JP2010105229A - Method for manufacturing plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a plastic lens having a high refraction index and excellent mold-releasability. <P>SOLUTION: In the method of manufacturing the plastic lens by casting and polymerizing a mixture of a compound (A) having two or more episulfide groups in a molecule, a sulfur-containing compound (B) having one or more SH groups in a molecule, an inorganic compound (C) having either one of a sulfur atom and a selenium atom, and an inner mold release agent (D), the composition containing at least the component (A) and the component (C) among the component (A), the component (B) and the component (C) are made to preliminarily react with each other until each component does not recrystallize and precipitate even when the component is cooled, and then the component (D) is added. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a plastic lens.

A plastic lens is lighter than a glass lens, and has various merits such as good moldability and workability, being hard to break and having high safety. For this reason, it is widely used in fields such as eyeglass lenses and camera lenses.
In the beginning, plastic lenses with a refractive index of 1.50 were widely used. However, in recent years, plastic lenses with a high refractive index have been developed for the purpose of thinning the lens. As a resin material (for example, see Patent Document 1) obtained by polymerizing an episulfide compound and a thiol compound, a resin material (for example, see Patent Document 2) comprising a sulfur-containing compound having a functional group capable of reacting with the episulfide compound. ), Resin materials composed of episulfide compounds, inorganic sulfur, thiol compounds and UV absorbers (for example, see Patent Document 3) and resin materials obtained by polymerizing episulfide compounds containing sulfur atoms (for example, see Patent Document 4) Has been.

WO89 / 10575 publication JP-A-3-81320 JP 2004-315556 A Japanese Patent Laid-Open No. 2001-2783

  However, the above-mentioned resin material has a limit in increasing the refractive index, or it can be increased by containing sulfur atoms, but on the other hand, it can be released from the mold after polymerization by containing sulfur atoms. There is a problem that it becomes difficult to mold a plastic lens well.

  Therefore, an object of the present invention is to provide a method for producing a plastic lens having a high refractive index and excellent releasability.

The present invention relates to (A) a compound having two or more episulfide groups in one molecule (B) a sulfur-containing compound having one or more SH groups in one molecule (C) at least one of a sulfur atom and a selenium atom. In a method for producing a plastic lens obtained by cast polymerization of a mixture of inorganic compound (D) internal mold release agent, and at least the component (A) among the component (A), component (B) and component (C) A composition comprising the component (C) is pre-reacted until each component is not precipitated by recrystallization even after cooling, and then the component (D) is added. It is a manufacturing method.
According to this invention, since the component (D) internal mold release agent is added after the preliminary reaction, there is no fear that the mold release property is deteriorated as in the case of simultaneously polymerizing the components (A) to (D). Therefore, it is possible to easily obtain a plastic lens having a good releasability and a high refractive index.

In the present invention, the cooling temperature after the preliminary reaction is preferably 10 ° C. or more and 35 ° C. or less.
In this invention, since the cooling temperature is 10 ° C. or more and 35 ° C. or less, each component can be made difficult to precipitate by recrystallization, and a plastic lens can be manufactured more easily.

In this invention, it is preferable that the addition amount of a component (D) is 0.1 ppm or more and 10000 ppm or less with respect to the total amount of a component (A), a component (B), and a component (C).
In this invention, since the addition amount of the component (D) is 0.1 ppm to 10000 ppm, the mold release property can be sufficiently improved by the internal mold release agent, and the internal mold release agent has an adverse effect on the appearance of the plastic lens. The fear of exerting the effects can be eliminated.

  Hereinafter, embodiments of the plastic lens manufacturing method of the present invention will be described in detail. In the present embodiment, a plastic lens for spectacles is exemplified. The spectacle lens manufactured in the present embodiment is thicker than a general plastic lens, and has a thickness of about 10 mm to 15 mm, for example.

The method for producing a spectacle lens in the present embodiment is a composition having at least the component (A) and the component (C) among the following component (A), component (B) and component (C). After pre-reacting until each component is no longer precipitated by recrystallization even when cooled below, component (D) is added to component (A), component (B) and component (C) in total. By adding 0.1 ppm to 10000 ppm to obtain a resin for optical materials, an injection step for filling the optical material resin into a molding mold, and exposing the molding mold under a predetermined temperature condition A curing step of curing the resin for optical material.
(A) Compound having two or more episulfide groups in one molecule (B) Sulfur-containing compound having one or more SH groups in one molecule (C) Inorganic compound having at least one of sulfur atom and selenium atom These will be described in detail.

