KR20180125871A - Isocyanate composition for optical lenses and preparation method thereof - Google Patents

Abstract

The present invention can easily manufacture an optical lens with high quality by controlling the composition of isocyanate used for manufacturing polythiourethane by manufacturing an isocyanate composition using an amine composition including: from 99% by weight to less than 100% by weight of m-xylylenediamine; more than 0 to 0.5% by weight of p-xylylenediamine; and one or more members selected from a group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in an amount of more than 0% by weight to 0.5% by weight or less.

Description

TECHNICAL FIELD [0001] The present invention relates to an isocyanate composition for use in an optical lens, and an ISOCYANATE COMPOSITION FOR OPTICAL LENSES AND PREPARATION METHOD THEREOF,

More particularly, the present invention relates to a method for producing a xylylene isocyanate-based composition used as a raw material in the production of a polythiourethane-based lens having excellent optical properties, and a method for producing A polymerizable composition obtained, a polythiourethane, and an optical material.

Plastic materials of various resins are widely used as optical materials such as eyeglass lenses and camera lenses because they are lightweight and easily breakable and excellent in dyeability compared with optical materials made of inorganic materials such as glass. In recent years, higher performance of optical materials is required, and specifically high transparency, high refractive index, low specific gravity, high heat resistance, and high impact resistance are required.

Polythiourethanes are widely used as optical materials due to their excellent optical properties and mechanical properties. Polythiourethanes can be prepared by reacting thiols with isocyanates, and lenses made from polythiourethanes are widely used because of their high refractive index, light weight, and relatively high impact resistance.

The isocyanate used as a raw material of the polythiourethane is synthesized with polythiourethanes having different structures depending on the number and position of the functional groups, and thus has a great influence on the physical properties of the product to be produced therefrom. Accordingly, a certain kind of isocyanate which can provide the desired end product properties is used.

In particular, xylylene diisocyanate (XDI) has both characteristics of alicyclic isocyanate (denitrification resistance, reactivity that can be easily controlled) and characteristics of aliphatic isocyanate (high mechanical properties, refractive index, etc.) Excellent properties can be realized in optical lens applications.

Korean Patent Publication No. 2012-0076329 (Jul.

Xylidene isocyanate is classified into o (ortho), m (meta), and p (para) -XDI according to the relative position of diisocyanate groups. Of these, m-XDI is suitable for the properties of optical lenses, It is most widely used as a raw material for an optical lens.

However, m-XDI sold in the market, even if purified, contains heterogeneous components such as a small amount of isomers and monoisocyanates, and due to these different components, it causes side reactions at the time of product manufacture, Which is disadvantageous for long-term storage, thereby causing a serious problem in an optical lens field in which a high level of transparency and optical characteristics are particularly required.

Therefore, it is necessary to remove the heterogeneous components in the m-XDI raw material prior to the production of the product, but these dissimilar components originate from the production of xylylenediamine, which is a raw material of xylylenediisocyanate, and have a chemical structure and chemical properties It is quite difficult to specify by the conventional method. In addition, efforts to remove all kinds of heterogeneous components are not only inefficient, but also complicate the process and result in high costs.

Accordingly, the present inventors have studied numerous heterogeneous components that can be incorporated into the m-XDI raw materials, and tried to find out the components particularly influential on the physical properties required for the optical lenses. As a result, they were included in the m-XDI raw material It has been found that the properties of the optical lens can be effectively met by merely adjusting the content of some specific heterogeneous components.

Therefore, in the embodiments described later, it is possible to effectively and appropriately satisfy the physical properties of the optical lens by specifying and controlling the kinds and contents of the components that have a great influence on the physical properties required for the optical lenses, among the different kinds of components contained in the m- Method.

Particularly, through the examples, it is intended to provide a method for controlling isocyanate components with a desired composition easily in the synthesis step of isocyanate by controlling amines, which are raw materials used in the synthesis, rather than isocyanates which are difficult to refine.

According to an embodiment, there is provided a process for preparing a first amine composition comprising: (1) preparing a first amine composition comprising m-xylylenediamine; (2) reducing the content of at least one of p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition to obtain a second amine composition; And (3) synthesizing an isocyanate from the second amine composition.

According to an embodiment, at least 99% by weight to less than 100% by weight of (a ') m-xylylenediisocyanate, based on the total weight of the composition; (b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And (c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% do.

According to an embodiment, there is provided a polymerizable composition comprising an isocyanate composition and a thiol, wherein the isocyanate composition comprises from 99% to 100% by weight of (a ') m-xylylenediisocyanate, based on the total weight of the isocyanate composition, under; (b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And (c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% / RTI >

According to an embodiment, there is provided an optical material comprising an isocyanate composition and a thiol-polymerized polythiourethane, wherein the isocyanate composition comprises, based on the total weight of the composition, at least 99% by weight of (a ') m-xylylenediisocyanate Less than 100% by weight; (b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And (c ') at least one selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% do.

