CN104725593A - Composition used for optical material and optical material employing the same - Google Patents

Abstract

The invention relates to a composition used for anoptical material and an optical material employing the same. Provided is a composition for an optical material, and the composition helps to predict, before the stage of polymerized solidification, changes of yellow, determine the good and the bad, and contains sulfuric polyester. A sulfuric polyester compound containing iron, chrome and nickle with the total amount of below 2.0ppm and the composition of a polyiso-(sulfur)-cyanate ester compound for the optical material are introduced to solve the problem of the invention. A compound of sulfuric polyester and episulfide for the optical material, containing iron, chrome and nickle with the total amount of below 2.0ppm is also introduced.

Description

Composition for optical material and use its optical material

Patent application of the present invention is the divisional application proposed for the application that the applying date is on 02 13rd, 2012, application number is 201210031805.3, denomination of invention is " composition for optical material and use its optical material ".

Technical field

The present invention relates to composition for optical material etc., particularly relate to and be suitable for plastic lens, prism, photoconductive fiber, information recording substrate (Ji Disk), the composition for optical material etc. of optical material, the particularly plastic lens such as spectral filter.And, the present invention relates to by the Polymerizable composition containing multi-thioalcohol compound and how different (sulphur) cyanate esters or multi-thioalcohol compound and episulfide is carried out being polymerized the method manufacturing the polyurethane series resin optical material with good optics physical property.

Background technology

Resinous optical material light weight compared with the optical material formed by inorganic materials not easily breaks and can dye.Therefore, in recent years, promptly universally in the such as optical material such as glasses lens, camera lens field to come.

Require the further high performance of resin for optical material.Specifically, high refractive index, high Abbe number, low-gravity, high heat resistance etc. are required.According to such requirement, develop so far and use various resin for optical material.

Wherein propose the scheme about polyurethane series resin energetically.Among polyurethane series resin, as most representative resin, the resin (with reference to patent documentation 1,2) making multi-thioalcohol compound and how different (sulphur) cyanate esters react and obtain can be enumerated.This resin is the excellents such as water white transparency, impact, dyeability, processibility.Wherein, the transparency of resin is as the requisite character of lens.

But, when manufacturing resin for optical material, be sometimes polymerized and the resin, the optical material that obtain can change color to yellow.Owing to being optical material purposes, if therefore variable color after solidification, can be all bad and produce huge loss.So, expect whether yellowish discoloration to occur after stage forecast solidification before curing and good and bad method can be judged.

In addition, be imbued with toughness due to plastic material light weight but also easily dye, therefore, being used for various optical material in recent years, especially glasses lens.For the performance of optical material, especially glasses lens special requirement, being low-gravity, high transparent and low yellow chromaticity, high heat resistance, high strength etc. as physical properties, is high refractive index and high Abbe number as optical property.High refractive index can make lens thin-walled property, and high Abbe number reduces the aberration of lens, but due to specific refractory power more rising, Abbe number more reduces, and therefore, implements the research making both simultaneously improve.Among these researchs, most representative method is the method (with reference to patent documentation 3) using episulfide compound.

In order to improve scale resistance, propose the composition (with reference to patent documentation 4) adding mercaptan compound in episulfide compound.Be that the research of target is also being carried out further with high refractive index, propose the composition (with reference to patent documentation 5,6) formed by sulphur, episulfide and mercaptan.

But there is the situation changing color to yellow when having carried out polymerizing curable in these compositions containing mercaptan.Owing to being optical material purposes, therefore, if variable color after solidification, can be all bad and produce huge loss.So, expect whether yellowish discoloration to occur after stage forecast solidification before curing and good and bad method can be judged.

Prior art document

Patent documentation

[patent documentation 1] Japanese Unexamined Patent Publication 7-252207 publication

[patent documentation 2] Japanese Unexamined Patent Publication 9-110956 publication

[patent documentation 3] Japanese Unexamined Patent Publication 9-110979 publication

[patent documentation 4] Japanese Unexamined Patent Publication 10-298287 publication

[patent documentation 5] Japanese Unexamined Patent Publication 2001-2783 publication

[patent documentation 6] Japanese Unexamined Patent Publication 2004-137481 publication

Summary of the invention

Problem to be solved by this invention is to provide can stage forecast before polymerizing curable whether yellowish discoloration occur after differentiating solidification and can judge good and bad, containing polythiol composition for optical material etc.

The present inventor is in view of these situations being concentrated on studies, result utilizes the total content containing iron, chromium, nickel to solve this problem at the polythiol of below 5.0ppm and the composition for optical material of how different (sulphur) cyanate esters, thus complete the present invention.And the present inventor utilizes the total content containing iron, chromium, nickel to solve this problem at the polythiol of below 5.0ppm and the composition for optical material of episulfide, thus completes the present invention.

That is, the present invention is as follows:

<1> composition for optical material, is characterized in that, the total content containing iron, chromium, nickel is at the multi-thioalcohol compound of below 5.0ppm and how different (sulphur) cyanate esters.

The composition for optical material of <2> according to above-mentioned <1>, wherein, described multi-thioalcohol compound is selected from 1,2-two [(2-mercapto ethyl) sulfenyl]-3-thio propane, two (thiopurine methyltransferase)-3,6,9-tri-thia-1,11-undecane two mercaptan, tetramethylolmethane four (3-thiohydracrylic acid) ester, two (thiopurine methyltransferase) thioether, 1, two (thiopurine methyltransferase) benzene and 1 of 3-, 1, at least one compound in 3,3-tetra-(thiopurine methyltransferase sulfenyl) propane.

The composition for optical material of <3> according to above-mentioned <1>, wherein, described how different (sulphur) cyanate esters is selected from 2, two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 5-, 2, two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 6-, two (isocyanatomethyl) hexanaphthene, dicyclohexyl methane diisocyanate, isophorone diisocyanate, 1, two (isocyanatomethyl) benzene of 3-and α, α, α ', at least one compound in α '-tetramethylxylylene diisocyanate.

<4> composition for optical material, is characterized in that, the total content containing iron, chromium and nickel is at the polythiol of below 5.0ppm and episulfide.

The composition for optical material of <5> according to above-mentioned <4>, wherein, further containing polyisocyanate compound.

The composition for optical material of <6> according to above-mentioned <4>, wherein, further containing sulphur.

<7> optical material, it is characterized in that, by the composition for optical material polymerization according to any one of above-mentioned <1> ~ <6> is obtained.

The optical material of <8> according to above-mentioned <7>, wherein, implements anneal after composition for optical material polymerization.

The manufacture method of a <9> composition for optical material, it is characterized in that, comprise the multi-thioalcohol compound of the total content of iron, chromium and nickel at below 5.0ppm and the operation of how different (sulphur) cyanate esters mixing.

The manufacture method of a <10> composition for optical material, is characterized in that, comprises the multi-thioalcohol compound of the total content of iron, chromium and nickel at below 5.0ppm and the operation of episulfide compound.

According to the present invention, can provide adopt conventional art comparatively difficulty, can stage forecast before polymerizing curable whether yellowish discoloration occurs after differentiating solidification and good and bad, containing multi-thioalcohol compound composition for optical material etc. can be judged.

Embodiment

1st embodiment of the present invention is a kind of composition for optical material, it is characterized in that, the total content containing iron, chromium, nickel is at the multi-thioalcohol compound of below 5.0ppm and how different (sulphur) cyanate esters.

2nd embodiment of the present invention is a kind of composition for optical material, it is characterized in that, the total content containing iron, chromium and nickel is at the polythiol of below 5.0ppm and episulfide.Multi-thioalcohol compound for the 1st embodiment of the present invention and the 2nd embodiment is not particularly limited, as long as have the compound of more than 2 thiol groups in 1 molecule.

As the object lesson of multi-thioalcohol compound, first two mercaptan can be enumerated, 1，2-ethandithiol, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,6-ethanthiol, 1,2,3-trithioglycerin, 1,1-cyclohexandithiol, 1,2-cyclohexandithiol, 2,2-dimethylpropane-1,3-bis-mercaptan, 3,4-dimethoxy-butane-1,2-bis-mercaptan, 2-methylcyclohexane-2,3-bis-mercaptan, two (mercapto methyl) hexanaphthene of 1,1-, two (2-mercaptoethyl) ester of mercaptosuccinic acid, 2,3-dimercapto-1-propyl alcohol (2-Thiovanic acid) ester, 2,3-dimercapto-1-propyl alcohol (3-thiohydracrylic acid) ester, diethylene glycol bis-(2-Thiovanic acid) ester, diethylene glycol bis-(3-thiohydracrylic acid) ester, 1,2-dimercapto propyl methyl ether, 2,3-dimercapto propyl methyl ether, 2,2-two (mercapto methyl)-1,3-dimercaptopropane, two (2-mercaptoethyl) ether, ethylene glycol bis (2-Thiovanic acid) ester, ethylene glycol bis (3-thiohydracrylic acid) ester, two (2-Thiovanic acid) ester of TriMethylolPropane(TMP), two (3-thiohydracrylic acid) ester of TriMethylolPropane(TMP), tetramethylolmethane four (2-Thiovanic acid) ester, tetramethylolmethane four (3-thiohydracrylic acid) ester, the fatty group polythiol compounds such as four (mercapto methyl) methane,