(Polymerizable composition)
The monomer compound which is the main component of the polymerizable composition is the above-described (A) compound or (B) compound. Resins obtained by polymerizing and curing compounds containing episulfide groups and disulfide epoxy compounds have a very high refractive index and an Abbe number that is almost the same as that of conventional resins. . On the other hand, the polymerization reactivity is high, and handling is difficult because the polymerization reaction proceeds while generating toxic gas even at 21 ° C. In addition, optical distortion is likely to occur after curing.
Here, the episulfide group is represented by the following formula (1).

  In the formula, X represents a sulfur atom or a selenium atom. When the sulfur atom of each terminal of two episulfide groups has couple | bonded together, it becomes a compound which has a 1 or more disulfide bond (SS) in a molecule | numerator, and has a thioepoxy group.

  Examples of the compound having two or more episulfide groups in the molecule include 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, , 3-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropyl) Thio) butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3-bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3 -Epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio) -2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, , 6-Bis (2,3-epithio (Lopylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 1,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2 , 3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3-epithiopropylthio) -1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- ( 2,3-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3- Thiapentane, 1- (2,3-epithio Propylthio) -2,2bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epithiopropylthio) -4- (2,3-epithio Propylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio)- 2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris (2,3 -Epithiopropylthiomethyl) -3,6 -Dithiaoctane, 1,1,1-tris {[2- (2,3-epithiopropylthio) ethyl] thiomethyl} -2- (2,3-epithiopropylthio) ethane, 1,1,2,2 Tetrakis {[2- (2,3-epithiopropylthio) ethyl] thiomethyl} ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3-epithio) Propylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3, 6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -5,7bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, etc. The chain aliphatic 2,3-epithiopropipropylene Thio compounds and 1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epi Thiopropylthiomethyl) cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2, 5-bis {[2- (2,3-epithiopropylthio) ethyl] thiomethyl} -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl Cycloaliphatic 2,3-epithiopropylthio compounds such as -1,4-dithiane, and 1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3 -Epithio (Lopylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene, 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epi Thiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropylthiomethyl) benzene, bis [4- (2,3-epithiopropylthio) phenyl] methane, 2,2-bis [4 -(2,3 epithiopropylthio) phenyl] propane, bis [4- (2,3-epithiopropylthio) phenyl] sulfide, bis [4- (2,3-epithiopropylthio) phenyl] sulfone, And aromatic 2,3-epithiopropylthio compounds such as 4,4′-bis (2,3-epithiopropylthio) biphenyl. These 1 type can be used individually or in combination of 2 or more types.

  Examples of the compound having one or more disulfide bonds (SS) in the molecule and at least one of an epoxy group and a thioepoxy group include bis (2,3-epoxypropyl) disulfide and bis (Thio) epoxy compounds having one disulfide bond in the molecule such as (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ) Ethane, bis (6,7-epithio-3,4-dithiaheptane) sulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2, 3-epithiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopro Examples thereof include (thio) epoxy compounds having two or more disulfide bonds in the molecule such as pyrdithioethylthio) -4-thiahexane and 1,2,3-tris (2,3-epithiopropyldithio) propane. These 1 type can be used individually or in combination of 2 or more types.

As the monomer compound, any one of a compound having two or more episulfide groups in the molecule and a disulfide epoxy compound can be used, and both can be used in combination.
For polymerizable compositions containing a compound having two or more episulfide groups in the molecule or a disulfide epoxy compound, adjustment of optical properties such as the refractive index of the resin obtained, impact resistance, specific gravity, etc. A resin modifier can be added for the purpose of improving the resin, such as adjusting the physical properties of the resin, or adjusting the viscosity of the monomer and other handling properties.

Examples of the resin modifier include compounds having two or more episulfide groups in the molecule, thiol compounds, mercapto organic acids, organic acids and anhydrides, amino acids, mercaptoamines, amines, (meth) acrylates, etc. The olefins containing are mentioned. Any of these resin modifiers may be used alone or in admixture of two or more.
As the curing catalyst in the polymerization reaction, tertiary amines, phosphines, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like are usually used. In addition, various substances such as chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, anti-coloring agents, dyes, fillers, and internal mold release agents may be added as necessary. Good.

