Xylylene diisocyanate composition, polymerizable composition, resin, molded body, optical element, and lens

Abstract

This xylylene diisocyanate composition contains a xylylene diisocyanate and a specific compound. The specific compound has a peak within the chemical shift value range of 2.44 ppm to 2.46 ppm based on chloroform in deuterated chloroform if 1H-NMR measurement is performed by mixing the xylylene diisocyanate composition with deuterated chloroform.

Description

Xylylene diisocyanate composition, polymerizable composition, resin, molded article, optical element, and lens

[0001] The present invention relates to a xylylene diisocyanate composition, a polymerizable composition, a resin, a molded article, an optical element, and a lens.

[0002] It has been known to produce a resin that can be used for optical elements such as lenses by reacting a xylylene diisocyanate composition with a polythiol (see Patent Document 1 below).

[0003] International Publication No. 2018 / 190290

[0004] In the production of the resin described in Patent Document 1, there are cases where it is desired to further improve the heat resistance.

[0005] The present invention provides a xylylene diisocyanate composition and a polymerizable composition that can be used to produce a resin having excellent heat resistance, as well as a resin, a molded article, an optical element, and a lens having excellent heat resistance.

[0006] The present invention [1] is a xylylene diisocyanate composition, which is obtained by mixing xylylene diisocyanate with deuterated chloroform. １ and a specific compound which, when measured by H-NMR, has a peak in the chemical shift range of 2.44 ppm to 2.46 ppm relative to chloroform in the deuterated chloroform.

[0007] The present invention [2] includes the xylylene diisocyanate composition according to the above [1], in which the proportion of the specific compound is 100 ppm or more by mass.

[0008] The present invention [3] includes the xylylene diisocyanate composition according to the above [1] or [2], in which the proportion of the specific compound is 10,000 ppm or less by mass.

[0009] The present invention [4] includes the xylylene diisocyanate composition according to the above [1] or [2], in which the proportion of the specific compound is 3000 ppm or less by mass.

[0010] The present invention [5] includes the xylylene diisocyanate composition according to any one of the above [1] to [4], which contains at least one of a urea compound represented by the following chemical formula (1) and a urea compound represented by the following chemical formula (2) as the specific compound:

[0011] Chemical formula (1):

[0012]

[0013] Chemical formula (2):

[0014]

[0015] The present invention [6] includes the xylylene diisocyanate composition according to any one of the above [1] to [5], further containing at least one of 4-methylbenzenesulfonamide and 4-methylbenzenesulfonyl isocyanate.

[0016] The present invention [7] includes the xylylene diisocyanate composition according to the above [6], in which the sum of the proportion of 4-methylbenzenesulfonamide in the xylylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is 2000 ppm or less by mass.

[0017] The present invention [8] includes the xylylene diisocyanate composition according to any one of the above [1] to [7], further containing at least one of monochloromethyl benzyl isocyanate and dichloromethyl benzyl isocyanate.

[0018] The present invention [9] includes the xylylene diisocyanate composition according to any one of the above [1] to [8], wherein the xylylene diisocyanate is obtained by reacting xylylene diamine with carbonyl dichloride or by reacting xylylene diamine hydrochloride with carbonyl dichloride.

[0019] The present invention

[10] includes a polymerizable composition containing the xylylene diisocyanate composition according to any one of the above [1] to [9] and an active hydrogen group-containing component.

[0020] The present invention

[11] is a method for manufacturing a mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane-based mercaptosilane, wherein the active hydrogen-containing component is selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, and bis(mercaptomethyl)-1,4-dithiane. The polymerizable composition according to

[10] above contains at least one polythiol selected from the group consisting of bis(mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0021] The present invention

[12] includes a resin that is a cured product of the polymerizable composition of the above

[10] or

[11] .

[0022] The present invention

[13] includes a molded article made of the resin of the above

[12] .

[0023] The present invention

[14] includes an optical element which is the molded article according to the above

[13] .

[0024] The present invention

[15] includes a lens, which is the optical element of the above

[14] .

