Isocyanate composition and polymerizable composition comprising same

Abstract

The present invention provides an isocyanate composition and a polymerizable composition comprising same, the isocyanate composition exhibiting improved storage stability for a long period of several months or more, thereby suppressing discoloration and clouding, while enhancing transparency when applied to optical products.

Description

Isocyanate composition and polymerizable composition containing the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0038067, filed March 19, 2024, and Korean Patent Application No. 10-2025-0035252, filed March 19, 2025, the entire contents of which are incorporated herein by reference.

[0003]

[0004] The present invention relates to an isocyanate composition and a polymerizable composition comprising the same, which can improve storage stability for a long period of time, such as several months or more, and suppress discoloration and white clouding, maintain excellent discoloration resistance when applied to optical products, and improve transparency.

[0005]

[0006] Isocyanate compounds are highly valuable not only in the chemical and resin industries, but also as precision chemical products, including optical materials. Xylylene diisocyanate (XDI), a representative example of an isocyanate compound, is a raw material for poly(thio)urethane, a high-value-added chemical used in advanced optical lenses and flexible displays. Demand is growing for this material.

[0007]

[0008] However, isocyanate compounds exhibit high reactivity, so they are prone to discoloration or clouding during storage by reacting with oxygen or moisture in the atmosphere. Furthermore, when isocyanate compounds are stored for extended periods, exceeding several months, they self-polymerize to form oligomers such as dimers and trimers of uretdione, which can lead to problems such as differences in polymerization, discoloration, and clouding during further polymerization and product application.

[0009]

[0010] Isocyanate compounds are used as raw materials for polyurethane, and are used in various ways, such as coatings, adhesives, paints, foams, and optical materials. However, when manufacturing polyurethane lenses using isocyanate compounds that have discolored or clouded, the molecular weight of the polymer solution rapidly increases, which causes a decrease in stirring power, an increase in filter time, and filter clogging, resulting in reduced workability. In addition, uneven polymerization of the manufactured lenses causes problems such as striae, reduced transparency, and discoloration.

[0011]

[0012] To solve these problems, XDI is packaged in a nitrogen-substituted state during the product packaging stage to ensure its storage stability. However, since the entire product is often not used at once, there is a possibility of exposure to the atmosphere, and discoloration or clouding of XDI often occurs due to exposure to the atmosphere.

[0013]

[0014] Accordingly, research and development are continuously being conducted on isocyanate compositions that can improve transparency while maintaining excellent discoloration resistance during the manufacture of optical products such as lenses, and that do not cause discoloration or white clouding even during long-term storage due to improved storage stability.

[0015]

[0016] The present invention aims to provide an isocyanate composition that has no concern about discoloration or white clouding even when stored for a long period of several months or more due to improved storage stability, and can improve the transparency of lenses when used as a raw material for optical products such as poly(thio)urethane lenses.

[0017]

[0018] In addition, the present invention seeks to provide a polymerizable composition comprising the above-described isocyanate composition and an optical article comprising a polymer obtained therefrom.

[0019]

[0020] According to one embodiment of the present invention, an isocyanate composition is provided, which comprises xylylene diisocyanate and a compound represented by the following chemical formula 1, wherein the content of the compound is greater than 60 ppm and less than or equal to 200 ppm:

[0021] [Chemical Formula 1]

[0022]

[0023] In the above chemical formula 1,

[0024] In the above chemical formula 1,

[0025] R 1 is hydrogen, methyl, or ethyl.

[0026]

[0027] In one embodiment, the content of the compound represented by the chemical formula 1 in the isocyanate composition may be greater than 62 ppm and less than or equal to 180 ppm.

[0028]

[0029] In one embodiment, the isocyanate composition may have a chlorine (Cl) content of 200 ppm or less based on the total weight of the isocyanate composition, as measured using combustion ion chromatography according to the American Society for Testing and Materials ASTM D 7359 method.

[0030]

[0031] In one embodiment, the isocyanate composition may have an APHA color index of 0.1 or more and 25 or less, measured using a spectrophotometer (Ultrascan Pro from HunterLab, light source: C / 2) according to the American Society for Testing and Materials ASTM E313 method.

[0032]

[0033] In one embodiment, the isocyanate composition may further include at least one selected from the group consisting of chloromethylbenzyl isocyanate, isocyanomethylbenzaldehyde, and isocyanomethylbenznitrile.

[0034]

[0035] In one embodiment, the isocyanate composition may have a uretdione content of 5 parts by weight or less based on 100 parts by weight of the isocyanate composition, measured after 12 months of storage.

[0036]

[0037] According to another embodiment of the present invention, a method for producing an isocyanate composition is provided, comprising the steps of: reacting xylylene diamine or a xylylene diamine salt with phosgene to obtain a reaction mixture; and purifying the reaction mixture at a temperature of more than 120°C and less than 230°C under reduced pressure.

[0038]

[0039] According to another embodiment of the present invention, a polymerizable composition is provided, comprising the isocyanate composition; and at least one of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0040]

[0041] The above polymerizable composition may further include at least one selected from the group consisting of a polymerization initiator, an internal release agent, and an ultraviolet absorber.

[0042]

[0043] In addition, according to another embodiment of the invention, a composition for polyisocyanate polymerization is provided, comprising the above-described isocyanate composition; and at least one multifunctional monomer compound selected from the group consisting of a multifunctional thiol compound, a multifunctional alcohol compound, and a multifunctional episulfide compound.

[0044]

[0045] In addition, according to another embodiment of the invention, a polyisocyanate composition is provided, which includes a polyisocyanate polymerized with the above-described isocyanate composition and a polyfunctional alcohol compound.

[0046]

[0047] In addition, according to another embodiment of the invention, a polyisocyanate composition is provided, which includes a polyisocyanate polymerized with the above-described isocyanate composition and a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound.

[0048]

[0049] According to another embodiment of the present invention, an optical article is provided comprising a polymer obtained by polymerizing the polymerizable composition.

[0050]

[0051] The isocyanate composition according to the present invention exhibits improved storage stability, suppressing discoloration or clouding even after long-term storage of several months or more, and improving transparency when applied to optical products. In addition, a polymer prepared by polymerizing the isocyanate composition with a multifunctional thiol compound, a multifunctional alcohol compound, or a multifunctional episulfide compound also exhibits excellent transparency, and is useful in the manufacture of products such as optical adhesives, optical glues, optical coatings, and optical lenses.

[0052]

[0053] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0054]

[0055] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0056]

[0057] Hereinafter, the present invention will be described in detail.

[0058]

[0059] Isocyanate composition

[0060] The isocyanate composition of the present invention comprises xylylene diisocyanate and a compound represented by the following chemical formula 1, and the content of the compound represented by the above chemical formula 1 satisfies a range of more than 60 ppm and less than or equal to 200 ppm:

[0061] [Chemical Formula 1]

[0062]

[0063] In the above chemical formula 1,

[0064] R 1 is hydrogen, methyl, or ethyl.

[0065]

[0066] Xylylene diisocyanate (XDI) is a main component of an isocyanate composition according to one embodiment of the present invention.

[0067]

[0068] Specifically, the xylylene diisocyanate may be at least one selected from the group consisting of 1,2-xylylene diisocyanate (o-xylylene diisocyanate, o-XDI), 1,3-xylylene diisocyanate (m-xylylene diisocyanate, m-XDI), and 1,4-xylylene diisocyanate (p-xylylene diisocyanate, p-XDI).

[0069]

[0070] Preferably, the xylylene diisocyanate may be m-XDI.

[0071]

[0072] The above xylylene diisocyanate is a main component of the above isocyanate composition, and the content of xylylene diisocyanate in the isocyanate composition may be 97.7 area% or more, 98.0 area% or more, 98.3 area% or more, 99.0 area% or more, or 99.2 area% or more, but 99.9 area% or less, as determined by GC area% analysis.

[0073]

[0074] Meanwhile, xylene diisocyanate (XDI) included in the isocyanate composition can be manufactured using a commercially available product or one of various synthetic methods known in this technical field, and the specific synthetic method is not particularly limited and can be applied, for example, it can be synthesized from xylene diamine.

[0075]

[0076] For example, XDI can be synthesized from xylene diamine via the phosgene method. For example, isocyanate can be prepared by directly reacting xylene diamine with phosgene in a solvent, or its carbonate or hydrochloride can be produced, and then XDI can be synthesized by reacting the amine salt with phosgene (COCl2).

