KR20210071354A - Diisocyanate composition, preparation method thereof and optical material using same - Google Patents

Abstract

Since a diisocyanate composition according to an embodiment of the present invention contains benzyl isocyanate having an ethyl group in the composition in an amount of 1 to 1,000 ppm, it is possible to prevent generation of striae and cloudiness, lower yellowness, and improve transmittance. Therefore, the diisocyanate composition may be usefully utilized to manufacture a high-quality optical material.

Description

Diisocyanate composition, manufacturing method thereof, and optical material using the same {DIISOCYANATE COMPOSITION, PREPARATION METHOD THEREOF AND OPTICAL MATERIAL USING SAME}

The embodiment relates to a diisocyanate composition, a method for preparing the same, and an optical material using the same, and more specifically, a diisocyanate composition comprising benzyl isocyanate having an ethyl group in an amount of 1 ppm to 1000 ppm in the composition, a method for preparing the same, and a method for using the same It relates to optical materials.

Since the plastic optical material is lightweight, does not break easily, and has excellent dyeability compared to an optical material made of an inorganic material such as glass, various resin plastic materials are widely used as optical materials for spectacle lenses, camera lenses, and the like. In recent years, further performance enhancement of optical materials has been demanded, and specifically, high transparency, high refractive index, low specific gravity, high heat resistance, high impact resistance, and the like are required.

Polythiourethane is widely used as an optical material due to its excellent optical and mechanical properties. Polythiourethane can be prepared by reacting thiol and isocyanate, and lenses made from polythiourethane are widely used because of their high refractive index, light weight, and relatively high impact resistance.

Isocyanate used as a raw material for polythiourethane is synthesized into polythiourethane having a different structure depending on the number and position of functional groups, and thus has a great influence on the physical properties of products manufactured therefrom. Accordingly, a specific type of isocyanate that can achieve the desired physical properties of the final product is used.

In particular, xylylene diisocyanate (XDI) has the properties of an alicyclic isocyanate (yellowing resistance, easy reactivity, etc.) and the properties of an aliphatic isocyanate (mechanical properties, refractive index, etc.) have.

These xylylene diisocyanates are classified into o(ortho), m(meta), and p(para)-XDI according to the relative positions of the diisocyanate groups. Among them, m-XDI is suitable for the physical properties of the optical lens and is commercially available. Because it is easy to use, it is most widely used as a raw material for optical lenses.

However, even when m-XDI is used for an optical material, there is a limit in realizing satisfactory optical properties due to high yellowness, streaks, white turbidity, etc. occur in the optical material, and Even if the optical properties are satisfied, mechanical properties may be deteriorated, and there may be problems in that the purity and yield of the diisocyanate composition or final product are reduced.

Therefore, there is an urgent need to develop a diisocyanate composition or a manufacturing method having a composition within a specific range in order to solve this problem and implement a high-quality optical material.

Korean Patent Publication No. 2012-0111171

The present invention was designed to solve the problems of the prior art, and by controlling the content of a specific component in the diisocyanate composition, it was found that the physical properties of the optical material can be effectively satisfied.

Therefore, an object of the embodiment of the present invention is to control the content of benzyl isocyanate having an ethyl group in the composition to prevent streaking and cloudiness of optical materials, to lower yellowness and to improve transmittance, and a method for preparing the same will provide

Another object of the embodiment of the present invention is to provide an optical material using the diisocyanate composition and a manufacturing method thereof.

According to an embodiment, obtaining a diamine hydrochloride composition; treating the diamine hydrochloride composition; and using the treated diamine hydrochloride composition, to obtain a diisocyanate composition, wherein the content of benzyl isocyanate having an ethyl group in the diisocyanate composition is 1 ppm to 1000 ppm, a method for producing a diisocyanate composition is provided .

According to another embodiment, there is provided a diisocyanate composition comprising diisocyanate, wherein the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm.

According to another embodiment, a first step of reacting a diamine with an aqueous hydrochloric acid solution to obtain a diamine hydrochloride composition; a second step of reacting the diamine hydrochloride composition with triphosgene at a temperature of 110 °C to 130 °C to obtain a diisocyanate composition; and a third step of mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold, wherein the diisocyanate composition includes diisocyanate, and the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm, a method for producing an optical material is provided.

According to another embodiment, an optical material comprising a diisocyanate composition and polythiourethane polymerized with thiol or episulfide, wherein the diisocyanate composition includes diisocyanate, and the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm, an optical material is provided.

According to the embodiment, by controlling the content of benzyl isocyanate having an ethyl group in the diisocyanate composition used for the preparation of the polythiourethane-based optical material, the optical properties such as preventing yellowness, streaking and cloudiness and improving transmittance are improved and at the same time Mechanical properties can be improved.

In addition, the method for producing a diisocyanate composition according to an embodiment of the present invention does not use phosgene gas, which is difficult to store and manage, and is highly toxic, and as a solid state at room temperature, it does not require a separate cooling storage device and has low toxicity. Since triphosgene is used, handleability and processability are excellent, and the content of benzyl isocyanate having an ethyl group can be simply controlled to a specific content. In addition, the method for producing diisocyanate according to the embodiment uses an aqueous hydrochloric acid solution without using hydrogen chloride gas for the production of diamine hydrochloride, which is an intermediate material, so that the reaction can proceed even at normal pressure, so an additional device for high-temperature heating and cooling is required and the yield can also be improved.

1 schematically shows a method for preparing a diisocyanate composition according to an embodiment.
2 shows an example of a process device for the reaction of diamine hydrochloride and triphosgene.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In addition, it should be understood that all numerical ranges indicating physical property values, contents, dimensions, etc. of the components described in the present specification are modified by the term "about" in all cases unless otherwise specified.

As used herein, "amine" means a compound having one or more amine groups at the terminal, "diamine" means a compound having two amine groups at the terminal, and an aliphatic chain, an aliphatic ring, and an aromatic ring. It may have a very diverse structure depending on the skeleton. Specific examples of the diamine include xylylenediamine (XDA), hexamethylenediamine (HDA), 2,2-dimethylpentanediamine, 2,2,4-trimethylhexanediamine, butenediamine, 1,3-butadiene-1, 4-diamine, 2,4,4-trimethylhexamethylenediamine, bis(aminoethyl)carbonate, 4,4'-methylenediamine (MDA), bis(aminoethyl)ether, bis(aminoethyl)benzene, bis(amino Propyl)benzene, α,α,α',α'-tetramethylxylylenediamine, bis(aminobutyl)benzene, bis(aminomethyl)naphthalene, bis(aminomethyl)diphenyl ether, bis(aminoethyl)phthalate , 2,6-di(aminomethyl)furan, xylylenediamine hydride (H6XDA), dicyclohexylmethanediamine, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine (IPDA), dicyclohexyldimethylmethanediamine, 2 ,2-Dimethyldicyclohexylmethanediamine, 2,5-bis(aminomethyl)bicyclo-[2,2,1]-heptane, 2,6-bis(aminomethyl)bicyclo-[2,2,1 ]-Heptane, 3,8-bis(aminomethyl)tricyclodecane, 3,9-bis(aminomethyl)tricyclodecane, 4,8-bis(aminomethyl)tricyclodecane, 4,9-bis(amino Methyl) tricyclodecane, norbornenediamine (NBDA), bis (aminomethyl) sulfide, bis (aminoethyl) sulfide, bis (aminopropyl) sulfide, bis (aminohexyl) sulfide, bis (aminomethyl) Sulfone, bis(aminomethyl)disulfide, bis(aminoethyl)disulfide, bis(aminopropyl)disulfide, bis(aminomethylthio)methane, bis(aminoethylthio)methane, bis(aminoethylthio)ethane, Bis(aminomethylthio)ethane etc. are mentioned. More specifically, the diamine is one selected from the group consisting of xylylenediamine (XDA), norbornenediamine (NBDA), hydrogenated xylylenediamine (H6XDA), isophoronediamine (IPDA), and hexamethylenediamine (HDA) may be more than The xylylenediamine (XDA) includes ortho-xylylenediamine (o-XDA), meta-xylylenediamine (m-XDA) and para-xylylenediamine (p-XDA).

