JP4309807B2 - Method for producing plastic lens comprising episulfide sulfur atom-containing resin - Google Patents

Description

  The present invention relates to a sulfur atom-containing resin material, particularly an episulfide-based sulfur atom-containing resin material, which is suitably used in the resin field such as an optical material that requires a high refractive index and high transparency.

In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.
The performance required for these plastic lenses is high refractive index and high Abbe number as optical performance, and high heat resistance, high impact resistance and low specific gravity as physical properties.

  Currently, polythiourethane resins in which sulfur atoms are introduced into the resin are known as resins that satisfy these required performances to some extent. The polythiourethane resin is a resin having an excellent balance such as high refractive index and good impact resistance (see, for example, Patent Document 1 and Patent Document 2).

  Further, in response to demands for higher refractive index and higher Abbe number, methods for improving the sulfur content of polythiol compounds used in polythiourethanes have also been proposed (for example, Patent Document 3 and Patent Document 4). Patent Document 5, Patent Document 6).

On the other hand, a method using an episulfide compound has been proposed as a material pursuing a high refractive index and a high Abbe number, although required physical properties relating to strength such as impact resistance are not satisfied. (For example, see Patent Document 7 and Patent Document 8)
JP-A-60-199016 JP-A-63-46213 Japanese Patent Laid-Open No. 02-270859 Japanese Patent Laid-Open No. 03-236386 JP 07-252207 A JP 2001-342172 A Japanese Patent Application Laid-Open No. 09-110979 JP 11-322930 A

  According to the methods of these patent documents, excellent performance as a plastic lens such as a high refractive index, a high Abbe number, and a low specific gravity can be realized. However, in the resin and plastic lenses obtained by these methods, at the time of manufacturing the lens, particularly in the polymerization stage, the generation of optical distortion of the lens due to the polymerization method and the different lens thickness is one cause of the yield reduction. In some cases, deformation, cracking, and chipping at the time of releasing a lens obtained by polymerization may contribute to a decrease in yield, and improvement has been desired. In particular, an expensive episulfide-based resin with a raw material cost and a lens made thereof have a great effect of cost reduction by improving the yield. The present inventors have examined whether this problem can be solved by changing the polymerization method.

As a result of intensive investigations to solve the above-mentioned problems, the present inventors have made the polymerization proceed to some extent at a certain temperature or lower, eliminate the fluidity of the raw material composition, and then proceed the polymerization at a certain temperature or higher. It was found that the occurrence of optical distortion can be greatly improved. At the same time, it was found that the lens deformation, cracking, and chipping during the mold release can be suppressed by setting the temperature at the time of mold release to a certain value or less, and a measure for improving the yield in lens manufacturing was found.
That is, by setting the polymerization conditions such that the process of eliminating the fluidity of the raw material composition, the process of further proceeding the polymerization, and the process of releasing the polymerized cured product proceed at a constant temperature condition, The present inventors have found a manufacturing method capable of suppressing the generated optical distortion, deformation, cracking and chipping and improving the yield, and have reached the present invention.

The present invention
[1] A method for producing a plastic lens comprising an episulfide sulfur atom-containing resin having the following steps 1 to 4 .
Step 1: A step of injecting a polymerizable composition containing a compound having one or more episulfide groups between molding molds held by a gasket or tape to substantially lose fluidity at 40 ° C. or lower.
Step 2: After the fluidity of the polymerizable composition is substantially lost in Step 1 above, the step of removing the gasket or tape from the mold Step 3 : The fluidity held between the molds is substantially reduced. A step of polymerizing and curing the lost polymerizable composition at 40 ° C. or higher
Process 4 : The process of releasing the hardening body obtained at the said process 3 from the said mold at the temperature of 70 degrees C or less.

  In the present invention, the “episulfide-based sulfur atom-containing resin” is a resin in which a sulfur atom is introduced into a polymer chain, or a resin existing in a resin in a state where sulfur is dissolved, The thing using the episulfide type compound as a main component or subcomponent of a composition is said. In addition, “consisting of an episulfide-based sulfur atom-containing resin” means that a part of the optical material is composed of the episulfide-based sulfur atom-containing resin, and that the entire optical material contains the episulfide-based sulfur atom. When it is made of resin, it includes both.

[2] to [ 5 ] are each one of preferred embodiments of the present invention.
[2] The polymerizable composition further contains at least one polythiol and at least one polyisocyanate, and the episulfide-based sulfur atom-containing resin obtained by polymerization and curing is a resin having a thiourethane bond. The method for producing a plastic lens according to [1].
[3] The method for producing a plastic lens according to [1] or [2], wherein the polymerizable composition further contains single sulfur .
[4] A plastic lens obtained by the manufacturing method according to any one of [1] to [3] .
[5] The plastic lens according to [4], which has a refractive index of 1.60 or more .

  According to the present invention, in the field of optical materials such as eyeglass lenses having a high refractive index and a high Abbe number, it is possible to improve the yield in the production of episulfide plastic lenses.

  Hereinafter, the present invention will be described in detail. First, the production method of the present invention will be described.

  In the “process for substantially losing fluidity” described in step 1 in the production method of the present invention, for example, in the case of cast polymerization, a monomer raw material composition (catalyst or ultraviolet ray) prepared for producing a lens is used. (Including those containing additives such as an absorbent and an internal mold release agent) are injected into the mold and polymerized at a temperature of 40 ° C. or lower. As a result, the fluidity of the lens raw material composition in the mold is lost (at a temperature of 40 ° C. or lower). Here, “the fluidity is lost” means that it is 10,000 mPa · s or more when specifically expressed in terms of viscosity. Usually, the viscosity is such that the raw material composition does not flow down even if inverted. .

  The “step of polymerizing and curing at 40 ° C. or higher” described in Step 2 means that the lens raw material composition in the mold that has already lost its fluidity at 40 ° C. or lower is further polymerized and cured at 40 ° C. or higher. The “step of releasing from the mold at 70 ° C. or lower” described in the step 3 means that the polymer cured in the mold is taken out from the mold at a temperature of 70 ° C. or lower.

  As a result of intensive studies by the present inventors, from the viewpoint of improving the yield, the step 1 is preferably performed at 40 ° C. or lower, but more preferably performed at 38 ° C. or lower. If it is carried out at 35 ° C. or lower, a more preferable result may be given. Considering the properties of the raw material monomers and considering the viscosity and melting point, step 1 is preferably performed at −20 ° C. or higher, more preferably −15 ° C. or higher. More preferably, it is carried out at -10 ° C or higher.

