KR20230132347A - Optical Material Composition Containing Polythiol Composition - Google Patents

Abstract

The present invention relates to the field of polymer materials technology, and specifically provides an optical material composition containing a polythiol composition, wherein the composition includes a first polysulfide compound and a second polysulfide compound in addition to an episulfide compound and a polyisocyanate compound, , where the first polysulfide compound is added in an amount of 0.01% to 5% of the total mass of the entire optical material composition. The optical material manufactured with this combination not only improved toughness while avoiding problems such as material streaks and cloudiness due to exothermic reaction or rapid curing, but also achieved a balance between the refractive index and Abbe number of the optical material.

Description

Optical material composition containing polythiol composition {Optical Material Composition Containing Polythiol Composition}

The present invention relates to the technical field of optical materials, and specifically to optical material compositions containing polythiol compositions.

Plastic lenses have outstanding advantages in lightness and toughness compared to existing high refractive index glass lenses. The characteristics of plastic lenses include low specific gravity, high transparency, and optical properties, and properties such as high refractive index, high Abbe number, high heat resistance, and high strength are especially required. A high refractive index enables a reduction in the thickness of the lens, and a high Abbe number enables a reduction in the chromatic aberration of the lens.

In order to achieve a high refractive index and high Abbe number, a number of organic compounds containing sulfur atoms have been reported in recent years, and an excellent balance between the refractive index and Abbe number of polythiol containing sulfur atoms has been demonstrated in Japanese Patent Publication No. 09- Disclosed in No. 110979; Considering the increased strength of the optical material, the addition of thiocarbamate was reported in Japanese Patent Application Laid-Open No. 11-352302 and Japanese Patent Application Publication No. 2001-131257 to achieve the purpose of the optical material.

Additionally, in order to maintain the refractive index of the material, Japanese Patent Laid-Open No. 2002-122701 introduced sulfur for manufacturing optical materials. However, in the case of materials made by introducing sulfur and thiocarbamate, there are foaming and uneven heating problems during the manufacturing process, which can seriously affect the yield of lenses by causing white turbidity and material streaks while polymerizing the materials into finished products. .

Therefore, overcoming the above-described shortcomings of the prior art and obtaining optical materials with better processing performance and high yield have become urgent tasks in this field.

In response to the above problems, the present invention provides an optical material composition containing a polythiol composition comprising a first polysulfide compound and a second polysulfide compound in addition to an episulfide compound and a polyisocyanate compound, wherein the first poly The sulfide compound is added in an amount of 0.01% to 5% of the total mass of the entire optical material composition. The optical material manufactured with this combination not only improved toughness while avoiding problems such as material streaks and cloudiness due to exothermic reaction or rapid curing, but also achieved a balance between the refractive index and Abbe number of the optical material.

The main difference between the present invention and the prior art is that the first polysulfide compound is introduced to form a system with the second polysulfide compound, which can increase the strength of the optical material while maintaining the refractive index of the optical material itself; In addition, due to the structural features of the compound, the polymerization process is relatively gentle and no material streaks are generated, which greatly improves the yield of optical lenses and overcomes problems in the prior art such as turbidity and material streaks caused by exothermic reaction or rapid curing.

It is included in the content of the present invention.

The technical solutions adopted in the present invention are as follows:

An optical material composition containing a polythiol composition comprising a first polysulfide compound and a second polysulfide compound in addition to an episulfide compound and a polyisocyanate compound, wherein the first polysulfide compound accounts for 0.01% of the total mass of the entire optical material composition. It is added in an amount of from 5% to 5%.

The structural formula of the first polysulfide compound is:

Here, x represents 0 or 1, m represents 1 or 2, and n represents 1, 2, 3, or 4.

Preferably, the first polysulfide compound is 3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in formula (1)) or 3,6,9 -Trithioundecane-1,11-dithiol (x = 0, m = 2, n = 1 in formula (1)) or bis (2- (2-mercaptoethyl) thioethyl) disulfide (formula ( 1) can be selected from x=1, m=2, n=1).

The second polysulfide compound is 2,2-thiodiethanethiol, 2,3-dithio(2-mercapto)-1-propanethiol, 1,5,9,13-tetramercapto-3,7, 11-Trithiatridecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiooctane, tetrakis(mercaptomethyl)methane, pentaerythritol tetrakis(3-mercapto) propionate), pentaerythritol tris(3-mercaptopropionate), 1,1,2,2-tetrakis(mercaptomethylthio)ethane, hexa(3-mercaptopropionate)dipentaeryth It may be selected from one or more of litol ester and pentaerythritol tetrakis(3-mercaptobutyric acid) ester.