(B) Sulfur-containing compound having one or more SH groups in one molecule The component (B) in the composition for optical materials of the present invention is a sulfur-containing compound having one or more SH groups in one molecule. The compound having one or more SH groups in one molecule is not particularly limited, but preferably a liquid sulfur-containing compound having a relatively low viscosity is used, and particularly preferably the reactivity and phase with other components. Those having good solubility, having a high refractive index as much as possible without reducing the glass transition temperature and toughness are used.
The sulfur-containing compound having one or more SH groups in one molecule of component (B) is a cyclic compound, even if it is a chain compound having a sulfide bond, polysulfide bond, or other functional group in addition to the SH group. Preferably, it is a polythiol compound having two or more SH groups, and particularly preferably a polythiol compound having a high sulfur content, which can be used alone or in combination of two or more. Specific examples of the compound include, but are not limited to, the following compounds.
Methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3 -Propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane- 2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto- 1-propanol (3-mercaptopropionate), die Lenglycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), Trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (mercapto) Chill) aliphatic polythiol compound such as methane.
1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercapto) Methyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2 , 4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (Mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercapto) Chill) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,2-bis (mercaptoethylthio) benzene, 1,3 -Bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3 , 5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1, 4- tris (mercaptoethylthio) benzene, 1,3,5-tris aromatic polythiol compounds containing (mercaptoethylthio) aromatic polythiol compound and a sulfur atom in addition to mercapto group such as benzene.
Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (2-mercapto Ethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl-1 , 11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl 1,11-mercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, tetrakis (2-mercaptoethylthiomethyl) methane , Tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2, 5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and the like Esters of thioglycolic acid and mercaptopropionic acid.
Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl Sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis 2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4 Dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodi Propionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) ), 4,4-dithio Dibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2, 3-dimercaptopropyl ester), bis (2,3-dimercaptopropyl ester) dithiodipropionate, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercapto) Methylthio) ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl-1,5-dimercapto-2, 4-dithiapentane, 3-mercaptomethyl-1,5-dimercapto-2,4-di Thiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3,7-dimercaptomethyl-1 , 9-dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethyl-1,6-dimercapto-2,5- Dithiahexane, 3-mercaptomethylthio-1,5-dimercapto-2-thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,4 , 8,11-tetramercapto-2,6,10-trithiaundecane, 1,4,9,12-tetra Lucapto-2,6,7,11-tetrathiaddecane, 2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia-1,7-heptanedithiol, 2,3,5 6,8,9-hexathia-1,10-decanedithiol, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2-bis (Mercaptomethylthio) methyl-1,3-dithietane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, 2-mercaptomethyl-6-mercapto-1,4-dithiacycloheptane, etc. An aliphatic polythiol compound containing a sulfur atom in addition to the mercapto group.
Heterocyclic compounds containing sulfur atoms in addition to mercapto groups such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptoethanol, 3-mercapto-1,2-propanediol Glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto 2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate) ), Pentaeri Ritolol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio A compound containing a hydroxy group in addition to a mercapto group such as -3-mercaptoethylthiobenzene.
2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (3-mercaptopropyl) -1,4- Dithian, 2- (2-mercaptoethyl) -5-mercaptomethyl-1,4-dithiane, 2- (2-mercaptoethyl) -5- (3-mercaptopropyl) -1,4-dithiane, 2-mercaptomethyl -5- (3-mercaptopropyl) -1,4-dithiane, 2,4-bis (mercaptomethyl) -1,3-dithiolane, 2-mercaptomethyl-5-mercapto-1,3-dithiolane, 2,2 -Bis (mercaptomethyl) -1,3-dithiolane, 2- (3-mercaptopropyl) -4-mercaptomethyl-1,3-dithiolane, 2,2-bis (mercaptomethyl) -1, , 5-trithiane, 2,4,5-tris (mercaptomethyl) -1,3-dithiolane, 2,2-bis (mercaptomethyl) -5-mercapto-1,3-dithiolane, 2- (1,2- Dimercaptoethyl) -4-mercaptomethyl-1,3-dithiolane, 2- (1,2-dimercaptoethyl) -4-mercapto-1,3,5-trithiane, 2- (3-mercaptopropyl) -4 , 5-bis (mercaptomethyl) -1,3-dithiolane, 2,2,4,5-tetrakis (mercaptomethyl) -1,3-dithiolane, 2- (1,2-dimercaptoethyl) -4,5 -Cyclic compounds such as bis (mercaptomethyl) -1,3-dithiolane.

