阅读说明：本技术 稳定性和反应性改善的异氰酸酯组合物，以及使用其的光学透镜 (Isocyanate composition having improved stability and reactivity, and optical lens using the same ) 是由 慎政焕 明正焕 韩赫熙 于 2018-12-26 设计创作，主要内容包括：实施方案涉及稳定性和反应性改善的异氰酸酯组合物,以及使用其的塑料光学透镜。由于组合物中氯的含量调整到22至500ppm,异氰酸酯组合物的稳定性得到改善,因此异氰酸酯组合物即使长时间储存也可以抑制反应性变差。因此,根据实施例的异氰酸酯组合物即使在制备后储存很长时间后再使用时,可以通过和硫醇基化合物聚合制备具有优异物理性质(例如折射率、阿贝数、透明度、玻璃转化温度、黄色指数)的聚硫代氨基甲酸酯基的光学材料,因此该异氰酸酯组合物能用于眼镜镜片、照相机镜头等领域。(Embodiments relate to an isocyanate composition having improved stability and reactivity, and a plastic optical lens using the same. Since the content of chlorine in the composition is adjusted to 22 to 500ppm, the stability of the isocyanate composition is improved, and thus the isocyanate composition can be inhibited from deteriorating in reactivity even when stored for a long time. Therefore, the isocyanate composition according to the example can prepare a polythiourethane-based optical material having excellent physical properties (e.g., refractive index, abbe number, transparency, glass transition temperature, yellow index) by polymerization with a thiol compound even when stored for a long time after preparation and then used in the fields of spectacle lenses, camera lenses, and the like.)

1. An isocyanate composition comprising a chlorine-based storage stabilizer and hydrogenated xylylene bis (methyl isocyanate) (H)₆XDI)，

Wherein the chlorine derived from the chlorine-based storage stabilizer is present in an amount of 22 to 500ppm in the total composition, and

the content of NCO groups contained in the entire composition is 42 to 45% by weight.

2. The isocyanate composition of claim 1, wherein said chlorine-based storage stabilizer comprises chloride ions.

3. The isocyanate composition of claim 1, wherein said chlorine-based storage stabilizer is selected from the group consisting of trichloromethylbenzene, benzyl chloride, benzoyl chloride and C_1-10Alkanoyl chloride.

4. The isocyanate composition according to claim 1, wherein the chlorine-based storage stabilizer is a compound represented by the following formula 1 or 2:

in the above formula, the first and second carbon atoms are,

n is an integer of 1 to 3;

r1 is C optionally substituted by halogen, hydroxy or amino_6-10An aryl group;

r2 is C_1-10An alkylene group;

r3 is C optionally substituted by halogen, hydroxy or amino_6-10Aryl, or C optionally substituted by halogen, hydroxy or amino_1-10An alkyl group.

5. The isocyanate composition according to claim 1, wherein when said isocyanate composition is left at a temperature of 80 ℃ for 6 months, an amount of a precipitate generated is 1% by weight or less based on the total weight of the composition.

6. The isocyanate composition according to claim 1, wherein said isocyanate composition is allowed to stand at a temperature of 80 ℃ for 6 months, and the difference in NCO group content between the initial composition and the composition after 6 months of standing is 5% by weight or less.

7. The isocyanate composition according to claim 1, wherein when said isocyanate composition is sealed and placed in a container in which a region in contact with the composition is not reacted with chlorine and left at a temperature of 80 ℃ for 6 months, the difference in NCO group content between the initial composition and the composition after 6 months of standing is 4% by weight or less.

8. An isocyanate composition comprising a chlorine-based storage stabilizer and hydrogenated xylylene bis (methyl isocyanate) (H)₆XDI)，

Wherein the content of NCO groups contained in the entire composition is 42 to 45% by weight, and

when the composition is sealed and placed in a container in which the area in contact with the composition is not reactive with chlorine and left at a temperature of 80 ℃ for 6 months, the difference in NCO group content between the initial composition and the composition after 6 months of standing is 4% by weight or less.

9. A method of preparing an isocyanate composition comprising: (1) preparation of a hydrogenated xylylene bis (methyl isocyanate) (H) from cyclohexanedimethanamine by the method of isocyanate Synthesis₆XDI);

(2) the content of chlorine contained in the hydrogenated xylylene bis (methyl isocyanate) -containing composition is adjusted to 22 to 500ppm,

wherein, when the composition is sealed and left at a temperature of 80 ℃ for 6 months, the difference in NCO group content in the initial composition and the composition after 6 months of left standing is 4% by weight or less.