In the present specification, "isocyanate" means a compound having an NCO group, "diisocyanate" means a compound having two NCO groups at the terminal, and according to the skeleton of an aliphatic chain, an aliphatic ring, and an aromatic ring It can have a wide variety of structures. Specific examples of the diisocyanate include xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis (isocyanatomethyl)-bicyclo[2.2.1]heptane, xylylene hydride diisocyanate (H6XDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), 1,2-diisocyanatobenzene , 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenylisocyanate)(MDI), 1,2-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)benzene, 1,4-bis(iso Cyanatomethyl)benzene, 1,2-bis(isocyanatoethyl)benzene, 1,3-bis(isocyanatoethyl)benzene, 1,4-bis(isocyanatoethyl)benzene, α ,α,α',α'-tetramethylxylylenediisocyanate, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethylphenyl)ether, norbornene diisocyanate (NBDI), bis(isocyanatomethyl) ) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydro Thiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, etc. can be heard More specifically, the diisocyanate is xylylene diisocyanate (XDI), norbornene diisocyanate (NBDI), hydrogenated xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI) and the group consisting of hexamethylene diisocyanate (HDI) It may be one or more selected from. The xylylene diisocyanate (XDI) includes ortho-xylylene diisocyanate (o-XDI), meta-xylylene diisocyanate (m-XDI) and para-xylylene diisocyanate (p-XDI).

As used herein, the term “composition” may refer to a form in which two or more chemical components are mixed or combined in a solid, liquid and/or gaseous phase while generally maintaining their respective unique properties.

In the present specification, the ppm unit means ppm based on weight.

A compound (eg, triphosgene) or a compound obtained as a result of the reaction (eg, diamine hydrochloride, diisocyanate) used in each reaction step according to the embodiment is generally a residual, side reaction or moisture of an unreacted sample in each reaction step. It exists in a mixed or combined state with heterogeneous components generated by reaction with or natural decomposition of compounds, and these heterogeneous components may be present together with the main component in a trace amount even after several purifications.

According to the above embodiment, since attention is paid to these heterogeneous components mixed or combined with the main compound, even a trace amount of the heterogeneous component is treated as a composition mixed or combined with the main compound, and the components and contents thereof are specifically exemplified.

In addition, in this specification, for clear and easy distinction between various compositions, terms are also described in combination with the name of the main component in the composition. For example, "diamine hydrochloride composition" means a composition containing diamine hydrochloride as a main component, and , "diisocyanate composition" means a composition comprising diisocyanate as a main component. At this time, the content of the main component in the composition may be 50% by weight or more, 80% by weight or more, or 90% by weight or more, for example, may be 90% by weight to 99.9% by weight.

[Diisocyanate composition]

According to an embodiment, the content of benzyl isocyanate including diisocyanate and having an ethyl group is 1 ppm to 1000 ppm.

According to the embodiment of the present invention, by controlling the content of benzyl isocyanate having an ethyl group in the diisocyanate composition used for the production of a polythiourethane-based optical material, yellowness, streaking and cloudiness are prevented and optical properties such as improvement of transmittance are improved. At the same time, mechanical properties can be improved.

When the content of benzyl isocyanate having an ethyl group is too large, when applied to an optical material, optical properties and mechanical properties may be adversely affected. In particular, the benzyl isocyanate having an ethyl group may precipitate as a solid when the concentration is higher than a certain concentration due to low solubility and may cause cloudiness, transmittance may decrease, and yellowness may increase.

The benzyl isocyanate having an ethyl group is a benzyl isocyanate having an ethyl group having a specific aromatic structure, specifically 1-ethyl-2-(isocyanatomethyl)benzene in which an ethyl group is substituted at the ortho (o) position, meta (m) From the group consisting of 1-ethyl-3-(isocyanatomethyl)benzene substituted with an ethyl group at the ) position and 1-ethyl-4-(isocyanatomethyl)benzene substituted with an ethyl group at the para (p) position It may include one or more selected.

According to an embodiment of the present invention, the benzyl isocyanate having an ethyl group is 1 selected from the group consisting of 1-ethyl-3-(isocyanatomethyl)benzene and 1-ethyl-4-(isocyanatomethyl)benzene. It may include more than one species. According to an embodiment of the present invention, benzyl isocyanates having an ethyl group, in particular said 1-ethyl-3-(isocyanatomethyl)benzene and/or 1-ethyl-4-(isocyanatomethyl)benzene, are added to a certain range. When included, it is possible to prevent the material having low solubility from precipitating as a solid, thereby preventing the occurrence of streaks and cloudiness of an optical material, for example, an optical lens, and it is possible to improve transmittance.

More specifically, the benzyl isocyanate having an ethyl group may include a compound of Formula 1 in which an ethyl group is substituted at the meta (m) position:

[Formula 1]

.

.

According to an embodiment of the present invention, the content of benzyl isocyanate having an ethyl group included in the composition is 1 ppm to 1000 ppm, 1 ppm to 800 ppm, 1 ppm to 700 ppm, 1 ppm to 500 ppm, 1 ppm to 350 ppm, 1 ppm to 300 ppm, 1 ppm to 250 ppm, 1 ppm to 200 ppm, 1 ppm to 150 ppm, 1 ppm to 100 ppm, 1 ppm to 50 ppm, or 10 ppm to 350 ppm. According to an embodiment of the present invention, by controlling the content of benzyl isocyanate having an ethyl group in the composition, in particular, the compound of Formula 1 in the above range, streaks and cloudiness can be prevented, and yellowness is lowered and transmittance is improved. can

If the content of benzyl isocyanate having an ethyl group cannot be controlled, cloudiness may occur and transmittance may be reduced. In addition, when the content of benzyl isocyanate having an ethyl group is too high, the purity or yield of a crude product, for example, a reaction product of a diamine hydrochloride composition and triphosgene (before distillation) may be reduced. For example, if the content of benzyl isocyanate having an ethyl group exceeds 1000 ppm, cloudiness may occur in the optical material using the composition, and transmittance may be reduced. In addition, even if there is no problem in the optical properties, the purity or yield of the diisocyanate composition, which is a reaction product of the diamine hydrochloride composition and triphosgene, may decrease.

On the other hand, the diisocyanate composition may include the diisocyanate in an amount of 99% by weight or more to less than 100% by weight based on the total weight of the composition.

The diisocyanate may include m-xylylene diisocyanate (m-XDI), p-xylylene diisocyanate (p-XDI), or a mixture thereof.

The diisocyanate composition according to the embodiment contains 99% by weight to less than 100% by weight of m-xylylenediisocyanate (m-XDI), for example, 99.5% by weight or more to less than 100% by weight, or 99.7% by weight or more to 100% by weight. It may contain less than % by weight.

When the m-xylylene diisocyanate is included in the composition in an amount less than the above content, due to the non-uniformity of polymerization reactivity and the chemical structure of the cured product, optical properties (especially streaking, transmittance, etc.) as well as mechanical properties (impact resistance, tensile strength, etc.) may be inhibited, and yellowing may occur depending on other mixed components.

According to one embodiment, the content of the benzyl isocyanate having an ethyl group in the composition, in particular, 1 ppm to 500 ppm, specifically 10 ppm to 350 ppm of the compound of Formula 1, and the m-xylylene diisocyanate in the composition Based on the total weight, 99.5% by weight or more and less than 100% by weight may be included.