(C) Inorganic compound having at least one of sulfur atom and selenium atom The component (C) in the composition for optical materials of the present invention is an inorganic compound having at least one of sulfur atom and selenium atom. The inorganic compound suitably used in the present invention is a compound as described in “Standard Chemistry Dictionary” (edited by the Chemical Society of Japan (1991) Maruzen), which contains a compound not containing carbon and carbon. Also refers to relatively simple compounds. For example, carbon disulfide and potassium thiocyanate, which are relatively simple compounds containing carbon, are treated as inorganic compounds. In the composition for optical materials of the present invention, it is possible to further increase the refractive index of the optical material by increasing the content of the inorganic compound.
Specific examples of the inorganic compound having a sulfur atom include sulfur, hydrogen sulfide, carbon disulfide, selenocarbon sulfide, ammonium sulfide, sulfur dioxide, sulfur trioxide and other sulfur oxides, thiocarbonate, sulfuric acid and salts thereof, sulfuric acid Hydrogen salt, sulfite, hyposulfite, persulfate, thiocyanate, thiosulfate, halides such as sulfur dichloride, thionyl chloride, thiophosgene, boron sulfide, nitrogen sulfide, silicon sulfide, phosphorus sulfide, arsenic sulfide, Examples thereof include metal sulfides and metal hydrosulfides. Among these, sulfur, carbon disulfide, phosphorus sulfide, selenium sulfide, metal sulfide and metal hydrosulfide are preferable, sulfur, carbon disulfide and selenium sulfide are more preferable, and sulfur is particularly preferable. .
Specific examples of the inorganic compound having a selenium atom include selenium, hydrogen selenide, selenium dioxide, carbon diselenide, and ammonium selenide except for the selenosulfuric sulfide and selenium sulfide, which are listed as specific examples of the inorganic compound having a sulfur atom. Selenium oxides such as selenium dioxide, selenic acid and salts thereof, selenous acid and salts thereof, hydrogen selenate, selenosulfuric acid and salts thereof, selenopyrosulfuric acid and salts thereof, halogens such as selenium tetrabromide and selenium oxychloride Chloride, selenocyanate, boron selenide, phosphorus selenide, arsenic selenide, metal selenide and the like. Among these, preferred are selenium, carbon diselenide, phosphorus selenide, and metal selenide, and particularly preferred are selenium and carbon diselenide.
These inorganic compounds having a sulfur atom and inorganic compounds having a selenium atom may be used alone or in combination of two or more.

(D) Internal mold release agent The internal mold release agent used in the present invention is, for example, a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, an acidic phosphate ester, liquid paraffin, wax, Examples include higher fatty acids and their metal salts, higher fatty acid esters, higher aliphatic alcohols, bisamides, polysiloxanes, aliphatic amine ethylene oxide adducts, etc. Among these, as appropriate from the combination of monomers, polymerization conditions, economy, and ease of handling. To be elected.
These internal release agents may be used alone or in combination of two or more.
The fluorine-based nonionic surfactant and the silicon-based nonionic surfactant used in the present invention are compounds having a perfluoroalkyl group or a dimethylpolysiloxane group in the molecule and a hydroxyalkyl group or a phosphate ester group. Fluorine-based nonionic surfactants include Unidyne DS-401 (manufactured by Daikin Industries, Ltd.), Unidyne DS-403 (manufactured by Daikin Industries, Ltd.), F-top EF122A (manufactured by Shin-Akita Kasei Co., Ltd.), F-top EF126 (Shin-Akita) Kasei Co., Ltd.) and F-Top EF301 (manufactured by Shin-Akita Kasei Co., Ltd.), and the latter silicon-based nonionic surfactant is Dow Co., Ltd., Q2-120A.
Generally, it is considered that the internal mold release agent is added at the time of preparing the raw material. In the present invention, at least the component (A) and the component (A) among the component (A), the component (B), and the component (C) are used. C) is preliminarily reacted until each component is not precipitated by recrystallization even when cooled to 10 ° C. or more and 35 ° C. or less, and then an internal mold release agent is added. This is because, in the present invention, if an internal mold release agent is added at the time of raw material preparation, the prepared raw material is pre-reacted at a high temperature (50 ° C. to 70 ° C.). This is because an unexpected reaction is caused to cause a thickening or distortion of the monomer, or a problem such as an abnormal appearance such that a plastic lens obtained by polymerization becomes white and cloudy.
In addition, the alkyl quaternary ammonium salt used in the present invention is generally known as a cationic surfactant, and includes alkyl quaternary ammonium halogen salts, phosphates, sulfates, and the like, which are chloride types. Examples include trimethylcetylammonium chloride, trimethylstearylammonium chloride, dimethylethylcetylammonium chloride, triethyldodecylammonium chloride, trioctylmethylammonium chloride, diethylcyclohexyldodecylammonium chloride and the like.

Examples of the acidic phosphate ester used in the present invention include isopropyl acid phosphate, diisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, octyl acid phosphate, dioctyl acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate. Examples include hete, tridecanol acid phosphate, bis (tridecanol acid) phosphate, and the like.
The higher fatty acid metal salt used in the present invention is a zinc salt such as stearic acid, oleic acid, octanoic acid, lauric acid, behenic acid, ricinoleic acid, calcium salt, magnesium salt, nickel salt, copper salt, etc. Specifically, zinc stearate, zinc oleate, zinc palmitate, zinc laurate, calcium stearate, calcium oleate, calcium palmitate, calcium laurate, magnesium stearate, magnesium oleate, magnesium laurate, magnesium palmitate , Nickel stearate, nickel oleate, nickel palmitate, nickel laurate, copper stearate, copper oleate, copper laurate, copper palmitate and the like.
The higher fatty acid ester used in the present invention includes, for example, higher fatty acids such as stearic acid, oleic acid, octanoic acid, lauric acid, and ricinoleic acid, and alcohols such as ethylene glycol, dihydroxypropane, dihydroxybutane, neopentyl glycol, and dihydroxyhexane. Ester.
The amount of the internal mold release agent used is in the range of 0.1 to 10,000 ppm based on the total weight of component (A), component (B), and component (C), alone or as a mixture of two or more.
If the addition amount is less than 0.1 ppm, the releasing ability deteriorates, and if it exceeds 10,000 ppm, the lens is clouded, or the lens is released from the mold early during polymerization, and the surface accuracy of the lens surface is deteriorated. In some cases, it is not necessarily limited because it varies depending on the composition of the monomer and the type of the release agent.