[0025] The xylylene diisocyanate composition and polymerizable composition of the present invention contain a specific compound. The specific compound is obtained by mixing the xylylene diisocyanate composition with deuterated chloroform. １ When measured by H-NMR, it has a peak in deuterated chloroform in the chemical shift range of 2.44 ppm to 2.46 ppm with chloroform as the reference.

[0026] By using a xylylene diisocyanate composition and a polymerizable composition containing a specific compound as raw materials, a resin having excellent heat resistance can be produced.

[0027] The resin of the present invention is a cured product of a polymerizable composition containing the xylylene diisocyanate composition.

[0028] The molded article, optical element, and lens of the present invention are made of the above resin.

[0029] Therefore, the resin, molded article, optical element, and lens of the present invention have excellent heat resistance.

[0030] 1. Xylylene diisocyanate composition The xylylene diisocyanate composition (XDI composition) contains xylylene diisocyanate (XDI) as a main component. Note that the "XDI composition" described here is the "second XDI composition" obtained by the "method for producing an XDI composition" described below.

[0031] Examples of XDI include 1,2-XDI (o-XDI), 1,3-XDI (m-XDI), and 1,4-XDI (p-XDI).

[0032] As XDI, preferably, 1,3-XDI (m-XDI) is used.

[0033] The XDI composition may contain two or more types of XDI.

[0034] The proportion (purity) of XDI in the XDI composition is, for example, 98.00 mass% or more, preferably 99.00 mass% or more, more preferably 99.30 mass% or more, even more preferably 99.60 mass% or more, and for example, 99.95 mass% or less.

[0035] The proportion of XDI in the XDI composition is measured by the method described in the Examples below.

[0036] The XDI composition contains a specific compound as a secondary component. The specific compound is obtained by mixing the xylylene diisocyanate composition with deuterated chloroform. １When measured by H-NMR, it has a peak in deuterated chloroform in the chemical shift range of 2.44 ppm to 2.46 ppm with chloroform as the reference.

[0037] １ H-NMR is measured under the measurement conditions described in the Examples below.

[0038] The XDI composition contains at least one of a urea compound represented by the following chemical formula (1) and a urea compound represented by the following chemical formula (2) as a specific compound.

[0039] Chemical formula (1):

[0040]

[0041] Chemical formula (2):

[0042]

[0043] The XDI composition may also contain a specific compound, a derivative obtained from XDI and 4-methylbenzenesulfonyl isocyanate (PTSI, also known as p-toluenesulfonyl isocyanate). Examples of the derivative include isocyanurates, allophanates, biurets, uretonimines, carbodiimides, and uretdiones.

[0044] When the specific compound is at least one of the urea compound represented by the above chemical formula (1) and the urea compound represented by the above chemical formula (2), the proportion of the specific compound in the XDI composition is, for example, 1 ppm or more, preferably 10 ppm or more, more preferably 100 ppm or more, more preferably 300 ppm or more, more preferably 600 ppm or more, and more preferably 1000 ppm or more, by mass.

[0045] When the proportion of the specific compound in the XDI composition is equal to or greater than the lower limit, the heat resistance of the resin produced using the XDI composition can be improved.

[0046] ​When the specific compound is at least one of the urea compound represented by the above chemical formula (1) and the urea compound represented by the above chemical formula (2), the proportion of the specific compound in the XDI composition is, for example, 10,000 ppm or less, preferably 7,000 ppm or less, more preferably 5,000 ppm or less, more preferably 3,500 ppm or less, more preferably 3,000 ppm or less, more preferably 2,800 ppm or less, and more preferably 2,500 ppm or less, on a mass basis.

[0047] When the proportion of the specific compound in the XDI composition is equal to or less than the upper limit, the yellowness index (YI value) of the resin produced using the XDI composition can be reduced.

[0048] In addition, the range of the proportion of the specific compound in the XDI composition can be set by combining any one of the upper limit values ​​of the proportion of the specific compound in the XDI composition described above with any one of the lower limit values ​​of the proportion of the specific compound in the XDI composition described above.