According to an embodiment, there is provided a process for preparing a first amine composition comprising: (1) preparing a first amine composition comprising m-xylylenediamine; (2) reducing the content of at least one of p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition to obtain a second amine composition; (3) synthesizing an isocyanate from the second amine composition to prepare an isocyanate composition; And (4) mixing the isocyanate composition with thiol and heat-curing the mixture in a mold.

According to the embodiment, it is possible to manufacture a high-quality optical lens by controlling the composition of isocyanate used in the production of the polythiourethane-based optical lens.

That is, by using an isocyanate composition containing 99% by weight or more of m-XDI for high-quality optical lenses and having a controlled amount of a specific kind of isomer and monoisocyanate which hinders the physical properties of the optical lens, Can be satisfied.

That is, the polythiourethane produced by using such an isocyanate composition is not only required to have properties such as refractive index, Abbe number, transparency and the like, which are basically required for an optical lens, but also properties such as yellow color, And thus it is useful in the fields of spectacle lenses, camera lenses and the like.

According to an embodiment, there is provided a process for preparing a first amine composition comprising: (1) preparing a first amine composition comprising m-xylylenediamine; (2) reducing the content of at least one of p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition to obtain a second amine composition; And (3) synthesizing an isocyanate from the second amine composition.

Hereinafter, a method for producing an isocyanate composition for an optical lens will be described in detail for each step.

The step (1) is a step of preparing a first amine composition containing m-xylylenediamine.

The first amine composition can be prepared directly or by purchasing a commercially available one.

The first amine composition comprises m-xylylenediamine as a main component. However, the first amine composition may contain an isomer (p-xylylenediamine) and a monoisocyanate (benzylamine, 4-methylbenzylamine, 4-cyanobenzylamine, etc.) in addition to the main component m- These may be produced as byproducts during the synthesis of the major component m-xylylenediamine.

Hereinafter, the production process of p-xylylene diamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine will be described while illustrating the production process of m-xylylenediamine.

In order to prepare m-xylylenediamine, first, the catalyst is reformed from the naphtha raw material through a conventional BTX process to obtain an aromatic mixture from which m-xylene is extracted.

Thereafter, m-xylylenediamine is prepared from the isophthalonitrile (Step B), as shown in Scheme 1 below, after the isophthalonitrile is prepared from the m-xylene (Step A).

 [Reaction Scheme 1]

For example, the preparation of m-xylylenediamine from m-xylene can be carried out by a process comprising the following steps as in US-A-8,212,080: (i) reacting ammonia and oxygen - ammoxidation of m-xylene by a gas-phase catalytic reaction of - containing gas to produce a p-ammoxidation gas containing dicyanobenzene; (ii) bringing the ammonia oxidation gas into direct contact with an organic solvent to absorb dicyanobenzene in an organic solvent to obtain a dicyanobenzene-containing solution; (iii) distilling the dicyanobenzene-containing solution to remove part or all of the compounds having lower boiling points than dicyanobenzene together with the organic solvent to obtain molten dicyanobenzene; (iv) dissolving the molten dicyanobenzene in a liquid ammonia solvent or a mixed solvent of one or more aromatic hydrocarbons and liquid ammonia to obtain a solution; (v) removing some or all of the insoluble components in the solution to separate the liquid; And (vi) hydrogenating the dicyanobenzene in the liquid in the liquid phase in the presence of a catalyst.

The first amine composition obtained through such a synthesis route further includes isomers and monoisocyanates other than m-xylylenediamine.

As an example, the first amine composition may further comprise p-xylylenediamine. Specifically, p-xylene may be partially contained in the m-xylene extracted from the BTX process, and the p-xylene may be prepared from p-xylylenediamine through the steps A and B (See Scheme 2 below).

[Reaction Scheme 2]

As another example, the first amine composition may further comprise benzylamine.

Specifically, the m-xylene extracted from the BTX process contains a part of toluene, and the toluene can be prepared as a benzylamine through the steps A and B (see the following reaction formula 3).

[Reaction Scheme 3]

As another example, the first amine composition may further comprise 4-methylbenzylamine. Specifically, the m-xylene extracted in the BTX process partially contains p-xylene, and only one methyl group in the methyl group of the p-xylene participates in the reaction of Step A to form 1-cyano-4- Methylbenzylamine (p-toluenitrile) can be prepared, and then, through the above step B, 4-methylbenzylamine (see Reaction Scheme 4 below).

[Reaction Scheme 4]

As another example, the first amine composition may further comprise 4-cyanobenzylamine. Specifically, p-xylene was partially contained in m-xylene extracted in the BTX process, and the p-xylylene was made into p-dicyanobenzene (terephthalonitrile) through the step A, Only one of the two cyano groups of the p-dicyanobenzene may then participate in the reaction of Step B above to give 4-cyanobenzylamine (see Scheme 5 below).

