CN108084386B - Polythiourethane resin for optical material and preparation method thereof - Google Patents
Polythiourethane resin for optical material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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Abstract
The present invention relates to a polythiourethane resin composition for optical materials, which is obtained by heating and curing a composition containing at least an organozirconium bismuth alloy complex, an isocyanate compound, and a thiol compound, and a method for producing the same. The polythiourethane resin composition for optical materials according to the present invention does not contain an organotin compound, and can improve the product yield without losing the optical, mechanical and heat-resistant properties of the resin due to a long pot life and high selectivity. The polythiourethane resin of the present invention is particularly suitable for use in articles such as lenses and prisms.
Description
Technical Field
The invention relates to a polythiourethane resin for optical material applications and a method for producing the same, which is obtained by heating and curing a composition containing at least an organozirconium bismuth alloy complex, an isocyanate compound, and a thiol compound. The polythiourethane resin obtained by the present invention is used for optical materials such as plastic lenses, prisms, and the like.
Background
In recent years, polythiourethane resins are increasingly used in optical material applications such as plastic lenses, prisms, and the like, which exhibit a remarkable balance of properties in terms of optics, machinery, and processing, relative to conventional materials (such as allyl diglycolate, polymethyl methacrylate, polycarbonate, and the like).
The polythiourethane resin is obtained by polymerizing a composition containing at least an isocyanate compound and a thiol compound. The basic reactions of the resin curing molding include a chain extension reaction and a crosslinking reaction under the action of a polymerization catalyst.
At present, organotin compounds widely used as polymerization catalysts for polythiourethane resins have a problem of limitation in use in more and more countries and regions due to their high toxicity, environmental stress, and the like. Therefore, in the industry of plastic lenses, replacement of organotin as a polymerization catalyst for polythiourethane resins has become a major problem in the industry.
Patent documents 1,2, 3 and 4 respectively report tin-free non-metallic catalysts compounded by amine hydrochloride, sulfonate or compound sulfonate, zinc compound and sulfonic acid, and the inventors know in the field of optical plastic lens industry that the novel polymerization catalysts disclosed in the above patent documents are not industrially applied, because the composition containing the polymerization catalyst has loss of mechanical and thermal stability of the plastic lens due to insufficient matching, or the composition containing the polymerization catalyst has narrow process tolerance, resulting in lens surface precision defect, and the yield of plastic lens products is not high.
Patent document 1: CN101511895B
Patent document 2: CN101627069B
Patent document 3: CN102066450B
Patent document 4: CN 102977309B.
Disclosure of Invention
Polymerizable compositions used in the polythiourethane plastic lens industry are required to ensure that the processing efficiency and the basic properties of the resin such as optical, mechanical and heat resistance of the lens product are not lost, and to ensure sufficient mixing and filling time by extending the pot life of the composition (monomer mixture) as much as possible, thereby improving the yield of the lens product.
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that by polymerizing a composition comprising at least an organozirconium bismuth alloy complex, an isocyanate-based compound, and a thiol-based compound, it is possible to achieve optimum matching and tolerance of processability of the composition (monomer mixture) to external processes during mixing and compounding of monomers, pouring into a mold, and temperature-programmed curing at 20 ℃ to 160 ℃ without containing an organotin compound; further, the polythiourethane resin obtained by polymerizing the composition does not lose the properties of the resin material such as optical, mechanical and heat resistance for plastic lens applications, and can remarkably prolong the pot life of the composition (monomer mixture), ensure sufficient mixing and filling time, and improve the yield in the process of lens product industrialization.
The invention relates to an organic zirconium bismuth alloy composite which is applied to polythiourethane resin optical materials, in particular to the industry of plastic lenses for the first time, thereby completing the invention.
The polythiourethane resin for optical materials does not contain an organotin compound, and can improve the product yield without losing the optical, mechanical, heat-resistant and other properties of the resin due to long pot life and high selectivity. The polythiourethane resin of the present invention is particularly suitable for use in articles such as lenses, prisms, and the like.