1, 2-thioresorcin, 1, 3-thioresorcin, 1, 4-thioresorcin, 1, two (mercapto methyl) benzene of 2-, 1, two (mercapto methyl) benzene of 3-, 1, two (mercapto methyl) benzene of 4-, 1, two (mercaptoethyl) benzene of 2-, 1, two (mercaptoethyl) benzene of 3-, 1, two (mercaptoethyl) benzene of 4-, 1, 2, 3-tri-thiol benzene, 1, 2, 4-tri-thiol benzene, 1, 3, 5-tri-thiol benzene, 1, 2, 3-tri-(mercapto methyl) benzene, 1, 2, 4-tri-(mercapto methyl) benzene, 1, 3, 5-tri-(mercapto methyl) benzene, 1, 2, 3-tri-(mercaptoethyl) benzene, 1, 2, 4-tri-(mercaptoethyl) benzene, 1, 3, 5-tri-(mercaptoethyl) benzene, 2, 5-toluene-dithiolate, 3, 4-toluene-dithiolate, 1, 3-bis-(p-methoxyphenyl) propane-2, 2-bis-mercaptan, 1, 3-diphenyl propane-2, 2-bis-mercaptan, phenylmethane-1, 1-bis-mercaptan, 2, the aromatic series multi-thioalcohol compounds such as 4-bis-(to mercaptophenyl) pentane,

1, two (mercaptoethyl sulfenyl) benzene, 1 of 2-, two (mercaptoethyl sulfenyl) benzene, 1 of 3-, two (mercaptoethyl sulfenyl) benzene, 1 of 4-, 2,3-tri-(mercapto methyl sulfenyl) benzene, 1,2,4-tri-(mercapto methyl sulfenyl) benzene, 1,3,5-tri-(mercapto methyl sulfenyl) benzene, 1,2,3-tri-(mercaptoethyl sulfenyl) benzene, 1,2, aromatic series multi-thioalcohol compound also containing sulphur atom beyond the sulfydryls such as 4-tri-(mercaptoethyl sulfenyl) benzene, 1,3,5-tri-(mercaptoethyl sulfenyl) benzene etc. and these core alkylide;

Two (mercapto methyl) thioether, two (mercapto methyl) disulfide, two (mercaptoethyl) thioether, two (mercaptoethyl) disulfide, two (mercaptopropyi) thioether, two (mercapto methyl sulfenyl) methane, two (2-mercaptoethyl sulfenyl) methane, two (3-mercaptopropyi sulfenyl) methane, two (mercapto methyl sulfenyl) ethane of 1,2-, two (the 2-mercaptoethyl sulfenyl) ethane of 1,2-, two (3-mercaptopropyi) ethane of 1,2-, two (mercapto methyl sulfenyl) propane of 1,3-, two (the 2-mercaptoethyl sulfenyl) propane of 1,3-, two (the 3-mercaptopropyi sulfenyl) propane of 1,3-, 1,2,3-tri-(mercapto methyl sulfenyl) propane, 1,2,3-tri-(2-mercaptoethyl sulfenyl) propane, 1,2,3-tri-(3-mercaptopropyi sulfenyl) propane, two [(2-mercaptoethyl) the sulfenyl]-3-thio propane of 1,2-, 4,8-dimercapto methyl isophthalic acid, 11-dimercapto-3,6,9-tri-thia undecane, 4,7-dimercapto methyl isophthalic acid, 11-dimercapto-3,6,9-tri-thia undecane, 5,7-dimercapto methyl isophthalic acid, 11-dimercapto-3,6,9-tri-thia undecane, two (mercapto methyl)-3,6,9-tri-thia-1,11-undecane two mercaptan, four (mercapto methyl butylthiomethyl) methane, four (2-mercaptoethyl butylthiomethyl) methane, four (3-mercaptopropyi butylthiomethyl) methane, two (2,3-dimercapto propyl group) thioether, two (1,3-dimercapto propyl group) thioether, 2,5-dimercapto-Isosorbide-5-Nitrae-dithiane, 2,5-dimercapto-methyl-1,4-dithiane, 2,5-dimercapto methyl-2,5-dimethyl-Isosorbide-5-Nitrae-dithiane, two (mercapto methyl) disulfide, two (mercaptoethyl) disulfide, fatty group polythiol compound also containing sulphur atom beyond the sulfydryls such as two (mercaptopropyi) disulfide, and the mercaptoacetate of these compounds and mercaptopropionic acid ester,

Two (2-Thiovanic acid) ester of methylol thioether, two (3-thiohydracrylic acid) ester of methylol thioether, two (2-Thiovanic acid) ester of hydroxyethyl thioether, two (3-thiohydracrylic acid) ester of hydroxyethyl thioether, two (2-Thiovanic acid) ester of hydroxypropyl sulphide, two (3-thiohydracrylic acid) ester of hydroxypropyl sulphide, two (2-Thiovanic acid) ester of methylol disulfide, two (3-thiohydracrylic acid) ester of methylol disulfide, two (2-Thiovanic acid) ester of hydroxyethyl disulfide, two (3-thiohydracrylic acid) ester of hydroxyethyl disulfide, two (2-Thiovanic acid) ester of hydroxypropyl disulfide, two (3-thiohydracrylic acid) ester of hydroxypropyl disulfide, two (2-Thiovanic acid) ester of 2-mercaptoethyl ether, two (3-thiohydracrylic acid) ester of 2-mercaptoethyl ether, two (2-Thiovanic acid) ester of Isosorbide-5-Nitrae-dithiane-2,5-glycol, two (3-thiohydracrylic acid) ester of Isosorbide-5-Nitrae-dithiane-2,5-glycol, two (2-mercaptoethyl) ester of thiodiglycolic acid, two (2-mercaptoethyl) ester of thiodipropionic acid, two (2-mercaptoethyl) ester of 4,4-sulfurous base two butyric acid, two (2-mercaptoethyl) ester of dithiodiglycollic acid, two (2-mercaptoethyl) ester of sub-disulfide group dipropionic acid, two (2-mercaptoethyl) ester of sub-disulfide group two butyric acid of 4,4-, two (2, the 3-dimercapto propyl group) ester of thiodiglycolic acid, two (2, the 3-dimercapto propyl group) ester of thiodipropionic acid, two (2, the 3-dimercapto propyl group) ester of dithiodiglycollic acid, the fatty group polythiol compound of sulphur atom and ester bond is also contained beyond other sulfydryls such as two (2, the 3-dimercapto propyl group) esters of sub-disulfide group dipropionic acid,

Heterogeneous ring compound also containing sulphur atom beyond the sulfydryls such as 3,4-thiophene two mercaptan, 2,5-dimercapto-1,3,4-thiadiazoles;

2 mercapto ethanol, 3-sulfydryl-1, 2-propylene glycol, glycerine two (Thiovanic acid) ester, 1-hydroxyl-4-sulfydryl hexanaphthene, 2, 4-dimercapto phenol, 2-sulfydryl quinhydrones, 4-mercapto-phenol, 3, 4-dimercapto-2-propyl alcohol, 1, 3-dimercapto-2-propyl alcohol, 2, 3-dimercapto-1-propyl alcohol, 1, 2-dimercapto-1, 3-butyleneglycol, tetramethylolmethane three (3-thiohydracrylic acid) ester, tetramethylolmethane list (3-thiohydracrylic acid) ester, two (3-thiohydracrylic acid) ester of tetramethylolmethane, tetramethylolmethane three (Thiovanic acid) ester, Dipentaerythritol five (3-thiohydracrylic acid) ester, methylol-three (mercaptoethyl butylthiomethyl) methane, compound also containing hydroxyl beyond the sulfydryls such as 1-hydroxyethyl sulfenyl-3-mercaptoethyl sulfenyl benzene,