  Step 2 is preferably performed at 40 ° C. or higher from the viewpoint of yield, but is preferably performed at 45 ° C. or higher, and more preferably performed at 50 ° C. or higher. Considering the performance such as the hue of the obtained lens, it is preferably carried out at 140 ° C. or lower, more preferably 135 ° C. or lower. More preferably, it is carried out at 130 ° C. or lower.

  Step 3 is preferably performed at 70 ° C. or lower, more preferably 65 ° C. or lower, from the viewpoint of yield in mold release, particularly lens deformation. More preferably, it is carried out at 60 ° C. or lower. From the viewpoint of yield in mold release, particularly lens cracking, step 3 is preferably performed at −20 ° C. or higher, more preferably −15 ° C. or higher. More preferably, it is carried out at -10 ° C or higher.

  Subsequently, the episulfide sulfur atom-containing resin optical material in the present invention will be described. The sulfur atom-containing resin in the present invention is a resin in which a sulfur atom is introduced into the polymer chain, and the sulfur atom is introduced into the polymer chain in the form of a sulfide bond, disulfide bond, thiourethane bond, thioester bond, or the like. It means that the resin has. In the case of the present invention, even if the polymer chain does not have a sulfur atom, a resin which is present in the resin in a state where sulfur is dissolved is also treated as a sulfur atom-containing resin. Among such sulfur atom-containing resins, for the episulfide sulfur atom-containing resin in the present invention, it is essential to use an episulfide compound as the main component or subcomponent of the raw material composition.

  Here, the specific example of the episulfide compound as a raw material of episulfide type | system | group sulfur atom containing resin is given. In the present invention, specific examples of episulfide compounds that can be used for producing episulfide-based sulfur atom-containing resins include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, and bis (epithioethyl). Epithioethyl compounds such as thio) methane, bis (epithioethylthio) benzene, bis [4- (epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane, bis (2,3 -Epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, , 2-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithio) Propylthio) propane, 1,3-bis (2,3-epithiopropylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) 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, 1,6-bis (2,3-epithiopropyl) Thio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2 , 3-Tris (2,3-epi Opropylthio) propane, 2,2-bis (2,3-epithiopropylthio) -1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithio) Propylthiomethyl) -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-epithiopropyl) Thio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epithiopropylthio) -4- (2,3-epi Thiopropylthiomethyl) -3-thiahe Xanthine, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithio) Propylthio) -4,5-bis (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-epithiopropipropyl Thio) 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-epithiopropylthiomethyl) -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) ) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane and other chain aliphatic 2,3-epithiopropylthio compounds, and

  1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthiomethyl) 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-1,4- Cycloaliphatic 2,3-epithiopropylthio compounds such as dithiane, and

  1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropyl) Thiomethyl) 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, 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc. Aromatic , 3-epithiopropylthio compound,

  Bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio-3,4-dithiaheptyl) sulfide, bis (6,7-epithio- 3,4-dithiaheptyl) disulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithiopropyldithiomethyl) benzene, , 6-Bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyl) Dithio) propane, 1,1,1,1-tetrakis (2,3-epithiopropyldithiomethyl) methane, 1,3-bis (2,3-epithiopropyldithio) -2-thiapro 1,4-bis (2,3-epithiopropyldithio) -2,3-dithiabutane, 1,1,1-tris (2,3-epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis (2,3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis (2,3-epithio) Propyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epithiopropyldithio) propane, 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 2 -[1,1-bis (2,3-epithiopropyldithio) methyl] -1,3-dithietane, 2- [1,1-bis (2,3-epithiopropyldithiomethylthio) methyl] -1, 3-di Compounds having a 2,3-epithiopropyl dithio skeleton of ethane,

  Monofunctional episulfide compounds such as ethylene sulfide, propylene sulfide, 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide, epithiochlorohydrin,

  Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2,3-epithiopropyloxy) butane 1,5-bis (2,3-epithiopropyloxy) pentane, 1,5-bis (2,3-epithiopropyloxy) -2-methylpentane, 1,5-bis (2,3-epi Thiopropyloxy) 3-thiapentane, 1,6-bis (2,3-epithiopropyloxy) hexane, 1,6-bis (2,3-epithiopropyloxy) -2-methylhexane, 3,8-bis (2, 3-epithiopropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropyloxy) propane, 2,2-bis (2,3-epithiopropyloxy) -1 , 3-bis (2,3-epithiopropyloxymethyl) propane, 2,2-bis (2,3-epithiopropyloxymethyl) -1- (2,3-epithiopropyloxy) butane, 1, 5-bis (2,3-epithiopropyloxy) -2- (2,3-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropyloxy) -2, 4-bis (2, -Epithiopropyloxymethyl) -3-thiapentane, 1- (2,3-epithiopropyloxy) -2,2-bis (2,3-epithiopropyloxymethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,5-bis (2,3-epithiopropyloxymethyl) 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,4-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8- Screw( 2,3-epithiopropyloxy) -2,5-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -2 , 4,5-tris (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl]- 2- (2,3-epithiopropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2 , 3-epithiopropyloxy) -4,8-bis (2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) ) -4,7-Bis 2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) -5,7-bis (2,3-epithiopropyl) Chain aliphatic 2,3-epithiopropyloxy compounds such as (oxymethyl) -3,6,9-trithiaundecane, and

  1,3-bis (2,3-epithiopropyloxy) cyclohexane, 1,4-bis (2,3-epithiopropyloxy) cyclohexane, 1,3-bis (2,3-epithiopropyloxymethyl) Cyclohexane, 1,4-bis (2,3-epithiopropyloxymethyl) cyclohexane, 2,5-bis (2,3-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropyloxymethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropyloxy compounds such as dithiane, and

  1,2-bis (2,3-epithiopropyloxy) benzene, 1,3-bis (2,3-epithiopropyloxy) benzene, 1,4-bis (2,3-epithiopropyloxy) benzene 1,2-bis (2,3-epithiopropyloxymethyl) benzene, 1,3-bis (2,3-epithiopropyloxymethyl) benzene, 1,4-bis (2,3-epithiopropyl) Oxymethyl) benzene, bis [4- (2,3-epithiopropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epithiopropyloxy) phenyl] propane, bis [4- ( 2,3-epithiopropyloxy) phenyl] sulfide, bis [4- (2,3-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epithiopropyloxy) It can be exemplified aromatic 2,3-epithiopropyl oxy compounds such biphenyl, but is not limited only to the exemplified compounds.