[0077]

[0078] As another example, XDI can be synthesized from xylene diamine via the non-phosgene method. For example, biscarbamate can be produced by reacting xylene diamine with urea and / or an N-unsubstituted carbamic acid ester and an alcohol. XDI can be produced by thermal decomposition or degassing of the biscarbamate, for example, in the presence of a catalyst.

[0079]

[0080] In particular, the isocyanate composition of the present invention, which comprises a compound represented by Chemical Formula 1 as described above, but whose content is greater than 60 ppm and less than 200 ppm, exhibits little clouding and discoloration even when stored for a long period of time, such as for several months or more, for example, for 12 months or more. In addition, poly(thio)urethane lenses and the like manufactured using such an isocyanate composition exhibit excellent transparency and can be suitably used as high-quality optical products.

[0081]

[0082] To secure these effects, the content of the compound represented by the above chemical formula 1 is more than 60 ppm, or 61 ppm or more, or 61.5 ppm or more, or 62 ppm or more, or 62.5 ppm or more, or 63 ppm or more, or 63.5 ppm or more, or 64 ppm or more, or 64.5 ppm or more, or 65 ppm or more, or 65.5 ppm or more, or 66 ppm or more, or 66.5 ppm or more, or 67 ppm or more, or 67.5 ppm or more, or 68 ppm or more, and 200 ppm or less, or 180 ppm or less, or 170 ppm or less, or 160 ppm or less, or 150 ppm or less, or 140 ppm or less, or 130 ppm or less, or 120 ppm or less, or 110 ppm or less, or 100 It can satisfy ppm or less.

[0083]

[0084] When the content of the compound represented by the chemical formula 1 in the above isocyanate composition is 60 ppm or less, the long-term storage stability of the isocyanate composition is reduced, and when it exceeds 200 ppm, there is a problem that the discoloration resistance of the poly(thio)urethane lens is reduced.

[0085]

[0086] Meanwhile, the isocyanate composition of the present invention comprises xylylene diisocyanate as an essential component and a compound represented by the above chemical formula 1, and comprises xylylene diisocyanate as a main component and a compound represented by the above chemical formula 1 as a secondary component.

[0087]

[0088] Preferably, the compound represented by the above chemical formula 1 may be represented by the following chemical formula 1-1, for example:

[0089] [Chemical Formula 1-1]

[0090] .

[0091]

[0092] The compound represented by the above chemical formula 1 can be manufactured using a commercially available product or one of various synthetic methods known in the art. The specific synthetic method is not particularly limited and can be applied. The specific manufacturing method is as shown in Manufacturing Example 1 described below.

[0093]

[0094] Meanwhile, the compound represented by the above chemical formula 1 may be added to xylylene diisocyanate as a separate additive or added through a side reaction during the manufacturing process, and the specific production method is not limited as long as the optimized content range as described above can be satisfied. Generally, xylylene diisocyanate is manufactured through a reaction and purification process of xylylene diamine or xylylene diamine hydrochloride or carbonate with phosgene, and in some cases, the compound represented by the above chemical formula 1 is generated due to a side reaction during the reaction and / or purification process. Therefore, by controlling the reaction conditions and / or purification conditions during the manufacturing of xylylene diisocyanate, the content of the compound represented by the above chemical formula 1 can be controlled within the above-described range.

[0095]

[0096] For example, the compound represented by the above chemical formula 1 is a chlorine compound produced as a byproduct in the production of xylylene diisocyanate described below. The compound represented by the above chemical formula 1 (dichloromethylbenzyl isocyanate, DCMBI) may be at least one selected from the group consisting of 2-(dichloromethyl)benzyl isocyanate (o-(dichloromethyl)benzyl isocyanate, o-DCMBI), 3-(dichloromethyl)benzyl isocyanate (m-(dichloromethyl)benzyl isocyanate, m-DCMBI), and 4-(dichloromethyl)benzyl isocyanate (p-(dichloromethyl)benzyl isocyanate, p-DCMBI) as structural isomers.

[0097]

[0098] In this way, the structural isomer of dichloromethylbenzyl isocyanate produced as a byproduct in the production of xylylene diisocyanate corresponds to the structural isomer of the xylylene diisocyanate produced. Therefore, the xylylene diisocyanate composition contains dichloromethylbenzyl isocyanate corresponding to the structural isomer of the above-mentioned xylylene diisocyanate. That is, the xylylene diisocyanate composition, when containing 1,2-xylylene diisocyanate (o-xylylene diisocyanate, o-XDI), contains 2-(dichloromethyl)benzyl isocyanate (o-(dichloromethyl)benzyl isocyanate, o-DCMBI), when containing 1,3-xylylene diisocyanate (m-xylylene diisocyanate, m-XDI), contains 3-(dichloromethyl)benzyl isocyanate (m-(dichloromethyl)benzyl isocyanate, m-DCMBI), and when containing 1,4-xylylene diisocyanate (p-xylylene diisocyanate, p-XDI), contains 4-(dichloromethyl)benzyl isocyanate (p-(dichloromethyl)benzyl isocyanate, Contains p-DCMBI).

[0099]

[0100] Preferably, the compound represented by the above chemical formula 1 (dichloromethylbenzyl isocyanate) may be 3-(dichloromethyl)benzyl isocyanate (m-(dichloromethyl)benzyl isocyanate, m-DCMBI).

[0101]

[0102] Accordingly, in order to manufacture an isocyanate composition according to one embodiment of the present invention, it is first necessary to analyze the content of the compound of formula 1 in xylylene diisocyanate, which is the main raw material of the isocyanate composition. Thereafter, the isocyanate composition of the present invention described above can be obtained by further adding the compound of formula 1 as needed, or adjusting the content of the compound of formula 1 in xylylene diisocyanate through a purification method such as distillation or column chromatography. The method for analyzing the content of the compound of formula 1 in the isocyanate composition is not particularly limited, and can be measured, for example, through gas chromatography (GC-MS).

[0103]

[0104] For example, the isocyanate composition according to one embodiment of the present invention can be prepared by a method of reacting xylylene diamine or a xylylene diamine salt (e.g., hydrochloride or carbonate) with phosgene to obtain a reaction mixture, and purifying the reaction mixture at a temperature of more than 120°C and less than 230°C under reduced pressure conditions. For example, the purification step can be performed under a reduced pressure condition of 1 bar or less, or 0.98 bar or less, or 0.95 bar or less, or 0.9 bar or less, and in a practical aspect, can be performed under a reduced pressure condition of 0.01 mbar or more. In addition, the purification step can be performed under a temperature condition of 125°C or more, or 130°C or more, or 140°C or more, and 225°C or less, or 220°C or less, or 210°C or less, or 200°C or less.

[0105]

[0106] At this time, the step of reacting the xylylene diamine or xylylene diamine salt with phosgene, i.e., the phosgenation reaction, can be performed according to a conventionally known method. For example, xylylene diamine or its salt is dispersed in one or more solvents selected from the group consisting of aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; chlorinated aromatic hydrocarbon solvents such as monochlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride, and phosgene is injected, and then the phosgenation reaction can be performed at a temperature of 100°C or higher, or 120°C or higher, and 150°C or lower, or 140°C or lower.

[0107]

[0108] For example, the method for preparing the isocyanate composition includes a step of reacting xylylene diamine or a xylylene diamine salt with phosgene to obtain a reaction mixture; and a step of removing a gas phase from the reaction mixture. In addition, the method may further include a desolvation step of removing a solvent from the reaction product from which the gas phase has been removed and a purification step of removing impurities. Specifically, the method includes a degassing step of removing a gas phase from the reaction mixture; and by performing the desolvation step of removing a solvent from the reaction product from which the gas phase has been removed and the purification step of removing impurities, an isocyanate composition including a compound represented by Chemical Formula 1 can be prepared. However, the method for preparing the isocyanate composition is not limited thereto, and an isocyanate composition having a content of the compound represented by Chemical Formula 1 of more than 60 ppm and less than 200 ppm can be prepared by controlling conditions during the phosgenation reaction, purification conditions, and / or purification techniques.

[0109]

[0110] In addition, the isocyanate composition according to one embodiment of the present invention may have a chlorine (Cl) component content of 200 ppm or less or more than 0 and 200 ppm or less based on the total weight of the isocyanate composition, as measured using combustion ion chromatography according to the American Society for Testing and Materials ASTM D 7359 method.