[Manufacture of plastic lenses]
First, the outline of the process for producing the lens of this embodiment by the casting polymerization method will be described with reference to FIGS.
FIG. 1 is a diagram showing a blending process according to an embodiment of the present invention. As shown in FIG. 1, in the preparation step, first, at least one of the compound 11 having two or more episulfide groups in one molecule as the component (A) and the sulfur atom and selenium atom as the component (C) is added. Polymerizable composition L1 containing inorganic compound 13 having, curing catalyst, and other components is prepared, and a preliminary reaction is performed while stirring at a temperature of 60 ° C. Thereafter, the polymerizable composition L2 obtained by the preliminary reaction is cooled to a temperature range of 10 ° C. or more and 35 ° C. or less, and the sulfur-containing compound 12 having at least one SH group in one molecule as the component (B) and the component The internal mold release agent 14 as (D) is added, and the curable composition L is obtained by stirring.

FIG. 2 is a diagram showing a concave mold and a convex mold for casting polymerization according to an embodiment of the present invention. As shown in FIG. 2, a cleaned mold 110 having a convex molding surface 111 of a lens and a convex mold 120 having a concave molding surface 121 of a lens are prepared.
Next, FIG. 3 is a figure which shows the shaping | molding mold for cast polymerization in embodiment of this invention. As shown in FIG. 3, the convex molding surface 111 and the concave molding surface 121 are opposed to each other, and an adhesive tape 130 is wound around the peripheral surfaces of the concave mold 110 and the convex mold 120 to seal the gap 140 between these molds. The molding mold 150 is assembled. On the other hand, a curable composition is prepared by blending the monomer compound with a curing catalyst and other components in a raw material blending tank (not shown).

  FIG. 4 is a diagram showing a raw material supply apparatus and a molding mold in the embodiment of the present invention. As shown in FIG. 4, the prepared curable composition L is distributed from a raw material preparation tank to a storage container 161 that is a pressure container of the raw material storage and supply device 160. The raw material storage and supply device 160 is transported to the place where it is injected into the molding mold, pressure gas is introduced into the storage container 161, and the curable composition L in the storage container 161 is injected through the injection pipe 162 and the valve 163 An injection process is performed in which the molding mold 150 assembled from the nozzle 164 is extruded and filled.

And FIG. 5 is a figure which shows the hardening process in embodiment of this invention. As shown in FIG. 5, the curable composition filled by placing the molding mold 150 in a temperature-controlled room (polymerization furnace) 170 and exposing the molding mold 150 to an environment set at a predetermined temperature and time. A curing step for polymerizing and curing L is performed.
Finally, FIG. 6 is a view showing a plastic lens in the embodiment of the present invention. As shown in FIG. 6, the plastic lens 180 can be obtained by removing the lens molds 110 and 120 from the cured plastic lens.

Below, it demonstrates still in detail about each above-mentioned process.
As the molding mold 150, for example, a molding mold 150 made of two sheets of glass whose side surfaces are held by an adhesive tape 130 as shown in FIG. 2 or a molding mold whose side surfaces are held by a gasket is preferably used.
In the injection step, first, a pilot hole is processed at a predetermined position of the adhesive tape 130, and an injection nozzle 164 is inserted into a pilot hole not shown. Since the convex lens molding mold 150 has a narrow gap between the two lens molding dies 110 and 120 on the outer peripheral portion, an injection nozzle 164 with a very thin tip is used so that insertion is possible between them. A pressure gas is introduced into the storage container 161 and the curable composition L filled in the storage container 161 is injected by being pushed out to the injection nozzle 164 through the injection pipe 162 and the valve 163, and the inside of the cavity 140 is curable. After filling with the composition L is detected and the valve 163 is closed to finish the injection, the injection port is sealed.

Next, the manufacturing method of the plastic lens 180 according to the present embodiment includes a curing step of polymerizing and curing the curable composition L filled in the molding mold 150 by exposing the molding mold 150 under a predetermined temperature condition.
As standard polymerization conditions, the temperature was raised from about 30 ° C. to about 100 ° C. over about 20 hours. After the polymerization, the molding mold is taken out from the polymerization furnace 170, the molded mold is disassembled and the cured plastic is taken out to obtain a plastic lens.