    Among the exemplified compounds, preferred compounds include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, and bis (2,3-epithiopropyl). Thio) methane and bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio- 3,4-dithiaheptyl) sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 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-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane, 1,1,1,1-tetrakis (2,3- Epithiopropyldithiomethyl) methane, 1,3-bis (2,3-epithiopropyldithio) -2-thiapropane, 1,4-bis (2,3-epithiopropyldithio) -2,3-dithiabutane, 1,1,1-tris (2,3-epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis (2 , 3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis (2,3-epithiopropyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epithiopropyl) Thio) propane, 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3-epithiopropyldithio) methyl] -1,3 -Dithietane, 2- [1,1-bis (2,3-epithiopropyldithiomethylthio) methyl] -1,3-dithietane, and more preferable compounds are bis (1,2-epithioethyl) sulfide, bis ( 1,2-epithioethyl) disulfide, and bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6 , 7-epithio-3,4-dithiaheptyl) sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithia 2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyl) Dithiomethyl) -2- (2,3-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane, 1,1,1,1- Tetrakis (2,3-epithiopropyldithiomethyl) methane, 1,3-bis (2,3-epithiopropyldithio) -2-thiapropane, 1,4-bis (2,3-epithiopropyldithio)- 2,3-dithiabutane, 1,1,1-tris (2,3-epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2 , 2-Tetra (2,3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis (2,3-epithiopropyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epi Thiopropyldithio) propane, 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3-epithiopropyldithio) methyl] -1 , 3-dithietane, 2- [1,1-bis (2,3-epithiopropyldithiomethylthio) methyl] -1,3-dithietane. Among the skeleton compounds as described above, episulfide compounds having a high sulfur atom content are more preferable.

  These episulfide compounds may be used alone or in combination of two or more.

  Examples of other resins having sulfide bonds or disulfide bonds in the polymer chain include those obtained by producing a polymer from a compound having a sulfide bond or disulfide bond in the molecule as a raw material. In addition, there is a case where a sulfide bond is formed by polymerization without having a sulfide bond in advance. Typical examples thereof include resins obtained by polymerizing and curing polyolefin compounds or polyepoxy compounds and polythiol compounds, and resins obtained by ring-opening polymerization of polythietane compounds.

  Here, a specific example is given. In the present invention, specific examples of polyolefin compounds that can be used for producing a sulfur atom-containing resin include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, and 2-hydroxyethyl. Acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, tri ethylene Recall dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, Bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxy) Diethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acrylic) Xydiethoxyphenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzine (Meth) acrylate compounds such as ruthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethylsulfide diacrylate, mercaptoethylsulfide dimethacrylate,

  Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m -Dioxane), vinyl compounds such as divinyl sulfide and divinyl disulfide, and diisopropenylbenzene are exemplified, but the compound is not limited to the exemplified compounds.

  Next, specific examples of usable polyepoxy compounds include polyhydric phenol compounds such as bisphenol A glycidyl ether and polyhydric phenols such as hydrogenated bisphenol A glycidyl ether obtained by condensation reaction of epihalohydrin compounds. Polyhydric compounds such as alcohol-based epoxy compounds obtained by condensation of alcohol compounds and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-hexahydrophthalic acid diglycidyl ester, etc. Glycidyl ester epoxy compounds obtained by condensation of organic acid compounds and epihalohydrin compounds, amine epoxy compounds obtained by condensation of secondary amine compounds and epihalohydrin compounds, etc. And the like b hexene diepoxide and an aliphatic polyvalent epoxy compound.

  Specific examples of the sulfide group-containing epoxide compound and the ether group-containing epoxide compound include bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis (2,3-epoxypropylthio). ) Methane, 1,2-bis (2,3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane 1,3-bis (2,3-epoxypropylthio) -2-methylpropane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) ) -2-Methylbutane, 1,3-bis (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) pen 1,5-bis (2,3-epoxypropylthio) -2-methylpentane, 1,5-bis (2,3-epoxypropylthio) -3-thiapentane, 1,6-bis (2,3 -Epoxypropylthio) hexane, 1,6-bis (2,3-epoxypropylthio) -2-methylhexane, 3,8-bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1, 2,3-tris (2,3-epoxypropylthio) propane, 2,2-bis (2,3-epoxypropylthio) -1,3-bis (2,3-epoxypropylthiomethyl) propane, 2, 2-bis (2,3-epoxypropylthiomethyl) -1- (2,3-epoxypropylthio) butane, 1,5-bis (2,3-epoxypropylthio) -2- (2,3-epoxy Propylchi Methyl) -3-thiapentane, 1,5-bis (2,3-epoxypropylthio) -2,4-bis (2,3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxy Propylthio) -2,2-bis (2,3-epoxypropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropylthio) -4- (2,3-epoxypropyl) Thiomethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2, 3-epoxypropylthio) -4,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,4-bis ( 2, 3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -2,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane 1,8-bis (2,3-epoxypropylthio) -2,4,5-tris (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2 -(2,3-epoxypropylthio) ethyl] thiomethyl] -2- (2,3-epoxypropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropylthio) Ethyl] thiomethyl] ethane, 1,11-bis (2,3-epoxypropylthio) -4,8-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11 Bis (2,3-epoxypropylthio) -4,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) ) -5,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane and the like chain aliphatic 2,3-epoxypropylthio compounds, and

  1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxypropylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropylthiomethyl) -2,5-dimethyl-1,4-dithiane A 2,3-epoxypropylthio compound, and

1,2-bis (2,3-epoxypropylthio) benzene, 1,3-bis (2,3-epoxypropylthio) benzene, 1,4-bis (2,3-epoxypropylthio) benzene, 1, 2-bis (2,3-epoxypropylthiomethyl) benzene, 1,3-bis (2,3-epoxypropylthiomethyl) benzene, 1,4-bis (2,3-epoxypropylthiomethyl) benzene, bis [4- (2,3-epoxypropylthio) phenyl] methane, 2,2-bis [4- (2,3-epoxypropylthio) phenyl] propane, bis [4- (2,3-epoxypropylthio) Aromatic 2 such as phenyl] sulfide, bis [4- (2,3-epoxypropylthio) phenyl] sulfone, 4,4′-bis (2,3-epoxypropylthio) biphenyl , 3-epoxypropylthio compound,
Monofunctional epoxy compounds such as ethylene oxide, propylene oxide, glycidol, epichlorohydrin,

