JP6048012B2 - Manufacturing method of optical material - Google Patents

Description

The present invention relates to a preliminary reaction solution obtained by subjecting a compound having two sulfur and episulfide groups in the molecule and a compound having one or more SH groups in the molecule to a prepolymerization reaction using a hindered amine having a specific structure as a preliminary polymerization catalyst, The present invention relates to an optical material obtained by polymerizing and curing a polymerizable composition containing a polymerization catalyst and having excellent releasability and substantially no striae, and a method for producing the same.

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.
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). .
In the above-mentioned reference, although an optical material having a high refractive index can be obtained, the releasability when demolding from the mold after polymerization and curing may be poor. The shape of the optical material is complex, and in particular, in the case of an optical lens, the smaller the radius of curvature of the lens, the more the release property tends to deteriorate. With a negative power lens, the release of a lens with a power of -15.0D or higher It was extremely difficult to improve the performance. If the releasability is poor, production time may be hindered due to an increase in working time and chipping of the optical material and / or mold, making the optical material and / or mold unusable. In order to improve the releasability of the optical material, generally, a method of improving the releasability by using a release agent is taken, and an external release agent and / or monomer used by being applied to a mold An internal mold release agent to be used for addition is known (see Patent Document 3).
However, the method of applying the release agent to the mold is very complicated, and there are problems such as the surface of the optical material being roughened by the external release agent and the optical material becoming cloudy. In addition, the internal mold release agent has a problem that even if it is added in a small amount, it causes turbidity in the optical material, affects the preliminary polymerization reaction and / or the polymerization reaction rate, and causes a large amount of striae in the optical material. It was. There has been a demand for an optical material having good releasability without any of these various effects and substantially free from striae, and a method for producing the same.

Japanese Patent Laid-Open No. 2001-2783 JP 2004-197005 A International Publication No. 89/10575

An object of the present invention is to provide a polymerizable composition comprising a pre-reaction solution obtained by pre-polymerizing a compound having two sulfur and episulfide groups in the molecule and a compound having one or more SH groups in the molecule and a polymerization catalyst. An object of the present invention is to improve releasability and reduce striae of a high refractive index optical material obtained by polymerizing and curing an object.
The striae here is a part 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 shape, and is caused by convection of the polymerizable composition due to polymerization heat generated during polymerization curing. It is caused by minute density in the optical material or non-uniform progression of the polymerization reaction. Therefore, in the case of an optical lens, as the minus power increases, the thickness of the outer periphery of the optical lens increases and striae often occur, and it is difficult to reduce the striae of the optical lens exceeding −12.5D. In addition, it is extremely difficult to reduce the striae of optical lenses exceeding -15.0D.

（ここで、ｍは０〜４の整数、ｎは０〜１の整数を表す。）

（ｃ）ＳＨ基を１個以上有する化合物（以下（ｃ）化合物）
（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） As a result of diligent research to solve the above-mentioned problems, the present inventor has 10 to 50 parts by mass of the following compound (a), 50 to 90 parts by mass of the following (b) compound (however, (a) compound and (b) compound And the following (c) compounds 1 to 20 are polymerized into a pre-reaction solution obtained by subjecting the following (d) compound 0.001 to 5 parts by mass to a pre-polymerization catalyst. The inventors have found that an optical material excellent in releasability and substantially free from striae can be obtained by polymerizing and curing a polymerizable composition to which a catalyst has been added.
(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 one or more SH groups (hereinafter referred to as (c) compound)
(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)

According to the present invention, an optical material obtained by polymerizing and curing a pre-reaction solution obtained by pre-polymerizing a compound having two sulfur and episulfide groups in the molecule and a compound having one or more SH groups and a polymerization catalyst can be easily obtained. The mold can be removed from the mold. Compared with conventional manufacturing methods, particularly when manufacturing optical lenses, optical lenses that are virtually free of striae even at high altitudes can be produced at a higher yield rate, improving the productivity of optical materials. It became possible.

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 by the influence of impurities tends 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) The amount of the compound added is such that the higher the sulfur atom content in the polymerizable composition for an optical material, the higher the refractive index of the optical material is 1.72. When the total mass of the compounds (a) and (b) is 100 parts by mass, it is used in an amount of 10 to 50 parts by mass. 45 mass parts, More preferably, it is 15-40 mass parts, Most preferably, it is 15-30 mass parts.