[0049] The proportion of a specific compound in the XDI composition is measured by the method described in the Examples below.

[0050] The XDI composition may further contain at least one of PTSI and 4-methylbenzenesulfonamide (PTSA, also known as p-toluenesulfonamide) as a secondary component.

[0051] The proportion of PTSI in the XDI composition is, by mass, for example, 15,000 ppm or less, preferably 12,000 ppm or less, more preferably 10,000 ppm or less, more preferably 8,000 ppm or less, more preferably 5,000 ppm or less, more preferably 2,000 ppm or less, more preferably 1,000 ppm or less, more preferably 300 ppm or less, and more preferably 100 ppm or less.

[0052] When the proportion of PTSI in the XDI composition is equal to or less than the upper limit, the yellowness of the resin produced from the XDI composition can be reduced.

[0053] Furthermore, the proportion of PTSI in the XDI composition is, for example, greater than 0 ppm, preferably 1 ppm or more, more preferably 5 ppm or more, more preferably 10 ppm or more, more preferably 20 ppm or more, and more preferably 40 ppm or more, by mass.

[0054] When the proportion of PTSI in the XDI composition is equal to or greater than the above lower limit, the storage stability of the XDI composition can be improved.

[0055] The range of the PTSI content in the XDI composition can be set by combining any one of the upper limit values ​​of the PTSI content in the XDI composition described above with any one of the lower limit values ​​of the PTSI content in the XDI composition described above.

[0056] The proportion of PTSI in the XDI composition is measured by the method described in the Examples below.

[0057] The proportion of PTSA in the XDI composition is, by mass, for example, 10,000 ppm or less, more preferably 8,000 ppm or less, more preferably 5,000 ppm or less, more preferably 2,000 ppm or less, more preferably 900 ppm or less, and more preferably 500 ppm or less.

[0058] When the proportion of PTSA in the XDI composition is equal to or less than the upper limit, it is possible to prevent the yellowness of the resin produced from the XDI composition from increasing due to a specific compound.

[0059] Furthermore, the proportion of PTSA in the XDI composition is, for example, greater than 0 ppm, preferably 1 ppm or more, more preferably 5 ppm or more, more preferably 10 ppm or more, more preferably 20 ppm or more, and more preferably 40 ppm or more, by mass.

[0060] When the proportion of PTSA in the XDI composition is equal to or greater than the above lower limit, the storage stability of the XDI composition can be improved.

[0061] The range of the PTSA content in the XDI composition can be set by combining any one of the upper limit values ​​of the PTSA content in the XDI composition described above with any one of the lower limit values ​​of the PTSA content in the XDI composition described above.

[0062] The proportion of PTSA in the XDI composition is measured by the method described in the Examples below.

[0063] The sum of the proportion of 4-methylbenzenesulfonamide in the xylylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is, on a mass basis, for example, 10,000 ppm, preferably 7,000 ppm or less, more preferably 5,000 ppm or less, more preferably 2,000 ppm or less, more preferably 1,700 ppm or less, and more preferably 1,500 ppm or less.

[0064] When the sum of the proportion of 4-methylbenzenesulfonamide in the xylylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is equal to or less than the above upper limit, the yellowness of the resin produced from the XDI composition can be reduced, and the heat resistance of the resin produced using the XDI composition can be improved.

[0065] The sum of the proportion of 4-methylbenzenesulfonamide in the xylylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is, for example, more than 0 ppm, and is preferably 1 ppm or more, more preferably 5 ppm or more, more preferably 10 ppm or more, more preferably 20 ppm or more, more preferably 40 ppm or more, more preferably 100 ppm or more, more preferably 300 ppm or more, and more preferably 500 ppm or more, on a mass basis.

[0066] When the sum of the proportion of 4-methylbenzenesulfonamide in the xylylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is equal to or greater than the above lower limit, the storage stability of the XDI composition can be improved.

[0067] The XDI composition may further contain at least one of monochloromethylbenzyl isocyanate (CBI) and dichloromethylbenzyl isocyanate (DCI) as a secondary component.

