Xylylene diisocyanate composition, its preparation method and use

Abstract

A xylylene diisocyanate composition and its preparation method and use, the xylylene diisocyanate composition comprising xylylene diisocyanate and 0.2 to 500 ppm of a compound represented by formula (1). A resin prepared from the provided xylylene diisocyanate composition has excellent discoloration resistance and can effectively suppress yellowing and / or clouding of the resin.

Description

Technical Field

[0001] This application relates to the technical field of isocyanates, and particularly to xylylene diisocyanate compositions, methods for preparing the same, and uses thereof.

Background Art

[0002] Xylylene diisocyanate belongs to aliphatic isocyanates and has conventionally been used as a raw material for polyurethane resins in various industrial products, particularly widely used in optical materials. Xylylene diisocyanate can be obtained by reacting xylylenediamine with phosgene (carbonyl chloride), and it is known that chlorides are generated as by-products when this reaction is carried out (see, for example, Patent Application GB1194459A).

[0003] However, for polyurethane resins, depending on the purpose and use, it is required to have excellent discoloration resistance. However, polyurethane resins produced from xylylene diisocyanate described in Patent Application GB1194459A may not be able to ensure sufficient discoloration resistance.

[0004] Therefore, in this field, there is an urgent need to provide a xylylene diisocyanate raw material that can stably produce resins with excellent discoloration resistance.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The following is a summary of the main subject to be described in detail in this text. This summary does not limit the scope of the claims.

[0006] In view of the deficiencies of the prior art, the first object of this application is to provide a xylylene diisocyanate composition. The polyurethane resin prepared from the xylylene diisocyanate composition has excellent discoloration resistance performance.

Means for Solving the Problems

[0007] To achieve this object, the present application adopts the following technical solutions. The present application provides a xylylene diisocyanate composition, which comprises xylylene diisocyanate and a compound represented by the formula (1) in an amount of 0.2 to 500 ppm (for example, 0.4 ppm, 0.6 ppm, 0.8 ppm, 1 ppm, 5 ppm, 6 ppm, 10 ppm, 12 ppm, 15 ppm, 20 ppm, 40 ppm, 50 ppm, 60 ppm, 100 ppm, 150 ppm, 200 ppm, 210 ppm, 250 ppm, 300 ppm, 320 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, etc.).

Chemical formula

[0008] The researchers of the present application found in the research that when the xylylene diisocyanate composition contains 0.2 to 500 ppm of the compound of the formula (1), the prepared resin has excellent discoloration resistance performance, effectively suppressing the yellowing and / or turbidity of the resin. When the content is less than 0.2 ppm or more than 500 ppm, the discoloration resistance performance will deteriorate.

[0009] The xylylene diisocyanate composition of the present application is a substantially single compound (i.e., xylylene diisocyanate) containing 97 wt.% or more of xylylene diisocyanate as the main component, but contains the compound represented by the chemical formula (1) as a sub-component, so it is defined as a xylylene diisocyanate composition.

[0010] In the present application, the xylylene diisocyanate composition is denoted as an XDI composition, xylylene diisocyanate is denoted as XDI, and the compound represented by the chemical formula (1) (isocyanatomethylbenzaldehyde) is denoted as IBA.

[0011] Preferably, the xylylene diisocyanate composition further contains a bromine compound. In terms of the mass of bromine element, the content of the bromine-containing compound is 0.5 to 50 ppm. For example, it can be 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 11 ppm, 12 ppm, 13 ppm, 14 ppm, 15 ppm, 16 ppm, 17 ppm, 18 ppm, 19 ppm, 20 ppm, 21 ppm, 22 ppm, 23 ppm, 24 ppm, 25 ppm, 26 ppm, 27 ppm, 28 ppm, 29 ppm, 30 ppm, 31 ppm, 32 ppm, 33 ppm, 34 ppm, 35 ppm, 36 ppm, 37 ppm, 38 ppm, 39 ppm, 40 ppm, 41 ppm, 42 ppm, 43 ppm, 44 ppm, 45 ppm, 46 ppm, 47 ppm, 48 ppm, 49 ppm, etc. If the bromine content is too high, it will cause deterioration of the yellowing resistance performance of the prepared resin. If the bromine content is too low, it will have high activity and cause the prepared resin to become non-uniform.

[0012] In the present application, the contents of the compound represented by formula (1) and the bromine compound are both based on the total mass of the composition.

[0013] Preferably, the xylylene diisocyanate includes any one or at least a combination of two or more of 1,2-xylylene diisocyanate (o-xylylene diisocyanate, o-XDI), 1,3-xylylene diisocyanate (m-xylylene diisocyanate, m-XDI), or 1,4-xylylene diisocyanate (p-xylylene diisocyanate, p-XDI). 1,3-xylylene diisocyanate and / or 1,4-xylylene diisocyanate is preferred, and 1,3-benzomethylene isocyanate is more preferred.

[0014] Preferably, the compound represented by the formula (1) is JPEG0007717827000002.jpg1928, JPEG0007717827000003.jpg1439 or JPEG0007717827000004.jpg1237, including any one or at least a combination of two or more of them.

[0015] In the present application, IBA is produced as a by-product in the production of XDI described below. Of course, it is also possible to artificially add it to obtain the required content. As structural isomers, IBA includes o-IBA, m-IBA, and p-IBA. One or more of these structural isomers of IBA may be included in the XDI composition.

[0016] In the present application, the content ratio of IBA can be measured by analysis using gas chromatography.

[0017] The second object of the present application is to provide a method for preparing the xylylene diisocyanate composition, and the preparation method includes: Step (1): An isocyanation step of subjecting xylylene diamine or xylylene diamine hydrochloride to an isocyanation reaction with phosgene in the presence of a reaction solvent to obtain a reaction product containing xylylene diisocyanate and a compound represented by the formula (1); Step (2): A solvent separation and purification step of removing the solvent from the reaction product obtained in Step (1), purifying the separated solvent to obtain a recycled solvent, and then returning it to the reaction system of Step (1); Step (3): A separation step of separating and purifying the solvent-removed reaction product obtained in Step (2) to obtain the xylylene diisocyanate composition.

[0018] The isocyanation step of Step (1) may be referred to as the phosgenation method, and the isocyanation reaction is a phosgenation reaction.

[0019] Specific examples of the phosgenation method include, for example, a method of directly reacting xylylene diamine with phosgene (which is also a cold-hot two-stage phosgenation method), and a method of reacting a hydrochloride obtained by reacting xylylene diamine with hydrochloric acid (hydrogen chloride) with phosgene in a reaction solvent (also referred to as the phosgenation method of amine hydrochloride). Preferably, the phosgenation method of amine hydrochloride is mentioned.

[0020] Preferably, the xylylenediamine hydrochloride is prepared by a salt formation step, and the salt formation step includes mixing xylylenediamine and hydrogen chloride in the presence of a reaction solvent to carry out a salt formation reaction to obtain the xylylenediamine hydrochloride. What is actually obtained in the salt formation step is a slurry containing xylylenediamine hydrochloride, and the slurry is directly used in the isocyanation step.

[0021] Preferably, the xylylenediamine (XDA) includes any one or at least two combinations of 1,2-xylylenediamine (o-xylylenediamine (o-XDA)), 1,3-xylylenediamine (m-xylylenediamine (m-XDA)), or 1,4-xylylenediamine (p-xylylenediamine (p-XDA)).

[0022] Preferably, the salt formation step includes introducing hydrogen chloride gas into a reaction solvent, then adding a reaction solvent amine solution containing xylylenediamine, and then stirring and mixing the hydrogen chloride gas and the amine solution to carry out a salt formation reaction to obtain the xylylenediamine hydrochloride.

[0023] Preferably, the content of xylylenediamine in the amine solution is 1.0 wt.% or more, for example, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, etc., and preferably 3.0 wt.% or more.

[0024] Preferably, the content of xylylenediamine in the amine solution is 50 wt.% or less, and preferably 30 wt.% or less.

[0025] Preferably, the salt formation temperature in the salt formation step is 0 °C or higher, for example, 1 °C, 5 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc., and it is preferably 10 °C or higher.

[0026] Preferably, the salt formation temperature in the salt formation step is 160 °C or lower, preferably 150 °C or lower, and more preferably 140 °C or lower.

[0027] Preferably, the salt formation step is carried out under normal pressure or pressurized conditions.

[0028] Preferably, the pressure (gauge pressure) in the salt formation step is 0.01 MPaG or higher, for example, 0.1 MPaG, 0.2 MPaG, 0.5 MPaG, 0.6 MPaG, 0.7 MPaG, 0.8 MPaG, 0.9 MPaG, etc., and it is more preferably 0.02 MPaG or higher.

[0029] Preferably, the pressure (gauge pressure) in the salt formation step is 1.0 MPaG or lower, preferably 0.5 MPaG or lower, and more preferably 0.4 MPaG or lower.

[0030] Preferably, step (1) specifically includes introducing phosgene gas into xylylenediamine hydrochloride to carry out an isocyanation reaction to obtain a reaction product containing xylylene diisocyanate and the compound represented by formula (1).

[0031] When carrying out the isocyanation reaction with phosgene using xylylenediamine hydrochloride, the following parameters are suitable, and thus a compound of formula (1) with a target content can be obtained. In addition, by adding IBA to the XDI composition, the content ratio of IBA in the XDI composition can also be adjusted.

[0032] Preferably, the molar amount of the phosgene is 4 times or more the molar amount of the xylylenediamine hydrochloride, for example, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 12 times, 14 times, 16 times, 18 times, 20 times, 22 times, 24 times, 26 times, 28 times, 30 times, 32 times, 34 times, 36 times, 38 times, 40 times, 42 times, 44 times, 46 times, 48 times, etc., and preferably 5 times or more, more preferably 6 times or more.