[0111]

[0112] Specifically, the content of the chlorine (Cl) component may be less than 200 ppm, or 190 ppm or less, or 180 ppm or less, or 170 ppm or less, or 160 ppm or less, or 150 ppm or less, or 145 ppm or less, or 140 ppm or less, or 135 ppm or less, or 132 ppm or less. However, in practical terms, the content of the chlorine (Cl) component may be 0.1 ppm or more, or 0.5 ppm or more, or 0.8 ppm or more, or 1 ppm or more, or 1.5 ppm or more, or 3 ppm or more, or 5 ppm or more, or 10 ppm or more, or 15 ppm or more, or 18 ppm or more, or 20 ppm or more, or 25 ppm or more, or 30 ppm or more, or 35 ppm or more, or 40 ppm or more, or 42 ppm or more, or 45 ppm or more, or 48 ppm or more, or 50 ppm or more, or 52 ppm or more, or 55 ppm or more, or 58 ppm or more, or 60 ppm or more, or 61 ppm or more. The content of the above chlorine (Cl) component may preferably be 150 ppm or less, or 145 ppm or less, or 140 ppm or less, or 135 ppm or less, and in practical terms may be 50 ppm or more, or 52 ppm or more, or 55 ppm or more, or 60 ppm or more.

[0113]

[0114] In addition, the isocyanate composition according to one embodiment of the present invention may have an APHA color index of 0.1 or more and 25 or less, as measured using a spectrophotometer (Ultrascan Pro from HunterLab, light source: C / 2) according to the American Society for Testing and Materials ASTM E313 method. Here, the isocyanate composition may have an APHA value of 0.1 or more and 10 or less immediately after production, and the APHA color index of the isocyanate composition may increase during storage. Specifically, the APHA color index immediately after preparation of the isocyanate composition may be 10 or less, or 9.5 or less, or 9 or less, or 8.5 or less, or 8 or less, and may be 0.1 or more, or 0.2 or more, or 0.5 or more, or 1 or more, or 1.5 or more, or 2 or more, or 2.5 or more, or 3 or more, or 3.5 or more, or 4 or more, or 4.5 or more, or 5 or more. In addition, the APHA color index of the isocyanate composition after storage for 12 months may be 25 or less, or 22 or less, or 20 or less, or 18 or less, and may be 0.5 or more, or 1 or more, or 3 or more, or 5 or more, or 8 or more, or 10 or more, or 12 or more, or 14 or more.

[0115]

[0116] Meanwhile, the isocyanate composition according to one embodiment of the present invention may further include at least one additional component selected from the group consisting of chloromethylbenzyl isocyanate, isocyanatomethyl benzaldehyde (IMBAl), and isocyanatomethyl benzamide (IMBAm).

[0117]

[0118] Specifically, the chloromethylbenzyl isocyanate may be represented by the following chemical formula 2, the isocyanatomethylbenzaldehyde may be represented by the following chemical formula 3, and the isocyanatomethyl benzamide (Isocyanatomethyl benzamide, IMBAm) may be represented by the following chemical formula 4.

[0119] [Chemical Formula 2]

[0120]

[0121] [Chemical Formula 3]

[0122]

[0123] [Chemical Formula 4]

[0124]

[0125] In the above chemical formulas 2 to 4,

[0126] R 1 are each independently hydrogen, methyl, or ethyl

[0127]

[0128] For example, the chloromethylbenzyl isocyanate may be represented by the following chemical formula 2-1, the isocyanatomethylbenzaldehyde may be represented by the following chemical formula 3-1, and the isocyanatomethylbenzamide may be represented by the following chemical formula 4-1.

[0129] [Chemical Formula 2-1]

[0130]

[0131] [Chemical Formula 3-1]

[0132]

[0133] [Chemical Formula 4-1]

[0134] .

[0135]

[0136] In an isocyanate composition according to one embodiment of the present invention, at least one additional component selected from the group consisting of chloromethylbenzyl isocyanate, isocyanatomethylbenzaldehyde, and isocyanatomethylbenzamide may be independently included in an amount of 0.5 parts by weight or less, or 0 or more and 0.5 parts by weight or less, per 100 parts by weight of the isocyanate composition.

[0137]

[0138] In particular, in the above isocyanate composition, immediately after preparation, the content of at least one additional component selected from the group consisting of chloromethylbenzyl isocyanate, isocyanatomethylbenzaldehyde, and isocyanatomethylbenzamide is independently less than 0.4 parts by weight, or 0.38 parts by weight or less, or 0.35 parts by weight or less, or 0.32 parts by weight or less, or 0.3 parts by weight or less, or 0.28 parts by weight or less, or 0.25 parts by weight or less, or 0.22 parts by weight or less, or 0.2 parts by weight or less, or 0.18 parts by weight or less, or 0.15 parts by weight or less, or 0.12 parts by weight or less, or 0.1 parts by weight or less, or 0.09 parts by weight or less, or 0.05 parts by weight or less, or 0.03 parts by weight or less, or 0.01 parts by weight or less, but 0.001 parts by weight or more, It may be 0.002 parts by weight or more, 0.003 parts by weight or more, or 0.005 parts by weight or more, or 0.007 parts by weight or more.

[0139]

[0140] Meanwhile, the isocyanate composition according to one embodiment of the present invention can reduce the rate at which the content of at least one additional component selected from the group consisting of isocyanatomethyl benzaldehyde (IMBAl) and isocyanatomethyl benzamide (IMBAm) increases after long-term storage for 12 months by optimizing the content of the compound (DCMBI) represented by the above chemical formula 1. For example, the at least one additional component selected from the group consisting of isocyanatomethyl benzaldehyde and isocyanatomethyl benzamide in the isocyanate composition stored for 12 months may be independently included in an amount of 0.01 part by weight or more and 0.5 part by weight or less, based on 100 parts by weight of the isocyanate composition. Specifically, as described above, after 12 months, at least one additional component of IMBAl and IMBAm in the XDI composition may be independently less than 0.4 parts by weight, or 0.38 parts by weight or less, or 0.35 parts by weight or less, or 0.32 parts by weight or less, or 0.3 parts by weight or less, or 0.28 parts by weight or less, or 0.25 parts by weight or less, or 0.22 parts by weight or less, or 0.2 parts by weight or less, or 0.18 parts by weight or less, or 0.15 parts by weight or less, or 0.12 parts by weight or less, or 0.1 parts by weight or less, or 0.09 parts by weight or less, but may be 0.02 parts by weight or more, or 0.03 parts by weight or more, or 0.04 parts by weight or more, or 0.05 parts by weight or more, or 0.06 parts by weight or more.

[0141]

[0142] Here, the content of at least one selected from the group consisting of chloromethylbenzyl isocyanate, isocyanatomethylbenzaldehyde, and isocyanatomethylbenzamide can be measured through component analysis using gas chromatography (GC), but is not limited thereto, and can be measured using other methods known in the technical field to which the present invention pertains. For example, a method for measuring the content of such additional components is as described in Test Example 3 described below.

[0143]

[0144] Specifically, the content of at least one selected from the group consisting of chloromethylbenzyl isocyanate, isocyanatomethylbenzaldehyde, and isocyanatomethylbenzamide can be measured by performing gas chromatography (GC) analysis under the following analysis conditions.

[0145]

[0146] 1. GC measurement conditions

[0147] Device; GC (Agilenet HP-7890A FID)

[0148] Column; DB-17 (30 m x 0.25 mm, 0.5 μm)

[0149] Split ratio; 100:1

[0150] Inlet temperature; 250 ℃

[0151] Detector temperature; 280 ℃

[0152] Oven temperature: 80℃ → 5℃ / min increase, 160℃ (maintained for 8 minutes) → 20℃ / min increase, 280℃ (maintained for 18 minutes)

[0153] Carrier gas; N2

[0154] Carrier gas flow rate; 1.0 ml / min (constant flow control)

[0155] Sample concentration: 1.0 wt% dichloromethane solution

[0156] Injection volume; 1.0 μL.

[0157]

[0158] When gas chromatography (GC) analysis is performed under the conditions described above, the content ratio of each compound with respect to the total weight of the isocyanate composition can be expressed as the content (weight%) of each component.