In addition, the p-xylylene diisocyanate is more than 0 wt% to 0.5 wt% or less, more than 0 wt% to 0.3 wt% or less, more than 0 wt% to 0.15 wt% or less, 0 wt% based on the total weight of the composition greater than 0.1% by weight, greater than 0% to 0.05% by weight, greater than 0% to 0.03% by weight, or greater than 0% to 0.01% by weight.

When the p-xylylene diisocyanate is included in the composition in excess of the above content, optical properties such as streaks or transmittance may be impaired due to non-uniformity in polymerization due to differences in reactivity or crystallization due to changes in the chemical structure of the polymer. .

The diisocyanate composition may include an isocyanate used in the manufacture of an optical material in addition to the m-xylylene diisocyanate and p-xylylene diisocyanate, specifically ortho-xylylene diisocyanate (o-XDI), norbornene diisocyanate (NBDI), hydride xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI), and may further include at least one selected from the group consisting of hexamethylene diisocyanate (HDI).

In addition, the diisocyanate composition of the present invention may further include at least one selected from the group consisting of methyl group-containing benzyl isocyanate and cyanobenzyl isocyanate.

At least one selected from the group consisting of the methyl group-containing benzyl isocyanate and cyanobenzyl isocyanate is, for example, 0.5 wt% or less, 0.3 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.02 wt% or less, or It may be included in 0.01 wt% or less.

When at least one selected from the group consisting of the methyl group-containing benzyl isocyanate and cyanobenzyl isocyanate is included in the composition in excess of the above content, the chemical structure of the polymer is also affected, so that in the final product, mechanical properties or heat resistance such as glass transition temperature properties may be degraded. In addition, under the influence of the cyano group, yellowing may occur during heat curing for lens manufacturing or depending on the external environment after manufacturing, which leads to fatal results for long-term reliability.

Therefore, the product manufactured using the composition-controlled diisocyanate composition as described above can not only satisfy high optical properties, but also implement satisfactory mechanical properties, so it is suitable for the manufacture of optical materials, specifically plastic optical lenses. It can be useful.

[Method for producing diisocyanate composition]

A method for preparing a diisocyanate composition according to an embodiment comprises the steps of obtaining a diamine hydrochloride composition; treating the diamine hydrochloride composition; and obtaining a diisocyanate composition by using the treated diamine hydrochloride composition, wherein the content of benzyl isocyanate having an ethyl group in the diisocyanate composition is 1 ppm to 1000 ppm.

1 schematically shows a method for preparing a diisocyanate composition according to an embodiment. In FIG. 1, R includes an aromatic ring, an aliphatic ring, an aliphatic chain, and the like, and as a specific example, R may be xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene, but is not limited thereto.

In the method for preparing a diisocyanate composition according to an embodiment of the present invention, the content of benzyl isocyanate having an ethyl group may be adjusted to 1 ppm to 1000 ppm by the above process. In particular, when reacting with triphosgene using the treated diamine hydrochloride composition, when the reaction temperature is reacted at a temperature of 110 ° C to 130 ° C, the content of benzyl isocyanate having an ethyl group can be efficiently controlled by a simple method.

In addition, by using an aqueous hydrochloric acid solution without using hydrogen chloride gas for the production of diamine hydrochloride, which is an intermediate material, the reaction can proceed even at normal pressure, so there is no need for an additional device for high-temperature heating and cooling, and the diisocyanate composition thus prepared, and It is possible to simultaneously improve the purity and yield of the final product of the optical material using this.

Preparation of diamine hydrochloride composition

The method for preparing a diisocyanate composition according to an embodiment of the present invention includes obtaining a diamine hydrochloride composition.

Obtaining the diamine hydrochloride composition may include reacting diamine and an aqueous hydrochloric acid solution. In addition, the diamine hydrochloride composition may be obtained in a solid phase by additionally adding a first organic solvent after the reaction of the diamine with the aqueous hydrochloric acid solution.

Scheme 1 below shows an example of the reaction of this step.

[Scheme 1]

In the above formula, R includes an aromatic ring, an aliphatic ring, an aliphatic chain, and the like, and as a specific example, R may be xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene, but is not limited thereto.

In the case of using hydrogen chloride gas in the prior art, since hydrochloride is generated as fine particles during the atmospheric reaction and the stirring state inside the reactor is not smooth, a process of raising the internal temperature of the reactor by increasing the pressure is additionally required, and the final process product There was also a problem of low yield.

However, according to the above embodiment, since the aqueous hydrochloric acid solution is used, it is possible to solve the problem that occurs when using hydrogen chloride gas in the prior art. Specifically, when an aqueous hydrochloric acid solution is used, the yield is high because the product produced through the reaction is in the form of a solid rather than in the form of a slurry, and a separate device or process for rapid cooling is not required because the reaction can be carried out even at atmospheric pressure.

The concentration of the aqueous hydrochloric acid solution may be 5 wt% to 50 wt%. When it is within the concentration range, it is possible to minimize the dissolution of hydrochloric acid in the aqueous hydrochloric acid solution, thereby increasing the final yield and improving handling.

Specifically, the concentration of the aqueous hydrochloric acid solution may be 10 wt% to 45 wt%, 20 wt% to 45 wt%, or 30 wt% to 40 wt%. More specifically, the aqueous hydrochloric acid solution may have a concentration of 20 wt% to 45 wt%.

The step of obtaining the diamine hydrochloride composition includes reacting diamine and an aqueous hydrochloric acid solution, and the diamine and the aqueous hydrochloric acid solution are added to the reaction at an equivalent ratio of 1: 2 to 5 at a temperature of 20 ° C to 60 ° C. When the equivalence ratio is within the range, it is possible to prevent the yield from being lowered due to dissolution due to the generation of moisture while reducing unreacted substances. Specifically, the diamine and the aqueous hydrochloric acid solution may be added to the reaction in an equivalent ratio of 1: 2 to 2.5.

The diamine and the aqueous hydrochloric acid solution may be added while maintaining a constant temperature inside the reactor.

The temperature inside the reactor when the diamine and the aqueous hydrochloric acid solution are added may be 20 °C to 100 °C. When it is within the above temperature range, it is possible to prevent the temperature from being higher than the boiling point and not suitable for the reaction or the reaction efficiency from being lowered because the temperature is too low.

Specifically, the temperature inside the reactor when the diamine and the aqueous hydrochloric acid solution are added may be from 20 °C to 60 °C, from 20 °C to less than 60 °C, from 20 °C to 50 °C, or from 20 °C to 40 °C.

More specifically, the diamine and the aqueous hydrochloric acid solution may be added to the reaction at an equivalent ratio of 1: 2 to 5 at a temperature of 20 ° C to 40 ° C.

In the conventional hydrochloride method, a large amount of heat is generated in the reaction process and rapid cooling through a separate cooler is required, whereas according to the above embodiment, a separate cooler is not required because the reactant is introduced while maintaining a low temperature.

The diamine and the aqueous hydrochloric acid solution may be added, for example, in the order of first introducing the hydrochloric acid aqueous solution into the reactor and then slowly introducing the diamine. The diamine and/or the aqueous hydrochloric acid solution may be added for 30 minutes to 1 hour.

After the addition of the diamine and the aqueous hydrochloric acid solution is completed, the internal temperature of the reactor may be cooled to 0 °C to 20 °C, 0 °C to 10 °C, or 10 °C to 20 °C.

The reaction of the diamine with the aqueous hydrochloric acid solution may be carried out at normal pressure, for example, may be performed while stirring for 30 minutes to 2 hours.

Through the reaction of the diamine with the aqueous hydrochloric acid solution, a reaction result in an aqueous solution state in which the diamine hydrochloride composition is dissolved in water may be obtained.