[0033] Preferably, the molar amount of the phosgene is 50 times or less the molar amount of the xylylenediamine hydrochloride, preferably 40 times or less, more preferably 30 times or less.

[0034] Preferably, the reaction temperature in the isocyanation step is 80°C or higher, for example, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc., and preferably 100°C or higher.

[0035] Preferably, the reaction temperature in the isocyanation step is 180°C or lower, preferably 170°C or lower, more preferably 160°C or lower.

[0036] Preferably, the time of the isocyanation reaction is 2 h or longer, for example, 3 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, etc., and preferably 4 h or longer.

[0037] Preferably, the time of the isocyanation reaction is 25 h or shorter, preferably 20 h or shorter.

[0038] Preferably, the isocyanation reaction is carried out under normal pressure or pressurized conditions.

[0039] Preferably, the pressure (gauge pressure) of the isocyanation reaction is 0 MPaG or more, for example, 0.0004 MPaG, 0.0008 MPaG, 0.001 MPaG, 0.002 MPaG, 0.006 MPaG, 0.01 MPaG, 0.02 MPaG, 0.03 MPaG, 0.05 MPaG, 0.1 MPaG, 0.2 MPaG, 0.3 MPaG, 0.4 MPaG, 0.5 MPaG, 0.6 MPaG, etc., preferably 0.0005 MPaG or more, more preferably 0.001 MPaG or more, even more preferably 0.003 MPaG or more, particularly preferably 0.01 MPaG or more, especially preferably 0.02 MPaG or more, and most preferably 0.03 MPaG or more.

[0040] Preferably, the pressure (gauge pressure) of the isocyanation reaction is 0.6 MPaG or less, preferably 0.4 MPaG or less, and more preferably 0.2 MPaG or less.

[0041] Preferably, the isocyanation step is a batch step or a continuous step, and a continuous step is preferred.

[0042] In the continuous process, the slurry (XDA hydrochloride) produced in the stirring tank is continuously transported from the stirring tank to a reaction tank different from the stirring tank, XDA hydrochloride and phosgene are reacted in the reaction tank, and the reaction liquid (reactants) is continuously taken out from the reaction tank. In the present application, the number of reaction kettles in the continuous process is not particularly limited, and by way of example, it may be 2, 3, 4, 5 or more.

[0043] If necessary, a degassing step, a solvent separation and purification step can be carried out on the reaction product of the isocyanation step, and a known degassing tower is used to remove gases such as the remaining carbonyl chloride gas and hydrogen chloride generated as a by-product from the reaction product. In the solvent separation and purification step, a known distillation tower is used to distill off the reaction solvent from the reaction liquid. After the solvent is purified, most of it returns to the salt formation and isocyanation steps.

[0044] In the present application, as the reaction solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as octane, decane, etc., alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, etc., halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, trichlorobenzene, etc., nitrogen-containing compounds such as nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, N,N'-dimethylimidazolidinone, etc., ethers such as dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc., ketones such as heptanone, diisobutyl ketone, methyl isobutyl ketone, methyl ethyl ketone, etc., fatty acid esters such as ethyl acetate, butyl acetate, pentyl acetate, ethoxyethyl acetate, etc., aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, methyl benzoate, etc. may be mentioned. The reaction solvent can be used alone or in combination of two or more kinds. Among the reaction solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

[0045] The reaction solvent includes a fresh solvent and / or a recycled solvent, and the "fresh solvent" is a reaction solvent that experiences the isocyanation step for the first time or a solvent that is added with the consumption in the solvent system.

[0046] Preferably, the water content of the reaction solvent is 1 to 500 ppm, for example, 2 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 210 ppm, 220 ppm, 230 ppm, 240 ppm, 250 ppm, 260 ppm, 270 ppm, 280 ppm, 290 ppm, 300 ppm, 310 ppm, 320 ppm, 330 ppm, 340 ppm, 350 ppm, 360 ppm, 370 ppm, 380 ppm, 390 ppm, 400 ppm, 410 ppm, 420 ppm, 430 ppm, 440 ppm, 450 ppm, 460 ppm, 470 ppm, 480 ppm, 490 ppm, etc.

[0047] Preferably, the water content of the recycled solvent is 1 to 500 ppm, for example, 2 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 210 ppm, 220 ppm, 230 ppm, 240 ppm, 250 ppm, 260 ppm, 270 ppm, 280 ppm, 290 ppm, 300 ppm, 310 ppm, 320 ppm, 330 ppm, 340 ppm, 350 ppm, 360 ppm, 370 ppm, 380 ppm, 390 ppm, 400 ppm, 410 ppm, 420 ppm, 430 ppm, 440 ppm, 450 ppm, 460 ppm, 470 ppm, 480 ppm, 490 ppm, etc.

[0048] In a preferred technical solution of the present application, controlling the water content of the recycled solvent to 1 to 500 ppm contributes to obtaining a composition in which the IBA content is in the range of 0.2 to 500 ppm. If the water content is too high, it will lead to an increase in side reactions in the isocyanation process and the separation process, and further result in too high an IBA content. If the water content is too low, it is disadvantageous for the production of IBA.

[0049] It should be noted that the water in the fresh solvent is unqualified, and after entering the system, it is necessary to participate in the reaction after the water becomes qualified through solvent purification.

[0050] In the present application, the water content of the reaction solvent and / or the recycled solvent can be controlled by a solvent purification column.

[0051] Preferably, the solvent purification column includes a tray distillation column or a packed distillation column.

[0052] Preferably, the number of theoretical plates of the solvent purification column is 2 or more, for example, 4, 6, 8, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., and preferably 5 or more.

[0053] Preferably, the number of theoretical plates of the solvent purification column is 60 or less, and preferably 40 or less.

[0054] Preferably, the top pressure of the solvent purification column is 0.1 kPa or more, for example, 0.2 kPa, 1 kPa, 5 kPa, 10 kPa, 30 kPa, 50 kPa, 70 kPa, 100 kPa, etc., and preferably 1 kPa or more.

[0055] Preferably, the top pressure of the solvent purification column is 300 kPa or less, and preferably 100 kPa or less.

[0056] Preferably, the reflux ratio at the top of the solvent purification column is 0.01 or more, for example, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 70, 80, 90, etc., and preferably 5 or more.

[0057] Preferably, the reflux ratio at the top of the solvent purification column is 100 or less, and preferably 90 or less.

[0058] Preferably, the water content of the recycled solvent is 1 to 500 ppm, for example, 10 ppm, 20 ppm, 40 ppm, 50 ppm, 80 ppm, 100 ppm, 120 ppm, 140 ppm, 160 ppm, 180 ppm, 200 ppm, 220 ppm, 240 ppm, 260 ppm, 280 ppm, 300 ppm, 320 ppm, 340 ppm, 360 ppm, 380 ppm, 400 ppm, 420 ppm, 440 ppm, 460 ppm, 480 ppm, etc.

[0059] If necessary, a de-tarring step can be carried out on the reaction product of the above solvent removal. Known de-tarring equipment, such as a short-path evaporator, etc., is used to remove the tar components from the reaction solution. Note that the reaction substance from which the tar components have been removed by the de-tarring step is referred to as an intermediate product substance.

[0060] Also, if necessary, the intermediate product substance can be distilled and purified, and the purification method is not particularly limited, and it can be carried out using industrial separation techniques, such as distillation, crystallization, etc.

[0061] Preferably, the distillation is carried out in a distillation column.

[0062] Preferably, the distillation column includes a tray distillation column or a packed distillation column.

[0063] In a preferred technical solution of the present application, by controlling the reaction conditions and separation conditions, the ratio of IBA can be adjusted to the above range. In addition, by adding IBA to the XDI composition, the content ratio of IBA in the XDI composition can also be adjusted.

[0064] Preferably, the number of theoretical plates of the distillation column is 2 or more, for example, 4, 6, 8, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., and preferably 5 or more.

[0065] Preferably, the number of theoretical plates of the distillation column is 60 or less, and preferably 40 or less.

[0066] Preferably, the top pressure of the distillation column is 0.1 kPa or more, for example, 0.2 kPa, 0.4 kPa, 0.6 kPa, 0.8 kPa, 1 kPa, 1.5 kPa, 2 kPa, 2.5 kPa, 3 kPa, 3.5 kPa, etc., and preferably 0.15 kPa or more.

[0067] Preferably, the top pressure of the distillation column is 4 kPa or less, and preferably 2.5 kPa or less.

[0068] Preferably, the top reflux ratio of the distillation column is 0.01 or more, for example, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 18, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, etc., and preferably 0.1 or more.

[0069] Preferably, the top reflux ratio of the distillation column is 60 or less, and preferably 40 or less.

[0070] In a preferred technical solution of the present application, the above method for manufacturing the XDI composition can be implemented, for example, by using the equipment flow diagram shown in FIG. 1. As shown in FIG. 1, it mainly includes one salt formation kettle 1. In the isocyanation unit described later, a three-step continuous isocyanation process (performed in a first phosgenation kettle 2, a second phosgenation kettle 3, and a third phosgenation kettle 4 in sequence) is implemented, and by appropriately adjusting the water content of the above solvent, the supply ratio of phosgene, the reaction temperature, the reaction pressure, the average residence time, etc., the production amounts of XDI and IBA are adjusted. A dephosgenation tower 5 and a solvent removal tower 6 are provided after the phosgenation kettle to perform dephosgenation and solvent removal on the reaction solution. The solvent is reused after the water content is controlled through a solvent purification tower 9. And a tar removal device 7 is provided after the solvent removal tower 6. The reaction product after solvent removal undergoes a tar removal process, and then enters a rectification tower 8 for rectification to obtain the final product.