1, 1, 3, 3-tetra-(mercapto methyl sulfenyl) propane, 1, 1, 2, 2-tetra-(mercapto methyl sulfenyl) ethane, 4, two (the mercapto methyl sulfenyl)-1 of 6-, 3-dithian, 1, 1, 5, 5-tetra-(mercapto methyl sulfenyl)-3-thia pentane, 1, 1, 6, 6-tetra-(mercapto methyl sulfenyl)-3, 4-dithia hexane, 2, two (mercapto methyl sulfenyl) sulfur alcohol of 2-, 2-(4, 5-dimercapto-2-thia amyl group)-1, 3-dithiolane, 2, two (mercapto methyl)-1 of 2-, 3-dithiolane, 2, 5-two (4, two (mercapto methyl the sulfenyl)-2-thia butyl of 4-)-1, 4-dithiane, 2, two (the mercapto methyl sulfenyl)-1 of 2-, 3-dimercaptopropane, 3-mercapto methyl sulfenyl-1, 7-dimercapto-2, 6-dithia heptane, 3, two (the mercapto methyl sulfenyl)-1 of 6-, 9-dimercapto-2, 5, 8-tri-thia nonane, 4, two (the mercapto methyl sulfenyl)-1 of 6-, 9-dimercapto-2, 5, 8-tri-thia nonane, 3-mercapto methyl sulfenyl-1, 6-dimercapto-2, 5-dithia hexane, 2-(2, two (mercapto methyl sulfenyl) ethyl of 2-)-1, 3-dithietane, 1, 1, 9, 9-tetra-(mercapto methyl sulfenyl)-5-(3, two (mercapto methyl the sulfenyl)-1-thia propyl group of 3-)-3, 7-dithia nonane, three (2, two (mercapto methyl sulfenyl) ethyl of 2-) methane, three (4, two (mercapto methyl the sulfenyl)-2-thia butyl of 4-) methane, four (2, two (mercapto methyl sulfenyl) ethyl of 2-) methane, four (4, two (mercapto methyl the sulfenyl)-2-thia butyl of 4-) methane, 3, 5, 9, 11-tetra-(mercapto methyl sulfenyl)-1, 13-dimercapto-2, 6, 8, 12-tetra-thia tridecane, 3, 5, 9, 11, 15, 17-six (mercapto methyl sulfenyl)-1, 19-dimercapto-2, 6, 8, 12, 14, 18-six thia nonadecane, 9-(2, two (mercapto methyl sulfenyl) ethyl of 2-)-3, 5, 13, 15-tetra-(mercapto methyl sulfenyl)-1, 17-dimercapto-2, 6, 8, 10, 12, 16-six thia heptadecane, 3, 4, 8, 9-tetra-(mercapto methyl sulfenyl)-1, 11-dimercapto-2, 5, 7, 10-tetra-thia undecane, 3, 4, 8, 9, 13, 14-six (mercapto methyl sulfenyl)-1, 16-dimercapto-2, 5, 7, 10, 12, 15-six thia n-Hexadecane, two (mercapto methyl sulfenyl) methyl of 8-{ }-3, 4, 12, 13-tetra-(sulfydryl methylthio group)-1, 15-dimercapto-2, 5, 7, 9, 11, 14-six thia pentadecane, 4, 6-two { 3, two (mercapto methyl the sulfenyl)-7-sulfydryl-2 of 5-, 6-dithia heptyl sulfenyl }-1, 3-dithiane, 4-{3, two (mercapto methyl the sulfenyl)-7-sulfydryl-2 of 5-, 6-dithia heptyl sulfenyl }-6-mercapto methyl sulfenyl-1, 3-dithiane, 1, two { the 4-(6-mercapto methyl sulfenyl)-1 of 1-, 3-dithiane base sulfenyl }-3, two (mercapto methyl sulfenyl) propane of 3-, 1, two { the 4-(6-mercapto methyl sulfenyl)-1 of 3-, 3-dithiane base sulfenyl }-1, two (mercapto methyl sulfenyl) propane of 3-, 1-{4 (6-mercapto methyl sulfenyl)-1, 3-dithiane base sulfenyl }-3-{2, two (mercapto methyl sulfenyl) ethyl of 2-}-7, two (the mercapto methyl sulfenyl)-2 of 9-, 4, 6, 10-tetra-thia undecane, 1-{4-(6-mercapto methyl sulfenyl)-1, 3-dithiane base sulfenyl }-3-{2-(1, 3-dithietane base) } methyl-7, two (the mercapto methyl sulfenyl)-2 of 9-, 4, 6, 10-tetra-thia undecane, 1, two { the 4-(6-mercapto methyl sulfenyl)-1 of 5-, 3-dithiane base sulfenyl }-3-{2-(1, 3-dithietane base) } methyl-2, 4-Dithiapentane, 4, two [the 3-{2-(1 of 6-, 3-dithietane base) } methyl-5-sulfydryl-2, 4-dithia pentylthio]-1, 3-dithiane, 4, two { the 4-(6-mercapto methyl sulfenyl)-1 of 6-, 3-dithiane base sulfenyl }-1, 3-dithiane, 4-{4-(6-mercapto methyl sulfenyl)-1, 3-dithiane base sulfenyl }-6-{4-(6-mercapto methyl sulfenyl)-1, 3-dithiane base sulfenyl }-1, 3-dithiane, 3-{2-(1, 3-dithietane base) } methyl-7, two (the mercapto methyl sulfenyl)-1 of 9-, 11-dimercapto-2, 4, 6, 10-tetra-thia undecane, 9-{2-(1, 3-dithietane base) } methyl-3, 5, 13, 15-tetra-(mercapto methyl sulfenyl)-1, 17-dimercapto-2, 6, 8, 10, 12, 16-six thia heptadecane, 3-{2-(1, 3-dithietane base) } methyl-7, 9, 13, 15-tetra-(mercapto methyl sulfenyl)-1, 17-dimercapto-2, 4, 6, 10, 12, 16-six thia heptadecane, 3, two { the 2-(1 of 7-, 3-dithietane base) } methyl isophthalic acid, 9-dimercapto-2, 4, 6, 8-tetra-thia nonane, 4-{3, 4, 8, 9-tetra-(mercapto methyl sulfenyl)-11-sulfydryl-2, 5, 7, 10-tetra-thia undecyl }-5-mercapto methyl sulfenyl-1, 3-dithiolane, 4, 5-two { 3, two (mercapto methyl the sulfenyl)-6-sulfydryl-2 of 4-, 5-dithia hexyl sulfenyl }-1, 3-dithiolane, 4-{3, two (mercapto methyl the sulfenyl)-6-sulfydryl-2 of 4-, 5-dithia hexyl sulfenyl }-5-mercapto methyl sulfenyl-1, 3-dithiolane, two (mercapto methyl sulfenyl) methyl-5 of 4-{3-, two (mercapto methyl the sulfenyl)-8-sulfydryl-2 of 6-, 4, 7-tri-thia octyl group }-5-mercapto methyl sulfenyl-1, 3-dithiolane, 2-[two { 3, two (mercapto methyl the sulfenyl)-6-sulfydryl-2 of 4-, 5-dithia hexyl sulfenyl } methyl]-1, 3-dithietane, 2-{3, two (mercapto methyl the sulfenyl)-6-sulfydryl-2 of 4-, 5-dithia hexyl sulfenyl } mercapto methyl butylthiomethyl-1, 3-dithietane, 2-{3, 4, 8, 9-tetra-(mercapto methyl sulfenyl)-11-sulfydryl-2, 5, 7, 10-tetra-thia undecyl sulfenyl } mercapto methyl butylthiomethyl-1, 3-dithietane, two (mercapto methyl sulfenyl) methyl-5 of 2-{3-, two (mercapto methyl the sulfenyl)-8-sulfydryl-2 of 6-, 4, 7-tri-thia octyl group } mercapto methyl butylthiomethyl-1, 3-dithietane, 4, two [the 1-{2-(1 of 5-, 3-dithietane base) }-3-sulfydryl-2-thia propyl group sulfenyl]-1, 3-dithiolane, 4-[1-{2-(1, 3-dithietane base) }-3-sulfydryl-2-thia propyl group sulfenyl]-5-{1, two (mercapto methyl the sulfenyl)-4-sulfydryl-3-thia butyl sulfenyl of 2-}-1, 3-dithiolane, 2-[two { 4-(5-mercapto methyl sulfenyl-1, 3-dithiolane base) sulfenyl }] methyl isophthalic acid, 3-dithietane, 4-{4-(5-mercapto methyl sulfenyl-1, 3-dithiolane base) sulfenyl }-5-[1-{2-(1, 3-dithietane base) }-3-sulfydryl-2-thia propyl group sulfenyl]-1, 3-dithiolane, their oligomer etc. has the compound of dithioacetals or two thio ketal ization skeletons further,

Three (mercapto methyl sulfenyl) methane, three (mercaptoethyl sulfenyl) methane, 1,1,5,5-tetra-(mercapto methyl sulfenyl)-2,4-Dithiapentane, two (4,4-two (mercapto methyl sulfenyl)-1,3-dithia butyl) (mercapto methyl sulfenyl) methane, three (4,4-two (mercapto methyl sulfenyl)-1,3-dithia butyl) methane, 2,4,6-tri-(mercapto methyl sulfenyl)-1,3,5-trithians, two (mercapto methyl sulfenyl)-1,3, the 5-trithians of 2,4-, 1,1,3,3-tetra-(mercapto methyl sulfenyl)-2-thiiranes, two (mercapto methyl) methylsulfany-1,3,5-trithian, three ((4-mercapto methyl-2,5-dithia cyclohexyl-1-base) methylsulfany) methane, two (mercapto methyl sulfenyl)-1, the 3-dithiolane of 2,4-, 2-mercaptoethyl sulfenyl-4-mercapto methyl-1,3-dithiolane, 2-(2,3-dimercapto propyl group sulfenyl)-1,3-dithiolane, 4-mercapto methyl-2-(2,3-dimercapto propyl group sulfenyl)-1,3-dithiolane, 4-mercapto methyl-2-(1,3-dimercapto-2-propyl group sulfenyl)-1,3-dithiolane, three (two (mercapto methyl the sulfenyl)-1-thia ethyl of 2,2-) methane, three (two (mercapto methyl the sulfenyl)-2-thia propyl group of 3,3-) methane, three (two (mercapto methyl the sulfenyl)-3-thia butyl of 4,4-) methane, 2,4,6-tri-(two (mercapto methyl the sulfenyl)-2-thia propyl group of 3,3-)-1,3,5-trithians, four (two (mercapto methyl the sulfenyl)-2-thia propyl group of 3,3-) methane etc., their oligomer etc. has the compound of trithio ortho-formiate skeleton further,

3,3 '-two (mercapto methyl sulfenyl)-1,5-dimercapto-2,4-Dithiapentane, 2,2 '-two (mercapto methyl sulfenyl)-1,3-dithiolane, 2,7-bis-(mercapto methyl)-1,4,5,9-tetra-thia spiral shell [4.4] nonane, 3,9-dimercapto-1,5,7,11-tetra-thia spiral shell [5.5] undecane, further their oligomer etc. have the compound etc. of ortho-thiocarbonic acid ester skeleton.

But multi-thioalcohol compound is not limited to above each exemplary compounds.And above each exemplary compounds may be used alone, can also be two or more kinds in combination.

Among above exemplary compounds, preferred compound is 1,2-two [(2-mercaptoethyl) sulfenyl]-3-thio propane, two (mercapto methyl)-3,6,9-tri-thia-1,11-undecane two mercaptan, tetramethylolmethane four (3-thiohydracrylic acid) ester, two (mercapto methyl) thioether, 1,3-two (mercapto methyl) benzene, 1,1,3,3-tetra-(mercapto methyl sulfenyl) propane.