The present invention will be described in detail below.
The present invention relates to a polythiourethane resin composition for optical material use and a method for producing the same. The polythiourethane resin composition for optical material use is obtained by subjecting a polymerizable composition containing at least an organozirconium bismuth alloy complex, an isocyanate compound and a thiol compound to at least mixing, casting and heat curing. The polythiourethane resin for the optical material is used for preparing plastic lenses for spectacles and the like by a post-processing mode and a method which are well known in the plastic lens industry.
The polythiourethane resin polymerizable composition according to the present invention comprises at least an organozirconium bismuth alloy complex, one or more isocyanate compounds, and one or more thiol compounds; in the organic zirconium bismuth alloy composite, the effective content of zirconium bismuth (calculated by the mass fraction of zirconium bismuth element in the organic zirconium bismuth carboxylate (organic zirconium bismuth alloy composite)) is 2-40%, the ratio of zirconium to bismuth is 1: 1-1: 10, the effective content of zirconium bismuth is 2-40%, preferably, the effective content of zirconium bismuth is 12-28%, and the ratio of zirconium to bismuth is preferably 1: 3-1: 6. The addition amount of the organic zirconium bismuth alloy composite with the zirconium bismuth ratio of 1:1 to 1:10 is more than 0.001 part by weight and less than 1 part by weight relative to 100 parts of the isocyanate compound and the thiol compound; preferably, 0.01 to 0.1 parts by weight; particularly preferably, it is 0.02 parts by weight or more and 0.08 parts by weight or less.
In the polythiourethane resin polymerizable composition relating to the present invention, the organozirconium bismuth alloy complex contained at least is compounded from one or more organic carboxylates of zirconium bismuth; the organic carboxylate of zirconium bismuth is selected from one or more than two of acetic acid, octanoic acid, isooctanoic acid and decanoate.
In the polythiourethane resin polymerizable composition according to the present invention, it is preferable that at least the organozirconium bismuth alloy composite contained therein further contains a liquid polybutadiene having an average molecular weight of 2000-6000 g/mol.
The polythiourethane resin polymerizable composition according to the present invention preferably further contains an aliphatic diacid ester compound in at least the organozirconium bismuth alloy composite contained therein.
At least comprises the organic zirconium bismuth alloy compound, wherein the liquid polybutadiene compound comprises non-functionalized liquid polybutadiene and/or maleic anhydride grafted liquid polybutadiene.
The non-functionalized liquid polybutadiene having an average molecular weight of 2000-6000g/mol and the maleic anhydride-grafted liquid polybutadiene according to the present invention are not particularly limited, but examples thereof include non-functionalized liquid polybutadiene such as POLYVEST 110(EVONIK) and POLYWEST130 (EVONIK); maleic anhydride grafted liquid polybutadiene such as POLYVEST EP MA120(EVONIK) and POLYVEST MA75 (EVONIK).
In the organic zirconium bismuth alloy composite at least contained in the polymerizable composition for polythiourethane resin according to the present invention, the aliphatic diacid ester compound is selected from one or more of dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, dioctyl adipate, diethyl sebacate, dibutyl sebacate, dioctyl sebacate, and dioctyl azelate.
In the organozirconium bismuth alloy composite contained in the polythiourethane resin polymerizable composition according to the invention, the mass ratio of the organocarboxylate of zirconium bismuth to the liquid polybutadiene is preferably 1.5:1 to 8:1, more preferably 2:1 to 6: 1.
In the organozirconium bismuth alloy composite contained in the polythiourethane resin polymerizable composition according to the invention, the mass ratio of the liquid polybutadiene compound to the aliphatic diacid ester compound is preferably 1:1.5 to 1:5, more preferably 1:2 to 1: 4.