Episulfide compounds include bis(β-epithiopropyl)disulfide, bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, and 1,3-bis(β- Epithiopropylthio)propane, 1,4-bis(β-epithiopropylthio)butane, bis(β-epithiopropyl)sulfide, bis(β-epithiopropylthio)ethyl)sulfide, 1,3 -bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane and 1 , 4-bis(β-epithiopropylthiomethyl)cyclohexane.

Polyisocyanate compounds include isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p -Tetramethylxylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)norbone is selected from one or more of:

Based on the above-mentioned alternatives, the inventors further defined the amounts of components of the composition in parts by weight as follows:

5-30 parts by weight of the second polysulfide compound, 60-90 parts by weight of the episulfide compound, and 3-15 parts by weight of the polyisocyanate compound.

More preferably:

5-20 parts by weight of the second polysulfide compound, 60-88 parts by weight of the episulfide compound, and 3-15 parts by weight of the polyisocyanate compound.

The first polysulfide compound can be more preferably used in an amount of 0.05-1% of the total mass of the entire optical material composition.

Based on the solution, a catalyst of 0.01-0.1% by weight of the total mass of the optical material composition is added to the optical material composition, and the catalyst is selected as tetrabutylphosphonium bromide.

After obtaining the optical material composition, the present inventor provides a method for producing the same through the following steps.

The first polysulfide compound, the second polysulfide compound, the episulfide compound, and the polyisocyanate compound are mixed well, a catalyst is added, and cured at a programmed temperature to obtain the desired optical material.

For more information, see the following overview:

The mixed raw material with the catalyst added is vacuum degassed and the solution is injected into the mold. Primary curing procedure: Raise to 20℃ and hold heat for 2 hours, then increase temperature from 20℃ to 55℃ for 12 hours, then increase temperature from 55℃ to 80℃ for 3 hours, then heat to 80℃ for 2 hours. held at °C, then lowered from 80°C to 60°C for 1 hour; Secondary curing is performed by maintaining heat at 100°C for 2 hours to obtain an optical material product.

The optical material prepared by the above method has high optical properties, high refractive index, uniform texture, transparency, and no white turbidity, greatly improving the yield of the optical material. The experimental results show that the ultra-high refractive index optical resin material provided by the present invention has a refractive index of 1.6960-1.7120, Abbe number of 37-40, glass transition temperature of 80℃-110℃, secondary curing yield of 98%-100%, uniform texture, and It has a white turbidity.

In summary, the present invention provides a special composition of polysulfide compounds as well as a suitable optical material system, which can effectively improve the toughness and impact resistance of optical materials, and eliminate the problems of material streaks and whiteness caused by exothermic reaction or rapid curing. Not only can this be avoided, but the yield can be greatly improved by achieving colorless and transparent optical materials by achieving a balance between the refractory index and Abbe number of the optical material.

Specific Embodiments

The description set forth below is intended to provide further explanation of the invention by way of specific embodiments to enable those skilled in the art to further understand the invention without limitation, and that any technique based on the principles described herein is within the scope of the invention. .

Embodiment 1

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanediol (x=0, m=1, n=1 in Chemical Formula (1)) 1 part by weight, 2,2-thiodiethanethiol 8 parts by weight, and iso Add 6 parts by weight of porone diisocyanate to 85 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is as follows.

Primary curing procedure: Raise to 20℃ and hold heat for 2 hours, then increase temperature from 20℃ to 55℃ for 12 hours, then increase temperature from 55℃ to 80℃ for 3 hours, then heat to 80℃ for 2 hours. held at °C, then lowered from 80°C to 60°C for 1 hour; Secondary curing is performed by maintaining heat at 100° C. for 2 hours to obtain the optical material product of Embodiment 1.

Embodiment 2

An optical material composition containing a polythiol composition composed and prepared as follows.

0.5 parts by weight of 3,6-dithio-1,8-octanediol (x=0, m=1, n=1 in Chemical Formula (1)), 8.5 parts by weight of 2,2-thiodiethanethiol, and iso Add 6 parts by weight of porone diisocyanate to 85 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 2.

Embodiment 3

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanediol (x=0, m=1, n=1 in Chemical Formula (1)) 0.05 parts by weight, 2,2-thiodiethanethiol 8.5 parts by weight, and iso Add 6.45 parts by weight of phoron diisocyanate to 85 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 3.