For the total content of the iron in polythiol, chromium, nickel, as long as the total content of iron, chromium, nickel can be measured, any measuring method, but preferably adopt ICP apparatus for analyzing luminosity to measure.Mensuration according to the rules method, with sulfuric acid, nitric acid etc. acid pre-treatment has been carried out to polythiol after carry out.Carry out these to measure, use the polythiol of total content at below 5.0ppm of iron, chromium, nickel.Preferably at below 2.0ppm, more preferably at below 1.0ppm, preferred at below 0.5ppm further, most preferably at below 0.3ppm.

When the total content of iron, chromium, nickel is more than 5.0ppm, these compositions containing polythiol change color to yellow when polymerizing curable and cannot use.Therefore, by measuring the total content of iron, chromium, nickel, without the need to making its polymerizing curable and measurable and differentiate whether change color to yellow and the quality of polythiol can be judged.

When the total content of iron, chromium, nickel is more than 5.0ppm, it is made to be effective means at below 5.0ppm through refining step.Further enforcement is refining to be become preferably, more preferably, further preferred, most preferred state be also effective means.As refining method, washing, distillation, post lock out operation, sorbent treatment, ion exchange resin treatment etc. can be enumerated, but preferably wash, distill.

Washing can use solvent, also can not use solvent, but usually use.As solvent, as long as dissolve the solvent of this polythiol, any solvent all can use, but preferred and the segregative ether of the water capacity, toluene, benzene, more preferably use toluene.Therefore, washing is carried out usually under the state being dissolved in toluene, removes toluene in the completed.

For distillation, according to the polythiol used, condition is different, as long as but the condition that can distill of this polythiol, any condition.Preferably under reduced pressure, 0.01 ~ 100Torr is more preferably.As long as there is not the temperature of decomposing in distillation temperature, but preferably 20 ~ 200 DEG C, more preferably 50 DEG C ~ 150 DEG C.

In the 1st embodiment of the present invention, the Polymerizable composition containing multi-thioalcohol compound and how different (sulphur) cyanate esters is polymerized, manufactures optical material polyurethane series resin thus.

How different (sulphur) cyanate esters for the 1st embodiment of the present invention is not particularly limited, as long as the compound that different (sulphur) in 1 molecule with more than 2 is cyanate ester based.In addition, " different (sulphur) cyanate " is meant to " isocyanic ester or lsothiocyanates ".

As the object lesson of how different (sulphur) cyanate esters, hexamethylene diisocyanate can be enumerated, 2, 2-dimethyl-penten vulcabond, 2, 2, 4-trimethylammonium hexamethylene diisocyanate, butene diisocyanate, 1, 3-divinyl-1, 4-vulcabond, 2, 4, 4-trimethyl hexamethylene diisocyanate, 1, 6, 11-undecane triisocyanate, 1, 3, 6-hexa-methylene triisocyanate, 1, 8-diisocyanate based-4-isocyanatomethyl octane, two (isocyanatoethyl) carbonic ether, two (isocyanatoethyl) ether, Methionin two isocyanato-methyl esters, the aliphatic polyisocyanate compounds such as Lysine triisocyanate,

2, the alicyclic polyisocyanates compounds such as two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 5-, 2,6-two (isocyanatomethyl)-dicyclo [2.2.1] heptane, two (isocyanatomethyl) hexanaphthene, dicyclohexyl methane diisocyanate, isophorone diisocyanates;

1,2-bis-isocyanato-benzene, 1,3-bis-isocyanato-benzene, Isosorbide-5-Nitrae-two isocyanato-benzene, 2,4-bis-isocyanato-toluene, ethylbenzene vulcabond, isopropyl benzene vulcabond, dimethyl benzene vulcabond, di-ethylbenzene diisocyanate, di-isopropyl phenylene diisocyanate, Three methyl Benzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4 '-methylene-bis (phenyl isocyanate), 4,4 '-methylene-bis (2-methylphenyl isocyanate), bibenzyl-4,4 '-vulcabond, two (isocyanatophenyi) ethane, two (isocyanatomethyl) benzene of 1,2-, two (isocyanatomethyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(isocyanatomethyl) benzene, two (isocyanatoethyl) benzene of 1,2-, two (isocyanatoethyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(isocyanatoethyl) benzene, two (isocyanatopropyl) benzene of 1,2-, two (isocyanatopropyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(isocyanatopropyl) benzene, α, α, α ', α '-tetramethylxylylene diisocyanate, two (isocyanatobutyl) benzene, two (isocyanatomethyl) naphthalene, two (isocyanatomethylbenzene base) ether, two (isocyanatoethyl) phthalic ester, 2,6-bis-(isocyanatomethyl) furans etc. has the polyisocyanate compound of aromatic cycle compound,

Two (isocyanatomethyl) thioether, two (isocyanatoethyl) thioether, two (isocyanatopropyl) thioether, two (isocyanato-hexyl) thioether, two (isocyanatomethyl) sulfone, two (isocyanatomethyl) disulfide, two (isocyanatoethyl) disulfide, two (isocyanatopropyl) disulfide, two (isocyanatomethyl sulfenyl) methane, two (isocyanatoethyl sulfenyl) methane, two (isocyanatomethyl sulfenyl) ethane, two (isocyanatoethyl sulfenyl) ethane, 1,5-bis-isocyanato--2-isocyanatomethyl-3-thia pentane, 1,2,3-tri-(isocyanatomethyl sulfenyl) propane, 1,2,3-tri-(isocyanatoethyl sulfenyl) propane, 3,5-dithia-1,2,6,7-tetraisocyanate in heptan, 2,6-bis-isocyanatomethyl-3,5-dithia-1,7-vulcabond in heptan, 2,5-bis-isocyanatomethyl thiophene, the sulfur-bearing aliphatic polyisocyanate compounds such as the pungent vulcabond of isocyanatoethyl sulfenyl-2,6-dithia-1,8-,

The aromatic thioether system polyisocyanate compounds such as 2-isocyanatophenyi-4-isocyanatophenyi thioether, two (4-isocyanatophenyi) thioether, two (4-isocyanatomethylbenzene base) thioether;

The aromatic series disulfide system polyisocyanate compounds such as two (4-isocyanatophenyi) disulfide, two (2-methyl-5-isocyanatophenyi) disulfide, two (3-methyl-5-isocyanatophenyi) disulfide, two (3-methyl-6-isocyanatophenyi) disulfide, two (4-methyl-5-isocyanatophenyi) disulfide, two (4-methoxyl group-3-isocyanatophenyi) disulfide;

2,5-bis-isocyanato-tetramethylene sulfide, 2,5-bis-isocyanatomethyl tetramethylene sulfide, 3,4-bis-isocyanatomethyl tetramethylene sulfide, 2,5-bis-isocyanato--1,4-dithiane, 2,5-bis-isocyanatomethyl-1,4-dithiane, 4,5-bis-isocyanato--1,3-dithiolanes, 4, two (isocyanatomethyl)-1 of 5-, 3-dithiolane, 4,5-bis-isocyanatomethyl-2-methyl isophthalic acids, the sulfur-bearing alicyclic polyisocyanates compounds such as 3-dithiolane;

1,2-diisothiocyanic acid root closes ethane, 1,6-diisothiocyanic acid root closes the aliphatics polyisothiocyanates compounds such as hexane, the alicyclic polyisothiocyanates compounds such as hexanaphthene diisothio-cyanate, 1, 2-diisothiocyanic acid root closes benzene, 1, 3-diisothiocyanic acid root closes benzene, 1, 4-diisothiocyanic acid root closes benzene, 2, 4-diisothiocyanic acid root closes toluene, 2, 5-diisothiocyanic acid root closes m-xylene, 4, 4 '-methylene-bis (PITC), 4, 4 '-methylene-bis (2-aminomethyl phenyl lsothiocyanates), 4, 4 '-methylene-bis (3-aminomethyl phenyl lsothiocyanates), 4, 4 '-diisothiocyanic acid root closes benzophenone, 4, 4 '-diisothiocyanic acid root closes-3, 3 '-dimethyl benzophenone, the aromatic series polyisothiocyanates compounds such as two (4-Isothiocyanato-phenyl) ether,

And then, the carbonyl polyisothiocyanates compounds such as 1,3-benzene dicarbonyl diisothiocyanate, Isosorbide-5-Nitrae-benzene dicarbonyl diisothiocyanate, (2,2-pyridine)-4,4-dicarbonyl diisothiocyanate; The sulfur-bearing aliphatics polyisothiocyanates compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanato ethane), dithio two (2-isothiocyanato ethane);

The sulfur-containing aromatic polyisothiocyanates compounds such as 1-isothiocyanato-4-[(2-isothiocyanato) alkylsulfonyl] benzene, thiobis (4-isothiocyanato benzene), alkylsulfonyl (4-isothiocyanato benzene), dithio two (4-isothiocyanato benzene); 2,5-diisothiocyanic acid root closes the alicyclic polyisothiocyanates compound of sulfur-bearing such as thiophene, 2,5-diisothiocyanic acid root conjunction-Isosorbide-5-Nitrae-dithiane;

1-isocyanato--6-isothiocyanato hexane, 1-isocyanato--4-isosulfocyanate radical trimethylcyclohexane, 1-isocyanato--4-isothiocyanato benzene, 4-methyl-3-isocyanato--1-isothiocyanato benzene, 2-isocyanato--4,6-diisothiocyanic acid root closes-1,3,5-triazine, 4-isocyanatophenyi-4-Isothiocyanato-phenyl thioether, 2-isocyanatoethyl-2-isothiocyanato ethyl disulfide etc. have how different (sulphur) cyanate esters of isocyanate group and isothiocyanate group.

And then, can also use the halogen substituents such as the chlorine substituent of above-claimed cpd, bromine substituent, alkyl substituents, alkoxy substituents, nitro substituent, with the prepolymer type modification body of polyvalent alcohol, carbodiimide modified body, urea modification body, biuret modified body, dimerization or trimerizing reaction product etc.

