KR20210071355A - 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 an aromatic compound having a halogen group in the composition in an amount of 5 to 1,000 ppm, it is possible to improve optical properties by prevention of striae and cloudiness generation and lowered yellowness, and improve mechanical properties with excellent impact resistance in an appropriate range, and thus, 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 having an aromatic compound having a halogen group in the composition of 5 ppm to 1000 ppm, a method for preparing the same, and an optical material using the same is about

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, streaks, white turbidity, or yellowness occur in the optical material, so there is a limit in realizing satisfactory optical properties, and optical properties such as streaks, white turbidity or yellowness Even if it satisfies the impact resistance, it is still difficult to satisfy them at the same time.

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 realize a high-quality optical material by simultaneously improving optical and mechanical properties.

Korean Patent Publication No. 2012-0111171

The present invention was designed to solve the problems of the prior art, and by including an aromatic compound having a halogen group in a specific content 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 is to control the content of the aromatic compound having a halogen group in the composition to prevent streaking and cloudiness of the optical material, reduce yellowness, and at the same time improve impact resistance, diisocyanate composition and method for preparing the same is to provide

An object of another embodiment is to provide a polymerizable composition for an optical material comprising the diisocyanate composition.

An object of another embodiment is to provide an optical material formed by curing the polymerizable composition for an optical material.

According to an embodiment, diisocyanate; And there is provided a diisocyanate composition comprising an aromatic compound having a halogen group in an amount of 5 ppm to 1000 ppm.

According to another embodiment, obtaining a diamine hydrochloride composition; and obtaining a diisocyanate composition using the diamine hydrochloride composition, wherein the diisocyanate composition includes an aromatic compound having a halogen group in an amount of 5 ppm to 1000 ppm, a method for producing a diisocyanate composition is provided.

According to another embodiment, diisocyanate; and a diisocyanate composition comprising an aromatic compound having a halogen group in an amount of 5 ppm to 1000 ppm. There is provided a polymerizable composition for an optical material.

According to another embodiment, an optical material is provided, which is formed by curing the polymerizable composition for an optical material, has an impact energy (E) of 0.4 J to 4.0 J, and has a yellowness of 22 or less.

According to the embodiment, a high-quality optical material may be manufactured by adjusting the composition of the diisocyanate composition used in the preparation of the polythiourethane-based optical material.

That is, by using a diisocyanate composition containing an aromatic compound having a halogen group in a specific content for a high-quality optical material, optical properties such as yellowness, streaking and cloudiness are improved, and mechanical properties such as impact resistance can be improved. have.

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 diisocyanate composition comprises a diisocyanate; and an aromatic compound having a halogen group in an amount of 5 ppm to 1000 ppm.

When the optical material is prepared by adjusting the content of the aromatic compound having a halogen group in the diisocyanate composition to an optimal range, the physical properties of the optical material, for example, the occurrence of streaks and cloudiness of the optical material (optical lens), and yellowness are reduced. The impact resistance can be improved at the same time as lowering.

According to one embodiment of the present invention, the aromatic compound having a halogen group may be artificially added to the diisocyanate composition.

In addition, the aromatic compound having a halogen group may be generated during the manufacturing process of the diisocyanate composition.

In addition, the aromatic compound having a halogen group may be generated during the manufacturing process of the diisocyanate composition, and some may be artificially added. That is, the aromatic compound having the halogen group may be generated during the manufacturing process of the diisocyanate composition, and when it is generated in a small amount, it may be artificially added to the composition so as to have a content of 5 ppm to 1000 ppm.

In the aromatic compound having a halogen group, the aromatic compound may include two or more halogen groups. In addition, the halogen may include chlorine.

Specifically, the aromatic compound having a halogen group may include the following Chemical Formula 1:

[Formula 1]

.

.

According to the embodiment, the content of the aromatic compound having a halogen group included in the composition is 5 ppm to 1000 ppm, 5 ppm to 750 ppm, 10 ppm to 700 ppm, 10 ppm to 500 ppm, 20 ppm to 500 ppm, 20 ppm to 350 ppm, 150 ppm to 500 ppm, 500 ppm to 750 ppm, 750 ppm to 900 ppm, or 20 ppm to 150 ppm. According to the embodiment of the present invention, by controlling the content of the aromatic compound having a halogen group included in the composition within the above range, it is possible to prevent the occurrence of streaks and cloudiness while improving the impact resistance and reduce yellowness.