[0071] And by appropriately adjusting the above tower top reflux ratio, etc. in the rectification separation described later, the content ratio of IBA in the XDI composition is adjusted.

[0072] Specifically, first, a reaction solvent is charged into the salt formation kettle. Then, hydrogen chloride gas is continuously supplied to the bottom of the salt formation kettle through a hydrogen chloride supply line at the above supply ratio. Also, through an amine supply line, the above amine solution in which XDA is dissolved in the reaction solvent is continuously supplied to the top of the salt formation kettle. Then, while maintaining the inside of the salt formation kettle at the above salt formation temperature and salt formation pressure, the hydrogen chloride gas and the amine solution are stirred and mixed with a stirring blade (salt formation process). Thereby, a slurry containing XDA hydrochloride is produced.

[0073] Then, the slurry containing XDA hydrochloride is continuously transported to the top of the phosgenation kettle through a hydrochloride transport line. That is, while continuously supplying hydrogen chloride gas and the amine solution to the salt formation kettle, the slurry containing XDA hydrochloride is continuously taken out from the salt formation kettle and transported to the phosgenation kettle.

[0074] Next, at the above supply ratio, tubes are inserted into the tops of the first phosgenation kettle, the second phosgenation kettle, and the third phosgenation kettle respectively to continuously supply phosgene. Then, while maintaining the inside of the first phosgenation kettle at the above reaction temperature and reaction pressure, the slurry and phosgene are stirred and mixed (isocyanation step of the first step). Thereby, XDA hydrochloride and carbonyl chloride are reacted to produce XDI as the main component, and IBA and bromine-containing compounds or their intermediates are produced as by-products.

[0075] Thereafter, through the reaction substance transport line, the reaction liquid containing XDI, IBA, bromine-containing compounds, and reaction solvent, etc. is continuously transported to the top of the second phosgenation kettle. That is, while continuously supplying the slurry and phosgene to the first phosgenation kettle, the primary phosgenated liquid is continuously taken out from the first phosgenation kettle and transported to the second phosgenation kettle.

[0076] Next, while maintaining the inside of the second phosgenation kettle at the above reaction temperature and reaction pressure, the primary reaction substances and phosgene are stirred and mixed in the second phosgenation kettle (isocyanation step of the second step).

[0077] Similarly, the third phosgenation kettle also performs the phosgenation reaction while introducing the secondary reaction substances (isocyanation step of the third step).

[0078] Thereby, the salt formation step and the isocyanation step are continuously carried out.

[0079] Thereafter, a reaction liquid containing XDI, IBA, bromine-containing compounds or their intermediates, and reaction solvent, etc. is produced. Note that the total residence time in the three-step isocyanation process is within the above range.

[0080] Next, through the reaction substance transport line, the above phosgenation reaction liquid is continuously transported to the middle part of the dephosgenation tower. The dephosgenation tower separates the phosgenated liquid into a gas containing phosgene and hydrogen chloride, etc., and a degassed substance in liquid form containing XDI, IBA, bromine-containing compounds or their intermediates, and reaction solvent, etc. (degassing step).

[0081] Next, the degassed substance is continuously transported into the stripping column through the degassed substance transport line. Then, the stripping column is used to distill off the reaction solvent from the degassed substance (solvent separation and purification step) to obtain a stripped substance containing XDI, IBA, and a bromine-containing compound or an intermediate thereof.

[0082] The reaction solvent returns to the salt formation and photochemical reaction system again through the solvent purification column, and the water content of the recycled solvent is controlled by controlling the operating conditions of the column (top pressure, top reflux ratio, residence time).

[0083] Next, the stripped substance is continuously transported to the upper part of the de-tarring apparatus through the stripped substance transport line. Then, the de-tarring apparatus is used to remove the tar components from the stripped substance to obtain an intermediate substance containing XDI, IBA, and a bromine-containing compound (de-tarring step).

[0084] Next, the intermediate substance is continuously transported into the rectifying column through the intermediate substance transport line. Then, under the conditions of the aforementioned rectifying step (bottom temperature, top temperature, top pressure, bottom reflux ratio, top reflux ratio, and residence time), low boilers are distilled off from the intermediate substance, and an XDI composition is collected from a position slightly below the middle of the column.

[0085] Thereby, an XDI composition containing XDI, IBA, and a bromine-containing compound can be continuously produced.

[0086] A third object of the present application is to provide a modified composition of a xylylene diisocyanate composition, wherein the modified composition is a modified composition obtained by modifying the xylylene diisocyanate composition described in the first object, and the modified xylylene diisocyanate in the modified composition contains (a) an isocyanurate group, (b) a uretdione group, (c) a biuret group, (d) a urethane group, (e) a ureido group, (f) an iminooxadiazinedione group, (g) an allophanate group, (h) a uretoimine group, or (i) a carbodiimide group, or a combination of at least two of them.

[0087] Those skilled in the art can modify the XDI composition using known methods as needed to obtain an XDI-modified composition, which is suitably used as a raw material for polyurethane resins as a polyisocyanate component and an active hydrogen group-containing component.

[0088] More specifically, the modified XDI containing the functional group (isocyanurate group) in (a) above is a trimer of XDI, and can be obtained, for example, by reacting the XDI composition in the presence of a known isocyanuration catalyst to isocyanurate the XDI therein.

[0089] The modified XDI containing the functional group (allophanate group) in (b) above can be obtained by reacting the XDI composition with an alcohol and then further reacting it in the presence of a known allophanatization catalyst.

[0090] The modified XDI containing the functional group (biuret group) in (c) above can be obtained by reacting the XDI composition with, for example, water, a tertiary alcohol (such as tertiary butanol, etc.), a secondary amine (such as dimethylamine, diethylamine, etc.), and then further reacting it in the presence of a known biuretization catalyst.

[0091] The modified XDI containing the functional group (urethane group) in (d) above can be obtained by reacting the XDI composition with a polyol component (such as trimethylolpropane, etc.).

[0092] The modified XDI containing the functional group (ureido group) in (e) above can be obtained by reacting the XDI composition with water, a polyamine component (described later), etc.

[0093] The modified XDI (asymmetric trimer) containing the functional group (iminooxadiazinedione group) in (f) above can be obtained by reacting the XDI composition in the presence of a known iminooxadiazinedionation catalyst to iminooxadiazinedionate (for example, trimerize) the XDI.

[0094] The modified XDI containing the functional group (uretdione group) of the above (g) can be obtained by heating the XDI composition at about 90°C to 200°C or by reacting in the presence of a known uretdionization catalyst to uretdionize (for example, dimerize) XDI.

[0095] The modified XDI containing the functional group (uretonimine group) of the above (h) can be obtained by reacting the XDI composition in the presence of a known carbodiimidization catalyst to form a carbodiimide group and then adding XDI to the carbodiimide group.

[0096] The modified XDI containing the functional group (carbodiimide group) of the above (i) can be obtained by reacting the XDI composition in the presence of a known carbodiimidization catalyst.

[0097] The XDI modified composition may contain at least one of the functional groups of the above (a) to (i), and may contain two or more of them. Such an XDI modified composition can be produced by appropriately using the above reactions in combination. Also, the XDI modified compositions can be used alone or in combination of two or more.

[0098] The fourth object of the present application is to provide a two-component polyurethane raw material, and the two-component polyurethane raw material includes Agent A and Agent B. Agent A includes the xylylene diisocyanate composition described in the first object and / or the modified composition described in the third object. Agent B includes an active hydrogen group-containing substance.

[0099] A two-component resin raw material with an isocyanate component containing an XDI composition and / or an XDI modified composition as Agent A and an active hydrogen group-containing component as Agent B can be suitably used for applications such as coating raw materials such as paints and adhesives, two-component curable seal raw materials, and potting agents. Such a two-component resin raw material is a raw material obtained by blending Agent A (curing agent) and Agent B (main agent) prepared immediately before use.

[0100] The coating raw material is a two-component curable resin raw material for forming a coating layer, and includes Agent A (hardener) and Agent B (main agent). The coating layer may include paints, adhesives, and the like.

[0101] When using the coating raw material as a paint, for example, paints for plastics, automotive exterior paints, automotive interior paints, paints for electrical / electronic materials, paints for optical materials (such as lenses), paints for building materials, glass coating layer paints, woodworking paints, film coating paints, ink paints, paints for artificial leather (coating agents), paints for tanks (coating agents), etc. can be mentioned.

[0102] Regarding Agent A, for example, as a polyisocyanate component, it includes, for example, an XDI modified composition (hereinafter referred to as the XDI modified composition for coating), preferably an XDI modified composition containing the functional group (isocyanurate group) of (a) above, and / or an XDI modified composition containing the functional group (urethane group) of (d) above. Also, if necessary, Agent A may include other aromatic isocyanates, aliphatic isocyanates, and araliphatic isocyanates.

[0103] In the XDI modified composition, the content ratio of IBA in the XDI composition used for modification is 0.2 ppm or more and 500 ppm or less.

[0104] When the content ratio of IBA in the XDI composition for coating is within the above range, discoloration of the coating material can be suppressed.

[0105] Regarding Agent B, for example, as an active hydrogen group-containing component, it includes, for example, the above-mentioned high molecular weight polyol. Regarding the high molecular weight polyol as a coating raw material (hereinafter referred to as the high molecular weight polyol for coating), for example, the above-mentioned acrylic polyol, the above-mentioned polyester polyol, and the above-mentioned fluoropolyol can be mentioned.