But how different (sulphur) cyanate esters is not limited to above each exemplary compounds.In addition, above each exemplary compounds may be used alone, can also be two or more kinds in combination.

Among above exemplary compounds, preferred compound is 2, two (isocyanatomethyl)-dicyclo [2.2.1] heptane, 2 of 5-, 6-two (isocyanatomethyl)-dicyclo [2.2.1] heptane, two (isocyanatomethyl) hexanaphthene, dicyclohexyl methane diisocyanate, isophorone diisocyanate, 1, two (isocyanatomethyl) benzene of 3-and α, α, α ', α '-tetramethylxylylene diisocyanate.

The usage ratio of multi-thioalcohol compound and how different (sulphur) cyanate esters is generally in the scope of SH base/NCO (NCS) base=0.5 ~ 3.0, preferably in the scope of 0.6 ~ 2.0, preferred in the scope of 0.8 ~ 1.3 further.

The composition for optical material of the 1st embodiment of the present invention is the composition of principal constituent with multi-thioalcohol compound and how different (sulphur) cyanate esters.In addition, the practicality that catalyzer, internal mold release, UV light absorber, bluing agent etc. become to assign to improve further arbitrarily resulting materials can certainly be added as required.Such as, polyurethane series lens can by injecting multi-thioalcohol compound, how different (sulphur) cyanate esters and any composition as required, carrying out being polymerized manufacturing in lens mould.

In the 2nd embodiment of the present invention, manufacture optical material polyurethane series resin by the Polymerizable composition containing multi-thioalcohol compound and episulfide compound is carried out polymerization.

The episulfide compound used in 2nd embodiment of the present invention comprises whole episulfide compounds, as object lesson be divided into have chain fatty race skeleton, aliphatic cyclic skeleton, aromatic backbone compound enumerate.

As the compound with chain fatty race skeleton, the compound represented by following (1) formula can be enumerated.

(wherein, m represents the integer of 0 ~ 4, and n represents the integer of 0 ~ 2.)

As the compound with aliphatic cyclic skeleton, following (2) formula or the compound represented by (3) formula can be enumerated.

(p, q separately represent the integer of 0 ~ 4.)

(p, q separately represent the integer of 0 ~ 4.)

As the compound with aromatic backbone, the compound represented by following (4) formula can be enumerated.

(p, q separately represent the integer of 0 ~ 4.)

Wherein preferred compound has chain fatty race skeleton, compound represented by above-mentioned (1) formula, be specifically two (β-epithiopropyl) thioether, two (β-epithiopropyl) disulfide, two (β-epithiopropyl sulfenyl) methane, 1, two (β-epithiopropyl sulfenyl) ethane, 1 of 2-, 3-two (β-epithiopropyl sulfenyl) propane, Isosorbide-5-Nitrae-bis-(β-epithiopropyl sulfenyl) butane.Particularly preferred compound is two (β-epithiopropyl) thioether (in above-mentioned (1) formula n=0), two (β-epithiopropyl) disulfides (in above-mentioned (1) formula m=0, n=1); Most preferred compound is two (β-epithiopropyl) thioethers (in above-mentioned (1) formula n=0).

In addition, as the episulfide compound with aliphatic cyclic skeleton, can 1 be enumerated, 3 and 1, two (β-epithiopropyl sulfenyl) hexanaphthene of 4-(p=0 in above-mentioned (2) formula, q=0), 1,3 and 1, two (β-epithiopropylthiomethyl) hexanaphthene of 4-(p=1 in above-mentioned (2) formula, q=1), 2, two (β-epithiopropyl sulfenyl)-Isosorbide-5-Nitrae-dithiane (in above-mentioned (3) formula p=0, q=0) of 5-etc.

In addition, as the episulfide compound with aromatic backbone, can 1 be enumerated, 3 and 1, two (β-epithiopropyl sulfenyl) benzene (in above-mentioned (4) formula p=0, q=0), 1,3 and 1 of 4-, two (β-epithiopropylthiomethyl) benzene (in above-mentioned (4) formula p=1, q=1) of 4-etc.

When making the total amount of polythiol and episulfide be 100 weight part, the polythiol of the composition for optical material of the 2nd embodiment of the present invention is generally 1 ~ 30 weight part, is preferably 2 ~ 20 weight parts, is particularly preferably 3 ~ 15 weight parts.

The composition for optical material of the 2nd embodiment of the present invention can add polyisocyanate compound further.This polyisocyanate compound comprises all compounds with multiple isocyanate group, can enumerate diethylidene vulcabond particularly, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, cyclohexyl diisocyanate, two (isocyanatomethyl) hexanaphthene of 1,3-, Isosorbide-5-Nitrae-bis-(isocyanatomethyl) hexanaphthene, isophorone diisocyanate, two (isocyanatomethyl) perhydronaphthalene of 2,6-, Lysine triisocyanate, 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, diaminoditolyl vulcabond, 4,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyl ether diisocyanate, 3-(2 '-isocyanic ester butylcyclohexyl) propylisocyanate, three (phenyl isocyanate base) thiophosphatephosphorothioate, isopropylidene two (cyclohexyl isocyanate), 2,2 '-bis-(4-isocyanatophenyi) propane, triphenylmethane triisocyanate, two (two isocyanato-tolyls) phenylmethane, 4,4 ', 4 "-triisocyanate base-2,5-dimethoxyaniline, 3,3 '-dimethoxy benzidine-4,4 '-vulcabond, 1,3-phenylene diisocyanate, Isosorbide-5-Nitrae-phenylene diisocyanate, 4,4 '-two isocyanato-biphenyl (4,4 '-diisocyanato biphenyl), 4,4 '-two isocyanato--3,3 '-dimethyl diphenyl, dicyclohexyl methyl hydride-4,4 '-vulcabond, 1,1 '-methylene-bis (4-isocyanato-benzene), 1,1 '-methylene-bis (3-methyl-4-isocyanato-benzene), m-xylylene diisocyanate, terephthalylidene vulcabond, two (1-isocyanato--1-methylethyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(1-isocyanato--1-methylethyl) benzene, two (2-isocyanato--2-propyl group) benzene of 1,3-, two (isocyanatomethyl) naphthalene of 2,6-, 1,5-naphthalene diisocyanate, two (isocyanatomethyl) tetrahydrochysene Dicyclopentadiene (DCPD), two (isocyanatomethyl) Dicyclopentadiene (DCPD), two (isocyanatomethyl) tetramethylene sulfide, two (isocyanatomethyl) norbornylene, two (isocyanatomethyl) diamantane, dimer acid diisocyanate, 1,3,5-tri-(1-isocyanato-hexyl) isocyanuric acid, thiodiethyl diisocyanate, thiodipropyl diisocyanate, sulfo-dihexyl vulcabond, two [(4-isocyanatomethyl) phenyl] thioether, 2,5-is diisocyanate based-Isosorbide-5-Nitrae-dithiane, 2,5-, bis-isocyanatomethyl-Isosorbide-5-Nitrae-dithiane, 2,5-bis-isocyanatomethyl thiophene, dithio diethyl vulcabond, the polyisocyanates such as dithiodipropyl, the isocyanate group of above-mentioned isocyanates is become isothiocyanate group in whole or in part and the compound etc. obtained.In addition, among above compound, for polyisocyanates, can enumerate and be reacted by biuret form and the isocyanates such as affixture of the dimer obtained, cyclic trimerization body and alcohol or mercaptan.Although show above object lesson, but the polyisocyanate compound that can be used in the composition for optical material of the 2nd embodiment of the present invention is not limited thereto, in addition, these polyisocyanate compounds may be used alone, can also be 2 or more kinds in combination.

Among above compound, preferred polyisocyanate compound is 1,3-two (isocyanatomethyl) hexanaphthene, m-xylylene diisocyanate, two (isocyanatomethyl) norbornylene, 2,5-bis-isocyanatomethyl-1,4-dithiane, 1,3-two (1-isocyanato--1-methylethyl) benzene; Most preferred polyisocyanate compound is m-xylylene diisocyanate.

Relative to composition for optical material total amount, the addition of above-mentioned polyisocyanate compound is generally 0.1 ~ 30 quality %, is preferably 0.5 ~ 20 quality %, is more preferably 1 ~ 15 quality %.

In addition, sulphur can be added in the composition for optical material of the 2nd embodiment of the present invention.When using sulphur, episulfide compound and sulphur is preferably made to carry out pre-reaction in advance.The condition optimization of this prepolymerization is-10 DEG C ~ 120 DEG C, 0.1 ~ 240 hour; Be more preferably 0 DEG C ~ 100 DEG C, 0.1 ~ 120 hour; Be particularly preferably 20 DEG C ~ 80 DEG C, 0.1 ~ 60 hour.Catalyzer is used to be effective in order to make pre-reaction carry out, as preference, 2-sulfydryl-1-Methylimidazole can be enumerated, triphenylphosphine, 3, 5-dimethyl pyrazole, N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (N-cyclohexcyl-2-benzothiazolyl sulfinamide), bis-pentamethylenethiuram tetrasulfide, tetrabutylthiuram disulfide, tetraethylthiuram disulfide, 1, 2, 3-triphenyl guanidine, 1, 3-diphenylguanidine, 1, 1, 3, 3-tetramethylene guanidine, aminoguanidine urea, trimethyl thiourea, tetraethyl-thiocarbamide, dimethyl ethyl thiourea, zinc dibutyl dithiocarbamate, zinc dibenzyldithiocarbamate, zinc diethyldithiocarbamate, ziram, methyl piperidine base dithiocarbamic acid methyl piperidine deng.And then, preferably by this prepolymerization make sulphur consume more than 10% (with before reacting for 100%), more preferably consume more than 20%.Pre-reaction can under the rare gas element such as air, nitrogen, normal pressure or carry out under airtight inferior, any ambiance of bringing by adding decompression.In addition, carry out degree in order to what detect pre-reaction, also can use liquid phase chromatography, index meter.