If the content of the aromatic compound having a halogen group cannot be controlled, impact resistance may be reduced, and even if the impact resistance is maintained, streaks and cloudiness may occur and yellowness may increase. For example, if the content of the aromatic compound having a halogen group is less than 5 ppm, the impact resistance of the optical material using the composition may be reduced. On the other hand, when the content of the aromatic compound having a halogen group exceeds 1000 ppm, the impact resistance of the optical material using the composition may be improved, but streaks or cloudiness may occur, and there is a fear that yellowness may increase.

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 m-xylylene diisocyanate (m-XDI) in an amount of 99% by weight or more to less than 100% by weight, specifically 99.5% by weight or more to less than 100% by weight, more specifically 99.7% by weight % or more to less than 100% 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, 20 ppm to 500 ppm of the aromatic compound having a halogen group in the composition, and the m-xylylene diisocyanate in an amount of 99.5 wt% or more to less than 100 wt% based on the total weight of the composition may include

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 for the manufacture of an optical lens in addition to the m-xylylene diisocyanate and p-xylylene diisocyanate, specifically ortho-xylylene diisocyanate (o-XDI), norbornene diisocyanate (NBDI), hydrogenated 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 according to an embodiment of the present invention may further include at least one selected from the group consisting of methylbenzyl isocyanate and cyanobenzyl isocyanate. Specifically, the diisocyanate composition according to an embodiment of the present invention may further include at least one selected from the group consisting of 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate.

At least one selected from the group consisting of 4-methylbenzyl isocyanate and 4-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 0.01% by weight or less.

When 4-methylbenzyl isocyanate or 4-cyanobenzyl isocyanate is included in the composition in excess of the above content, the equivalent ratio of the composition is changed due to a decrease in the average number of functional groups in the composition, and furthermore, the chemical structure of the polymer is affected, so that in the final product Mechanical properties or heat resistance properties such as glass transition temperature may be deteriorated. 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 excellent mechanical properties, so it is useful for the manufacture of optical materials, specifically plastic optical lenses. can be used

[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; and obtaining a diisocyanate composition using the diamine hydrochloride composition, wherein the diisocyanate composition includes an aromatic compound having a halogen group in an amount of 5 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.

According to an embodiment of the present invention, the content of the aromatic compound having a halogen group may be controlled by adding the aromatic compound having a halogen group to the diisocyanate composition. For example, according to one embodiment of the present invention, the content of the aromatic compound having a halogen group may be adjusted by adding the aromatic compound having a halogen group in the step of obtaining the diamine hydrochloride composition and/or obtaining the diisocyanate composition. can

In addition, the aromatic compound having a halogen group may be generated during the manufacturing process of the diisocyanate composition. For example, in the process of preparing the diisocyanate composition, in the step of obtaining the diamine hydrochloride composition and/or in the step of obtaining the diisocyanate composition, it may occur during the reaction process.

In addition, the aromatic compound having a halogen group may be generated during the manufacturing process of the diisocyanate composition, and some may be additionally added. That is, when the aromatic compound having a halogen group is generated in a small amount during the manufacturing process of the diisocyanate composition, it may be additionally added to the composition so as to have a content of 5 ppm to 1000 ppm.

By controlling the content of the aromatic compound having a halogen group included in the composition within the above range, when applied to an optical material, it is possible to simultaneously improve streaks and cloudiness while improving impact resistance.

Hereinafter, each step will be described in detail.

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 diamine and the aqueous hydrochloric acid solution may be added to the reaction in an equivalent ratio of 1: 2 to 5. 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 20°C to 60°C, 20°C to 50°C, or 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 60 ° 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.

According to an embodiment of the present invention, after obtaining the diamine hydrochloride composition, the method may further include treating 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, (1a) adding the aqueous hydrochloric acid solution to the first reactor; (1b) adding and stirring the diamine to the first reactor; and (1c) adding and stirring the first organic solvent to the first reactor may be sequentially performed.

More specifically, cooling the inside of the reactor to a temperature of 0 ℃ to 10 ℃ after the addition of the diamine in step (1b) before stirring; 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

A diisocyanate composition is obtained using the diamine hydrochloride composition and triphosgene.