[Reaction Scheme 5]

Accordingly, the first amine composition is selected from the group consisting of (a) m-xylylenediamine, (b) p-xylylenediamine, and (c) benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine. And the like.

The respective contents of the components (a) to (c) contained in the first amine composition of the step (1) are not particularly limited.

In one embodiment, the first amine composition comprises: (a) from greater than 90% to less than 100% by weight of m-xylylenediamine; (b) from greater than 0% to 5% by weight of p-xylylenediamine; And (c) at least one member selected from the group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in an amount of more than 0 wt% to 5 wt%.

As another example, the first amine composition comprises: (a) from greater than 90% to less than 99% by weight of m-xylylenediamine; (b) from greater than 0.5% to 5% by weight of p-xylylenediamine; And (c) at least one selected from the group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine, in an amount of more than 0.5% by weight to 5% by weight or less.

There may be no particular problem when the content of the components (b) and (c) in the amine composition for use in a conventional application is as described above. However, when used in optical lens applications in the amine composition, the contents of components (b) and (c) may affect optical properties. Therefore, it is necessary to appropriately adjust the contents of the components (b) and (c) contained in the amine composition by the following procedure.

In the step (2), the content of at least one of p-xylylene diamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition prepared above is reduced, Amine composition.

Preferably, the content of p-xylylenediamine in the first amine composition and the content of at least one of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine are reduced, Amine composition can be obtained.

More preferably, the content of both p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition is reduced to obtain a second amine composition whose composition is controlled have.

As an example, the second amine composition can be obtained by controlling the content of each amine component in the first amine composition by different kinds of boiling point and freezing point. The boiling point and freezing point of each amine component are summarized in Table 1 below.

Amine type constitutional formula Boiling point (℃) Freezing Point (℃) m-xylenediamine

265 14 p-xylylenediamine

230 63 Benzylamine

185 10 4-methylbenzylamine

195 13 4-cyanobenzylamine

275 20

For example, the second amine composition can be prepared by controlling the content of amine species in the composition through a method such as distillation, recrystallization, and the like.

According to one example, the content of p-xylylenediamine and 4-cyanobenzylamine can be controlled by removing the compound precipitated through recrystallization using the freezing point difference with m-xylylenediamine, and the content of benzylamine and The content of 4-methylbenzylamine can be controlled by removing the boiling point difference with m-xylylenediamine through distillation.

According to a specific example, the step of obtaining the second amine composition comprises: (2a) removing the distilled compound while raising the temperature of the first amine composition to 100 to 185 ° C under reduced pressure; And (2b) a step of removing the precipitated compound while cooling the first amine composition to 15 to 18 占 폚.

According to another specific example, the step of obtaining the second amine composition comprises: removing the distilled compound while raising the temperature of the first amine composition to 100 to 185 ° C under reduced pressure, cooling the precipitated compound to 15 to 18 ° C, Can be performed.

Wherein the compound distilled at the elevated temperature comprises benzylamine and 4-methylbenzylamine; The compound precipitated during the cooling may include p-xylylenediamine and 4-cyanobenzylamine.

Further, since distillation is carried out under reduced pressure, it is possible to remove even the temperature of the amine compound (benzylamine, 4-methylbenzylamine, etc.) to a temperature lower than the original boiling point (100 to 185 ° C) The temperature may be raised to 100 to 180 ° C, 120 to 180 ° C, 140 to 180 ° C, 160 to 180 ° C, 120 to 160 ° C, or 140 to 160 ° C.

Through the above process, a second amine composition controlled to a specific composition can be obtained.

For example, the second amine composition may contain from 99% by weight to less than 100% by weight of m-xylylenediamine (m-XDA), specifically from 99.5% by weight to less than 100% By weight or more and 99.7% by weight or more and less than 100% by weight.

In addition, the second amine composition may contain more than 0 wt% to 0.5 wt% of p-xylylenediamine (p-XDA), more specifically more than 0 wt% to 0.3 wt% By weight to 0.15% by weight or less.

Also, the second amine composition may include at least one member selected from the group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in an amount of more than 0 wt% to 0.5 wt% More than 0 wt% to 0.3 wt% or less, more specifically, 0 wt% or more to 0.15 wt% or less.

At this time, the second amine composition may contain more than 0 wt% to 0.15 wt% of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine, more specifically, more than 0 wt% and 0.1 wt% , More specifically from more than 0 wt% to 0.05 wt% or less.

According to a preferred embodiment, the second amine composition comprises, based on the total weight of the composition, (a) from 99% to less than 100% by weight of m-xylylenediamine; (b) more than 0 to 0.5% by weight of p-xylylenediamine; And (c) at least one member selected from the group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in an amount of more than 0 wt% to 0.5 wt% or less.