The isocyanate compound may be one or more compounds selected from aliphatic and alicyclic isocyanate compounds, including one or more compounds selected from the group consisting of dimethylene benzene diisocyanate, hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate;
the polythiourethane resin polymerizable composition according to the present invention may be one or more compounds selected from the group consisting of 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoacetate), 1,3, 3-tetrakis (mercaptomethylthio) propane and 1,1,2, 2-tetrakis (mercaptomethylthio) ethane.
In the polythiourethane resin polymerizable composition according to the present invention, the molar ratio of the mercapto group of the thiol compound to the isocyanate group of the isocyanate compound may be 0.8 to 1.2; preferably, the molar ratio of mercapto groups to isocyanate groups is from 0.9 to 1.1; particularly preferably, the molar ratio of mercapto groups to isocyanate groups is from 0.95 to 1.05.
The polythiourethane resin polymerizable composition according to the invention can give a polythiourethane resin having a refractive index (ne) of generally 1.56 to 1.67 after being cured by heating.
The polythiourethane resin polymerizable composition according to the invention can give a polythiourethane resin having an Abbe index (ve) of generally 30 to 44 after being cured by heating.
The polythiourethane resin polymerizable composition for optical material use of the invention may further contain at least one or more selected from the group consisting of a mold release agent, an ultraviolet absorber, a light stabilizer and an antioxidant.
The mold release agent, the ultraviolet absorber, the light stabilizer and the antioxidant are well known additives in the plastic lens industry.
The process for producing a polythiourethane resin for optical material use according to the present invention comprises at least the steps of mixing, casting and heat-curing the polythiourethane resin composition.
The present invention further provides a process for producing the polythiourethane resin composition for optical material use described above, which comprises mixing an isocyanate-based compound, an organozirconium bismuth alloy compound optionally containing a liquid polybutadiene compound having an average molecular weight of 2000-6000g/mol and/or an aliphatic diacid-based compound, and a thiol-based compound, and then casting and heat-curing the resulting mixture.
Further, the mixing process comprises the steps of weighing, stirring, degassing and filtering of each component compound in the polymerizable composition, wherein the mixing process can be carried out by stirring and then degassing, or can be carried out by stirring and degassing simultaneously; specifically, the stirring can be carried out for 0.5 to 1 hour under normal pressure, and then the vacuum degassing can be carried out for 0.5 to 1 hour, or the stirring and the degassing can be carried out for 0.5 to 1 hour simultaneously; the stirring speed is kept constant, preferably 50-150rpm, the vacuum degassing pressure is kept constant, preferably 133-400 pa; the filtration is preferably performed by using a polytetrafluoroethylene filter with a pore size of 0.5-1 μm.
The process for producing polythiourethane resin for optical material use according to the present invention comprises a casting step of injecting the polymerizable composition of the present invention between molds held by a gasket, a tape or the like; the heat curing step is not limited since it varies depending on factors such as the polymerizable composition, the kind and amount of the catalyst, and the shape of the mold, and is generally performed by gradually raising the temperature in a temperature range of 20 ℃ to 160 ℃ for 1 to 25 hours.
The polythiourethane resin obtained by the process for producing a polythiourethane resin for optical material use of the present invention can be subjected to annealing or the like as needed, and the annealing is generally carried out at 80 ℃ to 140 ℃ for 0.5 to 3 hours.
The polythiourethane resin composition for optical materials of the present invention is used for optical materials, particularly for plastic lenses.
Detailed Description
The inventors have found that by polymerizing a composition comprising at least a bicyclic amidine compound and/or an organic acid complex thereof, an isocyanate compound, and a thiol compound, the processability of the composition (monomer mixture) can be optimally matched and tolerated by external processes during monomer mixing, casting, and temperature-programmed curing at from 20 ℃ to 160 ℃ without the presence of an organotin compound. The polymerizable composition can ensure sufficient mixing and filling time due to the obvious prolonged service life, and can improve the qualification rate of lens products in the industrialization process on the premise of not losing optical, mechanical, heat-resistant and other resin properties for plastic lenses.