[0159]

[0160] For example, according to the above-described gas chromatography (GC) analysis, the retention time of xylylene diisocyanate (XDI) may represent a compound having a retention time of 27.9 to 29.0 minutes, isocyanatomethyl benzaldehyde (IMBAl) may represent a compound having a retention time of 24.7 to 26.4 minutes, and isocyanatomethyl benzamide (IMBAm) may represent a compound having a retention time of 30.7 to 32.8 minutes.

[0161]

[0162] In particular, by including at least one of the above-described isocyanomethylbenzaldehyde, isocyanatomethylbenzamide, etc. together with the compound represented by the above chemical formula 1 (dichloromethylbenzyl isocyanate, DCMBI), it is possible to suppress the generation of uretdione, a self-polymerizing compound, and additional impurities generated during long-term storage of several months or more, thereby reducing the increase in APHA and lens YI of the composition. For reference, the content of chloromethylbenzyl isocyanate does not change significantly during the storage process.

[0163]

[0164] An isocyanate composition according to one embodiment of the present invention may have a content of uretdione measured after long-term storage for 12 months, i.e., a content of uretdione in the XDI composition stored for 12 months (content of uretdione in the XDI composition after 12 months) of 5 parts by weight or less per 100 parts by weight of the isocyanate composition.

[0165]

[0166] Here, uretdione is a structure in which two NCOs of each of two xylylene diisocyanates (XDI) are bonded to each other in a ring form, and the structure is called uretdione, and two XDIs can be bonded to one ring. In addition, three XDIs can be produced in a form having two uretdione rings. At this time, the compound represented by the above chemical formula 1 (dichloromethylbenzyl isocyanate, DCMBI) can be produced by bonding between NCOs of various substances in the isocyanate composition, such as bonding between NCOs of XDI.

[0167]

[0168] Specifically, in the present invention, uretdione may be represented by the following chemical formula 5.

[0169] [Chemical Formula 5]

[0170]

[0171] In the above chemical formula 5,

[0172] R 1 are each independently hydrogen, methyl, or ethyl,

[0173] R' is each independently a chloromethyl group (-CH2Cl), a dichloromethyl group (-CHCl2), an aldehyde group (-CHO), or an amide group (-CONH2),

[0174] n is each independently 0 or 1.

[0175]

[0176] For example, the uretdione may be represented by any one of the following chemical formulas 5-1 to 5-3.

[0177] [Chemical Formula 5-1]

[0178]

[0179] [Chemical Formula 5-2]

[0180]

[0181] [Chemical Formula 5-3]

[0182]

[0183] In the above chemical formulas 5-1 to 5-3,

[0184] R' is as described above in the chemical formula 5.

[0185]

[0186] In particular, the content of uretdione, i.e., the content of uretdione measured after long-term storage of the isocyanate composition for 12 months (the content of uretdione in the XDI composition after 12 months), may be 5 parts by weight or less, or 0 to 5 parts by weight or less, based on 100 parts by weight of the isocyanate composition. The content of uretdione after 12 months of storage may preferably be less than 5 parts by weight, or 4.9 parts by weight or less, or 4.8 parts by weight or less, or 4.5 parts by weight or less, or 4.2 parts by weight or less, or 4 parts by weight or less, or 3.8 parts by weight or less, or 3.5 parts by weight or less, or 3.2 parts by weight or less, or 3 parts by weight or less, or 2.85 parts by weight or less, or 2.7 parts by weight or less. However, in terms of the actual self-polymerization process that occurs during long-term storage, the content of uretdione after 12 months of storage may be more than 0 part by weight, or 0.01 part by weight or more, or 0.02 part by weight or more, or 0.03 part by weight or more, or 0.04 part by weight or more, or 0.05 part by weight or more, or 0.06 part by weight or more, or 0.08 part by weight or more, or 0.1 part by weight or more.

[0187]

[0188] Here, the content of uretdione can be measured through infrared spectroscopy (IR) analysis, but is not limited thereto, and can be measured using other methods known in the art to which the present invention pertains. For example, a method for measuring the content of uretdione is as described in Test Example 3 described below.

[0189]

[0190] Specifically, the isocyanate composition of the present invention is heated at room temperature (about 15 o C to 25 o After storing for 12 months in a general tin can under the conditions of C), the content of uretdione can be measured through analysis of the isocyanate (XDI) composition obtained after 12 months of storage by infrared spectroscopy (IR). For example, after obtaining the infrared absorption spectrum for the isocyanate composition after 12 months of storage using the ATR mode of an FT-IR spectrometer (Varian 4100), the absorption peak of the uretdione carbonyl group (1770~1790cm -1 ) is measured, and the urethdione content (weight%) is calculated based on the absorption coefficient obtained from the calibration curve.

[0191]

[0192] When infrared spectroscopy (IR) analysis is performed under the conditions described above, the weight ratio of the uretdione compound to the total weight of the isocyanate composition can be expressed as content (weight %).

[0193]

[0194] Meanwhile, the isocyanate composition according to one embodiment of the present invention may have a chlorine (Cl) component content measured after long-term storage for 12 months that satisfies the aforementioned range measured in the initial stage after manufacturing.

[0195]

[0196] polymeric composition

[0197] According to another embodiment of the invention, a polymerizable composition for polyisocyanate polymerization is provided, which comprises, together with the above-described isocyanate composition, at least one polyfunctional monomer compound selected from the group consisting of a polyfunctional alcohol compound, a polyfunctional thiol compound, and a polyfunctional episulfide compound.

[0198]

[0199] The above polymerizable composition includes a compound represented by the above chemical formula 1 together with xylylene diisocyanate, and by using an isocyanate composition whose content satisfies more than 60 ppm and less than 200 ppm, it is easy to control reactivity during polymerization.

[0200]

[0201] The above polymerizable composition has high transparency and excellent impact strength, and can be suitably used as a high-quality optical material.

[0202]

[0203] The description of the isocyanate composition included in the above polymerizable composition is as described above.

[0204]

[0205] Preferably, the polymerization composition may contain the isocyanate composition and the polyfunctional monomer compound in a mixed state, or may contain them in a separate state. That is, within the polymerization composition, the isocyanate composition and the polyfunctional monomer compound 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.

[0206]

[0207] The above polyfunctional alcohol compound is a compound containing two or more hydroxyl groups (-OH) per molecule, and specifically, may be a compound having two or more, or three or more, and eight or less, or four or less hydroxyl groups per molecule. Specific examples include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, polypropylene glycol, polytetramethylene ether glycol, ethylene oxide-propylene oxide block copolymer, polyalkylene carbonate diol, and polycaprolactone diol; trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); Examples thereof include tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; pentahydric alcohols such as L-arabinitol, ribitol, and xylitol; hexahydric alcohols such as D-glucitol, D-mannitol, and galactitol; heptahydric alcohols such as trehalose; octahydric alcohols such as sucrose and maltose; and polyols, and any one of these or a mixture of two or more thereof may be used.

[0208]

[0209] The above multifunctional thiol compound is a compound containing two or more thiol groups (-SH) in one molecule, and specifically, it may be a compound having two or more, or three or more, and eight or fewer, or five or fewer thiol groups in the molecule.

[0210]

[0211] The above multifunctional thiol compound compounds include, for example, 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol, 1,9-dimercapto-3,7-dithianonane, 1,13-dimercapto-3,7,11-trithiatridecane, glycol di(3-mercaptopropionate), 1,4-dithiane-2,5-diyldimethanethiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane tri(3-mercaptopropionate), 4,8-di(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 5,9-di(mercaptoethyl)-1,12-dimercapto-3,7,10-trithiadodecane, pentaerythritol Pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate), 3,6,9,12-Tetrathiatetradecane-1,14-dithiol, 3,6,10,13-Tetrathiapentadecane-1,8,15-trithiolIt may be at least one selected from the group consisting of 15-trithiol.

[0212]

[0213] Specifically, the above polyvalent thiol may be added in an amount such that the molar ratio of the thiol group in the polyvalent thiol is 0.8 or more, or 0.9 or more, and 1.1 or less, or 1.0, per 1 mole of the isocyanate group of the isocyanate compound. If the molar ratio of the thiol group to the isocyanate group is less than 0.8 outside the above molar ratio range, the viscosity of the polymer produced may decrease due to the excess isocyanate group, and thus, the processability may decrease. In addition, if the molar ratio of the thiol group to the isocyanate group exceeds 1.1, the discoloration prevention effect may decrease due to the excess thiol group.