[0068] The proportion of DCI in the XDI composition is, by mass, for example, 0.1 ppm or more, preferably 0.3 ppm or more, more preferably 0.6 ppm or more, more preferably 1.0 ppm or more, and for example, 60 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, more preferably 20 ppm or less.

[0069] When the proportion of DCI in the XDI composition is within the above range, the yellowness of the resin produced from the XDI composition can be reduced.

[0070] The proportion of CBI in the XDI composition is, by mass, for example, 0.2 ppm or more, preferably 6 ppm or more, more preferably 100 ppm or more, and for example, 5000 ppm or less, preferably 4000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1600 ppm or less, and particularly preferably 1000 ppm or less.

[0071] The content of CBI is, for example, 2 times or more, preferably 10 times or more, more preferably 20 times or more, and for example, 800 times or less, preferably 300 times or less, more preferably 50 times or less, relative to the content of DCI.

[0072] When the proportion of CBI in the XDI composition is within the above range, the yellowness of the resin produced from the XDI composition can be reduced. In particular, when the content of CBI is equal to or less than the above upper limit, yellowing of the resin can be suppressed, and the urethane reaction during the production of the resin can proceed smoothly, thereby reliably improving the mechanical properties of the resin.

[0073] The proportion of DCI in the XDI composition and the proportion of CBI in the XDI composition are measured by the method described in the Examples below.

[0074] 2. Method for Producing XDI Composition The method for producing the XDI composition will now be described.

[0075] The method for producing the XDI composition includes, for example, a synthesis step, a purification step, and a purification step.

[0076] In the synthesis step, XDI is synthesized. In the synthesis step, XDI is synthesized by, for example, a hydrochloride method. When the hydrochloride method is used, the synthesis step includes a salt formation step and an isocyanate formation step.

[0077] In the salt formation step, xylylenediamine (XDA) and hydrogen chloride are mixed to produce xylylenediamine hydrochloride (XDA hydrochloride).

[0078] Examples of XDA include 1,2-XDA (o-XDA), 1,3-XDA (m-XDA), and 1,4-XDA (p-XDA), and preferably 1,3-XDA (m-XDA).

[0079] In the salt formation step, for example, XDA is reacted with hydrogen chloride in the presence of an inert solvent. Specifically, hydrogen chloride gas is mixed with a solution of XDA dissolved in an inert solvent, and the XDA and hydrogen chloride are reacted.

[0080] Examples of inert solvents include those described in paragraph

[0059] of WO 2018 / 190290. The inert solvents can be used alone or in combination of two or more. Among the inert solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

[0081] The mass proportion of XDA relative to the sum of the masses of XDA and the inert solvent (total amine concentration) is, for example, 3 mass% or more, preferably 5 mass% or more, and for example, 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less.

[0082] The supply ratio of hydrogen chloride is, for example, 2 moles or more, and for example, 10 moles or less, preferably 6 moles or less, and more preferably 4 moles or less, relative to 1 mole of XDA.

[0083] The reaction temperature in the salt formation step is, for example, 30°C or more, preferably 50°C or more, and for example, 160°C or less, preferably 150°C or less, more preferably 140°C or less.

[0084] The reaction pressure (gauge pressure) in the salt formation step is, for example, atmospheric pressure (0 MPaG) or more, preferably 0.01 MPaG or more, and for example, 1.0 MPaG or less, preferably 0.5 MPaG or less.

[0085] XDA reacts with hydrogen chloride to produce XDA hydrochloride, and a slurry containing XDA hydrochloride is obtained.

[0086] Next, in the isocyanation step, XDA hydrochloride is reacted with carbonyl dichloride to produce a reaction mass containing XDI. In the isocyanation step, carbonyl dichloride is mixed with a slurry containing XDA hydrochloride, and the XDA hydrochloride and carbonyl dichloride are reacted while removing the by-product hydrogen chloride gas. XDI is produced by the reaction between XDA hydrochloride and carbonyl dichloride. In other words, XDI is obtained by the reaction between XDA hydrochloride and carbonyl dichloride.