ビス（β−エピチオプロピル）スルフィド

ビス（β−エピチオプロピル）ジスルフィド 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, Most preferably, it is 70-85 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

Bis (β-epithiopropyl) disulfide

The compound (c) used in the present invention is a compound having one or more SH groups, a mercaptan derivative, a thiophenol derivative, and a mercaptan derivative having an unsaturated group such as vinyl, aromatic vinyl, methacryl, acryl, or allyl. And thiophenol derivatives. More specifically, examples of the mercaptan derivative include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, tert-nonyl mercaptan, tert-dodecyl mercaptan, benzyl mercaptan, 4-chlorobenzyl mercaptan , Ethyl thioglycolate, n-butyl thioglycolate, n-octyl thioglycolate, methyl 3-mercaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3-mercaptopropionate), n-butyl (3-mercaptopropionate), 2-ethylhexyl (3-L Monomercaptan derivatives such as captopropionate) and n-octyl (3-mercaptopropionate); methanedithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, 1,2-bis (2 -Mercaptoethylthio) ethane, 1,5-dimercapto-3-oxapentane, 1,8-dimethyl Capto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2, -Mercaptomethyl-1,4-dimercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1, 1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2- Mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate) , Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptocetate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercaptomethyl) Cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 2,5-bis (2-mercapto Ethyl) -1-thian, 1,4-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) ether, 2,2 -Bis (4-mercaptophenyl) propane, bis (4-mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, 2,5-dimercapto- Examples include polymercaptan derivatives such as 1,3,4-thiadiazole and 3,4-thiofedithiol. Examples of thiophenol derivatives include thiophenol, 4-ter-butylthiophenol, 2-methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1, Examples thereof include thiophenol derivatives such as 4-dimercaptobenzene. Further, mercaptan derivatives and thiophenol derivatives having an unsaturated group are specifically shown below. Examples of mercaptan derivatives having an unsaturated group include allyl mercaptan, 2-vinylbenzyl mercaptan, 3-vinylbenzyl mercaptan, 4-vinylbenzyl mercaptan and the like. Examples of the thiophenol derivative having an unsaturated group include a thiol compound mainly composed of one or more selected from the group consisting of 2-vinylthiophenol, 3-vinylthiophenol, 4-vinylthiophenol and the like. However, it is not limited to these exemplary compounds. When there is one SH group, the rate of increase in viscosity during the prepolymerization reaction decreases, but the Tg and refractive index of the obtained optical material tend to decrease. On the other hand, when the number of SH groups is 3 or more, the viscosity increase during the prepolymerization reaction may be remarkably large. Therefore, a compound having two SH groups in one molecule is preferable, and specific examples include methanedithiol. 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimercaptobutane, 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-mercaptoethyl) Oxy) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 2,3-dimercapto-1-p Panol, 1,3-dimercapto-2-propanol, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopro Pionate), 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- Screw (2-Mel Puttoethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethylthiomethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 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-mercapto Phenyl) sulfone, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4-mercaptomethylphenyl) propane, bis (4-mercaptomethylphenyl) ether, bis (4-mercaptomethylphenyl) sulfide, etc. It is done. 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 (also known as m-xylylenedithiol), 1,4-bis (mercaptomethyl) benzene (also known as p-xylylenedithiol). These compounds having one or more SH groups may be used alone or in combination of two or more.
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 preliminary reaction liquid viscosity at the time of prepolymerization reaction may rise rapidly. On the other hand, when the amount is larger than the above range, problems such as a decrease in Tg of the obtained optical material occur.

１，２，２，６，６−ペンタメチルピペリジル−４−メタクリレ−ト

１，２，２，６，６−ペンタメチルピペリジル−４−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 The compound (d) used in the present invention includes all the compounds represented by the formula (2), but has a low molecular weight in order to prevent compatibility with other composition components and the refractive index of the optical material. A compound is preferable, 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-4-methacrylate (the following structural formula (6)), 1,2,2,6,6-pentamethylpiperidyl-4 is preferable. -Acrylate (the following structural formula (7)) and / or 1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate (the following structural formula (8)). It is 1,2,2,6,6-pentamethylpiperidyl-4-methacrylate which is easily available industrially.
(D) The addition amount of a compound is 0.001-5 mass parts with respect to a total of 100 mass parts of (a) and (b) compound, Preferably it is 0.002-3 mass parts, More preferably Is 0.003 to 1 part by mass.