Relative to composition for optical material total amount, the addition of sulphur is generally 0.01 ~ 40 quality %, is preferably 0.1 ~ 30 quality %, is more preferably 0.5 ~ 25 quality %.

Below, be described the composition for optical material of the 1st embodiment of the present invention is polymerized the method manufacturing optical material.

As the catalyzer making the composition for optical material of the 1st embodiment of the present invention carry out polymerizing curable, use known polyurethane-reinforcement catalyzer.Because the addition of polymerizing catalyst changes according to the composition of composition, ratio of mixture and polymerizing curable method, therefore, cannot determine without exception, but relative to composition for optical material total amount, usual use 0.001 quality % ~ 5 quality %, preferred use 0.01 quality % ~ 1 quality %, most preferably uses 0.01 quality % ~ 0.5 quality %.If the addition of polymerizing catalyst is more than 5 quality %, then can there is the specific refractory power of cured article, thermotolerance reduces and painted situation.In addition, if be less than 0.001 quality %, then the situation of insufficient solidification and thermotolerance deficiency can be there is.

As the preference of ultraviolet screener, benzotriazole based compound can be enumerated.Wherein the object lesson of preferred compound is 2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, the chloro-2-(3 of 5-, 5-di-t-butyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl) the chloro-2H-benzotriazole of-5-, 2-(3,5-bis-tert-pentyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl)-2H-benzotriazole, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-)-2H-benzotriazole.As the preference of bluing agent, anthraquinone based compound can be enumerated.

In addition, when composition for optical material of the present invention is difficult to be peeled off by mould after polymerisation, also can use or add known outside and/or internal mold release to strengthen the release property of gained cured article by mould.So-called releasing agent, fluorine system nonionogenic tenside, silicon system nonionogenic tenside, phosphoric acid ester, acid phosphoric acid ester, oxidation ene-type phosphoric acid ester, an alkali metal salt of acid phosphoric acid ester, an alkali metal salt of oxidation ene-type acid phosphoric acid ester, an alkali metal salt of higher fatty acid, high-grade aliphatic ester, paraffin, wax, higher aliphatic acid amides, senior aliphat alcohol, polysiloxane-based, fatty amine ethylene oxide adduct etc. can be enumerated, they may be used alone, can also be two or more kinds in combination.Relative to composition for optical material total amount, addition is generally 0.0001 ~ 5 quality %.

To improve for the purpose of each physical property of polyurethane series resin, operability and polymerisation reactivity etc. further, except forming the multi-thioalcohol compound of urethane resin and different (sulphur) cyanate esters, the representative urethane such as active dydrogen compounds, epoxy compounds, olefin(e) compound, carbonate products, ester cpds such as amine can be added and form more than a kind compound beyond raw material.

The optical material formed by polyurethane series resin is manufactured by cast poymerization usually.Specifically, by multi-thioalcohol compound and the mixing of how different (sulphur) cyanate esters.After adopting appropriate means that this mixed solution (Polymerizable composition) is carried out deaeration as required, in injection optics material injection mould, usually heat lentamente from low temperature to high temperature and make it be polymerized.Afterwards, optical material is obtained by the demoulding.

In 1st embodiment of the present invention and the 2nd embodiment, preferably in advance degassed process is carried out to composition for optical material.Degassed process is before the compound that can carry out reacting with part or all of moiety, polymerizing catalyst, additive mix, when mixing or after mixing and under reduced pressure carry out.Preferably also under reduced pressure carry out when mixing or after mixing.Treatment condition carry out 1 minute ~ 24 hours under the decompression of 0.001 ~ 50torr, in 0 DEG C ~ 100 DEG C.Degree of pressure reduction is preferably 0.005 ~ 25torr, is more preferably 0.01 ~ 10torr, can change degree of pressure reduction in these scopes.Degassing time is preferably 5 minutes ~ 18 hours, is more preferably 10 minutes ~ 12 hours.Temperature time degassed is preferably 5 DEG C ~ 80 DEG C, is more preferably 10 DEG C ~ 60 DEG C, can change temperature in these scopes.From the viewpoint of raising degasifying effect, the interface when degassed process by upgrading resin-forming composition by the vibration etc. of stirring, being blown into the generation such as gas, ultrasonic wave is preferred operation.The composition removed by degassed process is the low boilers such as gas dissolved, low-molecular-weight mercaptan etc. such as hydrogen sulfide mainly, as long as present effect of the present invention, is not particularly limited the kind of the object component of removing.

And then, from the viewpoint of the quality improving further optical material of the present invention, also preferably these composition for optical material and/or each raw material before mixing are gone out impurity etc. with the metre filter in the aperture with about 0.05 ~ 10 μm and refines.

To above-mentioned reaction, the composition for optical material implantation glass of process, metal mould be completed, after facilitating polymerization curing reaction by the irradiation of heating, ultraviolet isoreactivity energy-ray, take out from mould.Manufacture optical material thus.Composition for optical material carries out polymerizing curable preferably by heating thus manufactures optical material.Now, set time is 0.1 ~ 200 hour, is generally 1 ~ 100 hour; Solidification value is-10 DEG C ~ 160 DEG C, is generally-10 DEG C ~ 140 DEG C.Polymerization keeps the specified time, carries out heating up with 0.1 DEG C ~ 100 DEG C/h, carry out lowering the temperature with 0.1 DEG C ~ 100 DEG C/h and condition that their combination is such gets off to carry out under can being the polymerization temperature specified.In addition, in the manufacture method of optical material of the present invention, the anneal implementing 10 minutes ~ 5 hours to cured article after completion of polymerization at the temperature of 50 ~ 150 DEG C preferably processes to remove optical material distortion.

The polyurethane series resin light weight adopting method of the present invention to manufacture also has the feature of excellent impact resistance, and then tone is good.Therefore, this resin is suitable for the purposes of the optical material such as lens, prism.Especially the purposes of the lens such as glasses lens, camera lens is very suitable for.

In addition, by antireflection, give high rigidity, improve wear resistance, improve chemical reagent resistance, give for the purpose of improvement that is anti-fog properties or that give fashion etc., optical material can implement the process of the physics aspect such as surface grinding, anti-electrostatic process, hard coat process, bloomed coating process, dyeing process, light modulation process, chemical aspect.

Below, be described the composition for optical material of the 2nd embodiment of the present invention is polymerized the method manufacturing optical material.

As the catalyzer composition for optical material of second embodiment of the present invention being carried out polymerizing curable, use amine, salt, phosphine compound.As object lesson, amine, quaternary ammonium salt, season can be enumerated salt, tertiary sulfonium salt, secondary iodine salt, phosphine compound.Wherein more preferably good with composition intermiscibility quaternary ammonium salt and season salt, phosphine compound; Preferred season further salt.As the object lesson of preferred compound, tetra-n-butyl ammonium bromide, tetraphenylphosphonibromide bromide ammonium, triethyl benzyl ammonia chloride, cetalkonium chloride, 1-dodecyl pyridinium chloride can be enumerated deng quaternary ammonium salt; Tetran-butylphosphonium bromide , tetraphenylphosphonibromide bromide in season salt; The phosphine compounds such as triphenylphosphine.Among these, preferred compound is triethyl benzyl ammonia chloride, tetran-butylphosphonium bromide further ; Most preferred compound is tetran-butylphosphonium bromide .Polymerizing catalyst may be used alone, can also be two or more kinds in combination.

Because the addition of polymerizing catalyst changes according to the composition of composition, ratio of mixture and polymerizing curable method, therefore, cannot determine without exception, but relative to composition for optical material total amount, usual use 0.001 quality % ~ 5 quality %, preferred use 0.01 quality % ~ 1 quality %, most preferably uses 0.01 quality % ~ 0.5 quality %.If the addition of polymerizing catalyst is more than 5 quality %, then can there is the specific refractory power of cured article, thermotolerance reduces and painted situation.In addition, if be less than 0.001 quality %, then can there is the situation of insufficient solidification, thermotolerance deficiency.

When making composition for optical material polymerizing curable, to extend for the purpose of working life, dispersion polymerization heating etc., polymerization adjusting agent can be added as required.As the halogenide that polymerization adjusting agent preferred compound is silicon, germanium, tin, antimony, preferred compound is the muriate with the germanium of alkyl, tin, antimony.Preferred compound is specifically dibutyl tin dichloride, butyl tin trichloride, dioctyl tindichloride, octyl group tin trichloride, dibutyl germanous chloride, butyl tri-chlorination germanium, phenylbenzene germanous chloride, phenyl tri-chlorination germanium, triphenyl antimony butter further; The object lesson of most preferred compound is dibutyl tin dichloride.Polymerization adjusting agent may be used alone, can also be two or more kinds in combination.

Relative to composition for optical material total amount, the addition of polymerization adjusting agent is generally 0.0001 ~ 5.0 quality %, is preferably 0.0005 ~ 3.0 quality %, is more preferably 0.001 ~ 2.0 quality %.

In addition, certainly the practicality that the additives such as known antioxidant, UV light absorber, bluing agent improve resulting materials further can be added when composition for optical material of the present invention is carried out polymerizing curable to obtain optical material.