  Bis (2,3-epoxypropyl) ether, bis (2,3-epoxypropyloxy) methane, 1,2-bis (2,3-epoxypropyloxy) ethane, 1,2-bis (2,3-epoxy) Propyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) -2-methylpropane, 1,4-bis (2,3 -Epoxypropyloxy) butane, 1,4-bis (2,3-epoxypropyloxy) -2-methylbutane, 1,3-bis (2,3-epoxypropyloxy) butane, 1,5-bis (2, 3-epoxypropyloxy) pentane, 1,5-bis (2,3-epoxypropyloxy) -2-methylpentane, 1,5-bis (2,3-epoxypropyloxy) 3-thiapentane, 1,6-bis (2,3-epoxypropyloxy) hexane, 1,6-bis (2,3-epoxypropyloxy) -2-methylhexane, 3,8-bis (2,3- Epoxypropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropyloxy) propane, 2,2-bis (2,3-epoxypropyloxy) -1,3-bis ( 2,3-epoxypropyloxymethyl) propane, 2,2-bis (2,3-epoxypropyloxymethyl) -1- (2,3-epoxypropyloxy) butane, 1,5-bis (2,3- Epoxypropyloxy) -2- (2,3-epoxypropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epoxypropyloxy) -2,4-bis (2, -Epoxypropyloxymethyl) -3-thiapentane, 1- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropyloxy) -4- (2,3-epoxypropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropyloxy) -4- (2,3-epoxy Propyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -4,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epoxypropyloxy) -4,4-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis ( 2,3-epoxypropyloxy) -2,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -2,4 5-tris (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] -2- (2, 3-epoxypropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epoxypropyloxy) -4,8-bis (2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -4,7-bis 2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -5,7-bis (2,3-epoxypropyloxymethyl) Chain aliphatic 2,3-epoxypropyloxy compounds such as -3,6,9-trithiaundecane, and

  1,3-bis (2,3-epoxypropyloxy) cyclohexane, 1,4-bis (2,3-epoxypropyloxy) cyclohexane, 1,3-bis (2,3-epoxypropyloxymethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropyloxymethyl) cyclohexane, 2,5-bis (2,3-epoxypropyloxymethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropyloxymethyl) -2,5-dimethyl-1,4-dithiane 2,3-epoxypropyloxy compounds, and

  1,2-bis (2,3-epoxypropyloxy) benzene, 1,3-bis (2,3-epoxypropyloxy) benzene, 1,4-bis (2,3-epoxypropyloxy) benzene, 1, 2-bis (2,3-epoxypropyloxymethyl) benzene, 1,3-bis (2,3-epoxypropyloxymethyl) benzene, 1,4-bis (2,3-epoxypropyloxymethyl) benzene, bis [4- (2,3-epoxypropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epoxypropyloxy) phenyl] propane, bis [4- (2,3-epoxypropyloxy) Phenyl] sulfide, bis [4- (2,3-epoxypropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epoxypropyloxy) It can be exemplified aromatic 2,3-epoxypropyloxy compounds such biphenyl, but is not limited only to the exemplified compounds.

  Next, specific examples of usable polythiol compounds include 1,1-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, thiomalic acid bis (2-mercaptoethyl ester), 2,3- Dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercap To-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercapto Propyl 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 (mercaptomethyl) aliphatic such as methane polythiol compound,

  1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) 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, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mer Puttoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiols such as 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, 1,2,4-tris (mercaptoethylthio) ) Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylated products,

  Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) Propane, 1,2,3-tris (2- Lucaptoethylthio) 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 (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3 -Dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-di Lucapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (Mercaptoethyl) disulfide, aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as bis (mercaptopropyl) disulfide, and esters of these 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), dithiodipropionic acid bis (2,3-dimercaptopropyl ester) and other mercapto groups, aliphatic polythiol compounds containing a sulfur atom and an ester bond, and 3,4-thiophenedithiol , Heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as 2,5-dimercapto-1,3,4-thiadiazole,

  2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol 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-mercapto Propionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3 Mercaptopropionate), hydroxymethyl - tris (mercaptoethylthiomethyl) methane, compounds containing 1-hydroxyethyl-thio-3-mercaptoethyl hydroxy group other than the mercapto group of thio benzene,

  1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1, 1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-Dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3-dithiacyclopentane, 2,5-bis (4,4- Bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) -1,3-propa Dithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 4,6-bis (mercapto) Methylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1 , 3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis ( Mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) me , Tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1 , 13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12, 14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8, 10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2 , 5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane 8- {bis (mercaptomethylthio) methyl} -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4, 6-bis {3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- {3,5-bis (mercaptomethylthio) -7-mercapto -2,6-dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1,1-bis {4- (6-mercaptomethylthio) -1,3-dithi Nilthio} -3,3-bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-bis (mercaptomethylthio) propane, 1- { 4- (6-Mercaptomethylthio) -1,3-dithianylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio) -2,4,6,10-tetra Thiaundecane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -2,4 , 6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithieta L)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5-mercapto-2,4-dithiapentylthio] -1,3- Dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 4- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -6 -{4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1 , 11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3-dithietanyl)} methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17- Zimmerka Put-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl)} methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithietanyl)} methyl-1,9-dimercapto-2,4,6 , 8-tetrathianonane, 4- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl} -5-mercaptomethylthio-1,3 -Dithiolane, 4,5-bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1,3-dithiolane, 4- {3,4-bis (mercaptomethyl) H ) -6-mercapto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8 -Mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithia Hexylthio} methyl] -1,3-dithietane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} mercaptomethylthiomethyl-1,3-dithietane, 2- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecylthio} mercapto Tylthiomethyl-1,3-dithietane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1, 3-dithietane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- ( 1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio} -1,3-dithiolane, 2- [ Bis {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio}] methyl-1,3-dithietane, 4- {4- (5-mercaptomethylthio-1,3-dithio Ranyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane and dithioacetal or dithioketal skeletons of these oligomers A compound having

  Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis [4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl] (mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 5-trithiacyclohexane, tris [(4-mercaptomethyl-2,5-dithi Cyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2 -(2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4- Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris [2,2-bis (mercaptomethylthio) -1-thiaethyl] methane, tris [3,3- Bis (mercaptomethylthio) -2-thiapropyl] methane, tris [4,4-bis (mercaptomethylthio) -3-thiabutyl] me 2,4,6-tris [3,3-bis (mercaptomethylthio) -2-thiapropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) -2-thiapropyl ] Compounds having an ortho trithioformate skeleton such as methane and further oligomers thereof,

  3,3′-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2′-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercapto) Methyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof. Examples include compounds having an orthotetrathiocarbonate skeleton, but are not limited to these exemplary compounds. These exemplary compounds may be used alone or in combination of two or more.