Treatment of diamine hydrochloride composition

The method for preparing a diisocyanate composition according to an embodiment of the present invention may include treating the diamine hydrochloride composition after obtaining the diamine hydrochloride composition.

For example, treating the diamine hydrochloride composition may include at least one of precipitating the diamine hydrochloride composition, filtering the diamine hydrochloride composition, drying the diamine hydrochloride composition, and washing the diamine hydrochloride composition. may contain one.

Specifically, a solid diamine hydrochloride composition may be precipitated by adding a first organic solvent to the reaction product. That is, the first organic solvent may induce precipitation of the solid diamine hydrochloride composition through crystallization. More specifically, the first organic solvent may be added to the reaction result, and after cooling, the reaction may proceed while further stirring.

The first organic solvent is specifically diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, dimethyl formamide, acetonitrile, acetone, trichloroethylene, tetrachloroethane, It may be at least one selected from the group consisting of trichloroethane, n-butanol, isobutanol, methyl ethyl ketone, methyl butyl ketone, isopropanol, hexane, chloroform and methyl acetate.

The input amount (weight) of the first organic solvent may be 1 to 5 times the weight of the diamine. When it is within the above dosage range, it is possible to prevent the use of excessive organic solvent while the yield of the final hydrochloride is high. Specifically, the first organic solvent may be added to the reaction in an amount of 1 to 2 times, or 1 to 1.5 times the weight of the diamine.

The cooling temperature after the input of the first organic solvent may be -10 °C to 10 °C or -5 °C to 5 °C. In addition, the additional reaction time after the cooling may be 30 minutes to 2 hours, or 30 minutes to 1 hour.

According to a specific example, the reaction of the diamine with the aqueous hydrochloric acid solution comprises the steps of (1a) introducing the aqueous hydrochloric acid solution into a first reactor; (1b) further adding the diamine to the first reactor and stirring; and (1c) additionally adding the first organic solvent to the first reactor and stirring.

More specifically, the reaction of the diamine with the aqueous hydrochloric acid solution comprises: cooling the inside of the reactor to a temperature of 0 °C to 10 °C before stirring after the diamine is added in step (1b); and cooling the inside of the reactor to a temperature of -5 °C to 5 °C after the input of the first organic solvent in step (1c) and before stirring.

After the first organic solvent is added, separation, filtration, washing and drying may be further performed. For example, a solid diamine hydrochloride composition may be obtained by separating the aqueous layer after the input of the first organic solvent, filtration, washing and drying. The washing may be performed one or more times using, for example, a solvent having a polarity of 5.7 or less. In addition, the drying may use vacuum drying, for example, may be performed at a temperature of 40 ℃ to 90 ℃ and a pressure of 2.0 torr or less.

As a result, impurities generated in the step of obtaining the diamine hydrochloride composition may be removed together with the first organic solvent. Accordingly, the method may further include removing impurities generated in the step of obtaining the diamine hydrochloride composition together with the first organic solvent. In the reaction process for preparing the diamine hydrochloride composition, impurities are generated and included in the first organic solvent, and the purity of the product can be increased by removing such impurities through the removing step of the first organic solvent.

According to the method, the diamine is reacted with an aqueous hydrochloric acid solution, and the solid diamine hydrochloride composition can be obtained with high purity through additional treatment such as precipitation, filtration, drying, and washing. On the other hand, when diamine is reacted with hydrogen chloride gas in an organic solvent as in the prior art, a slurry of diamine hydrochloride is obtained and purification is not easy.

The yield of the diamine hydrochloride composition thus obtained may be 50% or more, 65% or more, 80% or more, 85% or more, or 90% or more, and specifically 85% to 95%, or 88% to 92%. .

Meanwhile, the organic layer may be separated from the reactants and reused as an organic solvent. Accordingly, the recovery rate of the first organic solvent may be 80% or more, 85% or more, or 90% or more, and specifically, 80% to 95%, or 80% to 82%.

Preparation of diisocyanate composition

The method for preparing a diisocyanate composition according to an embodiment of the present invention includes treating the diamine hydrochloride composition and then using the treated diamine hydrochloride composition to obtain a diisocyanate composition.

The step of obtaining the diisocyanate composition may include reacting the diamine hydrochloride composition treated by a process comprising at least one of the steps of precipitation, filtration, drying, and/or washing with triphosgene.

In this case, the reaction of the diamine hydrochloride composition with triphosgene may be performed in a second organic solvent.

Scheme 2 below shows an example of the reaction of this step.

[Scheme 2]

In the above formula, R includes an aromatic ring, an aliphatic ring, an aliphatic chain, and the like, and as a specific example, R may be xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene, but is not limited thereto.

Specifically, the diamine hydrochloride composition prepared above is added to a second organic solvent, reacted with triphosgene (BTMC, bis(trichloromethyl)carbonate), and then purified to obtain a diisocyanate composition.

Specific examples of the second organic solvent include benzene, toluene, ethylbenzene, chlorobenzene, monochlorobenzene, 1,2-dichlorobenzene, dichloromethane, 1-chloro-n-butane, 1-chloro-n-pentane, 1 -Chloro-n-hexane, chloroform, carbon tetrachloride, n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, cyclooctane, and may be at least one selected from the group consisting of methylcyclohexane have.

The amount (weight) of the second organic solvent may be 1 to 5 times the weight of the diamine hydrochloride composition. When it is within the above dosage range, it is possible to prevent the use of an excessive organic solvent while the yield of the final diisocyanate is high. Specifically, the second organic solvent may be added to the reaction in an amount of 2 to 5 times, or 3 to 5 times the weight of the diamine hydrochloride composition.

In addition, obtaining the diisocyanate composition may include reacting the treated diamine hydrochloride composition with triphosgene at a temperature of 110 °C to 130 °C.

Specifically, when the treated diamine hydrochloride composition is reacted with triphosgene, the reaction temperature is 110 °C to 130 °C, more than 110 °C to less than 130 °C, 110 °C to 125 °C, 110 °C to less than 120 °C, or 120 °C to 130 °C.

According to an embodiment of the present invention, when the content of benzyl isocyanate having an ethyl group, particularly the compound of Formula 1, is high, it causes cloudiness and low permeability, and the compound is reacted under high temperature conditions (eg, phosgenation reaction) may occur more in Therefore, controlling the reaction temperature in the above range can be very important. When the diamine hydrochloride composition is reacted with triphosgene, if the reaction temperature is less than 110° C., the reaction between the diamine hydrochloride composition and triphosgene may not occur smoothly, and thus the yield may be lowered. In addition, when the reaction temperature exceeds 130° C., the content of benzyl isocyanate having an ethyl group in the diisocyanate composition may be increased, and optical properties of the optical material may be deteriorated.

According to the embodiment of the present invention, when the reaction of the diamine hydrochloride composition and triphosgene occurs within the range of 110°C to 130°C, the content of benzyl isocyanate having an ethyl group can be effectively controlled to 1 ppm to 1000 ppm, yield and purity can improve In addition, when the content of benzyl isocyanate having an ethyl group in the diisocyanate composition, particularly 1-ethyl-3-(isocyanatomethyl)benzene, is controlled within the above range, the transmittance is excellent, and yellowness, streaks and cloudiness are generated. can reduce In addition, since it is possible to implement an appropriate refractive index, when applied to an optical material, optical properties as well as mechanical properties are excellent, so that a good optical material can be obtained.

The reaction of the diamine hydrochloride composition and triphosgene may be performed for 5 to 100 hours. When it is within the reaction time range, the reaction time is not excessive, and generation of unreacted substances due to phosgene generation can be minimized. Specifically, the reaction of the diamine hydrochloride composition with triphosgene may be performed for 15 hours to 40 hours, 20 hours to 35 hours, or 24 hours to 30 hours.