The advantages of the present invention will be described in more detail with reference to examples. The following experimental methods were used to evaluate the polymerization speed, resin properties (refractive index, Abbe number, impact toughness and glass transition temperature), and stabilization of lens quality.
Polymerization rate: the viscosity of the composition after storage at 20. + -. 2 ℃ for 7, 8 and 9 hours was measured by mixing each compound sufficiently for 0.5 hour according to the formulation composition of the polymerizable composition, using a viscometer (Brookfield, DV-II + PRO) at a constant temperature of 20 ℃.
Refractive index and abbe index: the test was carried out at 20 ℃ using an Abbe refractometer (NAR-4T, ATAGO).
Impact strength: the impact strength of the standard resin sample strip was tested by a cantilever beam impact tester.
Glass transition temperature: the temperature rise speed is 10 ℃/min by adopting a differential scanning calorimeter for testing.
The qualified rate of the lens is as follows: and randomly selecting 100 plastic lenses, visually observing under a high-pressure mercury lamp, and calculating the qualified rate.
Example 1:
preparation of polythiourethane resin composition:
first, 52.0 parts by weight of dimethylene benzene diisocyanate, 0.050 parts by weight (500ppm) of an ultraviolet absorber (BASF, Tinuvin329), 0.10 parts by weight (1000ppm) of an internal mold release agent (STEPAN, Zelec UN), and 0.015 parts by weight (150ppm) of catalyst C1 were mixed at 10 to 20 ℃ and stirred for 20 minutes.
Next, 48.0 parts by weight of 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol was added. Meanwhile, the composition was stirred and degassed for 30 minutes under a vacuum condition of 133Pa at a stirring rotation speed of 100 rpm.
Finally, the composition was filtered with a1 μm teflon filter.
Polythiourethane resin composition polymerization speed test:
the viscosity of the compositions after storage at 20 + -2 deg.C for 7, 8, 9 hours, respectively, was measured with a viscometer (BROOKFIELD, DV-II + PRO), measuring temperature constant 20 deg.C, starting with time after thorough mixing and degassing.
Preparation of a polythiourethane resin performance evaluation sample:
filling or injecting the filtered composition into a special glass mold for testing refractive index, Abbe index and impact strength, then putting the glass mold filled with the composition into a polymerization oven, slowly raising the temperature from 20 ℃ to 130 ℃ for 24 hours, and curing and molding the composition. And testing the corresponding refractive index, Abbe index, impact strength and glass transition temperature after demolding.
Preparing a polythiourethane plastic lens:
the filtered composition is filled or injected into a glass mold held by a cushion tape, and then the composition-filled glass mold is placed into a polymerization oven and slowly heated from 20 ℃ to 130 ℃ over 24 hours to be cured and molded.
The demolded lens article is further annealed at 140 ℃ for 2 hours.
And randomly selecting 100 plastic lenses, visually observing under a high-pressure mercury lamp, and calculating the qualified rate.
Examples 2 to 8
With reference to example 1, the composition formulation, polymerization rate test, test specimen and lens preparation were carried out, the composition of the compositions being as shown in Table 1.
Comparative examples 1 to 4
With reference to example 1, the composition formulation, polymerization rate test, test specimen and lens preparation were carried out, the composition of the compositions being as shown in Table 1.
In examples 1-8 and comparative examples 1-4, the compounds involved in formulating the compositions include,
XDI: dimethylene benzene diisocyanate;
HXDI: 1, 3-bis (isocyanatomethyl) cyclohexane;
DMPT: 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol
PETMP: tetrakis (3-mercaptopropionic acid) pentaerythritol ester
C1: the composite material is formed by compounding zirconium isooctanoate and bismuth isooctanoate, wherein the effective content of zirconium and bismuth is 18 percent, the ratio of zirconium and bismuth is 1:4, the mass ratio of the organic composite of zirconium isooctanoate and bismuth isooctanoate to POLYWEST130(EVONIK) is 4:1, and the mass ratio of POLYWEST130(EVONIK) to dioctyl adipate is 1: 3.