10. The process for producing an isocyanate composition according to claim 9, wherein the step (2) is carried out by adding H to a mixture comprising₆XDI compositions are supplemented with at least one compound selected from the group consisting of trichloromethylbenzene, benzyl chloride, benzoyl chloride and C_1-10A chlorine-based storage stabilizer for an alkanoyl chloride, or a chlorine-based storage stabilizer comprising chloride ions.

11. Such asThe process for preparing an isocyanate composition of claim 9 wherein step (2) further comprises reacting a mixture comprising H₆The XDI compositions were thermally distilled.

12. A polymerizable composition comprising an isocyanate composition and a thiol compound,

wherein the isocyanate composition comprises a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI)，

The content of chlorine derived from the chlorine-based storage stabilizer in the isocyanate composition is 22 to 500ppm, and the content of NCO groups contained in the isocyanate composition is 42 to 45% by weight.

13. An optical lens comprising a polythiourethane formed by curing a polymerizable composition comprising an isocyanate composition and a thiol group compound,

wherein the isocyanate composition comprises a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI)，

The content of chlorine derived from the chlorine-based storage stabilizer in the isocyanate composition is 22 to 500ppm, and the content of NCO groups contained in the isocyanate composition is 42 to 45% by weight.

14. The optical lens of claim 13 having a Yellowness Index (YI) of 1 to 20 and a light transmission of 85.0 to 99.9% at a wavelength of 550 nm.

15. The optical lens of claim 13 having an abbe number of 30 to 45 and a glass transition temperature (Tg) of 75 to 120 ℃.

16. A method of manufacturing an optical lens comprising

(A) An isocyanate composition is provided which comprises an isocyanate composition,

(B) providing a thiol-based compound, wherein the thiol-based compound is a thiol-based compound,

(C) providing a polymerizable composition comprising the isocyanate composition and a thiol compound,

(D) curing the polymerizable composition to form a cured article,

wherein the isocyanate composition comprises a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI)，

The content of chlorine derived from the chlorine-based storage stabilizer in the isocyanate composition is 22 to 500ppm, and the content of NCO groups contained in the isocyanate composition is 42 to 45% by weight.

Technical Field

Background

Plastic optical materials are lightweight, not fragile, and excellent in dyeing property as compared with optical materials made of inorganic materials such as glass, and therefore they are widely used as optical materials for eyeglass lenses, camera lenses, and the like. Recently, there is a demand for optical materials having higher performance in terms of high transparency, high refractive index, low specific gravity, high heat resistance and high impact resistance.

Polythiourethanes in plastic optical materials are widely used as optical materials due to their excellent optical characteristics and excellent mechanical properties. Polythiourethanes can be prepared by reacting a thiol with an isocyanate. The physical properties of the mercaptans and/or isocyanates can significantly affect the physical properties of the polythiourethane to be prepared. Generally, lenses produced from polythiourethanes are widely used because of their high refractive index, lightness and relatively high impact resistance. However, they have disadvantages in that bubbles are generated in the polymerization reaction of thiol and isocyanate, reactivity is reduced, side reactions occur, or it is difficult to control the polymerization rate.

Research into enhancing the optical properties of lenses by varying the type and content of thiol and/or isocyanate as a raw material for polythiourethanes has been continued. For example, it has been attempted to improve the transparency of a lens by controlling the polymerization rate during polymerization by adjusting the water content in thiol (korean patent laid-open publication No. 2012-0076329).

In addition, a method of controlling the polymerization reaction by adjusting the kind and physical properties of isocyanate is well known. Isocyanates for polythiourethane polymerization are generally prepared by reacting aliphatic or aromatic amines with phosgene. For example, xylylenediamine, cyclohexanediamine, and the like can be reacted with phosgene to obtain xylylene bis (methyl isocyanate), hydrogenated xylylene bis (methyl isocyanate) (H)₆XDI), etc. (i.e., phosgene method). Alternatively, it may be reacted with a compound other than phosgene, which has an alkyl carbonate (alkyl carbonate) or an alkyl halocarbonyl (alkyl halocarbonyl) (i.e., a non-phosgene method).

The isocyanates obtained by the phosgene process are generally purified by distillation. This is not only to remove impurities from the isocyanate which is produced immediately after the reaction, but also to prevent dimers or trimers which are produced by the self-reaction of the NCO groups in the isocyanate.

For example, although xylylene diisocyanate is widely used because it has a high curing speed and a low yellowing degree in the preparation of lenses, it has disadvantages in that it is difficult to produce products having uniform characteristics due to the strong reactivity of NCO groups, and it loses its original physical properties due to side reactions upon long-term storage. In addition, not only does the self-reaction of the NCO groups cause side reactions, but the content of NCO groups may also change, thereby affecting reactivity. Therefore, there may be a problem that a phenomenon of solid matter precipitation or a phenomenon is further accelerated by reacting with moisture introduced from the environment. Various stabilizers may be used to prevent or mitigate this problem, but this may lead to yellowing or other problems in the production of polythiourethanes as they may affect reactivity. In addition, unlike other types of isocyanates, the difference in the amount of the xylylene bis (methyl isocyanate) depending on the kind and content of the additive has a greater side effect, which makes it difficult to find an optimum formulation. To overcome these disadvantages, there is an increasing demand for highly stable isocyanates.