    Among these polythiol compounds, it is preferable to select an aliphatic polythiol compound rather than an aromatic one in consideration of the optical properties of the resulting resin, particularly the Abbe number. Further, in view of optical properties, particularly refractive index requirements, it is more preferable to select a compound having a sulfur atom in addition to a thiol group such as a sulfide bond and / or a disulfide bond. A dithioacetal skeleton, a dithioketal skeleton, an orthotrithioformate skeleton More preferably, a compound having an orthotetrathiocarbonate skeleton is selected. In order to increase the three-dimensional crosslinkability in consideration of the heat resistance of the resulting resin, it is particularly preferable to select one or more polythiol compounds having three or more functions. As the most preferred polythiol in the above points, 2,5-bis (mercaptomethyl) -1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2 , 2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (me Captomethylthio) ethyl) -1,3-dithietane is a compound selected from at least one compound in the case of three or more functional groups and at least one compound selected from at least one compound and three or more functional compounds in the case of two or more functional groups. It is done.

  Examples of the resin having a thiourethane bond or a thioester bond in the polymer chain include those obtained by producing a polymer from a compound having a thiourethane bond or a thioester bond in the molecule. About the compound which has a thioester bond, what is necessary is just to use the compound which has a thioester bond among the above-mentioned exemplary compounds. In addition, there is a case where a thiourethane bond is formed by polymerization without having a thiourethane bond in advance. A typical example thereof is a resin obtained by polymerizing and curing the aforementioned polythiol compound and polyisocyanate compound.

  In the present invention, specific examples of polyiso (thio) cyanate compounds that can be used for producing a sulfur atom-containing resin include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, and 2,2,4-trimethyl. Hexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1, 3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate Xylylene diisocyanate, (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis Aliphatic polyisocyanate compounds such as (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesityrylene triisocyanate, 2,6-di (isocyanatomethyl) furan,

  Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2-dimethyldicyclohexylmethane diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,8-bis (isocyanato Fats such as methyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane Cyclic polyisocyanate compounds,

  Phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate , Biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl ) Ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, phenylisocyanatoethyl isocyanate, hexahydrobenzene diiso Annatto, aromatic polyisocyanate compound such as hexahydroterephthalic diphenylmethane-4,4-diisocyanate,

  Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis ( Isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1, Sulfur-containing aliphatic isocyanate compounds such as 5-diisocyanato-2-isocyanatomethyl-3-thiapentane,

  Diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, Aromatic sulfide isocyanate compounds such as 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate,

  Diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide 6,6-diisocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl disulfide-3 Aromatic disulfide-based isocyanate compounds such as 1,3-diisocyanate, sulfur-containing heterocyclic compounds such as 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene,

  In addition, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4- Dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4, Examples thereof include 5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane, but are not limited to the exemplified compounds. In addition, halogen-substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products and the like can also be used.

  Specific examples of the isothiocyanate compound include methyl isothiocyanate, ethyl isothiocyanate, n-propyl thioisocyanate, isopropyl isothiocyanate, n-butyl isothiocyanate, sec-butyl isothiocyanate, tert- Butyl isothiocyanate, pentyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate, decyl isothiocyanate, lauryl isothiocyanate, myristyl isothiocyanate, octadecyl isothiocyanate, 3-pentyl isothiocyanate Narate, 2-ethylhexyl isothiocyanate, 2,3-dimethylcyclohexyl isothiocyanate, 2-methoxyphenyl isothiocyanate, 4-methoxyphenyl Nyl isothiocyanate, α-methylbenzyl isothiocyanate, phenylethyl isothiocyanate, phenyl isothiocyanate, o-, m-, or p-tolyl isothiocyanate, cyclohexyl isothiocyanate, benzyl isothiocyanate, isothiocyan Monofunctional isothiocyanate compounds such as natomethylbicycloheptane,

Aliphatic polyisothiocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenyleneisopropylidenediisothiocyanate,
Alicyclic polyisothiocyanate compounds such as cyclohexane diisothiocyanate, diisothiocyanatomethylbicycloheptane,

  1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m Xylene, 4,4-diisothiocyanato-1,1-biphenyl, 1,1-methylenebis (4-isothiocyanatobenzene), 1,1-methylenebis (4-isothiocyanato-2-methylbenzene), 1, 1-methylenebis (4-isothiocyanato-3-methylbenzene), 1,1- (1,2-ethanediyl) bis (isothiocyanatobenzene), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyana -3,3-dimethylbenzophenone, diphenyl ether-4,4-diisothiocyanate, diphenylamine-4,4-di Aromatic isothiocyanate compounds such as soothiocyanate, further 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4-di Examples include carbonyl isothiocyanate compounds such as carbonyl diisothiocyanate, but are not limited to the exemplified compounds.

  Specific examples of the isothiocyanate compound containing one or more sulfur atoms in addition to the isothiocyanato group include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2- Sulfur-containing aliphatic isothiocyanate compounds such as isothiocyanatoethane), 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothiocyanato) Benzene), sulfur-containing aromatic isothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene), 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane, etc. Although sulfur heterocyclic compounds etc. are mentioned, it is not limited to an exemplary compound. Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products can also be used.

  Furthermore, the isothiocyanate compound which has an isocyanato group is also mentioned. Aliphatic and alicyclic compounds such as 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato- Aromatic compounds such as 1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and 4-isocyanato-4′-isothi In addition to isothiocyanato groups such as isocyanatodiphenyl sulfide and 2-isocyanato-2′-isothiocyanatodiethyl disulfide, compounds containing sulfur atoms are not limited to the exemplified compounds. Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products can also be used.

  Next, modification of the sulfur atom-containing resin of the present invention will be described. Adjustment of optical properties such as refractive index and Abbe number of the sulfur atom-containing resin of the present invention, hue, light resistance and weather resistance, heat resistance, impact resistance, hardness, specific gravity, linear expansion coefficient, polymerization shrinkage, water absorption In order to improve resin properties and handling properties, such as adjusting various physical properties such as hygroscopicity, chemical resistance and viscoelasticity, adjusting transmittance and transparency, etc., known compounds etc. are added to stabilizers and resin modifiers. It may be preferable to add as a quality agent for the purpose of obtaining a good resin. Examples of compounds that can be added to improve stability such as polymerization stability and thermal stability include compounds such as polymerization retarders, polymerization inhibitors, oxygen scavengers, and antioxidants. I don't mean.