Embodiment 4

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6,9-trithioundecane-1,11-dithiol (x=0, m=2, n=1 in formula (1)) 1 part by weight, 2,2-thiodiethanethiol 8 parts by weight And 6 parts by weight of isophorone diisocyanate is added to 85 parts by weight of bis(β-epithiopropyl)sulfide, mixed well, then 0.07 parts by weight of tetrabutylphosphonium bromide is added as a catalyst, then vacuum degassed and injected into the mold. ;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 4.

Embodiment 5

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6,9-trithioundecane-1,11-dithiol (x=0, m=2, n=1 in formula (1)) 0.5 parts by weight, 2,2-thiodiethanethiol 8.5 parts by weight And 6 parts by weight of isophorone diisocyanate is added to 85 parts by weight of bis(β-epithiopropyl)sulfide, mixed well, then 0.07 parts by weight of tetrabutylphosphonium bromide is added as a catalyst, then vacuum degassed and injected into the mold. ;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 5.

Embodiment 6

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in Formula (1)) 0.01 parts by weight, 2,2-thiodiethanethiol 8.99 parts by weight, and iso Add 6 parts by weight of porone diisocyanate to 85 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 6.

Embodiment 7

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in Formula (1)) 3 parts by weight, 2,2-thiodiethanethiol 6 parts by weight, and iso Add 7 parts by weight of porone diisocyanate to 84 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 7.

Embodiment 8

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in Chemical Formula (1)) 5 parts by weight, 2,2-thiodiethanethiol 6 parts by weight, and iso Add 7 parts by weight of porone diisocyanate to 82 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 8.

Embodiment 9

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in formula (1)) 3 parts by weight, 2,3-dithio(2-mercapto)- 6 parts by weight of 1-propanethiol and 7 parts by weight of isophorone diisocyanate were added to 84 parts by weight of bis(β-epithiopropyl)sulfide, mixed well, and then 0.07 parts by weight of tetrabutylphosphonium bromide was added as a catalyst. , vacuum degassed and injected into molds;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 9.

Embodiment Sun 10

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in formula (1)) 3 parts by weight, pentaerythritol tetrakis (3-mercaptopropionate ) 7 parts by weight and 6 parts by weight of hexamethylene diisocyanate were added to 84 parts by weight of bis (β-epithiopropyl) sulfide, mixed well, then 0.07 parts by weight of tetrabutylphosphonium bromide was added as a catalyst, and then vacuum degassed. pour into mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 10.

Embodiment Sun 11

An optical material composition containing a polythiol composition composed and prepared as follows.

3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in formula (1)) 3 parts by weight, 2,3-dithio(2-mercapto)- 7 parts by weight of 1-propanethiol and 6 parts by weight of hexamethylene diisocyanate were added to 84 parts by weight of bis(β-epithiopropyl)sulfide, mixed well, and then 0.07 parts by weight of tetrabutylphosphonium bromide was added as a catalyst. , vacuum degassed and injected into molds;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Embodiment 11.

Comparative Embodiment 1

An optical material composition comprised and prepared as follows.

9 parts by weight of 2,2-thiodiethanethiol, 6 parts by weight of isophorone diisocyanate, and 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst were added to 85 parts by weight of bis(β-epithiopropyl)sulfide and mixed well. , vacuum degassed and injected into molds;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Comparative Embodiment 1.

Comparative Embodiment 2

An optical material composition containing a polythiol composition composed and prepared as follows.

6 parts by weight of 3,6-dithio-1,8-octanedithiol (x=0, m=1, n=1 in Chemical Formula (1)), 6 parts by weight of 2,2-thiodiethanethiol, and isophorone Add 6 parts by weight of diisocyanate to 82 parts by weight of bis(β-epithiopropyl)sulfide, mix well, add 0.07 parts by weight of tetrabutylphosphonium bromide as a catalyst, degas under vacuum, and inject into a mold;

The curing procedure is the same as Embodiment 1 to obtain the optical material product of Comparative Embodiment 2.

Experimental Embodiment:

Various performance determinations are performed on the optical materials provided in Embodiments 1-11 and Comparative Embodiments 1-2.

Impact resistance test: The prepared optical material composition is injected into a lens mold, cured in a blast oven at a programmed temperature, and then free-falled and hit from a height of 1.27 m by small balls of different masses and the center of the lens is not broken. Obtain samples subject to US FDA standards.

Refractive index test: The prepared optical material composition is poured into a mold and cured in a blast oven at a planned temperature; Obtain a sample piece and make it into a 2mm*4mm*2mm sample block, measure the refractive index with a DR-4 Atago multi-wavelength Abbe refractometer, repeat 3 times and take the average value.

Glass transition temperature test: Prepare the optical material as a 3mm thick sample, place it in an aluminum crucible, raise it at a speed of 10℃/min, and evaluate the glass transition temperature (Tg) of the optical material according to the obtained test curve. The type of test instrument used is METTLER-DSC3.