C2: the zirconium acetate and the bismuth isooctanoate are compounded, the effective content of the zirconium and the bismuth is 20 percent, the ratio of the zirconium and the bismuth is 1:5, the mass ratio of the organic compound of the zirconium acetate and the bismuth isooctanoate to the POLYWEST110(EVONIK) is 4:1, and the mass ratio of the POLYWEST110(EVONIK) to the dioctyl adipate is 1: 3.
C3: the zirconium octoate and the bismuth decanoate are compounded, the effective content of the zirconium and the bismuth is 24 percent, the ratio of the zirconium and the bismuth is 1:5, the mass ratio of the zirconium octoate and the bismuth decanoate organic compound to the POLYVEST EP MA120(EVONIK) is 5:1, and the mass ratio of the POLYVEST EP MA120(EVONIK) to the dioctyl sebacate is 1: 4.
C4: the composite material is formed by compounding zirconium isooctanoate and bismuth isooctanoate, wherein the effective content of zirconium and bismuth is 18 percent, the ratio of zirconium to bismuth is 1:4, and the mass ratio of the organic composite of zirconium isooctanoate and bismuth isooctanoate to POLYWEST130(EVONIK) is 4: 1.
C5: zirconium octoate and bismuth decanoate are compounded, the effective content of zirconium and bismuth is 24%, the ratio of zirconium and bismuth is 1:5, and the mass ratio of the zirconium octoate and bismuth decanoate organic compound to POLYVEST EP MA120(EVONIK) is 5: 1.
DBC: dibutyl tin dichloride.
TEHC: triethylamine hydrochloride.
TABLE 1
TABLE 2
According to the above results, the present invention can achieve the best matching and tolerance of the processability of the composition (monomer mixture) to the external process without the organotin compound by polymerizing the composition comprising at least the organozirconium bismuth alloy composite, the isocyanate-based compound, and the thiol-based compound. The polymerizable composition can ensure sufficient mixing and filling time due to the obvious prolonged service life, and can improve the qualification rate of lens products in the industrialization process on the premise of not losing optical, mechanical, heat-resistant and other resin properties for plastic lenses.
Claims (17)
1. A polythiourethane resin composition for optical materials, comprising: isocyanate compounds, thiol compounds and organic zirconium bismuth alloy compounds,
wherein, the isocyanate compound and the thiol compound are used in such an amount that the molar ratio of the mercapto group of the thiol compound to the isocyanate group of the isocyanate compound is 0.8 to 1.2;
the amount of the organozirconium bismuth alloy composite added is 0.001 to 1 part by weight based on 100 parts by weight of the total weight of the isocyanate compound and the thiol compound,
wherein in the organic zirconium bismuth alloy compound, the effective content of zirconium bismuth is 2-40wt% according to the mass fraction of zirconium bismuth in the organic zirconium bismuth alloy compound, the ratio of zirconium to bismuth is 1:1 to 1:10,
the organic zirconium bismuth alloy compound is compounded by one or more than two organic carboxylates of zirconium bismuth,
the organic zirconium bismuth alloy compound at least comprises liquid polybutadiene with the average molecular weight of 2000-6000g/mol, and the mass ratio of the organic carboxylate of zirconium bismuth to the liquid polybutadiene is 1.5:1-8: 1.
2. The polythiourethane resin composition for optical materials according to claim 1, wherein the isocyanate compound and the thiol compound are used in such an amount that the molar ratio of the mercapto group of the thiol compound to the isocyanate group of the isocyanate compound is from 0.9 to 1.1;
the amount of the organozirconium bismuth alloy composite added is 0.01 to 0.1 parts by weight based on 100 parts by weight of the total weight of the isocyanate compound and the thiol compound.