[0106] Further, if necessary, a urethanization catalyst, a hydrolysis inhibitor, an antifoaming agent, a surfactant, a sliding property imparting agent, a surface conditioner, an antioxidant, a weather stabilizer, a pigment, a dye, a filler, a resin powder, etc. can be blended with Agent B in an appropriate ratio.

[0107] As a method for forming the coating material, for example, Agent A and Agent B are mixed, and the mixed solution is applied to a coating target object and cured using a known method.

[0108] Thereby, the coating material can be formed. Such a coating material is excellent in discoloration resistance.

[0109] The color difference (Δb) of the coating layer in the damp heat durability test (2000 hours) is, for example, 0.5 or more, for example, 2.4 or less, preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.9 or less.

[0110] The fifth object of the present application is to provide a polyurethane resin, and the polyurethane resin is obtained by reacting the xylylene diisocyanate composition described in the first object with an active hydrogen group-containing substance, or by reacting the modified composition described in the third object with an active hydrogen group-containing substance.

[0111] Examples of the active hydrogen group-containing substance include a polyol component (a component containing a polyol having two or more hydroxyl groups mainly), a polythiol component (a component containing a polythiol having two or more mercapto groups (thiol groups)), a polyamine component (a compound containing a polyamine having two or more amino groups mainly), etc.

[0112] Examples of the polyol component include a low molecular weight polyol and a high molecular weight polyol.

[0113] The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400.

[0114] Examples of low molecular weight polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane(7-22)diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol(C17-20), isosorbide, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octenyl-3,8-diol, diols such as bisphenol A, trihydric alcohols such as glycerin, trimethylolpropane, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, pentaols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, galactitol, talitol, inositol, dipentaerythritol, heptahydric alcohols such as berseitol, octahydric alcohols such as sucrose, and the like.

[0115] In addition, polyalkylene oxides having a number average molecular weight of 60 or more and less than 400 (random and / or block copolymers containing two or more alkylene oxides), obtained by adding alkylene oxides such as ethylene oxide and propylene oxide using the above alcohols as initiators, are also included in the low molecular weight polyols.

[0116] The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, for example, 10,000 or less, preferably 5,000 or less. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic acid-based polyol, polysiloxane polyol, fluoropolyol, and vinyl monomer-modified polyol.

[0117] Examples of the polyether polyol include polyoxy (C2-C3) alkylene polyol, polytetramethylene ether glycol, and polytrimethylene ether glycol. Examples of the polyoxy (C2-C3) alkylene polyol include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide using the above low molecular weight polyol as an initiator (random and / or block copolymers containing two or more alkylene oxides). Specific examples of the polyoxy (C2-3) alkylene group also include polyethylene glycol, polypropylene glycol, and polyethylene polypropylene copolymer.

[0118] Examples of the polytetramethylene ether glycol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran (polytetramethylene ether glycol), and an amorphous polytetramethylene ether glycol obtained by copolymerizing the polymerization unit of tetrahydrofuran with the above diol.

[0119] Also included is a plant-derived polytetramethylene ether glycol using tetrahydrofuran produced from a plant-derived raw material such as furfural as a starting material.

[0120] Examples of the polytrimethylene ether glycol include a polyol produced by polycondensation of plant-derived 1,3-propanediol.

[0121] Examples of the polyester polyol include a polycondensate obtained by reacting the above low molecular weight polyol (preferably a diol) with a polybasic acid (preferably a dibasic acid) under known conditions.

[0122] Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (C11 - C13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1 - dimethyl - 1,3 - dicarboxypropane, 3 - methyl - 3 - ethylglutaric acid, azelaic acid, sebacic acid, etc.; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc.; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.; alicyclic dicarboxylic acids such as hexahydrophthalic acid, etc.; other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, etc.; and acid anhydrides derived from these carboxylic acids such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2 - alkyl (C12 - C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, etc.; and acid halides derived from these carboxylic acids such as oxalyl chloride, adipic acid chloride, dodecanedioyl dichloride, etc.

[0123] Examples of the polyester polyol also include vegetable oil - based polyester polyols obtained by subjecting the above low molecular weight polyol to a condensation reaction with a hydroxyl - carboxylic acid such as a vegetable oil fatty acid containing a hydroxyl group (e.g., castor fatty acid containing ricinoleic acid, hydrogenated castor fatty acid containing 12 - hydroxystearic acid, etc.).

[0124] Examples of the polyester polyol further include polycaprolactone polyols, polyvalerolactone polyols obtained by ring - opening polymerization of lactones such as ε - caprolactone, γ - valerolactone, etc. using the above low molecular weight polyol (preferably a diol) as an initiator, and lactone - based polyester polyols obtained by copolymerizing them with the above diol.

[0125] Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above low molecular weight polyol (preferably diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above diol with the ring-opening polymer.

[0126] Regarding the polyurethane polyol, examples include polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol obtained by reacting the polyester polyol, polyether polyol, and / or polycarbonate polyol obtained by the above method with the above polyisocyanate (including XDI; the same applies hereinafter) at a ratio where the equivalent ratio (OH / NCO) of the hydroxyl group to the isocyanate group exceeds 1.

[0127] Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

[0128] Examples of the vegetable oil polyol include vegetable oils containing a hydroxyl group such as castor oil and coconut oil. For example, castor oil polyol, or an ester-modified castor oil polyol obtained by reacting castor oil polyol with polypropylene polyol.

[0129] Examples of the polyolefin polyol include polybutadiene polyol and a partially saponified ethylene-vinyl acetate copolymer.

[0130] Examples of the acrylic acid-based polyol include a copolymer obtained by copolymerizing an acrylate containing a hydroxyl group with a copolymerizable vinyl monomer copolymerizable with the acrylate containing a hydroxyl group.

[0131] Examples of the acrylate containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyl alkyl maleate, polyhydroxyl alkyl fumarate, etc. Preferably, 2-hydroxyethyl (meth)acrylate, etc. are mentioned.

[0132] Examples of the copolymerizable vinyl monomer include (meth)acrylic acid alkyl esters (having 1 to 12 carbon atoms) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl acrylate, isobornyl (meth)acrylate, etc., and examples include styrene, vinyltoluene, α-methylstyrene, etc.

[0133] The aromatic vinyl monomer is, for example, vinyl cyanide such as (meth)acrylonitrile, vinyl monomer containing a carboxyl group such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, etc., or its alkyl ester, and examples include alkane polyol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc., and vinyl monomer containing an isocyanate group such as 3-(2-isocyanate-2-propyl)-α-methylstyrene, etc.

[0134] The acrylic polyol can be obtained by copolymerizing these acrylates containing hydroxyl groups and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

[0135] The acrylic polyol includes, for example, polysiloxane polyol and fluoropolyol.

[0136] Examples of the polysiloxane polyol include an acrylic polyol obtained by blending a polysiloxane compound containing a vinyl group, such as γ-methacryloxypropyltrimethoxysilane, as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol.

[0137] Examples of the fluoropolyol include an acrylic polyol obtained by blending a fluorine compound containing a vinyl group, such as tetrafluoroethylene and chlorotrifluoroethylene, as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol.

[0138] The vinyl monomer-modified polyol can be obtained by reacting the above high molecular weight polyol with a vinyl monomer such as the above (meth)acrylate alkyl ester.

[0139] The above polyol component can be used alone or in combination of two or more.

[0140] In the reaction of the polyisocyanate component and the active hydrogen group-containing component, when the equivalent ratio of the active hydrogen group to the isocyanate group is less than 1, an isocyanate group-terminated polymer having an isocyanate group at the molecular end is formed, and when the equivalent ratio of the active hydrogen group to the isocyanate group exceeds 1, an active hydrogen group-terminated polymer having an active hydrogen group at the molecular end is formed. Both the isocyanate group-terminated polymer and the active hydrogen group-terminated polymer are included in the resin (polyurethane resin). The isocyanate group-terminated polymer is a one-component curable resin.

[0141] As uses of the polyurethane resin, specifically, inks, transfer foils, adhesives, binders, gels, elastomers, foams, adhesives, liquid-curing sealants, RIM molded products, microcellular polyurethanes, various microcapsules, optical materials, aqueous resins, thermosetting resins, active energy ray (e.g., electron beam, ultraviolet ray, etc.) curable resins, artificial and synthetic leathers, coagulation powders, robot members, moving members, medical and healthcare materials, base resins for carbon fiber reinforced plastics (CFRP), transparent rubbers, transparent rigid resins, waterproof materials, films, sheet materials, tubes, plates, speakers, sensors, organic electroluminescence members, solar power generation members, robot members, wearable members, sports goods, leisure goods, medical supplies, nursing care supplies, housing members, acoustic members, lighting members, chandeliers, outdoor electric lights, packaging, anti-vibration / anti-seismic / vibration damping members, soundproofing members, daily necessities, sundries, shock absorbers, bedding, stress absorbing materials, stress relaxing materials, interior and exterior members of automobiles, transportation machine members, members for office automation equipment, surface protection members for sundries, self-healing materials, health appliances, etc., can be suitably used.

[0142] The sixth object of the present application is to provide an elastomer material, and the elastomer material contains the polyurethane resin described in the fifth object.

[0143] Examples of the elastomer include thermoplastic polyurethane elastomer (TPU), thermosetting polyurethane elastomer (TSU), rollable polyurethane elastomer, and the like.

[0144] The elastomer contains a soft segment formed by the reaction of XDI and a high molecular weight polyol, and a hard segment formed by the reaction of XDI and a low molecular weight polyol and / or a low molecular weight polyamine.