According to another preferred example, the second amine composition comprises, based on the total weight of the composition, (a) from 99.7% by weight to less than 100% by weight of m-xylylenediamine; (b) more than 0 to 0.15% by weight of p-xylylenediamine; And (c) at least one member selected from the group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in an amount of more than 0 wt% to 0.15 wt% or less.

According to another preferred example, the second amine composition comprises, based on the total weight of the composition, (a) from 99.7 wt% to less than 100 wt% of m-xylylenediamine; (b) more than 0 to 0.15% by weight of p-xylylenediamine; And (c) benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine, respectively, in an amount of more than 0 wt% to 0.05 wt% or less.

In the step (3), an isocyanate is synthesized from the second amine composition to prepare an isocyanate composition.

Isocyanates can be synthesized from amines by phosgene or non-phosgene methods.

According to an example of the phosgene method, an amine is reacted with hydrochloric acid at a temperature of 30 ° C or lower in an ester solvent to obtain an amine hydrochloride, and the amine is reacted with phosgene at 120-170 ° C to synthesize an isocyanate .

 [Reaction Scheme 6]

According to an example of a non-phosgene method, to, as shown in Scheme 7, a haloalkyl amine C _{1 - 10} alkyl chloroformate or haloalkyl-di C _{1 - 10} alkyl carbonate and reacting bis producing a carbamate, the catalyst and high temperature conditions ( 130 to 250 ° C) in a solvent to synthesize an isocyanate.

[Reaction Scheme 7]

In the above scheme R 7 is a halo-C _{1 - 10} is alkyl.

Wherein said halo may be fluoro, chloro, bromo or iodo.

Preferably, the synthesis of (3), the second amine composition phosgene or halo C _{1 -} can be carried out, including ₁₀ alkyl chloroformate and reacting.

After the above-mentioned synthesis process, m-xylylenediamine in the composition is synthesized as m-xylylenediisocyanate as shown in Reaction Schemes 6 and 7.

Also, as shown in the following Reaction Schemes 8 to 11, p-xylylenediamine in the composition is synthesized as p-xylylenediisocyanate, benzylamine is synthesized as benzyl isocyanate, 4-methylbenzylamine is synthesized as 4-methylbenzyl isocyanate And 4-cyanobenzylamine is synthesized as 4-cyanobenzyl isocyanate.

 [Reaction Scheme 8]

[Reaction Scheme 9]

[Reaction Scheme 10]

[Reaction Scheme 11]

The isocyanate synthesized in the step (3) is at least one isocyanate of m-xylylene diisocyanate, p-xylylene diisocyanate, benzyl diisocyanate, 4-methylbenzyl diisocyanate and 4-cyanobenzyl diisocyanate.

According to the embodiment, since the amine composition which increases the content of m-xylylenediamine and lowers the content of p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine is used, the isocyanate composition Can have a high content of p-xylylenediisocyanate and a low content of p-xylylene diisocyanate, benzylisocyanate, 4-methylbenzylisocyanate and 4-cyanobenzylisocyanate.

According to the embodiment, as described above, there is provided an isocyanate composition for an optical lens produced by using a composition having controlled amine type and content.

That is, according to an embodiment, the amount of (a ') m-xylylenediisocyanate is from 99% by weight to less than 100% by weight, based on the total weight of the composition; (b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And (c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% or less.

The isocyanate composition for an optical lens according to the embodiment contains 99% by weight to less than 100% by weight of m-xylylenediisocyanate (m-XDI), specifically 99.5% by weight to less than 100% by weight, 99.7 wt% or more and less than 100 wt%.

The isocyanate composition for an optical lens according to the embodiment contains 0 to 0.5 wt% of p-xylylene diisocyanate (p-XDI), specifically 0 to 0.3 wt% And more than 0 wt% to 0.15 wt% or less.

The isocyanate composition for an optical lens according to the embodiment contains at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% More than 0 wt% to 0.3 wt% or less, more specifically, 0 wt% or more to 0.15 wt% or less.

At this time, the isocyanate composition for an optical lens according to the embodiment contains benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.15 wt% By weight or less, more specifically, from 0% by weight to 0.05% by weight or less.

When m-xylylenediisocyanate is contained in the composition in an amount less than the above-mentioned preferable content, the polymerization reactivity and the unevenness of the chemical structure of the cured product cause mechanical properties (impact resistance, Tensile strength, etc.) may be inhibited, and yellowing may occur depending on other incorporated components.

When p-xylylene diisocyanate is contained in the composition in an amount exceeding the above preferable amount, optical characteristics such as polymerization inconsistency due to the difference in reactivity or crystallization due to change in the chemical structure of the polymer, .