1,2,2,6,6-pentamethylpiperidyl-4-methacrylate

1,2,2,6,6-pentamethylpiperidyl-4-acrylate

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

Details of the prepolymerization reaction for obtaining the optical material of the present invention will be described below. The present invention is characterized in that a prepolymerization reaction of (a) sulfur as a compound and (c) a compound having one or more SH groups is carried out in the presence of the compound (b). 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 is a problem that the pre-reaction liquid (prepolymer) and / or the polymerizable composition comprising the pre-reaction liquid (prepolymer) has a high viscosity, has a high viscosity increase rate and a short pot life. 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. Furthermore, when the compound (d) was used as a prepolymerization catalyst, it was found that a prereaction liquid (prepolymer) having no sulfur precipitation as the compound (a) was obtained even at a reaction temperature near room temperature.

That is, in the present invention, (a) 10 to 50 parts by mass of the compound, (b) 50 to 90 parts by mass of the compound and (c) 1 to 20 parts by mass of the compound (d) 0.001 to 5 parts by mass of the compound are prepolymerized. A specific method for carrying out the prepolymerization reaction as a catalyst is as follows. The compounds (a), (b), (c) and (d) are 0 ° C. to 45 ° C., preferably 5 ° C. to 40 ° C., more preferably 10 ° C. to Stir and mix at 40 ° C. 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 stepwise, or several components may be mixed separately and then remixed in the same container.
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 obtained prereaction liquid (prepolymer), but 50% or more of the compound (a) is reacted. It is preferable to make it.
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.
Furthermore, a polymerization regulator can be added separately when mixing the polymerization catalyst as required, but it is preferable to add a polymerization regulator in order to appropriately control the polymerization reaction for obtaining the optical material.
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 derivatives, phosphine derivatives, quaternary ammonium salt derivatives, quaternary phosphonium salt derivatives, condensates of aldehyde and amine derivatives, salts of carboxylic acid and ammonia, urethane derivatives, thiourethanes Derivatives, guanidine derivatives, thiourea derivatives, thiazole derivatives, sulfenamide derivatives, thiuram derivatives, dithiocarbamate derivatives, xanthates, tertiary sulfonium salt derivatives, secondary iodonium salt derivatives, mineral acid derivatives, Lewis acid derivatives Organic acid derivatives, silicic acid derivatives, tetrafluoroboric acid derivatives, peroxides, azo derivatives, and acidic phosphoric acid 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.

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 derivative capable of reacting with at least one component of the composition 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, Derivatives having an SH group, epoxy derivatives, iso (thio) cyanate derivatives, carboxylic acid derivatives, carboxylic anhydride derivatives, phenol derivatives, amine derivatives, vinyl derivatives, allyl derivatives, acrylic derivatives, methacrylic derivatives and the like can be mentioned.

When the polymerizable composition prepared by the above method is polymerized and cured to obtain an optical material, it is preferable from the viewpoint of achieving high transparency of the optical material that the degassing treatment is performed before injection into the mold. The degassing treatment is preferably performed simultaneously with the mixing of the polymerization catalyst in order to improve the productivity. However, it can also be performed separately after the polymerizable composition is prepared. 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.

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.

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 and the optical material obtained by polymerization was performed by the following method.
[Viscosity of polymerizable composition]
Using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV10M type), the viscosity of the prepolymerized solution at 20 ° C. was measured.
[Measurement of heat resistance of optical materials]
The optical material is cut into a thickness of 3 mm, a 10 g load is applied to a 0.5 mmφ pin, the temperature is increased from 30 ° C. to 10 ° C./min, TMA measurement (manufactured by Seiko Instruments, TMA / SS6100) is performed, and the softening point temperature (Tg) was measured.
[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), the refractive index (ne) at the e-line at 25 ° C., and the Abbe number (νd) at the d-line. ) Was measured.
[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.
[Evaluation of releasability of optical materials (optical lenses)]
After polymerizing and curing the polymerizable composition, the state of the optical lens and the mold when releasing the produced optical material (optical lens) from the glass mold and the release workability are evaluated. Indicated.
A: When the optical lens is released from the glass mold, it can be easily released in a short time without damaging the optical lens and the mold.
○: When the optical lens is released from the glass mold, it can be released without damaging the optical lens and the mold.
Δ: When the optical lens is released from the glass mold, the optical lens and the mold are not damaged, but a part of the glass mold is attached to the optical lens or a part of the optical lens is attached to the glass mold. The mold release workability is extremely poor and requires a long time.
X: The mold cannot be released at all, or the optical lens and / or the glass mold is damaged.
[Color tone of optical material (YI value)]
The YI value of a circular flat plate of a polymerization cured product having a thickness of 2.5 mm and φ60 mm was measured using a spectrocolorimeter (manufactured by Color Techno System Co., Ltd., JS555).