As a specific example, the reaction of the diamine hydrochloride composition with triphosgene may be performed at a temperature of 110° C. to 130° C. for 5 hours to 100 hours.

The diamine hydrochloride composition and the triphosgene may be added to the reaction in an equivalent ratio of 1:1 to 5. When the equivalence ratio is within the range, it is possible to prevent the reaction time from increasing due to excessive input while the reaction efficiency is high. Specifically, the diamine hydrochloride composition and the triphosgene may be added to the reaction in an equivalent ratio of 1: 1.5 to 4, or 1: 2 to 2.5.

According to a specific example, the reaction of the diamine hydrochloride composition and triphosgene comprises the steps of (2a) introducing the second organic solvent to a second reactor; (2b) further adding the diamine hydrochloride composition to the second reactor and stirring; and (2c) additionally adding the triphosgene to the second reactor and stirring.

More specifically, the introduction of the triphosgene in the step (2c) is a solution in which the triphosgene is dissolved in the same solvent as the second organic solvent in the reactor at a temperature of 110° C. to 130° C. for a total of 25 to 40 hours. It may be divided into two or more times during the period.

In this case, the time for each injection of triphosgene may be 5 hours to 25 hours, or 10 hours to 14 hours.

In addition, the time for further reaction by stirring after the addition of triphosgene may be 2 hours to 5 hours or 3 hours to 4 hours.

After the reaction, the reactant may be cooled at a temperature of 90 °C to 110 °C.

The reaction product obtained through the above reaction may be further subjected to separation, filtration and distillation.

Using the treated diamine hydrochloride composition, after obtaining a diisocyanate composition, the step of distilling the diisocyanate composition may be further included.

The distillation may include primary distillation and secondary distillation.

For example, the step of obtaining the diisocyanate composition further comprises distilling the reaction product obtained by reacting the diamine hydrochloride composition, specifically, the treated diamine hydrochloride composition with the triphosgene, wherein the distillation is the reaction product It may include primary distillation at 40 °C to 60 °C for 2 hours to 8 hours, and secondary distillation at 100 °C to 120 °C for 2 hours to 10 hours. The primary distillation and/or secondary distillation may be performed at 0.5 Torr or less.

The organic solvent may be recovered and recycled through the primary distillation, and final diisocyanate may be obtained through the secondary distillation.

In addition, the yield of the diisocyanate composition (ie, crude) before the distillation may be 80% or more, 85% or more, or 90% or more.

In addition, the yield of the diisocyanate composition obtained after the distillation may be 80% or more, 85% or more, 90% or more, 90% or more, 95% or more, 98% or more, or 99% or more.

Measurement of color and transparency of reaction solution

The step of obtaining a diisocyanate composition from the diamine hydrochloride composition and triphosgene includes: (i) reacting the diamine hydrochloride composition with triphosgene in a reactor to obtain a reaction solution; (ii) measuring the color and transparency of the reaction solution; and (iii) obtaining a diisocyanate composition from the reaction solution.

In the reaction of the diamine hydrochloride composition and triphosgene, the reaction conditions can be adjusted by measuring the color and transparency of the reaction solution.

For example, in the reaction of obtaining xylylene diisocyanate from the xylylenediamine hydrochloride composition and triphosgene, the reaction solution at the initial stage of the reaction may be opaque, colorless to white, and the reaction solution at the time when the reaction is normally completed is transparent or transparent It is close to and may have a light brown color.

For example, in the step of measuring the color and transparency of the reaction solution, the reaction solution may exhibit a transparent light brown color.

Specifically, the reaction solution may have an L* value of 45 to 60, an a* value of 3 to 15, and a b* value of 15 to 30 in the CIE-LAB color coordinate. More specifically, the reaction solution may have an L* value of 50 to 55, an a* value of 5 to 10, and a b* value of 20 to 25 in the CIE-LAB color coordinate.

In addition, the reaction solution may have a transmittance of 60% or more, 70% or more, 80% or more, or 90% or more for light having a wavelength of 550 nm. In addition, the reaction solution may have a haze of 20% or less, 10% or less, 5% or less, or 3% or less. Specifically, the reaction solution may have a transmittance of 70% or more and a haze of 10% or less for light having a wavelength of 550 nm. More specifically, the reaction solution may have a transmittance of 80% or more and a haze of 5% or less for light having a wavelength of 550 nm.

On the other hand, if the reaction between the diamine hydrochloride composition and triphosgene is not completed, the reaction solution may be opaque or have a precipitate, and the color may be faint, white, or colorless. In addition, if a large number of side reactions occur, the reaction solution may be opaque or may exhibit a color other than light brown, for example, may exhibit a dark brown to dark color.

The reaction step of the diamine hydrochloride composition and triphosgene may be performed simultaneously with the step of measuring the color and transparency of the reaction solution.

That is, the color and transparency of the reaction solution can be measured in real time while the reaction of the diamine hydrochloride composition and triphosgene is in progress.

In addition, for more accurate measurement, color and transparency can be precisely measured by collecting a portion of the reaction solution. For example, the measurement of the color and transparency of the reaction solution may be performed by collecting a portion of the reaction solution and measuring the color and transparency of the collected reaction solution.

In this case, the reaction equivalent, reaction temperature, or reaction time may be adjusted according to the color and transparency of the reaction solution. For example, the end time of the reaction may be determined according to the color and transparency of the reaction solution. Specifically, the completion time of the reaction may be after the time when the reaction solution changes to a transparent light brown color.

As an example, the reactor may have a viewing window, and measurement of color and transparency of the reaction solution may be performed through the viewing window.

The reactor may be connected to one or more condensers, and after the gas generated in the reactor is transferred to the one or more condensers, the second organic solvent present in the gas may be condensed and recovered to the reactor.

The one or more condensers are connected to the first scrubber and the second scrubber, and the gas transferred from the reactor to the one or more condensers includes hydrogen chloride gas and phosgene gas, and the first scrubber converts the hydrogen chloride gas into water. Dissolving to produce an aqueous solution, the second scrubber can neutralize the phosgene gas by the NaOH aqueous solution.

In addition, the reactor may be connected to one or more stills, and the reaction solution may be transferred to the one or more stills, and the one or more stills may separate the diisocyanate composition and the second organic solvent from the reaction solution.

The separated second organic solvent may be recycled for the reaction between the diamine hydrochloride composition and triphosgene.

2 shows an example of a process device for the reaction of a diamine hydrochloride composition and triphosgene.

First, a second organic solvent and triphosgene are filled in the first tank T-1, and a constant temperature is maintained by reflux of hot water. The inside of the reactor (R-1) is replaced with nitrogen, and a second organic solvent is added thereto and stirred, the diamine hydrochloride composition is slowly added thereto and stirred while maintaining the inside of the reactor at a constant temperature.

Then, triphosgene in the second organic solvent is slowly introduced into the reactor (R-1) from the first tank (T-1). The input of triphosgene in the second organic solvent is carried out once or divided into two or more times, and at this time, stirring is performed while maintaining the internal temperature of the reactor (R-1) constant. After the addition is completed, an additional reaction is performed while stirring for a predetermined time. As an example, the color and transparency of the reaction solution are visually observed through the viewing window (G-1) provided in the reactor (R-1). As another example, the color and transparency of the reaction solution are measured with an optical instrument through the viewing window (G-1) provided in the reactor (R-1). The optical device may include a digital camera, a spectrometer, an optical analysis device, and the like.