When the benzyl isocyanate is contained in the composition in an amount exceeding the above preferable amount, the equivalent ratio of the composition is changed due to the decrease in the average number of functional groups in the composition, and furthermore, the chemical structure of the polymer is also influenced. Thus, the end product has heat resistance such as mechanical properties and glass transition temperature The characteristics may be degraded.

When the 4-methylbenzylisocyanate is included in the composition in an amount exceeding the above preferable amount, the equivalent ratio of the composition is changed due to the decrease in the average number of functional groups in the composition, and further, the chemical structure of the polymer is also affected. May be deteriorated.

When the 4-cyanobenzyl isocyanate is included in the composition in an amount exceeding the above preferable amount, the equivalent ratio of the composition is changed due to the decrease in the average number of functional groups in the composition, and further, the chemical structure of the polymer is also affected. The heat resistance characteristics such as the temperature may be lowered. Further, due to the influence of the cyano group, yellowing may occur depending on the external environment of the curing or after the production of the lens for manufacturing the lens, which results in a fatal result in long-term reliability.

Therefore, a product manufactured using the composition-controlled isocyanate composition as described above can satisfy high optical characteristics, and thus can be used for the production of an optical material, specifically, a plastic optical lens.

According to an embodiment, there is provided a polymerizable composition for an optical lens comprising the above-described isocyanate composition and a thiol.

That is, according to an embodiment, there is provided a polymerizable composition comprising an isocyanate composition and a thiol, wherein the isocyanate composition comprises (a ') at least 99% by weight of m-xylylenediisocyanate, % By weight; (b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And (c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% / RTI >

The polymerizable composition may contain the isocyanate composition and the thiol in a mixed state or in a separated state. That is, in the polymerizable composition, the isocyanate composition and the thiol may be in a state of being in contact with each other or separated from each other so as not to contact each other.

In the polymerizable composition, the molar ratio of the SH group / NCO group in the composition may be 0.5 to 3.0, more specifically 0.8 to 1.3.

The thiol may be a thiol oligomer or a polythiol, and may be used alone or in combination of two or more.

Specific examples of the thiol include 3,3'-thiobis [2- [(2-mercaptoethyl) thio] -1-propanethiol, bis (2- (2-mercaptoethylthio) (2-mercaptoethylthio) propane-1-thiol, 2,2-bis (2-mercaptoethylthio) (Mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) Bis (2,3-dimercapto propanyl) sulfide, bis (2,3-dimercaptopropane) sulfide, bis (2,3- Bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane, 1,2-bis [2- (mercaptoethyl) 2-mercaptoethylthio) propylthio-propane-1-thiol, 2 (2-mercaptoethylthio) -3-2-mercapto-3- [ , 2-bis- (3-mercap 2- (2-mercaptoethylthio) -propylthio) -butyl ester, 2- (2-mercaptoethylthio) -3- Ethylthio) propyl-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12- tetrathiatetradecane- 1,14-dithiol, S) -3 - ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4R, 14R) -4,14-bis (mercaptomethyl) (R-3-mercapto-2 - ((2-mercaptoethyl) thio) propyl) thio) propyl) (7R, 11S) -7,11-bis (2-mercaptoethyl) thio) propane- (Mercaptomethyl) -3,6,9,12,15-pentatiaheptadecane-1,17-dithiol, (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9 , 10,13,16-hexatiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,8-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropion (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) hexamethylene diisocyanate, 1,1,3,3-tetrakis (mercaptomethylthio) Propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, pentaetritol tetrakis Acetate), pentaerythritol tetrakis (3-mercaptopropionate), and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane.

The polymerizable composition may further contain additives such as an internal release agent, an ultraviolet absorber, a polymerization initiator, a heat stabilizer, a color correcting agent, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, .

Examples of the internal release agent include a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group or a phosphate ester group; A silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, diethylcyclohexadodecylammonium salt; The acid phosphate ester may be used singly or in combination of two or more thereof.

Examples of the ultraviolet absorber include benzophenone, benzotriazole, salicylate, cyanoacrylate, oxanilide, and the like.

As the polymerization initiator, an amine-based, phosphorus-based, organosilicate-based, organic copper-based, organic gallium, organic zirconium, organic iron-based, organic zinc, and organic aluminum may be used.

Examples of the thermal stabilizer include metal fatty acid salts, phosphorus, lead, and an organosilicate, which may be used alone or in combination of two or more.

Further, according to the embodiment, a polythiourethane obtained from the above-described polymerizable composition is provided. That is, the polythiourethane can be produced by polymerizing (and curing) an isocyanate composition in the polymerizable composition with a thiol.

Specific examples of the isocyanate compound are as described above.

The polymerization reaction may be carried out such that the molar ratio of the SH group / NCO group is 0.5 to 3.0, more specifically 0.8 to 1.3.