[0145] Such an elastomer can be produced, for example, by the reaction of a polyisocyanate component, a high molecular weight polyol (active hydrogen group-containing component), and a low molecular weight polyol and / or a low molecular weight polyamine (active hydrogen group-containing component). That is, the polyisocyanate component, the high molecular weight polyol, and the low molecular weight polyol and / or the low molecular weight polyamine are elastomer raw materials.

[0146] Regarding the high molecular weight polyol that is an elastomer raw material, for example, the above-mentioned polyester polyol (for example, polycaprolactone polyol, adipic acid-based polyester polyol (polyester polyol using adipic acid as a polybasic acid)), the above-mentioned polycarbonate polyol, and the above-mentioned polytetramethylene ether glycol (for example, polytetramethylene ether glycol) can be mentioned, and preferably adipic acid-based polyester polyol can be mentioned.

[0147] Regarding the low molecular weight polyol that is an elastomer raw material, for example, ethylene glycol, 1,4-butanediol, etc. can be mentioned, and preferably 1,4-butanediol can be mentioned.

[0148] Regarding the low molecular weight polyamine that is an elastomer raw material, for example, the above-mentioned low molecular weight polyamine can be mentioned.

[0149] The elastomer can be produced, for example, by a known method such as a one-shot method or a prepolymer method.

[0150] Regarding the production method of the elastomer, for example, bulk polymerization, solution polymerization, etc. can be used.

[0151] In the method for producing an elastomer, if necessary, known urethanization catalysts such as amines and organometallic compounds (e.g., organotin compounds, preferably dibutyldichlorotin, etc.) may be added to the elastomer raw materials. Further, if necessary, a plasticizer, an antiblocking agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a yellowing inhibitor, an antioxidant, a release agent, a pigment, a dye, a lubricant, a nucleating agent, a filler, a hydrolysis inhibitor, etc. may be blended with the elastomer in appropriate proportions.

[0152] Thereby, an elastomer can be produced. Such an elastomer not only suppresses clouding and has excellent color fastness, but also has excellent mechanical properties (elongation and strength).

[0153] The color difference (Δb) of the elastomer during the xenon lamp irradiation test (240 hours) is, for example, 1.0 or more, for example, less than 3.9, preferably 3.5 or less, and more preferably 3.0 or less. The color difference of the elastomer in the xenon lamp irradiation test is measured according to the method described in the examples below.

[0154] The seventh object of the present application is to provide an optical material, which is obtained by polymerizing the xylylene diisocyanate composition described in the first object and a polythiol compound, or by polymerizing the modified composition described in the third object and a polythiol compound.

[0155] In the present application, the polythiol compound is a compound containing at least two thiol groups.

[0156] Preferably, the optical material includes a plastic lens material, an automotive lamp cover material, a transparent roofing material, a lens material for a smartphone or a tablet.

[0157] Preferably, the polythiol compound is an aliphatic polythiol compound such as methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, bis(2-mercaptoethyl) thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), tetra(mercaptomethyl)methane; Aromatic polythiol compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tri(mercaptomethyl)benzene, 1,2,4-tri(mercaptomethyl)benzene, 1,3,5-tri(mercaptomethyl)benzene, 1,2,3-tri(mercaptoethyl)benzene, 1,2,4-tri(mercaptoethyl)benzene, 1,3,5-tri(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane; Aromatic polythiol compounds containing sulfur atoms other than mercapto groups, such as 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tri(mercaptomethylthio)benzene, 1,2,4-tri(mercaptomethylthio)benzene, 1,3,5-tri(mercaptomethylthio)benzene, 1,2,3-tri(mercaptoethylthio)benzene, 1,2,4-tri(mercaptoethylthio)benzene, 1,3,5-tri(mercaptoethylthio)benzene, and their alkylated products; Bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tri(mercaptomethylthio)propane, 1,2,3-tri(2-mercaptoethylthio)propane, 1,2,3-tri(3-mercaptopropylthio)propane, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, bis(1,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, and other aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups, and esters of these with mercaptoacetic acid and mercaptopropionic acid; Other aliphatic polythiol compounds containing sulfur atoms and ester bonds in addition to mercapto groups, such as hydroxymethylsulfide bis(2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate), hydroxyethylsulfide bis(2-mercaptoacetate), hydroxyethylsulfide bis(3-mercaptopropionate), hydroxypropylsulfide bis(2-mercaptoacetate), hydroxypropylsulfide bis(3-mercaptopropionate), hydroxymethyldisulfide bis(2-mercaptoacetate), hydroxymethyldisulfide bis(3-mercaptopropionate), hydroxyethyldisulfide bis(2-mercaptoacetate), hydroxyethyldisulfide bis(3-mercaptopropionate), hydroxypropyldisulfide bis(2-mercaptoacetate), hydroxypropyldisulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), thiodiacetic acid bis(2-mercaptoethyl), thiodipropionic acid bis(2-mercaptoethyl), 4,4'-thiodibutyric acid bis(2-mercaptoethyl), dithiodiacetic acid bis(2-mercaptoethyl), dithiodipropionic acid bis(2-mercaptoethyl), 4,4'-dithiodibutyric acid bis(2-mercaptoethyl), thiodiacetic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiacetic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid bis(2,3-dimercaptopropyl ester); Heterocyclic compounds containing sulfur atoms in addition to mercapto groups, such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole; Compounds containing a hydroxyl group in addition to a mercapto group, such as 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tri(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tri(mercaptoacetate), dipentaerythritol penta(3-mercaptopropionate), hydroxymethyl-tri(mercaptoethylthiomethyl)methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene; 1,1,3,3 - Tetrakis(mercaptomethylthio)propane, 1,1,2,2 - Tetrakis(mercaptomethylthio)ethane, 4,6 - Bis(mercaptomethylthio)-1,3 - dithiacyclohexane, 1,1,5,5 - Tetrakis(mercaptomethylthio)-3 - thiapentane, 1,1,6,6 - Tetrakis(mercaptomethylthio)-3,4 - dithiahexane, 2,2 - Bis(mercaptomethylthio)ethyl mercaptan, 2-(4,5 - Dimercapto - 2 - thiopentyl)-1,3 - dithiacyclopentane, 2,2 - Bis(mercaptomethyl)-1,3 - dithiacyclopentane, 2,5 - Bis(4,4 - Bis(mercaptomethylthio)-2 - thiabutyl)-1,4 - dithiane, 2,2 - Bis(mercaptomethylthio)-1,3 - propanedithiol, 3 - Mercaptomethylthio - 1,7 - dimercapto - 2,6 - dithiaheptane, 3,6 - Bis(mercaptomethylthio)-1,9 - dimercapto - 2,5,8 - trithianonane, 4,6 - Bis(mercaptomethylthio)-1,9 - dimercapto - 2,5,8 - trithianonane, 3 - Mercaptomethylthio - 1,6 - dimercapto - 2,5 - dithiahexane, 2-(2,2 - Bis(mercaptomethylthio)ethyl)-1,3 - dithiacyclobutane, 1,1,9,9 - Tetrakis(mercaptomethylthio)-5-(3,3 - Bis(mercaptomethylthio)-1 - thiapropyl)3,7 - dithianonane, Tri(2,2 - Bis(mercaptomethylthio)ethyl)methane, Tri(4,4 - Bis(mercaptomethylthio)-2 - thiabutyl)methane, Tetra(2,2 - Bis(mercaptomethylthio)ethyl)methane, Tetra(4,4 - Bis(mercaptomethylthio)-2 - thiabutyl)methane, 3,5,9,11 - Tetrakis(mercaptomethylthio)-1,13 - dimercapto - 2,6,8,12 - tetrathiatridecane, 3,5,9,11,15,17 - Hexakis(mercaptomethylthio)-1,19 - dimercapto - 2,6,8,12,14,18 - hexathianonadecane, 9-(2,2 - Bis(mercaptomethylthio)ethyl)-3,5,13,15 - Tetrakis(mercaptomethylthio)-1,17 - dimercapto - 2,6,8,10,12,16 - hexathiaheptadecane, 3,4,8,9 - Tetrakis(mercaptomethylthio)-1,11 - dimercapto - 2,5,7,10 - Tetrathiaundecane, 3,4,8,9,13,14 - hexa(mercaptomethylthio)-1,16 - dimercapto - 2,5,7,10,12,15 - hexathiahexadecane, 8 - {bis(mercaptomethylthio)methyl}-3,4,12,13 - tetra(mercaptomethylthio)-1,15 - dimercapto - 2,5,7,9,11,14 - hexathiapentadecane, 4,6 - bis{3,5 - bis(mercaptomethylthio)-7 - mercapto - 2,6 - dithiaheptylthio}-1,3 - dithiane, 4 - {3,5 - bis(mercaptomethylthio)-7 - mercapto - 2,6 - dithiaheptylthio}-6 - mercaptomethylthio - 1,3 - dithiane, 1,1 - bis{4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-3,3 - bis(mercaptomethylthio)propane, 1,3 - bis{4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-1,3 - bis(mercaptomethylthio)propane, 1 - {4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-3 - {2,2 - bis(mercaptomethylthio)ethyl}-7,9 - bis(mercaptomethylthio)-2,4,6,10 - tetrathiaundecane, 1 - {4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-3 - {2-(1,3 - dithiacyclobutyl)}methyl - 7,9 - bis(mercaptomethylthio)-2,4,6,10 - tetrathiaundecane, 1,5 - bis{4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-3 - {2-(1,3 - dithiacyclobutyl)}methyl - 2,4 - dithiapentane, 4,6 - bis[3 - {2-(1,3 - dithiacyclobutyl)}methyl - 5 - mercapto - 2,4 - dithiapentylthio]-1,3 - dithiane, 4,6 - bis{4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-1,3 - dithiane, 4 - {4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-6 - {4-(6 - mercaptomethylthio)-1,3 - dithianylthio}-1,3 - dithiane, 3 - {2-(1,3 - dithiacyclobutyl)}methyl - 7,9 - bis(mercaptomethylthio)-1,11 - dimercapto - 2,4,6,10 - tetrathiaundecane, 9 - {2-(1,3 - dithiacyclobutyl)}methyl - 3,5,13,15 - tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiadecane, 3-{2-(1,3-dithiacyclobutyl)}methyl-7,9,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiadecane, 3,7-bis{2-(1,3-dithiacyclobutyl)}methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4-{3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathioundecane}-5-mercaptomethylthio-1,3-dithiacyclopentane, 4,5-bis{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}-1,3-dithiacyclopentane, 4-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}-5-mercaptomethylthio-1,3-dithiacyclopentane, 4-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl}-5-mercaptomethylthio-1,3-dithiacyclopentane, 2-[bis{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}methyl]-1,3-dithiacyclobutane, 2-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-{3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathioundecanethio}mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl}mercaptomethylthiomethyl-1,3-dithiacyclobutane, 4,5-bis[1-{2-(1,3-dithiacyclobutyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiacyclopentane, 4-[1-{2-(1,3-dithiacyclobutyl)}-3-mercapto-2-thiapropylthio]-5-{1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio}-1,Compounds having a dithioacetal or dithioketal skeleton such as 3-dithiacyclopentane, 2-[bis{4-(5-mercaptomethylthio-1,3-dithiolane)thio}]methyl-1,3-dithiacyclobutane, 4-{4-(5-mercaptomethylthio-1,3-dithiolane)thio}-5-[1-{2-(1,3-dithiacyclobutyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiacyclopentane, and their oligomers; Tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, 1,1,5,5-tetra(mercaptomethylthio)-2,4-dithiapentane, bis(4,4-bis(mercaptomethylthio)-1,3-dithiabutyl)(mercaptomethylthio)methane, tris(4,4-bis(mercaptomethylthio)-1,3-dithiabutyl)methane, 2,4,6-tri(mercaptomethylthio)-1,3,5-trithiacyclohexane, 2,4-bis(mercaptomethylthio)-1,3,5-trithiacyclohexane, 1,1,3,3-tetra(mercaptomethylthio)-2-thiapropane, bis(mercaptomethyl)methylthio-1,3,5-trithiacyclohexane, tris((4-mercaptomethyl-2,5-dithiacyclohexyl-1-yl)methylthio)methane, 2,4-bis(mercaptomethylthio)-1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane, 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiacyclopentane, tris(2,2-bis(mercaptomethylthio)-1-thiaethyl)methane, tris(3,3-bis(mercaptomethylthio)-2-thiapropyl)methane, tris(4,4-bis(mercaptomethylthio)-3-thiabutyl)methane, 2,4,6-tri(3,3-bis(mercaptomethylthio)-2-thiapropyl)-1,3,5-trithiacyclohexane, tetra(3,3-bis(mercaptomethylthio)-2-thiapropyl)methane, etc., and compounds having an orthotrithioate skeleton such as their oligomers; Selected from compounds having an orthotetrathiocarbonate ester skeleton such as 3,3'-bis(mercaptomethylthio)-1,5-dimercapto-2,4-dithiapentane, 2,2'-bis(mercaptomethylthio)-1,3-dithiacyclopentane, 2,7-bis(mercaptomethyl)-1,4,5,9-tetrathiaspiro[4,4]nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro[5,5]undecane, and oligomers thereof.