3. The polythiourethane resin composition for optical materials according to claim 1, wherein the isocyanate compound and the thiol compound are used in such an amount that the molar ratio of the mercapto group of the thiol compound to the isocyanate group of the isocyanate compound is from 0.95 to 1.05;
the amount of the organozirconium bismuth alloy composite added is 0.02 parts by weight or more and 0.08 parts by weight or less based on 100 parts by weight of the total weight of the isocyanate compound and the thiol compound.
4. The polythiourethane resin composition for optical materials according to claim 1, wherein in the organozirconium bismuth alloy composite, the effective content of zirconium bismuth is 12 to 28% by weight, and the ratio of zirconium to bismuth is 1:3 to 1: 6.
5. The polythiourethane resin composition for optical materials according to any one of claims 1 to 4, wherein the organozirconium bismuth alloy composite further contains at least an aliphatic diacid ester compound.
6. The polythiourethane resin composition for optical materials according to any one of claims 1 to 4, wherein the organic carboxylic acid salt of zirconium bismuth is one or two or more selected from acetate, octanoate, isooctanoate and decanoate.
7. The polythiourethane resin composition for optical materials according to any one of claims 1 to 4, wherein the liquid polybutadiene compound is selected from non-functionalized liquid polybutadiene and/or maleic anhydride-grafted liquid polybutadiene.
8. The polythiourethane resin composition for optical materials according to claim 5, wherein: the aliphatic diacid ester compound is one or more than two selected from dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, dioctyl adipate, diethyl sebacate, dibutyl sebacate, dioctyl sebacate and dioctyl azelate.
9. The polythiourethane resin composition for optical materials according to claim 5, wherein the mass ratio of the organic carboxylate of zirconium bismuth to the liquid polybutadiene compound is 2:1 to 6: 1.
10. The polythiourethane resin composition for optical materials according to claim 5, wherein the mass ratio of the liquid polybutadiene compound to the aliphatic diacid ester compound is 1:1.5 to 1: 5.
11. The polythiourethane resin composition for optical materials according to claim 5, wherein the mass ratio of the liquid polybutadiene compound to the aliphatic diacid ester compound is 1:2 to 1: 4.
12. The polythiourethane resin composition for optical materials according to any one of claims 1 to 4, wherein the isocyanate-based compound is one or two or more compounds selected from aliphatic and alicyclic isocyanate compounds; the thiol compound is one or more selected from polythiol compounds.
13. The polythiourethane resin composition for optical materials according to claim 12, wherein the isocyanate-based compound is one or more compounds selected from the group consisting of hexamethylene diisocyanate, 1, 3-bis (isocyanotomethyl) cyclohexane, 2, 5-bis (isocyanotomethyl) -bicyclo [2.2.1] heptane, 2, 6-bis (isocyanotomethyl) -bicyclo [2.2.1] heptane, 4' -dicyclohexylmethane diisocyanate, and isophorone diisocyanate; the mercaptan compound is one or more compounds selected from 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoacetate), 1,3, 3-tetrakis (mercaptomethylthio) propane and 1,1,2, 2-tetrakis (mercaptomethylthio) ethane.
14. The method for producing the polythiourethane resin composition for optical materials described in any one of claims 1 to 13, wherein the method comprises mixing an isocyanate-based compound, an organozirconium bismuth alloy composite comprising a liquid polybutadiene having an average molecular weight of 2000-6000g/mol and optionally an aliphatic diacid-based compound, a thiol-based compound, and then casting and heat-curing the resulting mixture.
15. The method for producing a polythiourethane resin composition for optical materials according to claim 14, wherein at least one or more selected from the group consisting of a mold release agent, a light stabilizer and an antioxidant is further blended.
16. Use of the polythiourethane resin composition for optical materials described in any one of claims 1 to 13 for optical materials.
17. Use according to claim 16, wherein the optical material is a plastic lens.
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