  Here, in the casting polymerization of the plastic lens 180, a finished lens in which both surfaces of the plastic lens 180 are finished to a predetermined optical surface by transfer from the molding mold 150, and one side by transfer from the molding mold 150 is used. There is a case where a semi-finished lens is manufactured in which an optical surface is finished and an opposite surface is ground into an optical surface by polishing.

  Finished lenses are generally thin and the minimum thickness of both convex and concave lenses is about 1 mm. On the other hand, the semi-finished lens is slightly thick, and the minimum thickness is about 5 to 20 mm for both convex and concave lenses.

  The temperature at which the polymerized plastic lens is removed from the molding mold is, for example, 100 ° C. or less, more preferably 70 ° C. or less, and the time to lower the temperature from the maximum temperature is about 1 to 5 hours. The temperature can be lowered to about 1 hour.

  In order to stabilize the lens power of the obtained plastic lens 180 and remove optical distortion of the lens, it is preferable to reheat the plastic lens 180 taken out from the molding mold 150 and perform an annealing treatment. The processing temperature at this time is 70 degreeC-160 degreeC, Preferably it is 80 degreeC-140 degreeC. The treatment time is 10 minutes to 6 hours, preferably 1 hour to 3 hours.

  When the plastic lens 180 formed by polymerization is a finished lens, the final plastic lens 180 is obtained through processing steps such as dyeing, formation of a hard coat film, and formation of an antireflection film without polishing, if necessary.

  When the plastic lens 180 formed by polymerization is semi-finished, a polishing process is performed in which one surface is cut into a predetermined optical surface. After the polishing process, the final plastic lens 180 is obtained through processing steps such as dyeing, formation of a hard coat film, and formation of an antireflection film as necessary.

According to this embodiment, there are the following effects.
In the present embodiment, the polymerizable composition L1 containing the compound 11, the inorganic compound 13, and the curing catalyst and other components is prepared and subjected to a preliminary reaction with stirring at a temperature condition of 60 ° C., and then the sulfur-containing compound 12 and The internal mold release agent 14 is added, and the curable composition L is obtained by stirring.
For this reason, since the internal mold release agent 14 is added after the preliminary reaction, the mold release property as in the case of simultaneously polymerizing the compound 11, the sulfur-containing compound 12, the inorganic compound 13 and the internal mold release agent 14 may be deteriorated. There is no. Therefore, it is possible to easily obtain the plastic lens 180 having a good releasability and a high refractive index.

  Since the polymerizable composition L2 obtained by the preliminary reaction is cooled to a temperature range of 10 ° C. or more and 35 ° C. or less, each component can be hardly precipitated by recrystallization, and the plastic lens 180 is more easily manufactured. be able to.

  Since the addition amount of the internal release agent 14 is 0.1 ppm to 10000 ppm, the release property can be sufficiently improved by the internal release agent 14, and the internal release agent 14 adversely affects the appearance of the plastic lens 180. The fear of exerting the effects can be eliminated.

An example for confirming the effect of the present embodiment will be described.
[Example 1]
(Formation of plastic lens)
In the mixing vessel, 67 g of sulfur and 267 g of bis (β-epithiopropyl) sulfide were charged as raw materials.
Then, mixing and stirring were performed with the temperature inside the mixing vessel set to 65 ° C. Subsequently, 1.7 g of 2-mercapto-1-methylimidazole was added as a catalyst, and a preliminary reaction was performed at 60 ° C. until the refractive index (20 ° C.) became 1.679.
Thereafter, the obtained resin composition was cooled to 20 ° C. Then, 17 g of benzyl mercaptan, 0.1 g of triethylbenzylammonium chloride, 0.67 g of di-n-butyltin dichloride, and 0.353 mg of tetra-n-butylammonium bromide as the internal mold release agent 14 were mixed well to obtain a uniform solution. In addition, a uniform resin for optical materials was obtained. The obtained resin for optical materials was degassed under conditions of 13 × 10 ² Pa (10 torr) and 20 ° C. for 10 minutes.
This resin is poured into a mold imitating a mold for molding, that is, a mold molded by holding the periphery of two mirror-finished glass molds with an adhesive tape, and takes 20 hours from 30 ° C. to 100 ° C. The temperature was raised and polymerization was cured. After allowing to cool to room temperature, the polymerized and cured member was released from the mold to obtain a cured plastic lens.

[Examples 2 to 6]
The experiment was conducted by changing the amount of internal mold release agent 14 (tetra-n-butylammonium bromide) to 0.1 to 10,000 ppm. Other conditions are the same as in the first embodiment. The amount of internal mold release agent 14 added is shown in Table 1.