The gas (second organic solvent, hydrogen chloride, phosgene, etc.) existing inside the reactor R-1 is transferred to the first condenser C-1. The second organic solvent is primarily condensed by cooling in the first condenser (C-1) and recovered to the reactor (R-1), and the remaining gas is transferred to the second condenser (C-2). The second organic solvent is secondarily condensed by cooling in the second condenser (C-2) and recovered to the reactor (R-1), and the remaining gas is transferred to the third condenser (C-3). The second organic solvent is tertiarily condensed by cooling in the third condenser (C-3) and is recovered to the reactor (R-1).

After the second organic solvent is removed through the multi-stage condenser as described above, the remaining gas (hydrogen chloride, phosgene, etc.) is transferred to the first scrubber S-1. Hydrochloric acid aqueous solution is obtained by dissolving hydrogen chloride gas in water in the first scrubber S-2, and stored in the second tank T-2, and the remaining gas is transferred to the second scrubber S-2. In the second scrubber (S-2), using the sodium hydroxide aqueous solution stored in the third tank (T-3), phosgene (COCl ₂ ) It can be removed by neutralizing the gas.

The reaction solution obtained in the reactor (R-1) is sequentially transferred to the first still (D-1) and the second still (D-2), and through primary and secondary distillation, diisocyanate from the reaction solution The composition and the second organic solvent are separated.

The second organic solvent separated from the reaction solution may be transferred to and stored in the solvent recovery unit V-1, and then may be recycled for the reaction between the diamine hydrochloride composition and triphosgene.

In addition, the diisocyanate composition separated from the reaction solution may be provided as a final product through further filtration and drying.

[Manufacturing method of optical material]

A polymerizable composition for an optical material can be prepared by combining the diisocyanate prepared in the above embodiment with other components.

The polymerizable composition for an optical material includes diisocyanate, and the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm.

The polymerizable composition for an optical material further includes a thiol or episulfide.

An optical material, specifically, an optical lens may be manufactured by using the polymerizable composition for an optical material. For example, the optical lens may be manufactured by mixing the polymerizable composition for an optical material and curing it by heating in a mold.

A method of manufacturing an optical material according to an embodiment includes a first step of reacting diamine with an aqueous hydrochloric acid solution to obtain a diamine hydrochloride composition; a second step of reacting the diamine hydrochloride composition with triphosgene at a temperature of 110 °C to 130 °C to obtain a diisocyanate composition; and a third step of mixing the diisocyanate composition with thiol or episulfide and polymerization and curing in a mold, wherein the diisocyanate composition includes diisocyanate, and the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 is ppm.

In addition, the diamine may be xylylenediamine, and the diisocyanate composition may include xylylenediisocyanate.

The thiol may be a polythiol including two or more SH groups, and may have an aliphatic, alicyclic, or aromatic skeleton. The episulfide may have two or more thioepoxy groups, and may have an aliphatic, alicyclic, or aromatic skeleton.

Specific examples of the thiol include bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis(2-mercaptoethylthio ) Propane-1-thiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, tetrakis(mercaptomethyl)methane, 2-(2-mercaptoethylthio)propane-1,3 -dithiol, 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercaptopropanyl)sulfide, bis(2,3-dimercaptopropanyl) ) disulfide, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)ethane; Bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)disulfide, 2-(2-mer Captoethylthio)-3-2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2,2-bis-( 3-Mercapto-propionyloxymethyl)-butyl ester, 2-(2-mercaptoethylthio)-3-(2-(2-[3-mercapto-2-(2-mercaptoethylthio)- Propylthio]ethylthio)ethylthio)propane-1-thiol, (4R,11S)-4,11-bis(mercaptomethyl)-3,6,9,12-tetrathiatetradecane-1,14-dithi ol, (S)-3-((R-2,3-dimercaptopropyl)thio)propane-1,2-dithiol, (4R,14R)-4,14-bis(mercaptomethyl)-3, 6,9,12,15-pentathiaheptane-1,17-dithiol, (S)-3-((R-3-mercapto-2-((2-mercaptoethyl)thio)propyl)thio) Propyl)thio)-2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2-dithiol), (7R,11S)-7,11 -bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7,12-bis(mercaptomethyl)-3,6 ,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, penta Erythritol Tetra Kiss (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaethritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis ( 3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis (mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane, 2,5-bismercaptomethyl-1,4 -dithiane, bis(mercaptomethyl)-3,6,9-trithiaundecan-1,11-dithiol, and the like.

For example, the thiol is 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 2-(2, 3-bis(2-mercaptoethylthio)propylthio)ethanethiol, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,2-bis(2-(2-mercapto) Ethylthio)-3-mercaptopropylthio)-ethane, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 2-(2-mercaptoethylthio)-3-2 -Mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2,2'-thiodiethanethiol, 4,14-bis (mercaptomethyl)-3,6,9,12,15-pentathiahexadecane-1,17-dithiol, 2-(2-mercaptoethylthio)-3-[4-(1-{4- [3-Mercapto-2-(2-mercaptoethylthio)-propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol, pentaerythritol tetrakis (3-mercapto propionate), pentaerythritol mercaptoacetate, trimethylolpropane trismercaptopropionate, glycerol trimercaptopropionate, dipentaepitritol hexamercaptopropionate, 2,5-bismercaptomethyl -1,4-dithiane and the like.

The thiol may be any one or two or more of the exemplary compounds, but is not limited thereto.

In addition, specific examples of the episulfide include bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane , 1,2-bis(β-epithiopropylthio)propane, 1-(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)propane, 1,4-bis(β-epithio Propylthio)butane, 1,3-bis(β-epithiopropylthio)butane, 1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)butane, 1,5-bis( β-epithiopropylthio)pentane, 1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane, 1,6-bis(β-epithiopropylthio)hexane, 1- (β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane , 1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl]thio]ethane, tetrakis(β-epithiopropylthiomethyl)methane, 1 ,1,1-tris(β-epithiopropylthiomethyl)propane, 1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane, 1, 5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2-bis(β -Epithiopropylthiomethyl)-4-thiahexane, 1,5,6-tris(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3-thiahexane, 1,8- Bis(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,5-bis( β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3,6- Dithiaoctane, 1,8-bis(β-epithiopropylthio)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β -epithiopropylthio)-2,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,9-bis(β-epithiopropylthio)-5-(β-epi Thiopropylthiomethyl)-5-[(2-β -epithiopropylthioethyl)thiomethyl]-3,7-dithianonane, 1,10-bis(β-epithiopropylthio)-5,6-bis[(2-β-epithiopropylthioethyl) Thio]-3,6,9-trithiadecane, 1,11-bis(β-epithiopropylthio)-4,8-bis(β-epithiopropylthiomethyl)-3,6,9-trithia Undecane, 1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithioundecane, 1,11-bis(β -epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithioundecane, 1,11-bis(β-epithiopropylthio )-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithioundecane, 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis( β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β -epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, bis[4-(β-epithiopropylthio)cyclohexyl]sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 1,3- Bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β- epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β -epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfone, 4,4'-bis(β-epithiopropylthio)biphenyl, and the like.

The episulfide may be any one or two or more of the exemplary compounds, but is not limited thereto. In addition, the episulfide may be a compound in which at least one hydrogen of a thioepoxy group is substituted with a methyl group.

The polymerizable composition for an optical material may include the diisocyanate composition and the thiol or episulfide in a mixed state or in a separate state. That is, in the polymerizable composition, they may be in a mixed state in contact with each other, or may be in a separated state so as not to contact each other.

The polymerizable composition for an optical material may include the thiol or episulfide in a weight ratio of 2:8 to 8:2, 3:7 to 7:3, or 4:6 to 6:4 with the diisocyanate composition. have.

A catalyst, a chain extender, a crosslinking agent, a UV stabilizer, an antioxidant, a color inhibitor, a dye, a filler, a mold release agent, and the like may be further added according to the purpose in the preparation of the polymerizable composition for an optical material and the optical material.