[0214]

[0215] The above multifunctional episulfide compound may be a compound containing two or more episulfides, i.e., thioepoxy groups, in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton. In one example, the above multifunctional episulfide compound is 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-epithiopropylthio)butane, 1,3-bis(β-epithiopropylthio)butane, 1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)butane, 1,5-bis(β-epithiopropylthio)pentane, 1-(β-Epithopropylthio)-4-(β-Epithopropylthiomethyl)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-epithiopropylthiomethyl)-5-[(2-β-epithiopropylthioethyl)thiomethyl]-3,7-dithianonan, 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-trithiadecane, 1,11-Bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 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, It may include at least one selected from 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl] sulfide, bis[4-(β-epithiopropylthio)phenyl] sulfone, and 4,4'-bis(β-epithiopropylthio)biphenyl.

[0216]

[0217] The above polymerization composition may further include additives such as an internal release agent, an ultraviolet absorber, a urethane reaction catalyst, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, a filler, and a photosensitizer, as needed, within a range that does not impair the effect intended by the invention, and the content thereof may be appropriately determined within a range that does not impair the discoloration and discoloration inhibition properties of the composition.

[0218]

[0219] The above polymerization composition can control the occurrence of white turbidity by delaying or inhibiting the reaction rate and oligomerization of isocyanate due to the combination of two types of antioxidants included in the isocyanate composition.

[0220]

[0221] The polyol included in the above polymerizable composition is a compound having two or more hydroxyl groups, and compounds commonly used in the production of polyurethane can be used without limitation. For example, the polyol includes dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, etc.; trihydric alcohols such as glycerol, trimethylolethane, trimethylolpropane (TMP), etc.; tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.; pentahydric alcohols such as L-arabinitol, ribitol, xylitol, etc.; hexahydric alcohols such as D-glucitol, D-mannitol, galactitol, etc.; heptahydric alcohols such as trehalose, etc. Examples include octahydric alcohols such as sucrose and maltose, or low molecular weight polyols such as polyalkylene oxides having a number average molecular weight of 60 to 400.

[0222]

[0223] Among these, diethylene glycol, glycerol, trimethylolethane, trimethylolpropane or a mixture thereof may be used, and more specifically, it may be preferable to use a trihydric alcohol such as glycerol, trimethylolpropane or trimethylolethane alone, or to use the trihydric alcohol in combination with another polyol.

[0224]

[0225] The above polythiol is a compound having two or more mercapto groups, and compounds used in the production of polythiourethane can be used without limitation. For example, aliphatic polythiols such as 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianedecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianedecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianedecane can be used alone or in combination of two or more, but are not limited thereto.

[0226]

[0227] The above polymerizable composition may further include a polymerization initiator, an internal release agent, and an ultraviolet absorber, as needed.

[0228]

[0229] The polymerization initiator may be an amine-based, phosphorus-based, organotin-based, organocopper-based, organogallium-based, organozirconium-based, organozinc-based, organoaluminum-based, etc. The polymerization initiator may be included in an amount of 0.001 to 0.1 parts by weight based on 100 parts by weight of the polymerizable composition.

[0230]

[0231] The internal release agent may be selected from among fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group, or a phosphate ester group; quaternary alkyl ammonium salts, such as trimethyl cetyl ammonium salt, trimethylstearyl, dimethylethyl cetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, and diethylcyclohexadodecyl ammonium salt; and phosphoric acid ester compounds such as acidic phosphoric acid esters, which may be used alone or in combination of two or more. Preferably, a phosphoric acid ester compound may be used. The internal release agent may be used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the polymerizable composition.

[0232]

[0233] Examples of the above ultraviolet absorbent include benzotriazole compounds (specifically, Tinuvin 571, Tinuvin 213, Tinuvin 234, and Tinuvin P (all manufactured by BASF)), formamidine compounds (specifically, Zikasorb R, Zikasorb BS, ZIKA-FA02, ZIKA-FUA, ZIKA-FUV, ZIKA-UVS3, and ZIKA-UVS4 (all manufactured by ZIKO)), and Biosorb 583 (manufactured by Sakai Chemical Industry Co., Ltd.). The ultraviolet absorbent may be used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the polymerizable composition.

[0234]

[0235] The above polymerization composition includes a compound represented by the chemical formula 1 as described above in the isocyanate composition, but the content thereof is optimized to be more than 60 ppm and less than 200 ppm, so that the reaction rate and oligomerization of the isocyanate are delayed or suppressed, thereby controlling the occurrence of clouding and discoloration even when stored for a long period of time, such as more than several months, for example, more than 12 months, and at the same time, when used as a raw material for optical products such as poly(thio)urethane lenses, the transparency of the lenses can be improved.

[0236]

[0237] polyisocyanate composition

[0238] According to another embodiment of the invention, a polyisocyanate composition is provided, which comprises a polyisocyanate polymerized with the aforementioned isocyanate composition and a polyfunctional alcohol-based compound. The polyisocyanate produced by the reaction with the polyhydric alcohol exhibits excellent transparency and excellent adhesion / adhesion properties. Accordingly, the polyisocyanate can be used in coatings, adhesives, and the like, but is not limited thereto, and is useful in the production of optical adhesives, optical adhesives, optical coatings, or optical coatings.

[0239]

[0240] Here, the description of the polyfunctional alcohol compound can be applied in the same manner as described above.

[0241]

[0242] According to another embodiment of the invention, a polyisocyanate composition is provided, which comprises a polyisocyanate polymerized with the above-described isocyanate composition and a polyfunctional thiol compound or a polyfunctional episulfide compound. The polyisocyanate composition can be used in optical materials, such as, but not limited to, optical lenses.

[0243]

[0244] Here, the description of the multifunctional thiol compound and the multifunctional episulfide compound can be equally applied to the above.

[0245]

[0246] In the above polyisocyanate composition, the polymerization reaction of the isocyanate composition and the monomer compound (polyfunctional alcohol compound, polyfunctional thiol compound, polyfunctional episulfide compound) can be performed under atmospheric pressure and an inert gas atmosphere such as nitrogen or argon.

[0247]

[0248] The above polymerization reaction can be carried out at a temperature range of -15°C or higher, or 0°C or higher, and 200°C or lower, or 170°C or lower. For example, when a polyfunctional alcohol-based compound is used as the monomer compound, it is preferably carried out at 60 to 80°C, and when a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound is used as the monomer compound, it is preferably carried out at 100°C to 160°C.

[0249]

[0250] When the polymerization reaction is performed in the above temperature range, the reaction rate can be easily controlled without concern for discoloration, and the reaction efficiency can also be increased, which is preferable.

[0251]

[0252] The above polymerization reaction may be carried out under non-catalytic conditions, or may be carried out in the presence of a catalyst that typically promotes urethane reactions, such as a tin-based or amine-based catalyst. When carried out in the presence of a catalyst, the catalyst may be added together with the monomer compound at the step of adding the isocyanate-based mixture.

[0253]

[0254] In the case where a polyfunctional alcohol compound is used in the above polymerization reaction, the progress can be estimated by measuring the concentration of isocyanate groups in the polymerization reactant using the n-dibutylamine method using a transfer titration device, or by measuring the refractive index. In the present invention, the polymerization reaction can be performed until the concentration of isocyanate groups in the polymerization reactant reaches the calculated value of the isocyanate groups remaining after reacting with the monomer compound. As a result of the above polymerization reaction, a polyisocyanate is produced.

[0255]

[0256] The above polyisocyanate composition may further include additives such as an internal release agent, an ultraviolet absorber, a polymerization initiator, a heat stabilizer, an antioxidant, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, a filler, a photosensitizer, etc., as needed, within a range that does not impair the effect intended by the invention, and the content thereof may be appropriately determined within a range that does not impair the discoloration and discoloration inhibition properties of the composition.

[0257]

[0258] optical products

[0259] According to another embodiment of the invention, an article is provided, which comprises a polymer obtained by polymerizing the above-described isocyanate composition and at least one polyfunctional monomer compound selected from the group consisting of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0260]

[0261] This may also be an article comprising a polymer in which an isocyanate composition and a multifunctional monomer compound are polymerized in the aforementioned polymerization composition.