[0158] However, the polythiol compound is not limited to the compounds listed above. Also, each of the compounds listed above may be used alone or in combination of two or more.

[0159] Among the compounds listed above, particularly preferably, at least one polythiol compound selected from the group consisting of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetra(3-mercaptopropionate), 1,1,3,3-tetra(mercaptomethylthio)propane, and 2-mercaptoethanol is used.

[0160] Preferably, the method for preparing the optical material is carried out in the presence of a polymerization catalyst, and the polymerization catalyst is preferably an organotin compound, and examples thereof include dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride, and dialkyltin dicarboxylic acids such as dimethyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate.

[0161] Also, according to the purpose, in the method for producing the optical material, various auxiliary agents such as a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, and a mold release agent may be added as necessary.

[0162] Optical materials made of polyurethane resins are usually manufactured by injection polymerization. Specifically, a polythiol compound and an isocyanate compound are mixed, and appropriate auxiliaries may be added. If necessary, after defoaming this mixed solution (polymerizable composition) by adopting an appropriate method, it is injected into a mold for optical materials, and usually polymerized by gradually heating from a low temperature to a high temperature. Then, the optical material is obtained by demolding.

[0163] When the content ratio of IBA in the XDI composition or XDI-modified composition for optical materials is 0.2 ppm or more and 500 ppm or less, an optical material can be stably manufactured from the XDI composition or XDI-modified composition for optical materials. When the content ratio of IBA in the XDI composition or XDI-modified composition for optical materials is below the above upper limit, discoloration of the optical material can be suppressed.

[0164] The yellowing index YI of the optical material according to the present application can be controlled within 1.7 and at least 1.5.

Advantages of the Invention

[0165] Compared with the prior art, the present application has the following beneficial effects. The xylylene diisocyanate composition according to the present application contains 0.2 to 500 ppm of the compound of formula (1), and the prepared resin has excellent discoloration resistance performance and effectively suppresses yellowing and / or clouding of the resin.

[0166] After understanding through reading the detailed description, other aspects can be clarified.

Brief Description of the Drawings

[0167]

Figure 1

Explanation of Reference Numerals

[0168] 1 - Salt formation kettle, 2 - First phosgenation kettle, 3 - Second phosgenation kettle, 4 - Third phosgenation kettle, 5 - De-phosgenation tower, 6 - Solvent removal tower, 7 - Tar removal device, 8 - Rectification tower, 9 - Solvent purification tower.

Embodiment for Carrying out the Invention

[0169] (1) In the present application, the measurement methods for related tests are as follows.

[0170] 1. Content ratio of compound IBA First, using IBA with a purity of 99 mol% synthesized as described below as a standard substance, it was analyzed by gas chromatography under the following conditions, and a calibration curve was created from the area values of the obtained gas chromatogram (external standard method). Analytical instrument: Agilent 5977B GCMS, Column: DB-5 (30m × 0.25mm × 0.25um), Oven temperature: Held at 50°C for 2 minutes, heated to 80°C at a rate of 5 mL / min, then heated to 280°C at a rate of 15 mL / min and held for 10 minutes, Separation ratio: Splitless, Inlet temperature: 280°C, Detection temperature: 300°C, Carrier gas: Helium gas, Carrier gas flow rate: 1 mL / min (constant flow rate), Injection volume: 1 μL, Detection method: For SIM, the ion scan mode (161, 132) was selected.

[0171] 2. Content ratio of xylylene diisocyanate Using XDI with a purity of 99 mol% in the examples described below as a standard substance, it was analyzed by gas chromatography under the following conditions using the internal standard method. Instrument: Agilent 7890. (1) Column: DB-5 (30 m × 0.25 mm × 0.25 μm), (2) Injection volume: 0.5 μL, (3) Split ratio: 1 / 30, (4) Injection port temperature: 260 °C, (5) Column flow rate: 1.5 mL / min, (6) Programmed temperature rise: Hold at 100 °C for 1 minute, increase the temperature to 280 °C at 10 °C / min, and hold for 20 minutes, (7) FID detector temperature: 280 °C, (8) Hydrogen gas flow rate: 40 mL / min, air flow rate: 400 mL / min.

[0172] 3. The bromine element content in XDI was measured by ICP-OES analysis. Equipment: Thermo Scientific ICAP 7200 ICP-OES.

[0173] 4. The water content of the recycled solvent was measured by a Karl Fischer moisture meter. Equipment: Metrohm915 KF Ti-Touch.

[0174] 5. Calculation of the yellow index value (Y.I. value) of the optical material The yellow index of the lens was measured according to Chinese standard GB / T-2409-1980.

[0175] The optical materials of each of the following examples and comparative examples were made into circular flat plastic lenses with a thickness of 9 mm and a diameter of 75 mm. Using a spectrophotometer, the tristimulus values x, y, and z were measured. Y.I. was calculated using the following formula.

Equation

[0176] Note that the smaller the Y.I. value, the better the hue of the plastic lens, and the larger the Y.I. value, the worse the hue.

[0177] 6. Weather resistance test of the elastomer Next, using an injection molding machine (model number: NEX-140, Taifu Machinery), the elastomers of the following examples and comparative examples were injection molded under the conditions of a screw rotation speed of 100 rpm, a barrel temperature of 150 to 235 °C, a mold temperature of 20 °C, an injection time of 10 seconds, an injection speed of 60 mm / s, and a cooling time of 45 seconds.

[0178] Under the constant temperature and humidity conditions of 23 °C and a relative humidity of 55%, the obtained sheet material (thickness: 2 mm) was cured for 7 days to obtain the elastomer sheet materials of the following examples and comparative examples.

[0179] Then, after measuring the b value (b1, initial value) of the elastomer sheet material with a colorimetric pigment meter, a xenon lamp irradiation test was carried out. After 240 hours elapsed, the b value (b2) of the elastomer sheet material was measured in the same manner as above. The color difference Δb (=|b2 - b1|) of the elastomer sheet material in the xenon lamp irradiation test (240 hours) was calculated.