Further, in order to control the reaction rate, a reaction catalyst which is conventionally used in the production of polyurethane may be added. As the curing catalyst (polymerization initiator), a tin catalyst may be used. For example, dibutyl tin dichloride, tibutyl tin dilaurate, dimethyl tin dichloride and the like can be used.

Since the polythiourethane is prepared using the isocyanate composition controlled to the specific composition as described above, it has excellent optical properties.

Further, according to the embodiment, there is provided an optical material for an optical lens comprising the above-described polythiourethane.

That is, according to an embodiment, there is provided an optical material for an optical lens comprising an isocyanate composition and a thiol-polymerized polythiourethane, wherein the isocyanate composition comprises (a ') m-xylylenediisocyanate 99% to less than 100% by weight; (b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And (c ') at least one selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% or less.

The optical material for the optical lens may be produced by molding (and curing) an isocyanate composition in the polymerizable composition with a thiol.

Thus, the optical material obtained by using the isocyanate composition according to the embodiment has excellent optical properties. Therefore, the optical material can be usefully used as a spectacle lens, a camera lens, or the like. The optical material may preferably be a polythiourethane-based lens, i.e., a plastic optical lens.

According to an embodiment, there is provided a process for preparing a first amine composition comprising: (1) preparing a first amine composition comprising m-xylylenediamine; (2) reducing the content of at least one of p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition to obtain a second amine composition; (3) synthesizing an isocyanate from the second amine composition to prepare an isocyanate composition; And (4) mixing the isocyanate composition with thiol and heat-curing the mixture in a mold.

Steps (1) to (3) in the production method of the optical lens may be carried out according to the conditions and procedures as described in the above steps (1) to (3) of the method for producing an isocyanate composition. Thereafter, as in step (4) above, the isocyanate composition is mixed with thiol and heat cured in a mold.

To this end, the isocyanate composition is first mixed with thiol to prepare a polymerizable composition, the polymerizable composition is degassed under reduced pressure, and then injected into a mold for optical material molding. Such deaeration and mold injection can be performed, for example, at a temperature range of 20 to 40 占 폚.

After injection into the mold, the polymerization is usually carried out by gradually heating from a low temperature to a high temperature. The temperature of the polymerization reaction may be, for example, 30 to 150 ° C, more specifically 40 to 130 ° C. In order to control the reaction rate, a reaction catalyst which is usually used in the production of polyurethane may be added, and specific examples thereof are as exemplified above.

The resulting polythiourethane molding is separated from the mold to obtain the final optical lens. The optical lens thus produced is colorless and transparent and has excellent optical properties such as refractive index and Abbe number.

The refractive index of the optical lens may be 1.60 to 1.78, more preferably 1.65 to 1.75, and more preferably 1.69 to 1.75.

The Abbe number of the optical lens may be 20 or more, and more specifically may be 30 or more. For example, the optical lens may have an Abbe number in the range of 20 to 50, in the range of 25 to 50, in the range of 30 to 45, or in the range of 30 to 40.

The optical lens may have a light transmittance, for example, a light transmittance at a wavelength of 550 nm of 85.0% to 99.9%, more preferably 87.0% to 99.0%, or 87.0% to 95.0%.

The optical lens may have a yellowness index (YI) of 25 or less, or 20 or less, and specifically may be in the range of 1 to 25, in the range of 1 to 20, in the range of 3 to 20, or in the range of 5 to 15.

The optical lens may have a glass transition temperature (Tg) of 90 占 폚 or higher, or 95 占 폚 or higher, specifically 90-130 占 폚, 95-120 占 폚, or 95-115 占 폚.

According to a preferred example, the optical lens may have a yellowness index (YI) of 1 to 20 and a light transmittance of 85 to 99% at a wavelength of 550 nm. In this case, the optical lens may have an Abbe number of 30 to 45 and a glass transition temperature of 95 to 120 ° C.

The following examples illustrate more specific embodiments, but are not limited thereto.

Comparative Example  1 to 4: Preparation of isocyanate composition

The amine-A, amine-B, amine-C and amine-D compositions having the compositions listed in Table 2 below as amine starting materials were used for the isocyanate synthesis without further treatment.

First, 15 parts by weight of each of the amine starting materials was dissolved in 78 parts by weight of o-dichlorobenzene to prepare an amine solution. Then, 44 parts by weight of phosgene dissolved in 52 parts by weight of o-dichlorobenzene was cooled to 10 DEG C with a brine condenser and placed in a reaction vessel. At this time, the addition amount of the amine solution was adjusted to 5 moles of phosgene with respect to 1 mole of amine. Thereafter, the reaction vessel was sealed and the reaction solution was stirred for 2 hours. After further reaction for 3 hours at a temperature of 140 DEG C and a pressure of 3 kg / cm < ² >, the hydrochloric acid gas produced in the reaction was released. After the reaction was completed, an excess of phosgene was removed by a distillation process. The product was purified through fractional distillation under reduced pressure to give each m-xylylenediisocyanate composition.