  Specific examples of the resin modifier include known thietane compounds, dithiethane compounds, trithiethane compounds, thiolane compounds, dithiolane compounds, trithiolane compounds, dithian compounds, trithian compounds, amine compounds, hydroxy compounds including phenolic compounds, mercapto Organic acids, organic acids and anhydrides, amino acids and mercaptoamines, episulfide compounds and epoxy compounds other than the main components constituting the aforementioned sulfur atom-containing resin of the present invention, thiol compounds, iso (thio) cyanate Examples thereof include compounds, olefin compounds including (meth) acrylates, cyclic organic compounds having inorganic atoms or sulfur atoms or selenium atoms. Among these resin modifiers, olefins including epoxy compounds, iso (thio) cyanate compounds, and (meth) acrylates are more preferable for overcoming the brittleness of the resulting resin and improving impact resistance. Amine compounds, thiol compounds, and phenol compounds are preferred for improving the hue of the resulting resin. Among these, a compound having one or more SH groups is more preferable. A compound having two or more SH groups and having a sulfide bond is more preferable. Cyclic organic compounds and inorganic compounds having a sulfur atom or a selenium atom are preferable for improving the refractive index of the resin, and in particular, when a single sulfur is used, the operation is simple and the effect of improving the refractive index is particularly large. preferable. As a single sulfur addition amount, it is preferable to use 3 to 30% by weight based on the whole raw material composition. Considering the heat resistance and brittleness of the resulting resin, it is preferable to use 5 to 25% by weight.

  Furthermore, the above-mentioned several types of resin modifiers may be used alone or in combination of two or more. The amount of the resin modifier added varies depending on the structure of the compound constituting the raw material composition and cannot be generally limited, but is usually in the range of 0.001 wt% to 50 wt% with respect to the raw material composition. It is possible to add. Considering optical properties of the obtained resin, it is preferable that the addition amount is 0.005 wt% to 25 wt%. If it is 0.01 wt%-15 wt%, it is more preferable.

  The type and amount of the curing catalyst for obtaining the sulfur atom-containing resin of the present invention, the type and proportion of the monomer vary depending on the structure of the compound constituting the raw material composition, and cannot be generally limited. Types of amines other than resin modifiers, phosphines, organic acids and salts thereof, esters, anhydrides, inorganic acids, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like are usually used.

  Specific examples of the curing catalyst include triethylamine, tri-n-butylamine, tri-n-hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine. N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, N, N-dimethyl Cyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylanily N, N-diethylaniline, α-, β-, or γ-picoline, 2,2′-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo (5 , 4,0) -7-undecene, aliphatic and aromatic tertiary amines such as 2,4,6-tris (N, N-dimethylaminomethyl) phenol,

  Trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphine) Fino) phosphines such as ethane,

  Trifluoroacetic acid, trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate, trihalogenoacetic acid and its ester, anhydride, salt, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoro Trihalogenomethanesulfonic acid and its esters, anhydrides, salts, hydrochloric acid, sulfuric acid, nitric acid and the like, such as lomethanesulfonic anhydride, ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate,

Quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide,

Quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide,

Tertiary sulfonium salts such as trimethylsulfonium bromide and tributylsulfonium bromide, secondary iodium salts such as diphenyliodonium bromide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide , Diacetoxytetrabutyl distanoxane, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride, triphenylaluminum, acetylacetone aluminum, isopropoxide aluminum, tetrachlorotitanium and its complex, tetraiodotitanium, dichlorotitanium diisopropoxy , Titanium-based alkoxides such as titanium isopropoxide, calcium acetate, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride Lysine complex, boron trifluoride ethylamine complex, boron trifluoride acetic acid complex, boron trifluoride phosphate complex, boron trifluoride t-butylmethyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride THF complex Lewis acids such as boron trifluoride methylsulfide complexes, boron trifluoride phenol complexes, etc., boron trifluoride complexes and boron trichloride complexes, etc.

  2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), Radical polymerization catalysts such as t-butylperoxy-2-ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate,

Diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, triphenylsulfonium hexafluoroarsenic acid, (tolylcumyl) iodonium tetrakis (pentafluoro) Examples thereof include cationic polymerization catalysts such as phenyl) borate, but are not limited to the exemplified compounds.

  The above curing catalysts may be used singly or in combination of two or more. When two or more of these curing catalysts having different reactivity are used in combination, the handling property of the monomer, the optical properties of the resulting resin, the hue It is preferable because transparency and optical distortion (pulse separation) may be improved.

  Among the above compounds, preferred are tertiary amine compounds and phosphine compounds, quaternary ammonium salts, quaternary phosphonium salts, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyl. Organotin compounds such as tin oxide, diacetoxytetrabutyl distanoxane, diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid Cation heavy, such as triphenylsulfonium hexafluoroarsenate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate Is the catalysts.

  Although the addition amount of a curing catalyst is used in 0.001-10 wt% with respect to the total weight of a raw material composition, it is preferable to use it in 0.005-5 wt%. More preferably, it is used in the range of 0.01 to 1 wt%. When the addition amount of the curing catalyst is within this range, it is possible to produce a resin that is cured well, the pot life is maintained, and the resin obtained has good transparency and optical properties. There is. The curing catalyst may be added directly to the episulfide compound of the present invention, or may be added after being dissolved or dispersed in another compound constituting the raw material composition, but added after being dissolved or dispersed in another compound. May give better results. Furthermore, when a curing catalyst is added, a favorable result may be obtained if it is carried out in a nitrogen atmosphere or a dry gas atmosphere. Furthermore, in order to further draw out the performance of the obtained resin, it is preferable that the amount of unreacted functional groups remaining in the resin is 0.5 wt% or less with respect to the total weight of the resin. More preferably, it is 0.3 wt% or less.

  When molding the sulfur atom-containing resin of the present invention, as in the known molding method depending on the purpose, other stabilizers, resin modifiers, chain extenders, cross-linking agents, HALS systems are representative. Light stabilizers, UV absorbers typified by benzotriazoles, antioxidants typified by hindered phenols, anti-coloring agents, dyes typified by anthraquinone disperse dyes, bluing agents, fillers, silicones Various substances such as an external mold release agent or internal mold release agent represented by a system, and an adhesion improver may be added.