Example 1
(Preliminary polymerization reaction method and production method of polymerizable composition)
(A) 16.0 parts by mass of sulfur as the compound, (b) 84.0 parts by mass of bis (β-epithiopropyl) sulfide (hereinafter referred to as b-1 compound) as the compound, and (c) bis (2 -Mercaptoethyl) sulfide (hereinafter referred to as c-1 compound) in 8.6 parts by mass as (d) compound as 1,2,2,6,6-pentamethylpiperidyl-4-methacrylate (hereinafter referred to as d-1 compound) 0.020 parts by mass) was added, and a prepolymerization reaction was performed at 30 ° C. under normal pressure in a nitrogen atmosphere. The preliminary reaction solution 0.5 hours after the start of the reaction was transparent and yellow, and a solid solution such as sulfur was not observed. Furthermore, cooling was performed for 0.1 hour until the preliminary reaction liquid reached 20 ° C. The pre-reaction liquid after cooling was yellow and transparent, and precipitation of solids such as sulfur was not observed. 0.10 parts by mass of triethylbenzylammonium chloride as a polymerization catalyst and 0.25 parts by mass of dibutyltin dichloride as a polymerization regulator are added to the obtained preliminary reaction solution, and the mixture is stirred and mixed while degassing at 10 Torr to obtain a polymerizable composition. It was.
(Plastic lens manufacturing method)
The obtained polymerizable composition was filtered through a 1.0 μm PTFE membrane filter, and a glass mold (design power (S / C) -4.0D / 0.0D), gasket, glass mold (design power (S /C)-12.5D/0.0D) and gasket, and glass mold (design power (S / C) -15.0D / 0.0D) and three types of molds composed of gaskets are injected into each of 100 sets. did. These molds were heated in an oven from 20 ° C. to 100 ° C. over a period of 22 hours, gradually heated and polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical lens. Table 1 shows the results of releasability, striae of the optical lens, heat resistance (Tg), YI value, refractive index, and Abbe number.

Example 2
(Preliminary polymerization reaction method and production method of polymerizable composition)
(A-1) 16.0 parts by mass of sulfur as a compound, 84.0 parts by mass of bis (β-epithiopropyl) sulfide as a compound (b-1), bis (2- Mercaptoethyl) sulfide (7.8 parts by mass) was added (d-1) compound 1,2,2,6,6-pentamethylpiperidyl-4-methacrylate (0.020 parts by mass) under nitrogen atmosphere and normal pressure. , And prepolymerized at 30 ° C. The preliminary reaction solution 0.5 hours after the start of the reaction was transparent and yellow, and a solid solution such as sulfur was not observed. Furthermore, while degassing at 10 Torr, cooling was performed for 0.1 hour until the preliminary reaction solution reached 20 ° C. The pre-reaction liquid after cooling was yellow and transparent, and precipitation of solids such as sulfur was not observed. In the obtained preliminary reaction solution, 0.10 parts by mass of triethylbenzylammonium chloride as a polymerization catalyst and 0.25 parts by mass of dibutyltin dichloride as a polymerization regulator were added to bis (2-mercaptoethyl) sulfide 0 as a compound (c-1). It was dissolved in advance in 80 parts by mass and further stirred and mixed while degassing at 10 Torr to obtain a polymerizable composition.
(Plastic lens manufacturing method)
The obtained polymerizable composition was filtered through a 1.0 μm PTFE membrane filter, and a glass mold (design power (S / C) -4.0D / 0.0D), gasket, glass mold (design power (S /C)-12.5D/0.0D) and gasket, and glass mold (design power (S / C) -15.0D / 0.0D) and three types of molds composed of gaskets are injected into each of 100 sets. did. These molds were heated in an oven from 20 ° C. to 100 ° C. over a period of 22 hours, gradually heated and polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical lens. Table 1 shows the results of releasability, striae of the optical lens, heat resistance (Tg), YI value, refractive index, and Abbe number.

Examples 3-10
The same procedure as in Example 1 was performed except that each compound and amount shown in Table 1 were changed. In addition, Tables 1 and 2 show the results of releasability, striae, heat resistance (Tg), YI value, refractive index, and Abbe number of the obtained optical lens.

Examples 11-14
The same procedure as in Example 2 was performed except that each compound and amount shown in Table 1 were changed. Table 2 shows the results of releasability, striae, heat resistance (Tg), YI value, refractive index and Abbe number of the obtained optical lens.