The test results are shown in the table below.

actual sun impact resistance refractive index Tg Embodiment 1 64g 1.7035 90℃ Embodiment 2 32g 1.7028 90℃ Embodiment 3 32g 1.7008 91℃ Embodiment 4 64g 1.7098 89℃ Embodiment 5 32g 1.7068 86℃ Embodiment 6 16g 1.6985 94℃ Embodiment 7 64g 1.7045 83℃ Embodiment 8 32g 1.7058 82℃ Embodiment 9 32g 1.7049 98℃ Embodiment Sun 10 32g 1.7052 97℃ Embodiment Sun 11 32g 1.7055 100℃ comparison
Embodiment 1 <16g 1.7002 95℃ comparison
Embodiment 2 16g 1.7100 78℃

Note: Tg below 80°C is an unqualified product. The above measurements show that the optical material of the composition of the present invention has very good toughness and high impact resistance compared to the prior art and ensures that the refractive index of the material is not affected.

In addition, according to Comparative Embodiment 2, when the addition amount of the first polysulfide compound exceeds 5% and reaches 6%, the impact resistance of the resulting optical material is not improved but rather reduced compared to the addition of 5%, which is also The inventors prefer an addition rate of 0.05-1% for the first polysulfide compound, as it results in a decrease in Tg for the unqualified product.

The foregoing description of the disclosed embodiments is intended to enable any person skilled in the art to make or use the present invention. There are many modifications to these embodiments that will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not intended to be limited to these embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

An optical material composition containing a polythiol composition, characterized in that it comprises a first polysulfide compound and a second polysulfide compound in addition to the episulfide compound and the polyisocyanate compound, wherein the first polysulfide compound represents the total of the entire optical material composition. It is added in an amount of 0.01% to 5% of the mass, and the structural formula of the first polysulfide compound is as follows:

An optical material composition containing a polythiol composition where x represents 0 or 1, m represents 1 or 2, and n represents 1, 2, 3, or 4. According to claim 1,
The first polysulfide compound is a polythiol composition selected from 3,6-dithio-1,8-octanedithiol or 3,6,9-trithioundecane-1,11-dithiol. An optical material composition containing According to claim 1,
The second polysulfide compound is 2,2-thiodiethanethiol, 2,3-dithio(2-mercapto)-1-propanethiol, 1,5,9,13-tetramercapto-3,7, 11-Trithiatridecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiooctane, tetrakis(mercaptomethyl)methane, pentaerythritol tetrakis(3-mercapto) propionate), pentaerythritol tris(3-mercaptopropionate), 1,1,2,2-tetrakis(mercaptomethylthio)ethane, hexa(3-mercaptopropionate)dipentaeryth An optical material composition containing a polythiol composition selected from one or more of litol ester and pentaerythritol tetrakis(3-mercaptobutyric acid) ester. According to claim 1,
Episulfide compounds include bis(β-epithiopropyl)disulfide, bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, and 1,3-bis(β- Epithiopropylthio)propane, 1,4-bis(β-epithiopropylthio)butane, bis(β-epithiopropyl)sulfide, bis(β-epithiopropylthio)ethyl)sulfide, 1,3 -bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane and 1 An optical material composition containing a polythiol composition selected from one or more of 4-bis(β-epithiopropylthiomethyl)cyclohexane. According to claim 1,
Polyisocyanate compounds include isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, m-tetramethylxylylene diisocyanate, p -Tetramethylxylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)norbone An optical material composition containing a polythiol composition, characterized in that it is selected from one or more of phosphorus. According to claim 1,
The composition consists of 5-30 parts by weight of the second polysulfide compound, 60-90 parts by weight of the episulfide compound, and 3-15 parts by weight of the polyisocyanate compound, and the amount of the first polysulfide compound added is 0.01 of the total mass of the entire optical material composition. An optical material composition containing a polythiol composition of -5% by weight. According to claim 6,
The composition consists of 5-20 parts by weight of the second polysulfide compound, 60-88 parts by weight of the episulfide compound, and 3-15 parts by weight of the polyisocyanate compound, and the amount of the first polysulfide compound added is 0.05 parts by weight of the total mass of the entire optical material composition. An optical material composition containing a polythiol composition, characterized in that -1% by weight. According to claim 6,
An optical material composition containing a polythiol composition, characterized in that a catalyst of 0.01-0.1% by weight of the total mass of the optical material composition is added to the optical material composition, and the catalyst is selected as tetrabutylphosphonium bromide.