[Examples 7 to 9]
The internal mold release agent 14 (tetra-n-butylammonium bromide) was changed to tetra-n-butylammonium chloride, and the addition amount of the internal mold release agent 14 (tetra-n-butylammonium bromide) was 0.1 to The experiment was conducted at 10,000 ppm. Other conditions are the same as in Example 1. The amount of internal mold release agent 14 added is shown in Table 1.

[Example 10]
As a raw material, 67 g of sulfur, 267 g of bis (β-epithiopropyl) sulfide, and 3 g of benzyl mercaptan were charged into the mixing vessel.
Thereafter, mixing and stirring were performed at a temperature in the container of 65 ° C. Subsequently, 1.7 g of 2-mercapto-1-methylimidazole was added as a catalyst, and a preliminary reaction was performed at 60 ° C. until the refractive index (20 ° C.) became 1.679.
Thereafter, the obtained resin composition was cooled to 20 ° C. Then, 14 g of benzyl mercaptan, 0.1 g of triethylbenzylammonium chloride, 0.67 g of di-n-butyltin dichloride, and 0.353 mg of tetra-n-butylammonium bromide as an internal mold release agent 14 were mixed well and a uniform solution was added. And uniform resin for optical materials. Other conditions are the same as in Example 1.

[Comparative Examples 1-3]
The experiment was conducted by changing the amount of internal mold release agent 14 (tetra-n-butylammonium bromide) added to 0 ppm to 20000 ppm. Other conditions are the same as in the first embodiment. Table 2 shows the amount of the internal release agent 14 added.

[Comparative Example 4]
An internal mold release agent 14 (tetra-n-butylammonium bromide) was mixed and mixed before stirring at 65 ° C. for experiments. Other conditions are the same as in the first embodiment.

[Comparative Examples 5 to 7]
In the same manner as in Comparative Examples 2 and 3, the internal release agent 14 (tetra-n-butylammonium bromide) was changed to tetra-n-butylammonium chloride, and the internal release agent 14 (tetra-n-butylammonium chloride) was further changed. The experiment was conducted by changing the addition amount of bromide) to 0.05 ppm and 20000 ppm. Other conditions are the same as in the first embodiment. Table 2 shows the amount of the internal release agent 14 added.

[Comparative Example 7]
Internal release agent 14 (tetra-n-butylammonium bromide) was changed to tetra-n-butylammonium chloride, and internal release agent 14 (tetra-n-butylammonium chloride) was changed to 65 as in Comparative Example 4. The mixing was performed before stirring at 0 ° C., and the experiment was conducted. Other conditions are the same as in the first embodiment. Table 2 shows the amount of the internal release agent 14 added.

[Comparative Examples 8 and 9]
Experiments were performed by changing the cooling temperature to 5 ° C and 40 ° C. Other conditions are the same as in Comparative Example 5.

(Evaluation methods)
In order to confirm the effects of the examples, the releasability and appearance were evaluated.
The evaluation of releasability was judged by the probability that a lens crack or crack would occur at the time of release after superposing a lens having a thin edge. The evaluation criteria were 0% (◯), less than 30% (Δ), and 30% or more (×).
For appearance evaluation, the lens appearance after polymerization was judged by visual evaluation in a dark box. Evaluation criteria were as follows: no white turbidity occurred in the lens (◯), some white turbidity, but no problem in the quality of the lens (Δ), and white turbidity affecting the quality of the lens (×). The evaluation results are shown in Table 1.
Further, the refractive index of the resin composition was evaluated. The evaluation of the refractive index of the lens was carried out by e-line (wavelength 546 nm) using an Abbe refractometer manufactured by Atago.
In order to measure the refractive index, a 2 mm thick flat plate was generated and used for the measurement. The flat plate is injected with a resin composition into two glass flat plates whose outer periphery is sealed with tape so that the thickness is 2 mm, and polymerized, cured, released and annealed under the manufacturing conditions of the lens substrate. Processed and manufactured. When the refractive index of the obtained 2 mm-thick plastic plate was measured, nd = 1.75.

[Evaluation results]
The evaluation results of Examples 1 to 10 are shown in Table 1.
The evaluation results of Comparative Examples 1 to 9 are shown in Table 2.

* A: Bis (β-epithiopropyl) sulfide B: Benzyl mercaptan C: Sulfur

* Judgment of releasability ○: The probability of cracking and cracking in the lens is 0%
Δ: There is a probability that the lens will crack or crack, but less than 30% ×: The probability that the lens will crack or crack is 30% or more * Judgment of appearance ○: No distortion or cloudiness is observed.
Δ: There are some distortions and cloudiness, but there is no problem as a lens.
X: Many distortion and cloudiness generate | occur | produce and it has an influence on a lens.