Comparative Example 1
(Preliminary polymerization reaction method and production method of polymerizable composition)
(A-1) 16.0 parts by mass of sulfur as a compound and 84.0 parts by mass of bis (β-epithiopropyl) sulfide as a (b-1) compound were mixed well at 60 ° C. to obtain a uniform solution. Next, 0.50 part by mass of 2-mercapto-1-methylimidazole (referred to as MMI) was added as a prepolymerization catalyst, and a prepolymerization reaction was performed at 60 ° C. The obtained preliminary reaction liquid was cooled to 20 ° C. The pre-reaction liquid after cooling was yellow and transparent, and precipitation of solids such as sulfur was not observed. In the obtained preliminary reaction solution, 0.03 part by mass of triethylbenzylammonium chloride as a polymerization catalyst and 0.20 part by mass of dibutyltin dichloride as a polymerization regulator were added to bis (2-mercaptoethyl) sulfide 8 as a compound (c-1). It was dissolved in advance in 6 parts by mass, and stirred and mixed while degassing at 10 Torr to obtain a polymerizable composition.
(Plastic lens manufacturing method)
The obtained polymerizable composition was filtered through a 1.0 μm PTFE membrane filter, and a glass mold (design power (S / C) -4.0D / 0.0D), gasket, glass mold (design power (S /C)-12.5D/0.0D) and gasket, and glass mold (design power (S / C) -15.0D / 0.0D) and three types of molds composed of gaskets are injected into each of 100 sets. did. These molds were heated in an oven from 20 ° C. to 100 ° C. over a period of 22 hours, gradually heated and polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical lens. Table 3 shows the results of the releasability, the striae of the optical lens, the heat resistance (Tg), the YI value, the refractive index, and the Abbe number.

Comparative Example 2
(Preliminary polymerization reaction method and production method of polymerizable composition)
(A-1) 16.0 parts by mass of sulfur as a compound, 84.0 parts by mass of bis (β-epithiopropyl) sulfide as a (b-1) compound, and bis (2- Mercaptoethyl) sulfide (7.8 parts by mass) was mixed well at 60 ° C. to obtain a homogeneous solution. Next, 0.50 part by mass of 2-mercapto-1-methylimidazole (referred to as MMI) was added as a prepolymerization catalyst, and a prepolymerization reaction was performed at 60 ° C. The obtained preliminary reaction liquid was cooled to 20 ° C. The pre-reaction liquid after cooling was yellow and transparent, and precipitation of solids such as sulfur was not observed. In the obtained preliminary reaction liquid, 0.03 part by mass of triethylbenzylammonium chloride as a polymerization catalyst and 0.20 part by mass of dibutyltin dichloride as a polymerization regulator were added to bis (2-mercaptoethyl) sulfide 0 as a compound (c-1). It was dissolved in advance in 8 parts by mass and added with stirring while degassing at 10 Torr to obtain a polymerizable composition.
(Plastic lens manufacturing method)
The obtained polymerizable composition was filtered through a 1.0 μm PTFE membrane filter, and a glass mold (design power (S / C) -4.0D / 0.0D), gasket, glass mold (design power (S /C)-12.5D/0.0D) and gasket, and glass mold (design power (S / C) -15.0D / 0.0D) and three types of molds composed of gaskets are injected into each of 100 sets. did. These molds were heated in an oven from 20 ° C. to 100 ° C. over a period of 22 hours, gradually heated and polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical lens. Table 3 shows the results of the releasability, the striae of the optical lens, the heat resistance (Tg), the YI value, the refractive index, and the Abbe number.

Comparative Example 3
(D) Performed in the same manner as in Example 1 except that the amount of the compound was changed. However, rapid polymerization occurred and no optical material was obtained.

Comparative Example 4
(D) Performed in the same manner as in Example 1 except that the amount of the compound was changed. However, sulfur remained undissolved and a uniform optical material could not be obtained.