[0087] The supply ratio of carbonyl dichloride is, relative to 1 mole of XDA hydrochloride, for example, 4 moles or more, preferably 5 moles or more, more preferably 6 moles or more, and for example, 50 moles or less, preferably 40 moles or less, more preferably 30 moles or less.

[0088] The reaction time of the isocyanation step is, for example, 4 hours or more, preferably 6 hours or more, and for example, 25 hours or less, preferably 20 hours or less, more preferably 15 hours or less.

[0089] The reaction temperature in the isocyanation step is, for example, 90°C or more, preferably 100°C or more, more preferably 110°C or more, and for example, 190°C or less, preferably 180°C or less, more preferably 160°C or less.

[0090] The reaction pressure (gauge pressure) in the isocyanation step exceeds atmospheric pressure (0 MPaG), for example, and is preferably 0.0005 MPaG or more, more preferably 0.001 MPaG or more, more preferably 0.003 MPaG or more, more preferably 0.01 MPaG (10 kPaG) or more, more preferably 0.02 MPaG (20 kPaG) or more, more preferably 0.03 MPaG (30 kPaG) or more, and is, for example, 0.6 MPaG or less, preferably 0.4 MPaG or less, more preferably 0.2 MPaG or less.

[0091] The isocyanation step is preferably carried out continuously, i.e., the slurry containing XDA hydrochloride is continuously fed to a reaction vessel used in the isocyanation step, and the XDA hydrochloride is reacted with carbonyl dichloride in the reaction vessel while the reaction mass is continuously removed from the reaction vessel.

[0092] Next, gas components, inert solvents, and tar components are removed from the reaction mass.

[0093] The gaseous components include carbonyl dichloride that remains in the reaction mass without reacting with XDA hydrochloride in the isocyanation step and hydrogen chloride gas that is by-produced in the isocyanation step, and are removed from the reaction mass using, for example, a known degassing tower.

[0094] The inert solvent is distilled off from the reaction mass, for example, using a known distillation column.

[0095] Tar components are removed from the reaction mass, for example, using a known detarring device.

[0096] After the gas components, inert solvent, and tar components are removed, the proportion of XDI in the reaction mass is, for example, 80.0 mass% or more, preferably 90.0 mass% or more, more preferably 95.0 mass% or more, and for example, 99.0 mass% or less, preferably 98.5 mass% or less, more preferably 98.0 mass% or less.

[0097] Next, in the purification step, the reaction mass is purified. The purification step includes, for example, a low boiling point removal step and a rectification step.

[0098] In the low boiling point removal step, low boiling point components are removed from the reaction mass. The low boiling point components have a boiling point lower than that of XDI. In the low boiling point removal step, for example, the reaction mass is distilled in a low boiling point removal column to distill off the low boiling point components from the reaction mass.

[0099] Examples of the low boiling point removal tower include a plate tower and a packed tower, and preferably a packed tower. The number of theoretical plates of the low boiling point removal tower is, for example, 3 or more, preferably 5 or more, more preferably 7 or more, and for example, 40 or less, preferably 20 or less, more preferably 15 or less.

[0100] The temperature at the bottom of the low boiling separation tower is, for example, 130°C or higher, preferably 140°C or higher, more preferably 150°C or higher, and for example, 200°C or lower, preferably 190°C or lower, more preferably 180°C or lower.

[0101] The top temperature of the low boiling separation tower is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and for example, 160°C or lower, preferably 150°C or lower, more preferably 140°C or lower.

[0102] The pressure at the top of the low boiling separation tower is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, and for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0103] The top reflux ratio of the low boiling separation tower is, for example, 1 or more, preferably 5 or more, more preferably 10 or more, and for example, 80 or less, preferably 60 or less, more preferably 50 or less.

[0104] The residence time in the low boiling removal tower is, for example, 0.1 hour or more, preferably 0.2 hour or more, more preferably 0.3 hour or more, and for example, 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

[0105] By distillation using the low boiling point removal column, the reaction mass from which the low boiling point components have been distilled off is obtained as bottoms.

