphere. To the obtained reaction solution, 0.9 part by mass of c-1 compound, 0.37 part by mass of di-n-butyltin dichloride and 0.16 part by mass of triethylbenzylammonium chloride were added and cast while degassing at 10 Torr. It heated to 40 degreeC which is hour temperature, and the polymeric composition for optical materials without a turbidity was obtained. The viscosity of the obtained composition at 40 ° C., which is the casting temperature, was 30 mPa · s, and the viscosity after being held at the casting temperature for 3 hours was 260 mPa · s.
Subsequently, an optical lens was obtained by the method described in Example 1. The results are shown in Table 1.

Claims (4)

A pre-reaction solution is obtained by prereacting a mixture of the following (a) compound, the following (b) compound, and the following (c) compound at a reaction temperature T1 (T1 is 0 to 45 ° C.), and the pre-reaction solution is polymerized. A method for producing a polymerizable composition for an optical material, wherein a catalyst is added and the temperature is T2 (where T2 is T1-10 ° C to T1 + 10 ° C and 0-45 ° C).
(A) Sulfur (hereinafter referred to as (a) compound)
(B) Compound having two episulfide groups represented by the following formula (1) in the molecule (hereinafter referred to as 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 (hereinafter referred to as (c) compound) The said mixture contains the following (d) compound as a pre-reaction catalyst, The manufacturing method of the polymeric composition for optical materials of Claim 1 characterized by the above-mentioned.
(D) A compound represented by the following formula (2) (hereinafter referred to as (d) compound).

(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) The polymerizable composition for an optical material produced by the production method according to claim 1 or 2 is subjected to polymerization initial temperature T3 (where T3 is T2-10 ° C to T2 + 10 ° C and 0-40 ° C). And a method of producing an optical material.   An optical material produced by the method according to claim 3.