Comparative Example 5
(Preliminary polymerization reaction method and production method of polymerizable composition)
(A-1) 16.0 parts by mass of sulfur as a compound, 84.0 parts by mass of bis (β-epithiopropyl) sulfide as a (b-1) compound, and 0 as dioctyl acid phosphate Add 0.01 parts by mass and mix well at 60 ° C. to obtain a homogeneous solution. Next, 0.50 part by mass of 2-mercapto-1-methylimidazole (referred to as MMI) was added as a prepolymerization catalyst, and a prepolymerization reaction was performed at 60 ° C. After reacting 50% or more of sulfur, the obtained preliminary reaction liquid was cooled to 20 ° C. The pre-reaction liquid after cooling was yellow and transparent, and precipitation of solids such as sulfur was not observed. In the obtained preliminary reaction solution, 0.03 part by mass of triethylbenzylammonium chloride as a polymerization catalyst and 0.20 part by mass of dibutyltin dichloride as a polymerization regulator were added to bis (2-mercaptoethyl) sulfide 8 as a compound (c-1). It was dissolved in advance in 6 parts by mass, and stirred and mixed while degassing at 10 Torr to obtain a polymerizable composition.
(Plastic lens manufacturing method)
The obtained polymerizable composition was filtered through a 1.0 μm PTFE membrane filter, and a glass mold (design power (S / C) -4.0D / 0.0D), gasket, glass mold (design power (S /C)-12.5D/0.0D) and gasket, and glass mold (design power (S / C) -15.0D / 0.0D) and three types of molds composed of gaskets are injected into each of 100 sets. did. These molds were heated in an oven from 20 ° C. to 100 ° C. over a period of 22 hours, gradually heated and polymerized and cured, then cooled to room temperature, and released from the mold to obtain an optical lens. Table 3 shows the results of the releasability, the striae of the optical lens, the heat resistance (Tg), the YI value, the refractive index, and the Abbe number. However, thin turbidity occurred in all the obtained optical lenses.

Comparative Example 6
As an internal mold release agent, the same procedure as in Comparative Example 5 was performed except that 0.01 part by mass of DS-401 (manufactured by Daikin Industries) was used instead of dioctyl acid phosphate. The results are shown in Table 3. However, turbidity occurred in all the obtained optical lenses.

Comparative Example 7
The same procedure as in Comparative Example 1 was performed except that YSR-6209 (manufactured by Toshiba Silicon) was applied to the mold as an external mold release agent. However, turbidity occurred in all the obtained optical lenses, and the surface of the optical lenses became rough.

Comparative Example 8
(D) The same procedure as in Example 1 was conducted except that 2,2,6,6-tetramethylpiperidyl-4-methacrylate (referred to as TMPM) was used instead of the compound. However, rapid polymerization occurred and no optical material was obtained.

Comparative Example 9
(D) The same procedure as in Example 1 was conducted except that 1,2,2,6,6-pentamethylpiperidine (referred to as PMP) was used instead of the compound. However, rapid polymerization occurred and no optical material was obtained.

In addition, the symbol in the said Tables 1-3 means the following.
(A-1) sulfur (b-1) bis (β-epithiopropyl) sulfide (b-2) bis (β-epithiopropyl) disulfide (c-1) bis (2-mercaptoethyl) sulfide (c − 2) m-xylylenedithiol (c-3) 2,5-bis (mercaptomethyl) -1,4-dithiane (c-4) p-xylylenedithiol (c-5) 1,2-dimercaptoethane ( c-6) Thiophenol (d-1) 1,2,2,6,6-pentamethylpiperidyl-4-methacrylate (d-2) 1,2,2,6,6-pentamethylpiperidyl-4 Acrylate (d-3) 1,2,2,6,6-pentamethylpiperidyl-4-vinylbenzoate MMI: 2-mercapto-1-methylimidazole TMPM: 2,2,6,6-tetramethylpiperidyl -4-Methacrylate PM P: 1,2,2,6,6-pentamethylpiperidine TEBAC: triethylbenzylammonium chloride DBTC: dibutyltin dichloride

Claims (2)

10 to 50 parts by mass of the following compound (a) and 1 to 20 parts by mass of the following compound (c) in the presence of 50 to 90 parts by mass of the following compound (b) (however, the (a) compound and the (b) compound The total is 100 parts by mass ), and a polymerizable composition obtained by adding a polymerization catalyst to a preliminary reaction liquid obtained by performing a preliminary polymerization reaction using 0.001 to 5 parts by mass of the following (d) compound as a preliminary polymerization catalyst is polymerized and cured. Manufacturing method of optical material.
(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 one or more SH groups (compound (c))
(D) A compound represented by the following formula (2) (compound (d)).

(R represents an alkyl group having 1 to 4 carbon atoms, and X represents an organic group having 2 to 11 carbon atoms having any of a vinyl group, a vinylidene group, or a vinylene group . ) The polymerizable composition, a manufacturing method of the optical material according to claim 1 pre-reaction solution is further added as the and said polymerization catalyst and (c) compound.