After mixing these thiols or episulfides with the diisocyanate composition and other additives and defoaming, they are poured into a mold and polymerized while slowly rising from a low temperature to a high temperature, and the resin is cured by heating it to prepare an optical material.

The temperature of the polymerization reaction may be, for example, 20 °C to 150 °C, specifically 25 °C to 120 °C. In addition, in order to control the reaction rate, a reaction catalyst commonly used in the production of polythiourethane may be added, and specific types thereof are as exemplified above.

In addition, the manufactured optical material may have physical or physical properties such as anti-reflection, high hardness, abrasion resistance, chemical resistance, anti-fogging, surface polishing, antistatic treatment, hard coat treatment, anti-reflection coating treatment, dyeing treatment, etc., if necessary. A chemical treatment may be further carried out.

[Optical Materials]

An optical material according to one embodiment of the present invention is an optical material comprising a diisocyanate composition and polythiourethane polymerized with thiol or episulfide, wherein the diisocyanate composition includes diisocyanate, and benzyl isocyanate having an ethyl group The content of is 1 ppm to 1000 ppm.

The optical material according to an embodiment of the present invention has excellent transparency, refractive index, yellowness, etc., as well as improved transmittance, and can prevent streaks and cloudiness.

For example, the optical material may have a refractive index of 1.55 or more, specifically, a refractive index of 1.55 to 1.77. In addition, the optical material may have an Abbe's number of 30 to 50, specifically 30 to 45, or 31 to 40. In addition, the optical material may have a light transmittance of 80% or more, 85% or more, 87% or more, 89% or more, 90% or more, or 91% or more, which may be total light transmittance. In addition, the optical material may have a yellowness (Y.I.) of 30 or less, 25 or less, 22 or less, or 20 or less, for example, 1 to 25, or 10 to 22. Specifically, the optical material may have a transmittance of 85% or more and a yellowness of 22 or less. More specifically, the optical material may have a transmittance of 90% or more and a yellowness of 20 or less.

In addition, the optical material may have excellent impact energy within an appropriate range. Impact resistance energy is measured as the potential energy of the weight destroyed by dropping from a light steel ball to a heavy steel ball sequentially from a height of 127 cm on a test piece made of a flat plate with a diameter of 80 mm and a thickness of 1.2 mm at 20 ° C at room temperature according to the test standards of the US FDA can Specifically, 16 g, 32 g, 65 g, 100 g, 200 g, and 300 g of iron beads were used to observe whether the optical material, specifically, the optical lens, was damaged through a ball dropping test by height. The potential energy at the time of failure was calculated. For example, when the FDA standard is 16 g, 127 cm, the potential energy (Ep) is 0.2 (J) (Ep = mgh = 0.016 * 9.8 * 1.27 = 0.2 (J)), and the 16 g iron ball falling test If it passes, the potential energy (Ep) can be calculated using a 32 g iron bead, and if it passes, it is measured sequentially using 65 g, 100 g, 200 g, and 300 g iron beads to determine the final damage. The potential energy can be calculated when

The optical material according to the embodiment of the present invention calculated by the above method has excellent impact energy (E) of 0.6 J to 3.0 J, 0.6 J to 2.8 J, 0.8 J to 2.8 J, or 0.8 J to 1.6 J.

Therefore, when the diisocyanate composition in which the content of benzyl isocyanate having an ethyl group is controlled to a specific range is used for an optical material, transmittance can be improved, and optical properties such as yellowness, streaking and cloudiness are improved as well as , since it can also improve mechanical properties, the diisocyanate composition can be usefully utilized to manufacture high-quality spectacle lenses, camera lenses, and the like.

[Example]

More specific examples are exemplified below, but are not limited thereto.

Example 1

<Step 1: Preparation of diamine hydrochloride composition>

1009.4 g (9.46 mol) of a 35% aqueous hydrochloric acid solution was added to a 5L four-neck reactor, and the internal temperature of the reactor was cooled to 15 °C while stirring. Here, 600 g (4.4 mol) of metaxylylenediamine (m-XDA) was added while maintaining the reactor temperature below 60° C. for 1 hour. After completion of the input, the temperature inside the reactor was cooled to 10 °C, and after stirring for 1 hour, 1320.0 g of tetrahydrofuran was additionally added as an organic solvent, and the internal temperature was cooled to -5 °C and further stirred for 1 hour. After completion of the reaction, vacuum filtration was performed using a filter, and filtered tetrahydrofuran was recovered and reused. The recovery rate of the tetrahydrofuran was 82%. After vacuum filtration, a metaxylylenediamine (m-XDA) hydrochloride composition was obtained, and the final metaxylylenediamine was dried under conditions of a reactor external temperature of 90 °C and a vacuum pump of 0.1 Torr to remove the remaining organic solvent and moisture. (m-XDA) hydrochloride composition was obtained.

<Second Step: Preparation of Diisocyanate Composition>

800 g of the m-XDA hydrochloride composition and 3,550 g of orthodichlorobenzene (ODCB) prepared prior to reactor A were added, and the internal temperature of the reactor was heated at about 110° C. while stirring. 950 g of triphosgene (BTMC) and 800 g of ODCB were put into reactor B, and stirred and dissolved at about 60° C., and the reactor temperature was maintained at 110° C. to prevent precipitation, and it was added dropwise to reactor A over 24 hours. After completion of the dropping, stirring was performed for 4 hours. After completion of the reaction, nitrogen gas was blown into the solvent at 125° C. and degassed while bubbling. After cooling to 10 °C, the remaining solid was filtered using Celite. Thereafter, the organic solvent (ODCB) was removed and m-XDI was purified by distillation under distillation conditions below. The organic solvent removal (primary distillation) was carried out at a pressure of 0.5 torr or less and a temperature of 60 ° C. for 8 hours, and the distillation of m-XDI (second distillation) was performed at a pressure of 0.1 torr or less and a temperature of 120 ° C. This was carried out for 10 hours. As a result, an m-XDI composition containing 59 ppm of benzyl isocyanate (1-ethyl-3-(isocyanatomethyl)benzene) having an ethyl group was obtained.

<Manufacture of optical material>

4,8-bis(mercaptomethyl)-3,6,9-trithiaundecan-1,11-dithiol 49.3 parts by weight, 50.7 parts by weight of the m-XDI composition prepared above, 0.01 parts by weight of dibutyltin chloride , ^{0.1 parts by weight of ZELEC ®} UN Stepan's phosphate ester release agent was uniformly mixed, defoamed at 600 Pa for 1 hour, filtered through a 3 μm Teflon filter, and injected into a mold made of glass mold and tape. After maintaining the mold at 25° C. for 8 hours, the temperature was slowly raised to 130° C. for 8 hours at a constant rate, and polymerization was performed at 130° C. for 2 hours. After releasing the molded product from the mold, it was further cured at 120° C. for 2 hours to obtain an optical lens (optical material).

Examples 2 to 5

In the second step, triphosgene (BTMC) and ODCB were put into reactor B, and the reactor temperature was maintained at the reaction temperature shown in Table 1 below and dropped into reactor A, thereby 1-ethyl-3-(isocyanatomethyl) in the composition. Except for adjusting the content of benzene, an m-XDI composition and an optical lens were obtained in the same manner as in Example 1.

Comparative Examples 1 to 3

In the second step, triphosgene (BTMC) and ODCB were put into reactor B, and the reactor temperature was maintained at the reaction temperature shown in Table 1 below and dropped into reactor A, thereby 1-ethyl-3-(isocyanatomethyl) in the composition. Except for adjusting the content of benzene, an m-XDI composition and an optical lens were obtained in the same manner as in Example 1.