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 (ODCB), dichloromethane, 1-chloro-n-butane, 1-chloro-n- 1 selected from the group consisting of pentane, 1-chloro-n-hexane, chloroform, carbon tetrachloride, n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, cyclooctane and methylcyclohexane may be more than one species.

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.

The reaction temperature of the diamine hydrochloride composition and triphosgene may be 110 °C to 160 °C. When within the reaction temperature range, the reaction between diamine hydrochloride and triphosgene may be smooth, and the generation of impurities such as tar may be suppressed during final diisocyanate production. Specifically, the reaction temperature of the diamine hydrochloride composition and triphosgene may be 115 °C to 160 °C, 115 °C to 140 °C, 115 °C to less than 130 °C, 130 °C to 160 °C, or 120 °C to 150 °C.

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 130° C. to 160° 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.

The reaction of the diamine hydrochloride composition and triphosgene may include mixing the diamine hydrochloride composition and the second organic solvent to obtain a first solution; mixing triphosgene and the second organic solvent to obtain a second solution; and sequentially adding and stirring the second solution to the first solution. At this time, the input and stirring of the second solution may be performed at a temperature of 110 ℃ to 160 ℃. In addition, the input of the second solution may be divided into two or more times for a total of 25 to 40 hours. In addition, at this time, the input time for each time 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 may be 2 hours to 5 hours or 3 hours to 4 hours.

Alternatively, the reaction of the diamine hydrochloride composition with triphosgene is performed by (2a) adding 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 135° C. to 155° C. for a total of 25 hours to 40 hours. It may be divided into two or more times.

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.

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.

According to an embodiment of the present invention, the content of the aromatic compound having a halogen group included in the composition is determined after primary distillation in the process of obtaining the diamine hydrochloride composition, the process of obtaining the diisocyanate composition, and the process of obtaining the diisocyanate composition Alternatively, it may be controlled by adding an aromatic compound having a halogen group after secondary distillation. Alternatively, the content of the aromatic compound having a halogen group may be adjusted by adding the aromatic compound having a halogen group before mixing the diisocyanate composition with thiol or episulfide during the manufacture of the optical material. Alternatively, the content of the aromatic compound having a halogen group may be adjusted by dividing the content among the above time points. Alternatively, the aromatic compound having a halogen group may be generated in at least one of the above processes.

The yield of the diisocyanate thus obtained may be 80% or more, 85% or more, or 90% 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 metaxylylenediisocyanate from metaxylylenediamine hydrochloride 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 metaxylylenediamine hydrochloride 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 is diisocyanate; and a diisocyanate composition comprising an aromatic compound having a halogen group in a content of 5 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 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 content of the aromatic compound having a halogen group in the diisocyanate composition is 5 ppm to 1000 ppm.

The content of the aromatic compound having a halogen group is the diisocyanate in the reaction in the first step, in the second step, after the primary distillation in the second step, after the second distillation in the second step, or in the third step. It can be controlled by the addition of an aromatic compound having a halogen group before mixing the composition with a thiol or episulfide.

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.

Preferably, 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, trimethylolpropanetrismercaptopropionate, 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]

The optical material according to an embodiment of the present invention may be an optical material formed by curing the polymerizable composition. Specifically, the optical material is an optical material including the diisocyanate composition and polythiourethane in which thiol or episulfide is polymerized, and the content of the aromatic compound having a halogen group in the diisocyanate composition is 5 ppm to 1000 ppm .

The optical material is excellent in transparency, refractive index, yellowness, etc., as well as can improve impact resistance, and can prevent the occurrence of 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, or 87% or more, which may be a 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.

In addition, the optical material may have excellent impact energy within an appropriate range. Impact resistance energy is 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 be measured. 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 standards are 16 g and 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 fall test If it passes, the potential energy (Ep) can be calculated using a 32g iron bead, and when it passes, it is measured sequentially using 65 g, 100 g, 200 g, and 300 g iron beads and finally broken The potential energy of can be calculated.