As the preference of antioxidant, amphyl can be enumerated.Wherein preferred compound is polyatomic phenol, halogen substiuted phenols; Preferred compound is pyrocatechol, pyrogallol, alkyl replace catechol; Most preferred compound is pyrocatechol, pyrogallol.As the preference of ultraviolet screener, benzotriazole based compound can be enumerated.Wherein the object lesson of preferred compound is 2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, the chloro-2-(3 of 5-, 5-di-t-butyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl) the chloro-2H-benzotriazole of-5-, 2-(3,5-bis-tert-pentyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxy phenyl)-2H-benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl)-2H-benzotriazole, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-)-2H-benzotriazole.As the preference of bluing agent, anthraquinone based compound can be enumerated.

In addition, when composition for optical material of the present invention is easily peeled off by mould in polymerization, can use or add the adaptation that known outside and/or inner adaptation activator controlled, strengthened gained cured article and mould.As adaptation activator, can enumerate known silane coupling agent, titanate compound class etc., they may be used alone, can also be two or more kinds in combination.Relative to composition for optical material total amount, addition is generally 0.0001 ~ 5 quality %.On the contrary, when composition of the present invention is difficult to be peeled off by mould after polymerisation, also can use or add known outside and/or internal mold release to strengthen the release property of gained cured article by mould.So-called releasing agent, fluorine system nonionogenic tenside, silicon system nonionogenic tenside, phosphoric acid ester, acid phosphoric acid ester, oxidation ene-type acid phosphoric acid ester, an alkali metal salt of acid phosphoric acid ester, an alkali metal salt of oxidation ene-type acid phosphoric acid ester, an alkali metal salt of higher fatty acid, high-grade aliphatic ester, paraffin, wax, higher aliphatic acid amides, senior aliphat alcohol, polysiloxane-based, fatty amine ethylene oxide adduct etc. can be enumerated, they may be used alone, can also be two or more kinds in combination.Relative to composition for optical material total amount, addition is generally 0.0001 ~ 5 quality %.

Composition for optical material of the present invention is carried out polymerizing curable and be described as following content in further detail to the method manufacturing optical material.The additives such as above-mentioned each moiety, antioxidant, UV light absorber, polymerizing catalyst, radical polymerization initiator, adaptation activator, releasing agent all can be mixed in same container under stirring simultaneously, also each feed stage can be added mixing, after several composition can also being mixed respectively, in same container, carry out remix further.Each raw material and auxiliary material can mix with any order.Mix time, as long as design temperature, carry out these need time etc. make each composition well-mixed condition substantially.

To above-mentioned reaction, the composition for optical material implantation glass of process, metal mould be implemented, after polymerization curing reaction being carried out by the irradiation of heating, ultraviolet isoreactivity energy-ray, take out from mould.Manufacture optical material thus.Composition for optical material carries out polymerizing curable preferably by heating thus manufactures optical material.Now, set time is 0.1 ~ 200 hour, is generally 1 ~ 100 hour; Solidification value is-10 DEG C ~ 160 DEG C, is generally-10 DEG C ~ 140 DEG C.Polymerization keeps the specified time, carries out heating up with 0.1 DEG C ~ 100 DEG C/h, carry out lowering the temperature with 0.1 DEG C ~ 100 DEG C/h and condition that their combination is such gets off to carry out under can being the polymerization temperature specified.In addition, in the manufacture method of optical material of the present invention, the anneal implementing 10 minutes ~ 5 hours to cured article after completion of polymerization at the temperature of 50 ~ 150 DEG C is to remove the preferred process of optical material distortion.Can carry out as required further dyeing, the surface treatment such as hard coat, shock-resistance coating, antireflection, imparting are anti-fog properties.

Embodiment

, specifically describe the present invention by embodiment below, but the present invention is not limited to this.In addition, evaluation is adopted and is carried out in the following method.

The total content > of < iron, chromium, nickel: adopt SII NANOTECHNOLOGY Inc. ICP apparatus for analyzing luminosity SPS5520, determine the total content of the iron of polythiol, chromium, nickel.

The mensuration > of < yellow: adopt following polymerization process 1 ~ 4 or polymerization process A ~ D to make the flat board that thickness is 5mm, uses COLOR TECHNO Inc. colourimeter JS555 to determine YI value.

Compare with the YI value of the flat board adopting the total content of iron, chromium, nickel to make at the following polythiol of detectability (0.1ppm), with difference (△ YI) below 0.1 for ◎, 0.1 ~ 0.3 be zero, 0.3 ~ 0.5 is △, more than 0.5 be ×.Above, ◎ zero △ is qualified.

(making of blank sample)

Use iron, chromium, nickel total content detectability (0.1ppm) below 1,2-two [(2-mercaptoethyl) sulfenyl]-3-thio propane (being compd A below), two (mercapto methyl)-3,6,9-tri-thia-1,11-undecane two mercaptan (being compd B below), tetramethylolmethane four (thiohydracrylic acid) ester (being Compound C below), made according to following manufacture 1 ~ 4 flat board that thickness is 5mm.

Embodiment 1 ~ 3

Use 1 of the total content of the iron shown in table 1, chromium, nickel, two [(2-mercaptoethyl) the sulfenyl]-3-thio propane (compd A) of 2-, make composition for optical material of the present invention and optical material according to following method for making 1, tried to achieve △ YI compared with blank sample.The results are summarized in table 1.

Embodiment 4 ~ 6

Use two (mercapto methyls)-3 of the total content of the iron shown in table 1, chromium, nickel, 6,9-tri-thia-1,11-undecane two mercaptan (compd B), make composition for optical material of the present invention and optical material according to following method for making 2, tried to achieve △ YI compared with blank sample.The results are summarized in table 1.

Embodiment 7 ~ 9

Use 1 of the total content of the iron shown in table 1, chromium, nickel, tetramethylolmethane four (thiohydracrylic acid) ester (Compound C) of the total content of two [(2-mercaptoethyl) the sulfenyl]-3-thio propane (compd A) of 2-and the iron shown in table 1, chromium, nickel has made composition for optical material of the present invention and optical material according to following method for making 3, tries to achieve △ YI compared with blank sample.The results are summarized in table 1.

Embodiment 10 ~ 12

Use two (mercapto methyls)-3 of the total content of the iron shown in table 1, chromium, nickel, 6,9-tri-thia-1, tetramethylolmethane four (thiohydracrylic acid) ester (Compound C) of the total content of 11-undecane two mercaptan (compd B) and the iron shown in table 1, chromium, nickel has made composition for optical material of the present invention and optical material according to following method for making 4, tries to achieve △ YI compared with blank sample.The results are summarized in table 1.

Comparative example 1

Use 1 of the total content of the iron shown in table 1, chromium, nickel, two [(2-mercaptoethyl) the sulfenyl]-3-thio propane (compd A) of 2-has made composition for optical material and the optical material of comparative example according to following method for making 1, tries to achieve △ YI compared with blank sample.The results are summarized in table 1.

Comparative example 2

Use two (mercapto methyls)-3 of the total content of the iron shown in table 1, chromium, nickel, 6,9-tri-thia-1,11-undecane two mercaptan (compd B) has made composition for optical material and the optical material of comparative example according to following method for making 2, tries to achieve △ YI compared with blank sample.The results are summarized in table 1.

Comparative example 3

Use 1 of the total content of the iron shown in table 1, chromium, nickel, tetramethylolmethane four (thiohydracrylic acid) ester (Compound C) of the total content of two [(2-mercaptoethyl) the sulfenyl]-3-thio propane (compd A) of 2-and the iron shown in table 1, chromium, nickel has made composition for optical material and the optical material of comparative example according to following method for making 3, try to achieve △ YI compared with blank sample.The results are summarized in table 1.

Comparative example 4

Use two (mercapto methyls)-3 of the total content of the iron shown in table 1, chromium, nickel, 6,9-tri-thia-1, tetramethylolmethane four (thiohydracrylic acid) ester (Compound C) of the total content of 11-undecane two mercaptan (compd B) and the iron shown in table 1, chromium, nickel has made composition for optical material and the optical material of comparative example according to following method for making 4, try to achieve △ YI compared with blank sample.The results are summarized in table 1.

In addition, the method for making used in above-described embodiment and comparative example is specifically, as follows:

method for making 1

Make as dibutyl tin dichloride 0.05 weight part of curing catalysts, dioctylphosphoric acid ester 0.10 weight part at 10 ~ 15 DEG C mixed dissolution in two (isocyanatomethyl) benzene (being compounds X below) 52 weight parts of 1,3-.Two [(2-mercaptoethyl) sulfenyl]-3-thio propane (compd A) 48 weight part of further mixing 1,2-, becomes homogeneous solution.This mixed after liquid carries out deaeration in 1 hour under 600Pa, filter with the PTFE strainer of 1 μm, injection diameter is the mould of 70mm ,+5D, is heated to 130 DEG C makes it be polymerized with 24 hours from 40 DEG C.The demoulding afterwards, thus obtain optical material.

method for making 2

Make as dibutyl tin dichloride 0.05 weight part of curing catalysts, dioctylphosphoric acid ester 0.10 weight part at 10 ~ 15 DEG C mixed dissolution in two (isocyanatomethyl) benzene (compounds X) 51 weight part of 1,3-.Further mixing two (mercapto methyl)-3,6,9-tri-thia-1,11-undecane two mercaptan (compd B) 49 weight part, becomes homogeneous solution.This mixed after liquid carries out deaeration in 1 hour under 600Pa, filter with the PTFE strainer of 1 μm, injection diameter is the mould of 70mm ,+5D, is heated to 130 DEG C makes it be polymerized with 24 hours from 40 DEG C.The demoulding afterwards, thus obtain optical material.