The reaction temperature of Examples and Comparative Examples, m-XDI obtained thereby, and the yield and purity are summarized in Table 1 below.

reaction temperature
(Drop temperature)
(℃) 1-ethyl-3-(isocyanatomethyl)benzene
(ppm) before distillation
(crude m-XDI) after distillation
(m-XDI) water
(%) yield
(%) water
(%) yield
(%) Example 1 110 59 ppm 99.1 82 99.9 96 Example 2 115 251 ppm 99.2 85 99.9 96 Example 3 120 422 ppm 99.1 92 99.9 96 Example 4 125 620 ppm 99.0 93 99.9 94 Example 5 130 985 ppm 98.8 94 99.9 95 Comparative Example 1 140 1107 ppm 98.5 94 99.8 95 Comparative Example 2 150 1356 ppm 98.2 93 99.7 95 Comparative Example 3 160 1558 ppm 98.1 93 99.6 95

<Evaluation method>

The Examples and Comparative Examples were evaluated as follows.

(1) refractive index (nd20)

The solid-state refractive index (nd20) was measured at 20 °C using an Abbe refractometer DR-M4.

(2) Yellowness (YI) and light transmittance

For the optical lens, chromaticity coordinates x and y were measured using a colorimeter (Colormate, Scinco), and then the measured values were applied to Equation 1 below to calculate yellowness. In addition, the transmittance at a wavelength of 550 nm in the spectrum obtained using the same instrument was shown as transmittance.

[Equation 1]

Y.I. = (234x+106y+106)/y

(3) McLee

A lens having a diameter of 75 mm, -2.00, -8.00 D was manufactured, and a Mercury lamp light source was transmitted through the manufactured lens, and the transmitted light was projected on a white plate to determine whether stria occurred by the presence or absence of contrast.

(4) cloudiness

The cured lens was irradiated to the projector in a dark place, and the presence or absence of a cloudy lens or an opaque material was visually checked.

No cloudiness: when the lens is cloudy or there is no opaque material

Cloudy: When the lens is cloudy or there is an opaque material

(5) Gas chromatography (GC) measurement

-Agilent 6890/7890

- Carrier: He

-Injector: 250 ℃

-Oven: 40~320℃

-Column: HP-1, Wax, 30m

-Detector: FID, 300℃

(6) GC MS measurement

-Agilent 7890B (GC), 5977A (MS)

-Mass range: 1.6 ~ 1050 amu

-Source: electron ionization (EI) (inert extractor EI source)

-Mass spectrometer: quadrupole analyzer

Oven: 40℃(6min)-10℃/min-140℃(5min)-15℃/min-290℃(15min)

Column: Rxi-5MS, ID 0.25 mm, L 30 m

Optical material (lens) properties McLee cloudiness transmittance Yellowness (Y.I.) refractive index Example 1 none none 91 20 1.669 Example 2 none none 90 19 1.669 Example 3 none none 91 20 1.669 Example 4 none none 90 20 1.669 Example 5 none none 91 20 1.669 Comparative Example 1 none has exist 89 22 1.669 Comparative Example 2 none has exist 85 23 1.669 Comparative Example 3 none has exist 84 23 1.669

As shown in the above table, when an optical lens was prepared as an optical material using the diisocyanate composition of the example of the present invention, it was confirmed that the transmittance was superior to that of the optical lens of the comparative example, and there was no streaking and cloudiness.

Specifically, all of the optical lenses of Examples 1 to 5 did not have streaks and white turbidity, and transmittance was mostly high at 91% or more, yellowness was also as low as 20 or less, and had an appropriate refractive index.

On the other hand, the optical lenses of Comparative Examples 1 to 3, in which the content of 1-ethyl-3-(isocyanatomethyl)benzene exceeds 1000 ppm, not only caused cloudiness, but also had a transmittance of 89% or less. It was significantly reduced compared to the optical lenses of 1 to 5.

Therefore, the diisocyanate composition according to an embodiment of the present invention has excellent optical properties as well as mechanical properties when applied to an optical lens, and thus is suitable for use as a high-quality optical lens.

Claims (17)

obtaining a diamine hydrochloride composition;
treating the diamine hydrochloride composition; and
Using the treated diamine hydrochloride composition, comprising the step of obtaining a diisocyanate composition,
The content of benzyl isocyanate having an ethyl group in the diisocyanate composition is 1 ppm to 1000 ppm, a method for producing a diisocyanate composition.
The method of claim 1,
A method for producing a diisocyanate composition, wherein the step of obtaining the diisocyanate composition comprises reacting the treated diamine hydrochloride composition with triphosgene at a temperature of 110°C to 130°C.
3. The method of claim 2,
The method for producing a diisocyanate composition, wherein the step of obtaining the diisocyanate composition further comprises distilling the reaction product obtained after the reaction.
4. The method of claim 3,
The distillation is a primary distillation of the reaction product at 40 ° C. to 60 ° C. for 2 hours to 8 hours, and
A method for preparing a diisocyanate composition, comprising secondary distillation at 100°C to 120°C for 2 hours to 10 hours.
The method of claim 1,
The step of obtaining the diamine hydrochloride composition comprises reacting diamine and an aqueous hydrochloric acid solution,
The diamine and the aqueous hydrochloric acid solution are added to the reaction at an equivalent ratio of 1: 2 to 5 at a temperature of 20 ° C. or more to 60 ° C., a method for producing a diisocyanate composition.
6. The method of claim 5,
The diamine is xylylenediamine,
The method for producing a diisocyanate composition, wherein the diisocyanate composition comprises xylylene diisocyanate.
diisocyanate;
The diisocyanate composition, wherein the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm.
8. The method of claim 7,
A diisocyanate composition comprising the diisocyanate in an amount of greater than or equal to 99% by weight and less than 100% by weight based on the total weight of the composition.
8. The method of claim 7,
The content of benzyl isocyanate having an ethyl group is 1 ppm to 500 ppm, the diisocyanate composition.
8. The method of claim 7,
The benzyl isocyanate having an ethyl group is 1-ethyl-2-(isocyanatomethyl)benzene, 1-ethyl-3-(isocyanatomethyl)benzene, and 1-ethyl-4-(isocyanatomethyl)benzene. ) A diisocyanate composition comprising at least one selected from the group consisting of benzene.
8. The method of claim 7,
A diisocyanate composition, wherein the benzyl isocyanate having an ethyl group comprises a compound of Formula 1 below:
[Formula 1]

.
8. The method of claim 7,
A diisocyanate composition, wherein the diisocyanate comprises m-xylylene diisocyanate, p-xylylene diisocyanate, or a mixture thereof.
13. The method according to claim 11 or 12,
10 ppm to 350 ppm of the compound of Formula 1,
A diisocyanate composition comprising the m-xylylene diisocyanate in an amount of 99.5% by weight or more and less than 100% by weight based on the total weight of the composition.
13. The method of claim 12,
The diisocyanate composition, wherein the p-xylylene diisocyanate is included in an amount of greater than 0% by weight to 0.5% by weight or less based on the total weight of the composition.
a first step of reacting diamine with an aqueous hydrochloric acid solution to obtain a diamine hydrochloride composition;
a second step of reacting the diamine hydrochloride composition with triphosgene at a temperature of 110° C. to 130° C. to obtain a diisocyanate composition; and
a third step of mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold,
The method for producing an optical material, wherein the diisocyanate composition includes diisocyanate, and the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm.
An optical material comprising a diisocyanate composition and polythiourethane polymerized with thiol or episulfide, the optical material comprising:
An optical material, wherein the diisocyanate composition includes diisocyanate, and the content of benzyl isocyanate having an ethyl group is 1 ppm to 1000 ppm.
17. The method of claim 16,
The optical material has a transmittance of 90% or more and a yellowness of 20 or less.

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