The optical material according to the embodiment of the present invention calculated by the above method has an impact energy (E) of 0.4 J to 4.0 J, 0.4 J to 3.7 J, 0.6 J to 4.0 J, 0.6 J to 3.7 J, 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, by using the diisocyanate composition in which the aromatic compound having a halogen group is added in a specific amount in an optical material, optical properties such as yellowness, streaking and cloudiness are improved, and mechanical properties such as impact resistance can be improved at the same time. Therefore, it 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 temperature inside 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 reactor internal temperature was cooled to 10 ℃ and stirred for 1 hour, 1320.0 g of tetrahydrofuran was additionally added as an organic solvent, and the internal temperature was cooled to -5 ℃ 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 meta-xylylene diamine (m-XDA) hydrochloride composition was obtained, and to remove the remaining organic solvent and moisture, drying was performed at an external temperature of the reactor at 90 ° C. and a vacuum pump of 0.1 Torr to remove the final meta-xylylene diamine ( 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 in the reactor A were added, and the internal temperature of the reactor was heated at about 125° C. while stirring. 950 g of triphosgene (BTMC) and 800 g of ODCB were put in reactor B, and stirred and dissolved at about 60° C., and the temperature was maintained at 125° 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. After the distillation (second distillation), 1,3-bis(chloromethyl)benzene was added to obtain an m-XDI composition in which the concentration of 1,3-bis(chloromethyl)benzene was adjusted to 5 ppm.

<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 12

An m-XDI composition and an optical lens were obtained in the same manner as in Example 1, except that the input timing and concentration of 1,3-bis(chloromethyl)benzene were adjusted as shown in Table 1 below.

Comparative Examples 1 to 7

An m-XDI composition and an optical lens were obtained in the same manner as in Example 1, except that the time and concentration of 1,3-bis(chloromethyl)benzene were adjusted as shown in Table 1 below.

<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 (Y.I.) and Transmittance

An optical lens was manufactured in the form of a cylinder having a radius of 16 mm and a height of 45 mm, and the light was transmitted in the height direction to measure the yellowness and transmittance. Yellowness was calculated by the following equation based on the measurement results of x and y. Y.I = (234x + 106y) / 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) Impact resistance

In accordance with the test standards of the US FDA, the impact resistance is obtained by dropping a test piece made of a flat plate with a diameter of 80 mm and a thickness of 1.2 mm at 20 ° C. measured.

Weight of iron beads: Using steel beads of 16 g, 32 g, 65 g, 100 g, 200 g, and 300, observe whether the lens is damaged through a ball dropping test by height, and the position at the time of damage Calculate the energy.

Calculation Example-1) The potential energy (Ep) is based on FDA standards of 16 g and 127 cm.

Ep = mgh = 0.016*9.8*1.27=0.2(J)

Calculation example-2) In case of industrial safety standards 67 g, 127 cm

Ep = mgh = 0.067*9.8*1.27=0.83(J)

m-xylylene diisocyanate
(weight%) 1,3-bis(chloromethyl)benzene additive optical lens input
point of view input
density McLee cloudiness transmittance Y.I. impact resistance Example 1 99.9 after distillation 5 ppm none none 91% 19 0.4 J Example 2 99.9 before mixing 5 ppm none none 91% 19 0.4 J Example 3 99.9 after distillation 20 ppm none none 91% 20 0.8 J Example 4 99.9 before mixing 20 ppm none none 91% 19 0.8 J Example 5 99.9 after distillation 150 ppm none none 90% 19 1.2 J Example 6 99.9 before mixing 150 ppm none none 90% 20 1.2 J Example 7 99.9 after distillation 300 ppm none none 89% 21 2.5 J Example 8 99.9 before mixing 300 ppm none none 89% 21 2.5 J Example 9 99.9 after distillation 500 ppm none none 89% 22 2.5 J Example 10 99.9 before mixing 500 ppm none none 88% 22 2.5 J Example 11 99.9 after distillation 800 ppm none none 88% 22 3.7 J Example 12 99.9 after distillation 1000 ppm none none 88% 22 3.7 J Comparative Example 1 99.9 input X 0.0 none none 91% 20 0.2 J Comparative Example 2 99.9 after distillation 1 ppm none none 91% 20 0.2 J Comparative Example 3 99.9 before mixing 1 ppm none none 91% 19 0.2 J Comparative Example 4 99.9 after distillation 3-4 ppm none none 91% 19 0.2 J Comparative Example 5 99.9 before mixing 3-4 ppm none none 91% 20 0.2 J Comparative Example 6 99.9 after distillation 1100 ppm none U 84% 24 3.7 J Comparative Example 7 99.9 before mixing 1100 ppm none U 84% 26 3.7 J

As shown in the table above, when an optical lens is manufactured as an optical material using the diisocyanate composition of the example of the present invention, the impact resistance is excellent in an appropriate range compared to the optical lens of the comparative example, and there is no streaking and cloudiness, It was confirmed that the yellowness was reduced.