  Examples of the internal release agent used in the present invention may be any as long as they have a releasability effect and do not impair physical properties such as transparency of the resin, but preferably a surfactant. Is used. Surfactants that are preferably used as release agents are roughly classified into ionic surfactants and nonionic surfactants, and ionic surfactants are classified into anionic surfactants and cationic surfactants. The Examples of anionic surfactants include sulfate ester, sulfonate ester, and phosphate ester. Of these, phosphate ester surfactants are preferred, and acidic phosphate ester anionic surfactants are particularly preferred. Is preferred. In addition, the internal mold release agent as used herein includes those exhibiting a mold release effect among the above-described various catalysts, and may include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal release agents may be used alone or in combination of two or more. These are appropriately selected from monomer combinations, polymerization conditions, economy, and ease of handling. The amount of the internal mold release agent used is usually in the range of 1 to 10,000 ppm based on the total weight of the gun composition, either alone or as a mixture of two or more. When the addition amount is 1 ppm or more, the release ability is good, and when it is 10000 ppm or less, release from the mold during the casting polymerization is suppressed, and deterioration of surface accuracy of the lens surface and white turbidity of the obtained lens are prevented. Can do. The addition amount of various additives other than the internal mold release agent that enables the above addition varies depending on the type, structure, and effect of each additive and cannot be generally limited, but usually the total weight of the raw material composition Is used in the range of 0.001 to 10 wt%, but is preferably used in the range of 0.01 to 5 wt%. The dye is preferably used in the range of 1 ppb to 100 ppm instead of this range. Within these ranges, a well-cured resin can be produced, and a resin having good transparency and optical properties may be obtained.

  A typical polymerization method for obtaining the sulfur atom-containing resin (for example, plastic lens) of the present invention is cast polymerization. That is, the raw material composition of the sulfur atom-containing resin of the present invention is injected between molding molds held by a gasket or a tape. The injection operation is preferably performed in a normal atmosphere as long as there is no particular problem, but better results may be obtained if it is performed in a nitrogen atmosphere or a dry gas atmosphere. The inside of the mold may be replaced with nitrogen gas or dry gas in advance. Here, if necessary, the raw material composition may be mixed with a curing catalyst and a resin modifier, or may be previously subjected to operations such as depressurization at 10 kPa or less such as defoaming operation, filter filtration and the like. Next, it is cured by polymerization in a heatable apparatus such as an oven or water, and the sulfur atom-containing resin can be taken out.

  The polymerization method for obtaining the sulfur atom-containing resin of the present invention, the polymerization conditions, and the like are within the range satisfying the conditions defined in claim 1 depending on the type and amount of the curing catalyst used, the type and ratio of the monomer, It can be selected appropriately.

  The polymerization conditions of the raw material composition of the present invention injected into the molding mold vary depending on the composition and structure of the raw material composition, and the conditions largely depend on the type of resin modifier, the type of curing catalyst, the shape of the molding mold, etc. Although it is different, it can be appropriately selected within a range satisfying the conditions defined in claim 1. The polymerization time is 0.01 to 100 hours, preferably 0.05 to 50 hours. More preferably, it is performed for 0.1 to 25 hours. In some cases, it is possible to perform polymerization by combining the temperature conditions with programs such as low temperature, temperature increase, and temperature decrease.

  Furthermore, the raw material composition of the sulfur atom-containing resin of the present invention can shorten the polymerization time by irradiating energy rays such as electron beams and ultraviolet rays. In this case, a curing catalyst such as a radical polymerization catalyst or a cationic polymerization catalyst described as the above-described curing catalyst may be added. Moreover, about the cured resin taken out, you may perform processes, such as annealing, as needed. The annealing conditions vary depending on the structure of the compound constituting the raw material composition to be cured, the structure of the resin to be obtained, and the like, and cannot be generally limited, but are usually performed at 30 ° C. to 200 ° C. preferable. More preferably, it is carried out at 70 ° C to 130 ° C.

  Furthermore, the sulfur atom-containing resin of the present invention can be obtained as a molded product of various forms by changing the molding mold during the casting polymerization, and has a high refractive index such as a spectacle lens, a camera lens, and a light emitting diode (LED). And can be used for various applications that require a resin that takes advantage of transparency. In particular, it is suitable as an optical material such as a spectacle lens and a camera lens. The refractive index of the optical material of the present invention is usually 1.60 or more, preferably 1.67 or more, more preferably 1.70 or more, particularly from the viewpoint of fashionability of a spectacle lens produced using the same. Preferably it is 1.74 or more.

  In the lens using the sulfur atom-containing resin of the present invention thus obtained, if necessary, antireflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging properties, or fashionability. In order to improve the application, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, and dyeing treatment can be performed.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. Of the performance tests of the obtained sulfur atom-containing resin, the optical properties and physical properties were evaluated by the following test methods.

Refractive index (ne) Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
-Heat resistance: Tg in the TMA penetration method (50 g load, pin tip 0.5 mmφ) was regarded as heat resistance.
-Resin transparency: Observed visually under a high-pressure mercury lamp. Cloudy ones were marked with x, and ones with excellent transparency were marked with ◯.
Optical distortion: Optical distortion was visually observed under a high-pressure mercury lamp. Among the 10 lenses prepared, one having one or more optical distortions was rated as x, and one having no optical distortion was marked as ◯.
-Lens cracks and chipping: The lens after mold release was visually observed to check for cracks and chipping. Of the 10 lenses prepared, one having one or more cracks or chips was marked with x, and one with no cracks or chips was marked with ◯.

[Example 1]
270 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane and 30.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane in a beaker at room temperature of 20 ° C., UV absorption After mixing and dissolving 0.3 g of Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.) as an agent, 0.6 g of N, N-dimethylcyclohexylamine was added as a curing catalyst and the mixture was degassed for 0.4 hours under reduced pressure. Then, it inject | poured into the mold mold (-6D) for lens preparation which consists of a glass mold and a gasket. After holding this mold at 35 ° C. for 8 hours and then removing the gasket, the liquid in the mold was not fluid. That is, the step of substantially losing fluidity was performed at 35 ° C. Then, it heated up gradually from 40 degreeC to 120 degreeC, and also superposed | polymerized in 14 hours. After completion of the polymerization, the product was gradually cooled and the lens was removed from the mold at 10 ° C. The obtained resin was excellent in transparency, free from distortion, and had a good appearance without deformation, cracking or chipping upon release.

  When the optical properties of the obtained resin were measured, the refractive index was ne = 1.77 and νe = 30. Ten lenses prepared at the same time were confirmed and similar results were obtained. The results are summarized in Table 1.

[Example 2]
In a beaker at room temperature of 20 ° C., 40.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane, 35.0 g of m-xylylene diisocyanate, 0.015 g of dimethyltin diacetate as a curing catalyst, and as an ultraviolet absorber After mixing 0.3 g of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) to make a uniform solution, 225 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane and tetra as an internal mold release agent 0.1 g of n-butylphosphonium bromide was added and mixed. The obtained mixture was degassed under reduced pressure for 0.4 hours, and then poured into a lens mold (-6D) made of a glass mold and a gasket. When the mold was held at 35 ° C. for 15 hours and then the gasket was removed, the liquid in the mold was not fluid. That is, the step of substantially losing fluidity was performed at 35 ° C. Then, it heated up gradually from 40 degreeC to 120 degreeC, and also superposed | polymerized in 14 hours. After completion of the polymerization, the mixture was gradually cooled, and the lens was removed from the mold at 5 ° C. The obtained resin was excellent in transparency, free from distortion, and had a good appearance without deformation, cracking or chipping upon release.