[0262]

[0263] Polyisocyanate compositions exhibit excellent transparency and excellent adhesion properties, making them applicable to a wide range of fields. Specifically, they can be utilized in various ways, not only as coating agents, adhesives, and glues, but also as optical materials. More preferably, the product can be used as an optical adhesive, an optical adhesive, an optical coating, or an optical lens.

[0264]

[0265] The above article may be manufactured by performing a molding process after a polymerization reaction in the above composition, or may be manufactured through a molding process using the above polymerization composition. In the latter case, the polymerization reaction occurs simultaneously during the molding process.

[0266]

[0267] Preferably, when used as an optical lens, the composition may be polymerized from an isocyanate composition and a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound, and in this case, the polymerization composition including the isocyanate composition and the polyfunctional thiol-based compound or the polyfunctional episulfide-based compound may be injected into a lens mold, and then the temperature of the mold may be increased to perform a polymerization reaction between the isocyanate-based compound and the polyfunctional monomer compound. At this time, the mold is heated to a temperature range in which a urethane polymerization reaction occurs, and after the polymerization reaction is completed, the manufactured polymer, specifically, polythiourethane, may be separated from the mold to obtain an optical lens.

[0268]

[0269] For example, an optical lens according to another embodiment of the present invention may have an Abbe number (Ve) of 25 or more, or 28 or more, or 30 or more, or 31 or more, or 31.4 or more, and in practical terms, may be 50 or less, or 45 or less, or 43 or less, or 40 or less, or 38 or less, or 35 or less, or 32 or less. A method for measuring the Abbe number (Ve) is as described in Test Example 2 described below, and a detailed description thereof is omitted.

[0270]

[0271] In addition, the optical lens is a xenon arc light source (illuminance 0.51 W / m 2 @340nm, 50% humidity, 60 temperature oC) After 110 hours of exposure under accelerated conditions, when comparing the YI values ​​before and after exposure, the weather resistance index ΔYI, which is a deviation, may be 0.55 or less, or greater than 0 and 0.55 or less. The weather resistance index ΔYI of the lens may preferably be 0.54 or less, or 0.53 or less, and in some cases, may be 0.01 or more, or 0.05 or more, or 0.1 or more, or 0.2 or more, or 0.3 or more, or 0.4 or more, or 0.45 or more, or 0.47 or more.

[0272]

[0273] The yellowness (YI) of the above lens can be measured using a spectrophotometer (Ultrascan Pro from HunterLab) according to the method of the American Society for Testing and Materials ASTM D1209.

[0274]

[0275] In addition, the optical lens does not show any striae when observed with the naked eye through a xenon lamp as a light source.

[0276]

[0277] Accordingly, the optical lens can minimize cracking and discoloration due to uneven polymerization and maintain excellent transparency.

[0278]

[0279] Meanwhile, an optical lens according to another embodiment of the present invention, even when manufactured using an isocyanate composition that has been stored for a long period of time, such as 12 months as described above with respect to the isocyanate composition, has a yellowness (YI) that is significantly lowered to 5 or less, and there is no concern about discoloration or white clouding even during long-term storage, and can maintain excellent discoloration resistance and improve transparency. Preferably, the yellowness (YI) of the lens may be 4.8 or less, or 4.6 or less, or 4.4 or less, or 4.3 or less, even when manufactured using an isocyanate composition that has been stored for a long period of time, such as 12 months, and in some cases, may be 0.01 or more, or 0.1 or more, or 0.5 or more, or 1 or more, or 1.5 or more, or 3 or more, or 3.5 or more, or 3.8 or more, or 4 or more.

[0280]

[0281] Here, the method for measuring the yellowness (YI) and weatherability index ΔYI of the optical lens described above is as described in Test Example 2 described below, and a detailed description thereof is omitted.

[0282]

[0283] An optical element comprising a polymer polymerized with a polymerizable composition comprising the isocyanate composition of the present invention described above exhibits high transparency and improved impact resistance. Accordingly, the optical element can be usefully used as an eyeglass lens, a camera lens, an adhesive requiring transparency, a resin, and the like.

[0284]

[0285] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0286]

[0287] [Example]

[0288] Manufacturing Example 1: Manufacturing of 3-dichloromethylbenzyl isocyanate (DCMBI)

[0289] To a mixed solution of 10 g (76.3 mmol) of 3-cyanobenzaldehyde and 500 mL of dichloromethane (CH2Cl2, dichloromethane), 76 g (191.6 mmol) of tungsten chloride was added, and the mixture was reacted for 4 hours under reflux of dichloromethane, and then cooled to room temperature. Then, 200 mL of an aqueous sodium bicarbonate solution and 1100 mL of an aqueous 1 N sodium hydroxide solution were slowly added thereto in sequence while maintaining the temperature below 10°C. Then, the organic solvent layer, the dichloromethane layer, was separated, and the aqueous layer was additionally extracted twice with 500 mL of dichloromethane. The dichloromethane layer obtained by this separation and the dichloromethane layer obtained by the extraction process were mixed, and the dichloromethane layer was washed with 800 mL of salt water and then dried with magnesium sulfate. After drying in this way, magnesium sulfate was filtered off from the dichloromethane layer, and dichloromethane was distilled off to obtain a concentrate. Then, 13.2 g of 3-(dichloromethyl)benzonitrile was obtained from the concentrate by silica gel column chromatography.

[0290]

[0291] Next, 135 mL of a tetrahydrofuran solution of borane-dimethylsulfide complex (2 M in THF) was added dropwise to a mixed solution of 10 g (53.8 mmol) of 3-(dichloromethyl)benzonitrile and 150 mL of tetrahydrofuran at room temperature, and the mixture was stirred for 24 hours. After the reaction, the reaction solution was immersed in ice water to cool it down, and 35 mL of a 2 M hydrochloric acid solution was slowly added. Then, 300 mL of ethyl acetate was added to the reaction solution, and the mixture was stirred for 10 minutes. Then, the ethyl acetate layer was separated and removed, and the mixture was immersed in ice water again, and 85 mL of 1 M sodium hydroxide was slowly added to the reaction solution. After this, the reaction solution was extracted four times with 250 mL of dichloromethane, and the obtained dichloromethane layer was dried over magnesium sulfate.

[0292]

[0293] After drying in this manner, magnesium sulfate was filtered from the dichloromethane layer, and then dichloromethane was distilled off to obtain 5.5 g of 3-(dichloromethyl)benzylamine.

[0294]

[0295] Next, a mixed solution of 5.5 g (28.9 mmol) of 3-(dichloromethyl)benzylamine obtained above and 90 mL of o-dichlorobenzene was added dropwise to a mixed solution of 15.1 g (50.9 mmol) of triphosgene and 90 mL of o-dichlorobenzene, and the mixture was reacted at 120°C for 3 hours. After the reaction, the mixture was cooled to room temperature, and o-dichlorobenzene was distilled off to obtain a concentrate. Then, the concentrate was purified by silica gel column chromatography to obtain 3.3 g of 3-(dichloromethyl)benzyl isocyanate (DCMBI).

[0296]

[0297] Examples 1 to 3: Preparation of isocyanate compositions

[0298] After measuring the content of 3-(dichloromethyl)benzyl isocyanate (DCMBI) through GC analysis as shown in Test Example 1 below, 3-(dichloromethyl)benzyl isocyanate (DCMBI) was added to each of meta-xylene diisocyanate (TCI product) so as to obtain the DCMBI content values ​​in Table 1 below, thereby preparing the isocyanate compositions of Examples 1 to 3, respectively.

[0299]

[0300] Comparative Examples 1 to 3: Preparation of isocyanate compositions

[0301] After measuring the content of 3-(dichloromethyl)benzyl isocyanate (DCMBI) through GC analysis as shown in Test Example 1 below, 3-(dichloromethyl)benzyl isocyanate (DCMBI) was added to each of meta-xylene diisocyanate (TCI product) so as to obtain the DCMBI content values ​​in Table 1 below, thereby preparing isocyanate compositions of Comparative Examples 1 to 3, respectively.

[0302]

[0303] [Example 1]

[0304] For the isocyanate compositions of the examples and comparative examples, the content of 3-(dichloromethyl)benzyl isocyanate (DCMBI) was measured by the following method, and the measured values ​​are shown in Table 1 below.