Example  1: Preparation of isocyanate composition

Step (1): Preparation of amine composition

An amine composition was prepared comprising 81.1% by weight of m-XDI, 4.5% by weight of p-XDI, 3.7% by weight of benzylamine, 5.6% by weight of 4-methylentenamine and 5.1% by weight of 4-cyanobenzylamine.

Step (2): Content Control of Amine Composition by Ingredient

The amine composition prepared above was placed in a five-stage distillation apparatus, And distillation was carried out while raising the temperature to 180 ° C. During distillation, benzylamine and 4-methylbenzylamine were sequentially distilled off. After cooling to 20 캜, p-xylylenediamine and 4-cyanobenzylamine were sequentially precipitated and removed.

The obtained composition was named "amine-E ", analyzed by gas chromatography (GC), and the composition was summarized in Table 2 below.

Step (3): Synthesis of isocyanate

Using the amine-E composition, isocyanates were synthesized in the same manner as in Comparative Examples 1 to 4 to obtain an isocyanate composition.

Amine component (% by weight) Amine-A Amine-B Amine-C Amine-D Amine-E m-XDA 93.25 95.21 93.22 93.22 99.89 p-XDA 4.63 0.12 0.13 0.31 0.08 Benzylamine 0.52 3.61 0.33 0.21 <0.01 4-methylbenzylamine 0.39 0.21 5.55 0.71 <0.01 4-cyanobenzylamine 0.35 0.36 0.64 5.1 <0.01 Other 0.86 0.49 0.13 0.45 <0.03

The isocyanate compositions prepared in the above Comparative Examples and Examples were analyzed by gas chromatography (GC), and the compositions were summarized in Table 3 below.

The isocyanate component (% by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 m-XDI 93.2 95.21 93.4 93.3 99.88 p-XDI 4.7 0.15 0.15 0.28 0.09 Benzyl isocyanate 0.5 3.55 0.31 0.17 <0.01 4-methylbenzylisocyanate 0.39 0.26 5.7 0.73 <0.01 4-cyanobenzyl isocyanate 0.33 0.32 0.4 4.9 <0.01 Other 0.88 0.51 0.04 0.62 <0.03

Test Example : Evaluation of Optical Lens

520.7 g of the isocyanate composition prepared in Example 1 or Comparative Examples 1 to 4, 479.3 g of 3,3'-thiobis [2- [(2-mercaptoethyl) thio] -1-propanethiol as a thiol, 0.15 g of dodecyl tin dichloride, and 0.80 g of Zelec ^TM UN from Stepan as an internal mold release agent were mixed uniformly to prepare respective polymerizable compositions.

The polymerizable composition was stirred under reduced pressure for 30 minutes in a nitrogen atmosphere at room temperature to remove air bubbles and filtered through a Teflon filter of 3 탆.

The filtered polymerizable composition was injected into a glass mold assembled with an adhesive tape by using nitrogen pressure. The glass mold into which the polymerizable composition was injected was placed in a forced circulation oven, and the temperature was raised from 25 占 폚 to 120 占 폚 at a rate of 5 占 폚 / min and polymerization was carried out at 120 占 폚 for 18 hours. Thereafter, the polymerized resin was further cured at 130 DEG C for 4 hours, and a lens was released from the glass mold to obtain each optical lens having a center thickness of about 1.2 mm.

The optical properties of the optical lenses prepared in Example 1 and Comparative Examples 1 to 4, respectively, were evaluated in the following manner and summarized in Table 4.

(1) Refractive index and Abbe number

The refractive index and the Abbe number at 20 ° C were measured using an Abbe refractometer DR-M4 model manufactured by Atago Co., Ltd. for the optical lens.

(2) Yellowness (YI) and light transmittance

The chromaticity coordinates x and y of the optical lens were measured using a colorimetric colorimeter (Colormate, Scinco), and the measured values were applied to the following equation 1 to calculate the yellowness degree. The transmittance at a wavelength of 550 nm in the spectrum obtained using the same instrument is shown as a transmittance.

[Equation 1]

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

(3) Glass transition temperature (Tg)

The glass transition temperature (Tg) of the optical lens was measured by a peening method using a thermal mechanical analyzer (TMA Q400, TA instruments) under a load of 50 g, a pin tip of 0.5 mm and a heating rate of 10 ° C / min.

(4) McGill

100 lenses of the optical lens were observed under a mercury lamp with naked eyes, and the lens having a nonuniformity was classified as having a malignancy to calculate a percentage. As a result, the incidence of malignancy was less than 5%, and the incidence was 5% or more.