Specifically, all of the optical lenses of Examples 1 to 12 did not have streaks and white turbidity, and transmittance was mostly high at 88% or more, yellowness was also as low as 22 or less, and excellent impact resistance was 0.4 J to 3.7 J did.

On the other hand, similar results were obtained irrespective of the timing of addition of the 1,3-bis(chloromethyl)benzene before mixing the diisocyanate composition with thiol or episulfide or after distillation.

On the other hand, as in Comparative Examples 1 to 5, when the content of 1,3-bis(chloromethyl)benzene was 4 ppm or less, streaks and cloudiness did not occur, but the impact resistance was very low at 0.2 J.

On the other hand, as in 6 and 7 in comparison, when the content of 1,3-bis(chloromethyl)benzene was 1100 ppm and the content was too large, cloudiness occurred and the transmittance was very low, 84% or less. In addition, it was confirmed that the yellowness also increased to 24-26.

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)

diisocyanate; and
A diisocyanate composition comprising an aromatic compound having a halogen group in a content of 5 ppm to 1000 ppm.
The method of claim 1,
wherein the diisocyanate is greater than or equal to 99% by weight and less than 100% by weight based on the total weight of the composition.
The method of claim 1,
The content of the aromatic compound having a halogen group is 5 ppm to 750 ppm, diisocyanate composition.
The method of claim 1,
The aromatic compound contains two or more halogen groups,
The diisocyanate composition, wherein the halogen comprises chlorine.
5. The method of claim 4,
A diisocyanate composition, wherein the aromatic compound having a halogen group includes a compound of Formula 1 below:
[Formula 1]

.
The method of claim 1,
A diisocyanate composition, wherein the diisocyanate comprises m-xylylene diisocyanate, p-xylylene diisocyanate, or a mixture thereof.
7. The method of claim 6,
20 ppm to 500 ppm of the aromatic compound having the halogen group,
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.
7. The method of claim 6,
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.
obtaining a diamine hydrochloride composition; and
Comprising the step of obtaining a diisocyanate composition using the diamine hydrochloride composition,
The method for producing a diisocyanate composition, wherein the diisocyanate composition comprises an aromatic compound having a halogen group in an amount of 5 ppm to 1000 ppm.
10. The method of claim 9,
After obtaining the diamine hydrochloride composition, further comprising the step of treating the diamine hydrochloride composition,
A method for producing a diisocyanate composition, wherein the step of obtaining the diisocyanate composition comprises reacting the treated diamine hydrochloride composition with triphosgene.
11. The method of claim 10,
The step of obtaining the diisocyanate composition further comprises distilling the reaction product obtained after the reaction of the treated diamine hydrochloride composition with the triphosgene,
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.
11. The method of claim 10,
The diamine hydrochloride composition and the triphosgene are added to the reaction in an equivalent ratio of 1:1 to 5,
The reaction of the diamine hydrochloride composition and triphosgene is carried out at a temperature of 110 ℃ to 160 ℃, a method for producing a diisocyanate composition.
10. The method of claim 9,
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 a temperature of 20 to 60 °C in an equivalent ratio of 1: 2 to 5, a method for producing a diisocyanate composition.
14. The method of claim 13,
The diamine is xylylenediamine,
The method for producing a diisocyanate composition, wherein the diisocyanate composition comprises xylylene diisocyanate.
diisocyanate; and
A polymerizable composition for an optical material, comprising a diisocyanate composition comprising an aromatic compound having a halogen group in a content of 5 ppm to 1000 ppm.
16. The method of claim 15,
The polymerizable composition for an optical material further comprising a thiol or episulfide.
The polymerizable composition according to claim 15 is formed by curing,
An optical material having an impact energy (E) of 0.4 J to 4.0 J and a yellowness degree of 22 or less.

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