Disclosure of Invention

Technical problem

When xylylene diisocyanate (diisocyanate) is used in the production of optical materials, various side reactions may occur due to its high reactivity, which may generate solid substances and seriously affect the optical characteristics of the optical materials. In order to solve this problem, attempts have been made to reduce impurities in the xylylene bis (methyl isocyanate) which may affect the reactivity to a very slight amount. However, it is commercially difficult to minimize the amount of impurities and the use of this method also results in significant expense. As a result of the investigation, the inventors of the present invention found that if benzene bis (methyl isocyanate) (H) is hydrogenated₆XDI) composition contains a certain amount of chlorine, it is possible to improve stability and prevent decrease in reactivity.

Accordingly, one embodiment is directed to a xylylene bis (methyl isocyanate) composition having improved stability and reactivity by adjusting the amount of chlorine to a specific range and a method for preparing the same.

In addition, one embodiment is directed to a polymeric composition, an optical material, and a method for manufacturing a plastic optical lens using the benzene bis (methyl isocyanate) composition.

Means for solving the problems

According to one embodiment, an isocyanate composition is provided comprising a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI) wherein the content of chlorine derived from the chlorine-based storage stabilizer is 22 to 500ppm in the entire composition and the content of NCO groups contained in the entire composition is 42 to 45% by weight.

According to another embodiment, an isocyanate composition is provided comprising a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI) wherein the NCO group content contained in the entire composition is 42 to 45% by weight, and when the composition is sealed and placed in a container which does not react with chlorine in a region in contact with the composition, and left at a temperature of 80 ℃ for 6 months, the difference in NCO group content between the initial composition and the composition after 6 months of standing is 4% by weight or less.

According to yet another embodiment, a method of making is providedA process for preparing an isocyanate composition comprising: (1) preparation of a hydrogenated xylylene bis (methyl isocyanate) (H) from cyclohexanedimethanamine by the method of isocyanate Synthesis₆XDI); (2) the content of chlorine contained in the hydrogenated xylylene bis (methyl isocyanate) -containing composition is adjusted to 22 to 500ppm, wherein, when H is contained₆The composition of XDI was sealed and placed in a container in which the area in contact with the composition did not react with chlorine, and left at a temperature of 80 ℃ for 6 months, the difference in NCO group content between the initial composition and the composition after 6 months of standing was 4% by weight or less.

According to yet another embodiment, a polymerizable composition is provided comprising an isocyanate composition and a thiol compound, wherein the isocyanate composition comprises a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI) wherein the content of chlorine derived from the chlorine-based storage stabilizer in the isocyanate composition is from 22 to 500ppm and the content of NCO groups contained in the isocyanate composition is from 42 to 45% by weight.

According to yet another embodiment, there is provided an optical lens comprising a polythiourethane formed by curing a polymerizable composition comprising an isocyanate composition and a thiol compound, wherein the isocyanate composition comprises a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI), the content of chlorine derived from the chlorine-based storage stabilizer in the isocyanate composition is 22 to 500ppm, and the content of NCO groups contained in the isocyanate composition is 42 to 45% by weight.

According to yet another embodiment, a method of making an optical lens is provided comprising (a) providing an isocyanate composition, (B) providing a thiol compound, (C) providing a polymerizable composition comprising the isocyanate composition and the thiol compound, (D) curing the polymerizable composition, wherein the isocyanate composition comprises a chlorine-based storage stabilizer and hydrogenated phenylene bis (methyl isocyanate) (H)₆XDI) in which the content of chlorine derived from the chlorine-based storage stabilizer is 22 to 500ppm, and NCO groups contained in the isocyanate compositionThe amount is 42 to 45% by weight.

The invention has the advantages of

The isocyanate composition according to the embodiment includes chlorine in an amount to improve stability, thereby preventing a decrease in reactivity even when stored for a long time.

Therefore, even if the isocyanate composition according to the embodiment is used after being stored for a long time after its preparation, the isocyanate composition may be polymerized with thiol to prepare a polythiourethane-based optical material having excellent properties in terms of refractive index, abbe number, transparency, glass transition temperature, yellowness index, and the like. It can be preferably used for eyeglass lenses, camera lenses, etc.

Embodiments relate to isocyanate compositions having improved stability and reactivity and optical lenses made therefrom.