  When the optical properties of the obtained resin were measured, the refractive index was ne = 1.75 and νe = 30. Ten lenses prepared at the same time were confirmed and similar results were obtained. The results are summarized in Table 1.

[Example 3]
In a beaker at room temperature of 20 ° C., 30.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane, 25.0 g of m-xylylene diisocyanate, 0.010 g of dimethyltin diacetate as a curing catalyst, and as an ultraviolet absorber After mixing 0.3 g of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) to make a uniform solution, 225 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 20.0 g of sulfur and the inside Tetra-n-butylphosphonium bromide (0.1 g) was added as a release agent and mixed. The obtained mixture was degassed under reduced pressure for 0.4 hours, and then poured into a lens mold (-6D) made of a glass mold and a gasket. After holding this mold at 35 ° C. for 12 hours and then removing the gasket, the liquid in the mold was not fluid. That is, the step of substantially losing fluidity was performed at 35 ° C. Then, it heated up gradually from 40 degreeC to 120 degreeC, and also superposed | polymerized in 14 hours. After completion of the polymerization, the mixture was gradually cooled and the lens was removed from the mold at 15 ° C. The obtained resin was excellent in transparency, free from distortion, and had a good appearance without deformation, cracking or chipping upon release.

  When the optical properties of the obtained resin were measured, the refractive index was ne = 1.76 and νe = 30. Ten lenses prepared at the same time were confirmed and similar results were obtained. The results are summarized in Table 1.

[Comparative Example 1]
270 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane and 30.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane in a beaker at room temperature of 20 ° C., UV absorption After mixing and dissolving 0.3 g of Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.) as an agent, 0.6 g of N, N-dimethylcyclohexylamine was added as a curing catalyst and the mixture was degassed for 0.4 hours under reduced pressure. Then, it inject | poured into the mold mold (-6D) for lens preparation which consists of a glass mold and a gasket. The mold was heated from 35 ° C. to 60 ° C. in 3 hours, and the gasket was tried to be removed at 40 ° C., but it was liquid and fluid. Subsequently, the temperature was raised from 60 ° C. to 120 ° C. over 8 hours to proceed the polymerization. That is, the process of substantially losing fluidity was performed in a temperature range exceeding 40 ° C. After completion of the polymerization, the mixture was gradually cooled, and the lens was removed from the mold at 80 ° C. Although the obtained resin was excellent in transparency, optical distortion was severe. Further, deformation occurred at the time of mold release, and the appearance was distorted.

  When the optical properties of the obtained resin were measured, the refractive index was ne = 1.77 and νe = 30. Ten lenses prepared at the same time were confirmed and similar results were obtained. The results are summarized in Table 1.

[Comparative Example 2]
280 g of trimethylolpropane tris (2,3-epithiopropylthioglycolate) and 20.0 g of trimethylolpropane tris (thioglycolate) in a beaker at room temperature of 20 ° C., Biosorb 583 (manufactured by Kyodo Yakuhin) as an ultraviolet absorber After mixing and dissolving 0.3 g, adding 0.6 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixing the mixture is degassed for 0.4 hours under reduced pressure, and then a lens made of a glass mold and a gasket is prepared. Was injected into a mold (-6D). The mold was heated from 35 ° C. to 80 ° C. over 3 hours, and the gasket was tried to be removed at 40 ° C., but it was liquid and fluid. Subsequently, the temperature was raised from 80 ° C. to 120 ° C. over 3 hours to proceed the polymerization. That is, the process of substantially losing fluidity was performed in a temperature range exceeding 40 ° C. After completion of the polymerization, the mixture was gradually cooled, and the lens was removed from the mold at 25 ° C. Although the obtained resin was excellent in transparency, optical distortion was severe. At that time, there was no deformation, cracking or chipping at the time of mold release, and the appearance was good.

  When the optical properties of the obtained test piece were measured, the refractive index was ne = 1.62 and νe = 42. Ten lenses prepared at the same time were confirmed and similar results were obtained. The results are summarized in Table 1.

[Comparative Example 3]
After preparing the monomer raw material in the same manner as in Comparative Example 1, the monomer raw material was poured into a lens mold (-6D) composed of a glass mold and a gasket. The mold was held at 20 ° C. for 8 hours and then heated from 20 to 60 ° C. in 2 hours. At 40 ° C., the gasket was removed, but it was liquid and fluid. Subsequently, the temperature was raised from 60 ° C. to 120 ° C. over 5 hours to proceed the polymerization. That is, the process of substantially losing fluidity was performed in a temperature range exceeding 40 ° C. After the completion of polymerization, the mixture was gradually cooled, and the lens was removed from the mold at -25 ° C. Although the obtained resin was excellent in transparency, optical distortion was severe. At that time, although there was no deformation at the time of mold release, cracks and chips were observed and the appearance was not good.

  When the optical properties of the obtained test piece were measured, the refractive index was ne = 1.62 and νe = 42. Ten lenses prepared at the same time were confirmed and similar results were obtained. The results are summarized in Table 1.

Claims (5)

Method for producing a plastic lens made of the episulfide sulfur atom-containing resin having the following 1-4 steps.
Step 1: A step of injecting a polymerizable composition containing a compound having one or more episulfide groups between molding molds held by a gasket or tape to substantially lose fluidity at 40 ° C. or lower.
Step 2: After the fluidity of the polymerizable composition is substantially lost in Step 1 above, the step of removing the gasket or tape from the mold Step 3 : The fluidity held between the molds is substantially reduced. A step of polymerizing and curing the lost polymerizable composition at 40 ° C. or higher
Process 4 : The process of releasing the hardening body obtained at the said process 3 from the said mold at the temperature of 70 degrees C or less. 2. The polymerizable composition further contains at least one polythiol and at least one polyisocyanate, and the episulfide-based sulfur atom-containing resin obtained by polymerization and curing is a resin having a thiourethane bond. The manufacturing method of the plastic lens of description. The method for producing a plastic lens according to claim 1, wherein the polymerizable composition further contains single sulfur . The plastic lens obtained by the manufacturing method of any one of Claims 1 thru | or 3. The plastic lens according to claim 4, wherein the refractive index is 1.60 or more.