[0305]

[0306] <DCMBI 함량 측정 방법>

[0307] Using DCMBI with a purity of 99 mol% synthesized according to Manufacturing Example 1 as a standard material, the sample was analyzed by gas chromatography under the following conditions, and a calibration curve was created by adding a standard material to an XDI sample. (Standard material addition method)

[0308]

[0309] Next, the XDI compositions of the above-described examples and comparative examples were analyzed by gas chromatography under the following conditions to obtain the molar number of DCMBI. This was converted to mass, and the content ratio of DCMBI in the XDI compositions of each of the examples and comparative examples described below was calculated.

[0310]

[0311] 1. GC measurement conditions

[0312] Device; GC-MS (Agilenet 8890 5977C)

[0313] Column; DB-17MS (30 m x 0.25 mm, 0.25 μm)

[0314] Split B; 3:1

[0315] Inlet temperature; 200℃

[0316] Detector temperature; 280℃

[0317] Oven temperature: 50℃ (maintained for 3 minutes) → 10℃ / min, 280℃ (maintained for 6 minutes)

[0318] carrier gas; He

[0319] Carrier gas flow rate; 1.0ml / min (constant flow control)

[0320] Sample concentration: 1.0 mass% dichloromethane solution

[0321] Injection volume; 1.0μL

[0322] Detection method; SIM mode (monitoring ions: m / z 180, 215)

[0323]

[0324] DCMBI content (ppm) Example 168 Example 2100 Example 3150 Comparative Example 15 Comparative Example 240 Comparative Example 3330

[0325]

[0326] Manufacturing Example 2: Manufacturing of XDI adduct

[0327] Under a nitrogen atmosphere, 300 g of each of the m-XDI compositions of the examples and comparative examples was placed in a round flask and stirred. The temperature of the flask was then raised to 70°C and maintained, followed by dropwise addition of 26.7 g of trimethylolpropane (TMP). After completion of the dropwise addition, the reaction temperature was maintained at 70°C until the isocyanate group concentration reached the calculated value of 33%.

[0328]

[0329] After the reaction was completed, the resulting reactant was purified using a thin film evaporator (TFE) to separate unreacted XDI and obtain an XDI-TMP adduct.

[0330]

[0331] The obtained XDI-TMP adduct was diluted with ethyl acetate and then used (solid content 75 wt%).

[0332]

[0333] The color of the XDI additive thus obtained was measured by sensory evaluation and is shown in Table 2 below.

[0334]

[0335] Manufacturing Example 3: Manufacturing of an optical lens

[0336] Each of the isocyanate compositions manufactured in Examples and Comparative Examples was stirred and mixed at room temperature (23°C) for 20 minutes with 62.4 g, 0.16 g of ZELEC™ UN (manufactured by Stepan) as an internal release agent, and 0.80 g of Tinuvin® 329 (manufactured by BASF) as an ultraviolet absorber, to prepare a mixture. 0.024 g of DBTC (dibutyltin dichloride) was added to the mixture and stirred for 10 minutes. 57.6 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added, and the mixture was stirred for 1 hour while degassing under a pressure condition of 5 mbar to prepare a composition for polyisocyanate polymerization.

[0337]

[0338] The prepared polyisocyanate polymerization composition was filtered using a 1 μm PTFE filter and then injected into a mold formed from a glass mold and tape, respectively. The mold was then placed in an oven and polymerization was performed for 20 hours while gradually increasing the temperature from 10°C to 120°C. After completion of the polymerization, the mold was taken out of the oven and released to obtain each plastic optical lens. The obtained optical lenses were annealed at 120°C for 6 hours to produce optical lenses having a thickness of 9 mm, respectively.

[0339]

[0340] [Example 2]

[0341] For the isocyanate compositions of the examples and comparative examples and the XDI adducts and optical lenses manufactured using the same, the physical properties were evaluated as follows at an initial stage within 5 days after each manufacture, and the measurement results are shown in Table 2 below.

[0342]

[0343] <XDI 조성물의 Cl 함량 측정>

[0344] The content of chlorine (Cl) components was measured through elemental analysis of the isocyanate compositions manufactured in the examples and comparative examples using combustion ion chromatography according to the American Society for Testing and Materials ASTM D 7359 method, and the results are shown in Table 2 below.

[0345]

[0346] <XDI 조성물의 APHA 측정>

[0347] According to the American Society for Testing and Materials ASTM E313 method, the APHA color (color) of each isocyanate composition manufactured in the examples and comparative examples was measured (light source: C / 2) using a spectrophotometer (Ultrascan Pro, HunterLab), and the results are shown in Table 2 below.

[0348]

[0349] Abbe number of the lens

[0350] Each flat lens manufactured using the isocyanate compositions of the examples and comparative examples was brought into close contact with the measurement section of the Abbe refractometer (DR-M4) of ATAGO, and then the refractive index was measured using the C', F', and E' filters, and the Abbe number (ν) was calculated according to the following equation 1. e ) was measured.

[0351] [Formula 1]

[0352]

[0353] In the above equation 1,

[0354] ν e is Abbe's number,

[0355] n e is the refractive index at the Fraunhofere line (wavelength 546.1 nm),

[0356] n F ' is the refractive index at the Fraunhofer F line (wavelength 480.0 nm),

[0357] n C Refractive index at the ':Fraunhofer C' line (wavelength 643.9 nm).

[0358]

[0359] At this time, the higher the Abbe number, the higher the clarity of the lens.

[0360]

[0361] <Weather resistance evaluation of lenses>

[0362] Each lens manufactured using the isocyanate compositions of the examples and comparative examples was exposed to a xenon arc light source (illuminance 0.51 W / m 2 @340nm, 50% humidity, 60 temperature o C) After 110 hours of exposure under accelerated conditions, the YI values ​​before and after exposure were compared.

[0363]

[0364] According to the method of American Society for Testing and Materials ASTM D1209, yellowness (YI) was measured using a spectrophotometer (Ultrascan Pro from HunterLab), and then the difference in yellowness ΔYI between the lenses before and after exposure to a light source was calculated according to Equation 2 below to evaluate weatherability.

[0365] [Formula 2]

[0366] Weatherability (ΔYI) = Lens YI after exposure to light source - YI before exposure to light source.

[0367]

[0368] The smaller the yellowness difference obtained in this way, i.e., the weatherability ΔYI, the less yellowing of the isocyanate (XDI) composition.

[0369]

[0370] Lens Stroke Evaluation

[0371] Each lens manufactured using the isocyanate compositions of the examples and comparative examples was visually observed using a xenon lamp as a light source, and the striae of the lenses were evaluated in the following three stages.

[0372] - No Mac: ◎

[0373] - Slightly noticeable bruising: ○

[0374] - Lots of Macs: Δ.

[0375]

[0376] [Example 3]

[0377] For the isocyanate compositions of the examples and comparative examples, the XDI adducts manufactured using the same, and the optical lenses, the physical properties were evaluated as follows after storage for 12 months, and the measurement results are shown in Table 2 below.

[0378]

[0379] Specifically, the isocyanate compositions of the examples and comparative examples were heated at a temperature of 15 o It was stored in a general tin can under conditions of C for 12 months. Then, after 12 months of storage, APHA measurement, YI measurement after lens manufacturing, and GC analysis of XDI were performed using the isocyanate (XDI) composition in the same manner as in Test Example 2.

[0380]

[0381] In particular, after 12 months of storage, XDI was examined with a fluorescent lamp and a zirconium lamp, respectively, to check for white turbidity with the naked eye, and if white turbidity was confirmed, lens manufacturing was not carried out.

[0382]

[0383] <Content of urethdione in XDI composition after 12 months of storage>

[0384] The content of urethdione in the XDI composition after 12 months of storage was measured by performing infrared spectroscopy (IR) analysis based on the production of urethdione XDI as follows.

[0385]

[0386] (1) Manufacturing of urethdione XDI

[0387] 100 g of xylene diisocyanate (XDI) was added at room temperature under dry nitrogen, and 1 g of trisodecyl phosphite and 2 g of 4-dimethylaminopyridine as catalysts were stirred. After 20 hours, the reaction mixture was quenched with dibutyl phosphate and then subjected to thin-film distillation. After thin-film distillation, uretdione XDI having the following chemical formula 5-1 was obtained.