method for making 3

Make as dibutyl tin dichloride 0.06 weight part of curing catalysts, dioctylphosphoric acid ester 0.12 weight part at 10 ~ 15 DEG C mixed dissolution in 2, mixture (being compound Y below) 50.6 weight parts of two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 5-and two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 2,6-.Further mixing 1, two [(2-mercaptoethyl) sulfenyl]-3-thio propane (compd A) 25.5 weight part of 2-and tetramethylolmethane four (thiohydracrylic acid) ester (Compound C) 23.9 weight part, become homogeneous solution.This mixed after liquid carries out deaeration in 1 hour under 600Pa, filter with the PTFE strainer of 1 μm, injection diameter is the mould of 70mm ,+5D, is heated to 130 DEG C makes it be polymerized with 24 hours from 40 DEG C.The demoulding afterwards, thus obtain optical material.

method for making 4

Make as dibutyl tin dichloride 0.06 weight part of curing catalysts, dioctylphosphoric acid ester 0.12 weight part at 10 ~ 15 DEG C mixed dissolution in 2, mixture (compound Y) 50.6 weight parts of two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 5-and two (isocyanatomethyl)-dicyclo [2.2.1] heptane of 2,6-.Two (mercapto methyl)-3 of further mixing, 6,9-tri-thia-1,11-undecane two mercaptan (compd B) 25.5 weight part and tetramethylolmethane four (thiohydracrylic acid) ester (Compound C) 23.9 weight part, become homogeneous solution.This mixed after liquid carries out deaeration in 1 hour under 600Pa, filter with the PTFE strainer of 1 μm, injection diameter is the mould of 70mm ,+5D, is heated to 130 DEG C makes it be polymerized with 24 hours from 40 DEG C.The demoulding afterwards, thus obtain optical material.

[table 1]

In the above-described embodiment, by employ meet iron, chromium, nickel total content be polymerized at the composition for optical material of the polythiol of below 5.0ppm condition, can prevent thus solidify after yellow.Therefore, according to the present invention, before polyreaction, can predict whether yellow occurs in advance after polymerizing curable, judge good and bad, thus optionally only can manufacture the optical material of good proterties.So effective utilization of composition for optical material and the manufacture of excellent optical material all can realize.

(polymerization process A)

The tetrabutyl phosphonium bromide of 0.1 weight part is added in the composition formed by two (2-mercaptoethyl) thioethers of 5 weight parts, two (β-epithiopropyl) thioethers of 95 weight parts as polymerizing catalyst, after at room temperature mixing equably, carry out degassed process.Adopt the PTFE strainer of 1 μm to filter afterwards, inject mold, be heated to 100 DEG C with 20 hours from 20 DEG C and make its polymerizing curable.The demoulding afterwards, thus obtain optical material.

(polymerization process B)

The tetrabutyl phosphonium bromide of 0.2 weight part is added in the tetramethylxylylene diisocyanate of two (β-epithiopropyl) thioethers of 1,3-two (mercapto methyl) benzene of 14 weight parts, 77 weight parts, 9 weight parts , 0.05 weight part dibutyl tin dichloride as polymerizing catalyst, at room temperature equably mixing after carry out degassed process.Adopt the PTFE strainer of 1 μm to filter afterwards, inject mold, be heated to 100 DEG C with 20 hours from 20 DEG C and make its polymerizing curable.The demoulding afterwards, thus obtain optical material.

(polymerization process C)

In the sulphur of two (β-epithiopropyl) thioethers of 79 weight parts, 14 weight parts, add the mercaptomethylimi dazole of 0.05 weight part, make its pre-reaction at 60 DEG C.After being cooled to 20 DEG C afterwards, add two (2-mercaptoethyl) thioether, the dibutyl tin dichloride of 0.2 weight part, the mixed solutions as the triethyl benzyl ammonia chloride of 0.03 weight part of catalyzer of 7 weight parts, carry out degassed process after mixing equably.Adopt the PTFE strainer of 1 μm to filter afterwards, inject mold, be heated to 100 DEG C with 20 hours from 20 DEG C and make its polymerizing curable.The demoulding afterwards, thus obtain optical material.

(polymerization process D)

The tetrabutyl phosphonium bromide of 0.1 weight part is added in the m-xylylene diisocyanate of the sulphur of two (β-epithiopropyl) thioethers of the tetramethylolmethane tetrathio propionic ester of two (2-mercaptoethyl) thioethers of 6 weight parts, 6 weight parts, 80 weight parts, 1 weight part, 7 weight parts , 0.05 weight part dibutyl tin dichloride, at room temperature equably mixing after carry out degassed process.Adopt the PTFE strainer of 1 μm to filter afterwards, inject mold, be heated to 100 DEG C with 20 hours from 20 DEG C and make its polymerizing curable.The demoulding afterwards, thus obtain optical material.

(making of blank sample)

Use the total content of iron, chromium, nickel at detectability (0.1ppm) two (2-mercaptoethyl) thioether, mphenylenedimethylim-two mercaptan, tetramethylolmethane tetrathio propionic esters below, adopt the method for polymerization process A ~ D to make the flat board that thickness is 5mm.

Embodiment 13 ~ 15

Use two (2-mercaptoethyl) thioethers of the total content of the iron shown in table 2, chromium, nickel, adopt the method for polymerization process A to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 2.

Embodiment 16 ~ 18

Use mphenylenedimethylim-two mercaptan of the total content of the iron shown in table 2, chromium, nickel, adopt the method for polymerization process B to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 2.

Embodiment 19 ~ 21

Use two (2-mercaptoethyl) thioethers of the total content of the iron shown in table 2, chromium, nickel, adopt the method for polymerization process C to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 2.

Embodiment 22 ~ 24

Use two (2-mercaptoethyl) thioether, the tetramethylolmethane tetrathio propionic esters of the total content of the iron shown in table 3, chromium, nickel, adopt the method for polymerization process D to make the flat board that thickness is 5mm.△ YI is tried to achieve compared with blank sample.The results are summarized in table 3.

Comparative example 5

Use two (2-mercaptoethyl) thioethers of the total content of the iron shown in table 3, chromium, nickel, adopt the method for polymerization process A to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 3.

Comparative example 6

Use mphenylenedimethylim-two mercaptan of the total content of the iron shown in table 3, chromium, nickel, adopt the method for polymerization process B to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 3.

Comparative example 7

Use two (2-mercaptoethyl) thioethers of the total content of the iron shown in table 3, chromium, nickel, adopt the method for polymerization process C to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 3.

Comparative example 8

Use two (2-mercaptoethyl) thioether, the tetramethylolmethane tetrathio propionic esters of the total content of the iron shown in table 3, chromium, nickel, adopt the method for polymerization process D to make the flat board that thickness is 5mm, try to achieve △ YI compared with blank sample.The results are summarized in table 3.

[table 2]

[table 3]

In the above-described embodiment, by employ meet iron, chromium, nickel total content be polymerized at the composition for optical material of the polythiol of below 5.0ppm condition, can prevent thus solidify after yellow.Therefore, according to the present invention, before polyreaction, can predict whether yellow occurs in advance after polymerizing curable, judge good and bad, thus optionally only can manufacture the optical material of good proterties.So effective utilization of composition for optical material, the manufacture of excellent optical material all can realize.

Claims (8)

1. a composition for optical material, is characterized in that, the total content containing iron, chromium and nickel is at the multi-thioalcohol compound of below 2.0ppm and how different (sulphur) cyanate esters.

2. composition for optical material according to claim 1, wherein, described multi-thioalcohol compound is selected from 1,2-two [(2-mercapto ethyl) sulfenyl]-3-thio propane, two (thiopurine methyltransferase)-3,6,9-tri-thia-1,11-undecane two mercaptan, tetramethylolmethane four (3-thiohydracrylic acid) ester, two (thiopurine methyltransferase) thioether, 1, two (thiopurine methyltransferase) benzene and 1 of 3-, 1, at least one compound in 3,3-tetra-(thiopurine methyltransferase sulfenyl) propane.

3. composition for optical material according to claim 1, wherein, described how different (sulphur) cyanate esters is selected from 2, two (isocyanatomethyl)-dicyclo [2.2.1] heptane, 2 of 5-, 6-two (isocyanatomethyl)-dicyclo [2.2.1] heptane, two (isocyanatomethyl) hexanaphthene, dicyclohexyl methane diisocyanate, isophorone diisocyanate, 1, two (isocyanatomethyl) benzene of 3-and α, α, α ', α ' at least one compound in-tetramethylxylylene diisocyanate.

4. an optical material, is characterized in that, by the composition for optical material polymerization according to any one of claims 1 to 3 being obtained.

5. optical material according to claim 4, wherein, implements anneal after composition for optical material polymerization.

6. a manufacture method for composition for optical material, is characterized in that, comprises the multi-thioalcohol compound of the total content of iron, chromium and nickel at below 2.0ppm and the operation of how different (sulphur) cyanate esters mixing.

7. an acquisition comprises the method for the multi-thioalcohol compound raw material of the composition for optical material of multi-thioalcohol compound and how different (sulphur) cyanate esters, wherein, measure the total content of iron, chromium and nickel in multi-thioalcohol compound, the total content of final selection iron, chromium and nickel, at the multi-thioalcohol compound of below 2.0ppm, obtains the multi-thioalcohol compound raw material of composition for optical material.

8. a manufacture method for composition for optical material, is characterized in that, the method is the manufacture method of the composition for optical material comprising multi-thioalcohol compound and how different (sulphur) cyanate esters, and the method comprises following operation,

Operation (1): the total content measuring iron, chromium and nickel in multi-thioalcohol compound, finally selects the multi-thioalcohol compound of total content at below 2.0ppm of iron, chromium and nickel, obtains the operation of the multi-thioalcohol compound raw material of composition for optical material;

Operation (2): the operation that the multi-thioalcohol compound raw material obtained in operation (1) and how different (sulphur) cyanate esters are mixed.