In Examples 1, 7, and 10, the internal release agent 14 was added after the preliminary reaction to obtain a plastic lens 180 having good release properties and appearance. On the other hand, in Comparative Examples 4 and 7, the internal mold release agent 14 was added before mixing and stirring to obtain a plastic lens 180 having a poor appearance.
Therefore, it was found that the plastic lens 180 having a good appearance can be obtained by adding the internal release agent 14 after the preliminary reaction.

In Examples 1-10, the addition amount of the internal mold release agent 14 is 0.1 ppm to 10000 ppm, while Comparative Examples 2 and 5 are 0.05 ppm. For this reason, Examples 1 to 10 can obtain good or no problem releasing properties and appearance, and Comparative Examples 2 and 5 cannot obtain sufficient releasing properties due to an insufficient amount of the internal releasing agent 14 added. It was. In Comparative Example 3, when 20000 ppm of the internal release agent 14 was added, the release property was good, but the appearance was poor due to the internal release agent 14.
Therefore, it was found that by adding the internal release agent 14 in the range of 0.1 ppm to 10000 ppm, a plastic lens 180 having good release properties and appearance can be obtained.

In Examples 1 to 10, the cooling temperature after the preliminary reaction is 20 ° C., while Comparative Examples 8 and 9 are 5 ° C. and 40 ° C., respectively. For this reason, Examples 1 to 10 were able to obtain good or satisfactory releasability and appearance, and Comparative Examples 8 and 9 were poor in appearance. This is because in Comparative Example 8, the cooling temperature was too low, so that precipitation due to recrystallization occurred, and in Comparative Example 9, the cooling temperature was too high, so the cooling effect was small and distortion during polymerization occurred.
Therefore, it was found that by setting the cooling temperature after the preliminary reaction to 10 ° C. or more and 35 ° C. or less, it is possible to obtain the plastic lens 180 having good releasability and appearance.

  Further, in the examples and comparative examples, the influence on the releasability and the appearance due to the type of the internal release agent 14 cannot be confirmed, so that tetra-n-butylammonium bromide or tetra-n-butylammonium is used as the internal release agent 14. It has been found that any of the chlorides can be used.

  Furthermore, since the releasability and appearance of Example 10 and Examples 1 and 7 were both good, the presence or absence of benzyl mercaptan in the preliminary reaction does not affect the releasability and appearance at all. all right.

  INDUSTRIAL APPLICABILITY The present invention can be used as a plastic lens for eyeglasses, and can be suitably used as a dustproof glass, dustproof crystal, condenser lens, prism, optical disk antireflection, display antireflection, solar cell antireflection, and optical isolator manufacturing method. .

The figure which shows the preparation process which concerns on embodiment of this invention. The figure which shows the concave type and convex type | mold for casting polymerization which concern on embodiment of this invention. The figure which shows the shaping | molding mold for cast polymerization in embodiment of this invention. The figure which shows the raw material supply apparatus and shaping | molding mold in embodiment of this invention. The figure which shows the hardening process in embodiment of this invention. The figure which shows the plastic lens in embodiment of this invention.

Explanation of symbols

  L ... curable composition, L1 ... polymerizable composition, L2 ... polymerizable composition, 11 ... compound, 12 ... sulfur-containing compound, 13 ... inorganic compound, 14 ... internal mold release agent, 110 ... concave mold, 111 ... convex surface Molding surface, 120 ... convex mold, 121 ... concave molding surface, 130 ... adhesive tape, 140 ... cavity, 150 ... molding mold, 160 ... raw material storage and supply device, 161 ... storage container, 162 ... injection pipe, 163 ... valve, 164 ... Injection nozzle, 170 ... Constant temperature chamber (polymerization furnace), 180 ... Plastic lens

Claims (3)

(A) Compound having two or more episulfide groups in one molecule (B) Sulfur-containing compound having one or more SH groups in one molecule (C) Inorganic compound having at least one of sulfur atom and selenium atom ( D) In a method for producing a plastic lens obtained by cast polymerization of a mixture of internal mold release agents,
A composition having at least the component (A) and the component (C) among the component (A), the component (B) and the component (C),
After pre-reacting until each component is no longer precipitated by recrystallization even after cooling,
The manufacturing method of the plastic lens characterized by adding a component (D). It is a manufacturing method of the plastic lens of Claim 1, Comprising:
The method for producing a plastic lens, wherein the cooling temperature after the preliminary reaction is 10 ° C. or more and 35 ° C. or less. A method for producing a plastic lens according to claim 1 or 2,
A method for producing a plastic lens, wherein the amount of component (D) added is 0.1 ppm or more and 10,000 ppm or less with respect to the total amount of component (A), component (B), and component (C).