[0180] Regarding the xenon lamp irradiation test, a super xenon weather meter (Weibang Instruments) was used, and the test was carried out under the conditions of a black panel temperature of 89 °C, a relative humidity of 50%, and a xenon lamp irradiance of 100 W / m 2 (irradiation wavelength 300 - 400 nm).

[0181] 7. Color difference (color change) in the damp heat durability test of the coating layer The b value (b1, initial value) of a polyethylene terephthalate substrate (hereinafter referred to as a sample) with a coating layer formed thereon in each of the following examples and comparative examples was measured with a color difference meter (3nh NR10QC). Next, using a thermo-hygrostat (Gaotie Instruments), the sample was held for 2000 hours under the conditions of 85 °C and a relative humidity of 85%. After 2000 hours elapsed, the b value (b2) of the sample was measured in the same manner as above. The color difference Δb (=|b2 - b1|) of the coating layer in the damp heat test was calculated.

[0182] (2) Preparation of reference substances According to the following synthesis route, IBA shown in the above chemical formula (1) was synthesized. [Chemistry]

[0183] To a 50 mL three-necked flask equipped with a reflux condenser and a water separator, 6.5 g (50 mmol) of 3-cyanobenzaldehyde, 4.35 g (70 mmol) of ethylene glycol, 15 mL of cyclohexane as a water-carrying agent, and 0.4 g (6% of the mass of 3-cyanobenzaldehyde) of diatomaceous earth were added. After heating under reflux with stirring for 2 hours, it was cooled, the diatomaceous earth was filtered off and recovered, and after removing cyclohexane by rotary evaporation, 7.88 g of colorless transparent aromatic liquid 3-cyanobenzaldehyde ethylene acetal was obtained, and the yield was 90%.

[0184] At room temperature, 10.1 mL (19.2 mmol) of a tetrahydrofuran solution of borane-dimethyl sulfide complex was added dropwise to a mixed solution of 674 mg (3.85 mmol) of 3-cyanobenzaldehyde ethylene acetal and 14.0 mL of tetrahydrofuran, and then stirred for 23 hours to react.

[0185] After the reaction, while cooling the reaction solution with ice, 10 mL of water was added dropwise to the reaction solution, and then 2.5 mL (5.0 mmol) of 2M hydrochloric acid was added and reacted at room temperature for 2 hours. Next, 20 mL of ethyl acetate was added to the reaction solution, and the reaction solution was washed with stirring. After separating and removing the ethyl acetate layer, 6 mL of 1M sodium hydroxide was added to the reaction solution, and the reaction solution was extracted 4 times with 15 mL of dichloromethane. The obtained dichloromethane layer was dried over magnesium sulfate. After drying, magnesium sulfate was filtered off from the dichloromethane layer, and then dichloromethane was distilled off to obtain 434.0 mg (2.28 mmol) of 3-(aminomethyl)benzaldehyde.

[0186] 1 The 3-(aminomethyl)benzaldehyde obtained was analyzed by 1H-NMR (270 MHz, CDCl3). 1 1H NMR (400 MHz, DMSO) δ 9.88 (s, 1H), 8.69 (b, 2H), 7.65 - 7.40 (m, 4H), 4.35 (s, 2H).

[0187] Next, phosgene was introduced into a mixed solution of 337.4 mg (1.78 mmol) of 3-(aminomethyl)benzaldehyde obtained above and 7.0 mL of chlorobenzene, and the mixture was reacted at 120 °C. The reaction was stopped when the reaction solution became clear. After cooling to room temperature, chlorobenzene was distilled off to obtain a concentrated solution, and 278.0 mg (1.29 mmol) of 3-(isocyanatomethyl)benzaldehyde (IBA) was obtained.

[0188] 1 H-NMR (270 MHz, CDCl3), 13 The 3-(isocyanatomethyl)benzaldehyde (IBA) obtained was analyzed by 13C-NMR (100 MHz, CDCl3). 1 H-NMR (400 MHz, CDCl3) δ 9.86 (s, 1H), 7.65 - 7.36 (m, 4H), 4.63 (s, 2H). 13 13C-NMR (100 MHz, CDCl3) δ 191.0, 139.4, 139.2, 133.7, 130.1, 129.1, 126.9, 125.0, 54.6.

[0189] To facilitate the understanding of the present application, the following examples are listed. It should be made clear to those skilled in the art that the examples are only for assisting the understanding of the present application and should not be regarded as specific limitations to the present application.

[0190] In addition, "parts" and "%" are based on mass unless otherwise specified.

[0191] [Examples 1 to 7, Comparative Example 1] The examples and comparative examples each provided an XDI composition, and the details of the specific composition are shown in Table 1.

[0192] The preparation method of the XDI composition is as follows. The XDI composition was produced according to the process shown in Fig. 1. Specifically, 800 parts by mass of chlorobenzene was charged into the salt formation kettle shown in Fig. 1. Next, the salt formation temperature in the salt formation kettle was adjusted to 30 °C, and the salt formation pressure (gauge pressure) in the salt formation kettle was adjusted to 0.05 MPaG. Then, 128 parts by mass of HCl gas was introduced into the salt formation kettle through the hydrogen chloride supply line, and a mixed solution (amine solution) of 150 parts by mass of 1,3-XDA and 1050 parts by mass of chlorobenzene was charged into the salt formation kettle through the amine supply line. Thereby, a slurry with a 1,3-XDA hydrochloride concentration of 11.5 wt.% was prepared.

[0193] Next, HCl gas was continuously blown into the salt formation kettle through the hydrogen chloride supply line at a supply rate of 64 parts by mass / hr, and an amine solution with a 1,3-XDA concentration of 7.5 wt.% was charged into the salt formation kettle through the amine supply line at a supply rate of 1000 parts by mass / hr. At the same time, the slurry containing 1,3-XDA hydrochloride was transported to the first phosgenation kettle through the hydrochloride transport line.

[0194] Next, phosgene was continuously introduced into the first, second, and third phosgenation kettles at the supply rates shown in Table 1. The reaction temperature and reaction pressure (gauge pressure) of the three reaction kettles, the supply ratio of phosgene to 1 mol of 1,3-XDA hydrochloride, and the water content of the recycled solvent are shown in Table 1.

[0195] Thereby, 1,3-XDA hydrochloride was reacted with phosgene to produce 1,3-XDI, and a reaction substance containing 1,3-XDI was prepared. Also, a part of the unreacted phosgene was condensed in the condenser and returned to the phosgenation kettle.

[0196] Next, the photochemical reaction solution was continuously transported to the dephosgenation column. Then, the reaction substance was degassed in the dephosgenation column. Next, the degassed substance was discharged from the dephosgenation column through the degassed substance transport line and continuously transported to the solvent removal column. Thereby, 120 parts by mass of a solvent-removed substance with an m-1,3-XDI concentration of 95 wt.% was prepared.

[0197] Next, the desolventized substance was discharged from the desolventization tower through the desolventized substance transport line, and the separated solvent was purified in the solvent purification tower and reused.

[0198] The solvent purification tower was filled with packing corresponding to 15 theoretical plates, and its operating conditions were as follows. Bottom temperature: 80 - 130 °C, Top temperature: 60 - 120 °C, Top pressure: as shown in Table 1, Top reflux ratio: as shown in Table 1, Residence time: 0.5 - 10 h, Control of the water content in the reused solvent: as shown in Table 1.

[0199] The desolventized substance was continuously transported to the de-tarring device. Then, the desolventized substance was de-tarred in the de-tarring device to prepare an intermediate product substance. The content ratios of chlorobenzene (MCB), XDI, IBA, and bromine element in the intermediate product substance are shown in Table 1.

[0200] Next, the intermediate product substance was continuously transported to the rectification tower at a supply rate of 100 parts by mass / hr. The rectification tower was filled with packing corresponding to 20 theoretical plates. Then, in the rectification tower, light components were separated from the top, and an XDI composition product was collected from the tower.

[0201] The rectification conditions in the rectification tower were as follows. Bottom temperature: 145 - 160 °C, Top temperature: 100 - 130 °C, Top pressure: 0 - 500 Pa, Residence time: 1 - 10 h, The take-off amount and the top reflux ratio in the rectification process are shown in Table 1.

[0202] Thereby, an XDI composition was produced. The content ratios of XDI, IBA, and bromine element in the XDI composition are shown in Table 1.

[0203] [Comparative Example 2] The XDI composition obtained in Example 1 was mixed with the XDI composition in Comparative Example 3 at a ratio of 1:1 under nitrogen gas protection to obtain the XDI composition of Comparative Example 2.

[0204] [Comparative Example 3] As Comparative Example 3, XDI prepared in Example 1 of Patent Application US5196572A was used.

[0205]

Table 1

[0206] Performance test The XDI compositions of the above Examples and Comparative Examples were used in the preparation of various resin materials for performance evaluation, specifically as follows.

[0207] 1. Elastomer (TPU) (1) Preparation method Into a four-necked flask equipped with a stirrer, thermometer, reflux tube and nitrogen supply line, 198 parts by mass of each XDI composition (polyisocyanate component) of Examples 1 to 7 and Comparative Examples 1, 2 and 3, and 531.2 parts by mass of an adipic acid-based polyester polyol (manufactured by Mitsui Chemicals, TAKELAC U-2024, active hydrogen group-containing component) having a number average molecular weight of 2000 were charged, and the reaction was carried out at 80 °C under a nitrogen gas atmosphere until the NCO group content reached 9.1 wt.% to produce an isocyanate group-terminated prepolymer.