Evaluation items Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Refractive Index (nd) 1.6672 1.6674 1.6679 1.6673 1.6662 Abbe number (ve) 29.3 30.2 29.3 28.3 31.2 Light transmittance (%) 85 80 81 75 90 Tg (占 폚) 95 85 73 80 103 Yellowness 33 35 37 72 12 McGill Bad
(15%) Bad
(18%) Bad
(9%) Bad
(11%) Good
(3%)

As shown in Table 4, the optical lens using the isocyanate composition of Example 1 adjusted to the desired composition was evaluated to be excellent in both refractive index, Abbe number, transmittance, Tg, yellowness and malignancy test.

On the other hand, optical lenses using the isocyanate compositions of Comparative Examples 1-4 outside the preferred composition were evaluated poorly in at least one of the properties tested.

In particular, the optical lens prepared from the composition of Comparative Example 1 having an excessive amount of p-XDI was poor in terms of light transmittance, Abbe number and maly phenomenon, and the optical lens prepared from the composition of Comparative Example 2 having an excess of benzylisocyanate The optical lens prepared from the composition of Comparative Example 3, which was poor in terms of light transmittance, glass transition temperature, yellowness and maly phenomenon, and had an excessive amount of 4-methylbenzylisocyanate, exhibited excellent optical transmittance, glass transition temperature, And the optical lens prepared from the composition of Comparative Example 4 having an excessive amount of 4-cyanobenzylisocyanate was poor in terms of light transmittance, glass transition temperature, yellowness and malting phenomenon, Respectively.

Claims (12)

(1) preparing a first amine composition comprising m-xylylenediamine;
(2) reducing the content of at least one of p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition to obtain a second amine composition; And
(3) synthesizing an isocyanate from the second amine composition.
The method according to claim 1,
Wherein the second amine composition comprises, based on the total weight of the composition,
(a) from 99% to less than 100% by weight of m-xylylenediamine;
(b) more than 0 to 0.5% by weight of p-xylylenediamine; And
(c) at least one member selected from the group consisting of benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in an amount of more than 0 wt% to 0.5 wt% or less.
The method according to claim 1,
Wherein the second amine composition comprises, based on the total weight of the composition,
(a) 99.7 wt% or more and less than 100 wt% of m-xylylenediamine;
(b) more than 0 to 0.15% by weight of p-xylylenediamine; And
(c) benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine, respectively, in an amount of more than 0 wt% to 0.05 wt% or less.
The method according to claim 1,
Wherein the step of obtaining the second amine composition is carried out by reducing the content of both p-xylylenediamine, benzylamine, 4-methylbenzylamine and 4-cyanobenzylamine in the first amine composition, &Lt; / RTI &gt;
The method according to claim 1,
Wherein the step of obtaining the second amine composition comprises:
(2a) removing the distilled compound while raising the temperature of the first amine composition to 100 to 185 ° C under reduced pressure; And
(2b) a step of removing the precipitated compound while cooling the first amine composition to 15 to 18 占 폚.
The method according to claim 1,
Wherein the step of obtaining the second amine composition comprises:
Wherein the first amine composition is heated to 100 to 185 DEG C under reduced pressure to remove the distilled compound and then cooled to 15 to 18 DEG C to remove the precipitated compound.
The method according to claim 1,
Wherein the step of synthesizing the isocyanate comprises:
And reacting said second amine composition with phosgene or halo C1-10 alkyl chloroformate.
8. The method of claim 7,
Wherein the isocyanate is at least one isocyanate selected from the group consisting of m-xylylenediisocyanate, p-xylylene diisocyanate, benzyl diisocyanate, 4-methylbenzyl diisocyanate and 4-cyanobenzyl diisocyanate. Way.
8. The method of claim 7,
Wherein the isocyanate composition comprises, based on the total weight of the composition,
(a ') m-xylylenediisocyanate at 99 wt% or more and less than 100 wt%;
(b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And
(c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% .
Based on the total weight of the composition,
(a ') m-xylylenediisocyanate at 99 wt% or more and less than 100 wt%;
(b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And
(c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate in an amount of more than 0 wt% to 0.5 wt% or less.
1. A polymerizable composition comprising an isocyanate composition and a thiol,
Wherein the isocyanate composition comprises
Based on the total weight of the isocyanate composition,
(a ') m-xylylenediisocyanate at 99 wt% or more and less than 100 wt%;
(b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And
(c ') at least one member selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate is contained in an amount of more than 0 wt% to 0.5 wt% or less.
1. An optical material comprising an isocyanate composition and a thiol-polymerized polythiourethane,
Wherein the isocyanate composition comprises, based on the total weight of the composition,
(a ') m-xylylenediisocyanate at 99 wt% or more and less than 100 wt%;
(b ') more than 0 to 0.5% by weight of p-xylylene diisocyanate; And
(c ') at least one selected from the group consisting of benzyl isocyanate, 4-methylbenzyl isocyanate and 4-cyanobenzyl isocyanate is contained in an amount of more than 0 wt% to 0.5 wt% or less.