[0388] [Chemical Formula 5-1]

[0389]

[0390]

[0391] 13 C-NMR (100 MHz, CDCl3) δ156.6, 137.7 135.9, 129.4, 127.4, 126.5, 126.1, 123.3, 46.2, 44.2.

[0392]

[0393] (2) Measurement of urethdione content in XDI composition after 12 months of storage

[0394] XDI of 12-month storage for examples and comparative examples was measured using the ATR mode of an FT-IR spectrometer (Varian 4100).

[0395]

[0396] The manufactured uretdione XDI has an absorption peak of the uretdione carbonyl group (1770-1790 cm -1 ) has. Using the manufactured uretdione XDI as a standard material, a calibration curve was created. In all infrared absorption spectra of XDI stored for 12 months, 1770 cm-1 ~1790 cm -1 An absorption peak with a peak upper portion was observed. The weight of urethdione was calculated based on the absorption coefficient obtained from the calibration curve. Then, the content (%) of urethdione in the XDI composition was derived based on Equation 3 below.

[0397] [Formula 3]

[0398] Uretdione (%) = Weight of uretdione / Weight of total XDI composition X 100.

[0399]

[0400] <IMBAl, IMBAm content ratio in 12-month XDI composition>

[0401] Isocyanatomethyl benzaldehyde (IMBAl) of the following chemical formula 3-1 and isocyanatomethyl benzamide (IMBAm) of the following chemical formula 4-1, which are generated during storage in the isocyanate compositions manufactured in the examples and comparative examples, and their contents were derived by analysis through gas chromatography (GC).

[0402] [Chemical Formula 3-1]

[0403]

[0404] [Chemical Formula 4-1]

[0405] .

[0406]

[0407] Specifically, as a result of performing the analysis under the following conditions, the content ratio of each compound was shown with respect to the total weight of the isocyanate composition, and the retention time of XDI represents a compound of 27.9 to 29.0 minutes, IMBAl represents a compound of 24.7 to 26.4 minutes, and IMBAm represents a compound of 30.7 to 32.8 minutes. Here, the initial content values ​​of each component measured before long-term storage in the isocyanate composition were IMBAl 0.007 wt% and IMBAm 0 wt%.

[0408]

[0409] 1. GC measurement conditions

[0410] Device; GC (Agilenet HP-7890A FID)

[0411] Column; DB-17 (30 m x 0.25 mm, 0.5 μm)

[0412] Split ratio; 100:1

[0413] Inlet temperature; 250 ℃

[0414] Detector temperature; 280 ℃

[0415] Oven temperature: 80℃ → 5℃ / min increase, 160℃ (maintained for 8 minutes) → 20℃ / min increase, 280℃ (maintained for 18 minutes)

[0416] Carrier gas; N2

[0417] Carrier gas flow rate; 1.0 ml / min (constant flow control)

[0418] Sample concentration: 1.0 wt% dichloromethane solution

[0419] Injection volume; 1.0 μL.

[0420]

[0421] For the isocyanate compositions of the examples and comparative examples and the XDI adducts and optical lenses manufactured using the same, the physical properties were evaluated at the initial stage within 5 days after manufacture and after long-term storage for 12 months, as follows, and the measurement results are shown in Table 2.

[0422]

[0423] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 XDI composition, XDI adduct, and initial properties after manufacturing the lens DC MBI (ppm) 68 100 150 540 330 Cl content (ppm) 6 19 5 13 240 49 20 1 Lens Abbe number (Ve) 3 1.4 3 1.7 3 1.8 3 1.3 3 1.2 3 2.2 Strait ◎◎◎◎◎○ Lens weatherability ΔYI 0.4 7 0.4 7 0.5 3 0.5 5 0.5 5 - Color after manufacturing the XDI adduct Transparent Transparent Transparent Cloudy Transparent Yellowish Transparent Physical properties after 12 months of storage APHA of XDI composition 18 16 14 Visible cloudy 30 37 Lens YI 4.2 8 4.2 7 4.1 8 -5.1 5.8 IMBAl in the XDI composition Content (wt%) 0.130.090.060.30.250.05 IMBAm content (wt%) in XDI composition 0.090.070.050.360.420.05 Uretdione content (wt%) in XDI composition 2.71.20.110.15.30.02

[0424]

[0425] As shown in Table 2 above, the isocyanate compositions of Examples 1, 2, and 3, which include DCMBI, a compound represented by Chemical Formula 1, in the isocyanate composition according to the present invention, and optimize the content to 68 ppm, 100 ppm, and 150 ppm, respectively, have improved Abbe numbers when manufacturing lenses compared to Comparative Examples 1 to 3. A higher Abbe number indicates lower dispersion, providing a clear image. In addition, the storage stability is improved even for a long period of time exceeding several months, and the APHA value is significantly lower, so that discoloration and clouding are suppressed, and the increase in the content ratio of uretdione due to impurities that may increase during storage in XDI and self-polymerization of XDI is suppressed, thereby minimizing product deterioration for 12 months, and it can be confirmed that the yellowness of the optical lens can be significantly reduced.

[0426]

[0427] On the other hand, when the content of DCMBI was significantly low, such as 5 ppm in Comparative Example 1, the stability was poor due to the heat exposure process during the manufacturing of the XDI adduct, resulting in a white clouding phenomenon, and haze also occurred in the lenses after 12 months. Even when the content of DCMBI was 40 ppm in Comparative Example 2, the content was insufficient to maintain storage stability, so that the color of XDI itself was not maintained when stored for more than 12 months, and it had APHA 30, and the lenses also had a high yellowness with a YI of 5.1. In addition, the contents of impurities such as IMBAl, IMBAm, and uretdione also showed relatively high values, and in particular, it was confirmed that the content of uretdione increased significantly to 5.3 wt%. In addition, when the content of DCMBI was excessively increased to 330 ppm as in Comparative Example 3, the Cl content of XDI itself was also high at 201 ppm, and the XDI adduct also exhibited a yellowish phenomenon, and it was confirmed that the lens had a high yellowness of YI of 5.8 even when stored for more than 12 months.

[0428]

[0429] Therefore, it can be seen that by optimizing the content of the compound (DCMBI) represented by the chemical formula 1 in the isocyanate composition according to the present invention, the reactivity of xylene diisocyanate (XDI) itself can be controlled, thereby also maintaining excellent stability of XDI itself. In addition, due to this, the storage stability of the isocyanate composition is improved, so that discoloration and white turbidity are suppressed, and excellent discoloration resistance is maintained when applied to optical products, and transparency can be improved, thereby having an excellent effect.

Claims

1. An isocyanate composition comprising xylylene diisocyanate and a compound represented by the following chemical formula 1, wherein the content of the compound represented by the chemical formula 1 is greater than 60 ppm and less than or equal to 200 ppm: [Chemical Formula 1] In the above chemical formula 1, R 1 is hydrogen, methyl, or ethyl.

2. In paragraph 1, The content of the compound represented by the above chemical formula 1 is 62 ppm or more and 180 ppm or less, Isocyanate composition.

3. In paragraph 1, The above isocyanate composition has a chlorine (Cl) content of 200 ppm or less based on the total weight of the isocyanate composition, as measured using combustion ion chromatography according to the American Society for Testing and Materials ASTM D 7359 method. Isocyanate composition.

4. In paragraph 1, The above isocyanate composition has an APHA color index of 0.1 or more and 25 or less, measured using a spectrophotometer (Ultrascan Pro from HunterLab, light source: C / 2) according to the American Society for Testing and Materials ASTM E313 method. Isocyanate composition.

5. In paragraph 1, The above isocyanate composition further comprises at least one selected from the group consisting of chloromethylbenzyl isocyanate, isocyanomethylbenzaldehyde and isocyanomethylbenznitrile. Isocyanate composition.

6. In paragraph 1, The above isocyanate composition has a uretdione content of 5 parts by weight or less based on 100 parts by weight of the isocyanate composition, measured after 12 months of storage. Isocyanate composition.

7. The isocyanate composition of paragraph 1; and At least one of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound; A polymerizable composition comprising:

8. In paragraph 7, Further comprising at least one selected from the group consisting of a polymerization initiator, an internal release agent, and an ultraviolet absorber. Polymerizable composition.

9. An optical article comprising a polymer in which the polymerizable composition of paragraph 7 is polymerized.

10. In paragraph 9, The above article is an optical adhesive, an optical glue, an optical coating, or an optical lens. Optical items.

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