[0208] Also, 3.9 parts by mass of a heat stabilizer (Ciba Specialty Chemicals, IRGANOX 245) and 0.07 parts by mass of a solution in which stannous octoate (Innochem reagent) as a catalyst was diluted to 4 wt.% with diisononyl adipate (XIYASHIJI) were added to the isocyanate group-terminated prepolymer, and they were stirred and mixed for about 1 minute at 600 rpm using a mechanical stirrer (IKA, Germany, RW20). Next, 131.9 parts by mass of 1,4-butanediol (Innochem reagent) previously adjusted to 80°C as a chain extender was added to the isocyanate group-terminated prepolymer. Further, the mixed solution of the isocyanate group-terminated prepolymer and the chain extender was stirred well for about 2 minutes until the whole became uniform.

[0209] Next, the mixed solution was poured into a stainless steel plate whose temperature had been previously adjusted to 150°C, reacted at 150°C for 1 hour, and then reacted at 100°C for 23 hours to produce an elastomer.

[0210] Thereafter, the elastomer was removed from the plate and cured for 7 days under constant temperature and humidity conditions of room temperature 23°C and relative humidity 55%.

[0211] (2) Performance Evaluation The color difference in the xenon lamp irradiation test of the obtained elastomer (TPU) was measured, and the results are shown in Table 2.

[0212] 2. Optical Material (Plastic Lens Material) (1) Preparation Method 0.001 parts by mass of dibutyltin dichloride, 0.07 parts by mass of an internal mold release agent (ZELECUN, acidic phosphate ester, manufactured by Stepan), 0.05 parts by mass of an ultraviolet absorber (Biosorb 583, manufactured by Sakai Chemical Industry Co., Ltd.), and 36.4 parts by mass of each XDI composition of Examples 1 to 7 and Comparative Examples 1, 2, and 3 were charged into a flask. Thereafter, these were stirred and dissolved at 25°C for 1 hour to prepare a polyisocyanate component.

[0213] Thereafter, 33.6 parts by mass of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane (polythiol component) was charged into the polyisocyanate component and mixed to prepare a polymerizable composition.

[0214] After degassing the polymerizable composition at 600 Pa for 1 hour, it was filtered through a 3-μm PTFE filter. Thereafter, it was poured into a mold composed of a glass mold and tape. The mold was put into an oven, and the temperature was gradually raised from 10°C to 120°C, and polymerization was carried out for 18 hours. After the polymerization was completed, the mold was taken out of the oven and demolded to produce an optical material.

[0215] (2) Performance evaluation The Y.I. value of the obtained plastic lens was measured. The results are shown in Table 2.

[0216] 3. Two-component polyurethane coating material (including Agent A and Agent B) (1) Preparation method Preparation of Agent A-1 463.3 parts by mass of the XDI composition of each of Examples 1 to 7 and Comparative Examples 1, 2, and 3 and 36.7 parts by mass of trimethylolpropane were mixed and reacted at 70°C for 6 hours in a nitrogen gas atmosphere. For the reaction solution, unreacted XDI was distilled off using a thin-film distillation apparatus to produce an XDI-modified composition. The XDI-modified composition contained urethane groups, which are reaction products of XDI and trimethylolpropane.

[0217] Ethyl acetate was added to the XDI-modified composition so that the solid content became 75 wt.%, and a polyisocyanate component (Agent A-1) was produced. The NCO group content in the polyisocyanate component is 11.8 wt.%.

[0218] Preparation of Agent A-2 To 100 parts by mass of each of the XDI compositions of Examples 1 to 7 and Comparative Examples 1, 2, and 3, 2 parts by mass of 1,3 - butanediol was added, and the temperature was raised to 75°C under a nitrogen gas atmosphere, and the urethanization reaction was carried out for 2 hours. The equivalent ratio (NCO / OH) of the isocyanate group of XDI to the hydroxyl group of 1,3 - butanediol was 24. Next, at the same temperature, as an isocyanurate - forming catalyst, a solution of hydroxide of tetrabutylammonium (37% methanol solution) 0.1 phr (0.037 phr in terms of solid content) was blended, and the isocyanuration reaction was terminated 4 hours after the start of the reaction. The obtained reaction solution was passed through a thin - film distillation apparatus (temperature 150°C, vacuum degree 50 Pa) to remove unreacted XDI (distillation yield 60 wt.%), and thereby an XDI - modified product composition was produced. The XDI - modified product composition contained an isocyanurate group which is a trimer of XDI. Ethyl acetate was added to the XDI - modified product composition so that the solid content became 75 wt.%, and a polyisocyanate component (Agent A - 2) was produced.

[0219] Regarding the preparation of Agent B Using a paint shaker, 40 parts by mass of a fluoropolyol (manufactured by DAIKIN INDUSTRIES, LTD., ZEFFLE GK - 570, solid - content hydroxyl value: 64 mgKOH / g, solvent: butyl acetate), 52.5 parts by mass of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., CR93), 33.8 parts by mass of butyl acetate, and 110 parts by mass of glass beads with a diameter of 2 mm were stirred for 2 hours. Then, the glass beads were removed from the mixed solution by filtration. Then, a solvent was added so that the solid - content concentration became 58 wt.%, and an active - hydrogen - group - containing component (Agent B) was produced. The content ratio of titanium oxide in the active - hydrogen - group - containing component was 45 wt.%.

[0220] (2) Performance evaluation The obtained polyisocyanate component (Agent A-1 or Agent A-2) and the active hydrogen group-containing component (Agent B) were mixed so that the equivalent ratio of isocyanate groups to hydroxyl groups (NCO / OH) became 1.0 to prepare a mixed solution. Next, butyl acetate was added to the mixed solution so that the NV value (coating film component mass) became 60%. Then, the mixed solution was applied to the surface of a polyethylene terephthalate (PET) substrate and cured by heating at 120°C for 2 minutes. Next, the PET substrate coated with the mixed solution was cured at 60°C for 2 days. Thereby, a coating layer having a thickness of about 15 μm was formed on the PET substrate.

[0221] The weather resistance of the coating layer (color difference Δb (=|b2 - b1|) of the coating layer in the damp heat test) was measured. The results are shown in Table 2.

[0222]

Table 2

[0223] From Table 1, it was found that by controlling the content of IBA in the XDI composition within 0.2 to 500 ppm, the discoloration resistance performance of the resin prepared with the composition can be effectively improved. When the content of IBA exceeds 500 nm (Comparative Example 1), is less than 0.2 ppm (Comparative Example 2), or does not contain IBA at all, the discoloration resistance performance does not reach that of the present application, and the XDI composition according to the present application has better future application potential in various resin materials.

Claims

1. A xylylene diisocyanate composition comprising xylylene diisocyanate and a compound represented by the formula (1) in an amount of 0.2 to 500 ppm, wherein 【Chemical 1】 the xylylene diisocyanate composition further comprises a bromine-containing compound, and the content of the bromine-containing compound is 0.5 to 50 ppm in terms of the mass of bromine element. The xylylene diisocyanate composition.

2. The xylylene diisocyanate composition according to claim 1, wherein the xylylene diisocyanate comprises any one or at least two combinations of 1,2-xylylene diisocyanate, 1,3-xylylene diisocyanate or 1,4-xylylene diisocyanate.

3. The xylylene diisocyanate composition according to claim 2, wherein the xylylene diisocyanate composition is 1,3-xylylene diisocyanate and / or 1,4-xylylene diisocyanate.

4. The xylylene diisocyanate composition according to claim 3, wherein the xylylene diisocyanate composition is 1,3-benzomethylene isocyanate.

5. The compound represented by the formula (1) is 、 or The xylylene diisocyanate composition according to claim 1, which comprises any one or at least two combinations thereof.

6. A method for preparing the xylylene diisocyanate composition according to any one of claims 1 to 5, comprising: Step (1): An isocyanation step of subjecting xylylenediamine or xylylenediamine hydrochloride to an isocyanation reaction with phosgene in the presence of a reaction solvent to obtain a reaction product containing xylylene diisocyanate and a compound represented by the formula (1); Step (2): A solvent separation and purification step of removing the solvent from the reaction product obtained in step (1), purifying the separated solvent to obtain a recycled solvent, and then returning it to the reaction system of step (1); Step (3): A separation step of separating and purifying the solvent-removed reaction product obtained in step (2) to obtain the xylylene diisocyanate composition.

7. The preparation method according to claim 6, wherein the reaction solvent comprises a fresh solvent and / or a recycled solvent.

8. The preparation method according to claim 6, wherein the water content of the reaction solvent is 1 to 500 ppm.

9. The preparation method according to claim 6, wherein the water content of the recycled solvent is 1 to 500 ppm.

10. A modified composition of a xylylene diisocyanate composition obtained by modifying the xylylene diisocyanate composition according to any one of claims 1 to 5, wherein the modified xylylene diisocyanate in the modified composition is a modified composition of a xylylene diisocyanate composition containing any one kind or a combination of at least two kinds of (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) urethane group, (e) ureido group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group.

11. comprising Agent A and Agent B, wherein Agent A contains the xylylene diisocyanate composition according to any one of claims 1 to 5 and / or the modified composition according to claim 10, and Agent B is a two-component polyurethane raw material containing an active hydrogen group-containing substance.

12. A polyurethane resin obtained by reacting the xylylene diisocyanate composition according to any one of claims 1 to 5 with an active hydrogen group-containing substance, or by reacting the modified composition according to claim 10 with an active hydrogen group-containing substance.

13. An elastomer material containing the polyurethane resin according to claim 12.

14. An optical material obtained by polymerizing the xylylene diisocyanate composition according to any one of claims 1 to 5 with a polythiol compound, or by polymerizing the modified composition according to claim 10 with a polythiol compound.

15. The optical material according to claim 14, wherein the optical material includes a plastic lens material, an automobile lamp cover material, a transparent roofing material, a lens material for a smartphone or a tablet.

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