[0106] Next, in the rectification step, the reaction mass after the low boiling point removal step is further distilled (rectified) using a rectification column.

[0107] Examples of the rectification column include a plate column and a packed column, and preferably a packed column. The number of theoretical plates of the rectification column is, for example, 1 or more, and for example, 20 or less, preferably 10 or less, and more preferably 5 or less.

[0108] The bottom temperature of the rectification column is, for example, 120°C or more, preferably 130°C or more, more preferably 140°C or more, and for example, 190°C or less, preferably 180°C or less, more preferably 170°C or less.

[0109] The top temperature of the rectification column is, for example, 90°C or more, preferably 110°C or more, more preferably 130°C or more, and for example, 180°C or less, preferably 170°C or less, more preferably 160°C or less.

[0110] The top pressure of the rectification column is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, and for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0111] The column top reflux ratio of the rectification column is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, and for example, 50 or less, preferably 20 or less, more preferably 10 or less.

[0112] The residence time in the rectification column is, for example, 0.2 hours or more, preferably 0.5 hours or more, more preferably 1.0 hour or more, and for example, 20 hours or less, preferably 10 hours or less.

[0113] The fractionation step yields a fraction containing XDI (first XDI composition), which contains DCI and CBI.

[0114] Next, in the production step, the above-mentioned urea compound is produced.

[0115] To produce the urea compound, for example, PTSA is added to the first XDI composition and stirred while heating.

[0116] The heating temperature in the production step is, for example, 40°C or higher, preferably 50°C or higher, more preferably 60°C or higher, and for example, 120°C or lower, preferably 100°C or lower, more preferably 80°C or lower.

[0117] The heating time in the production step is, for example, 1 hour or more, preferably 3 hours or more, more preferably 5 hours or more, more preferably 8 hours or more, and for example, 48 hours or less, preferably 36 hours or less, more preferably 24 hours or less, more preferably 12 hours or less.

[0118] In the production step, PTSA and XDI react to produce the above-described urea compound, thereby obtaining the above-described XDI composition (second XDI composition).

[0119] If necessary, PTSI may be added to and mixed with the obtained XDI composition (second XDI composition).

[0120] Furthermore, the method for producing an XDI composition may not include a production step, but may include, for example, a salt formation step, an isocyanation step, a purification step, and a mixing step.

[0121] In the mixing step, the above-mentioned urea compound, and optionally PTSA and PTSI, are added to the first XDI composition and mixed.

[0122] This method also makes it possible to obtain the above-mentioned XDI composition.

[0123] 3. Uses of the XDI Composition The XDI composition described above is used as a raw material for resins, which are produced by reacting an isocyanate component containing the XDI composition with an active hydrogen group-containing component.

[0124] The active hydrogen group-containing component contains an active hydrogen group-containing compound.

[0125] Examples of active hydrogen group-containing compounds include polyols, polythiols, and polyamines.

[0126] The active hydrogen group-containing compound can be used alone or in combination of two or more kinds.

[0127] From the viewpoint of optical properties, the active hydrogen group-containing compound is preferably a polythiol. The active hydrogen group-containing component is preferably a polythiol composition containing a polythiol as a main component.

[0128] The proportion of polythiol in the polythiol composition is, for example, 50 mass % or more, preferably 60 mass % or more, more preferably 70 mass % or more, and more preferably 80 mass % or more.

[0129] The proportion of polythiol in the polythiol composition is measured, for example, by high performance liquid chromatography.

[0130] The polythiol has a plurality of mercapto groups. The polythiol does not contain the subcomponents described below. Examples of the polythiol include an aliphatic polythiol, an aromatic polythiol, and a heterocyclic polythiol.

[0131] Examples of aliphatic polythiols include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), ), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 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-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7 -dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-Dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercapto propionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane.

[0132] Examples of aromatic polythiols include 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, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol.

[0133] Heterocyclic polythiols include, for example, 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, and bismuthiol.

[0134] The polythiols can be used alone or in combination of two or more kinds.

[0135] Furthermore, preferred examples of polythiol include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, ... and at least one selected from the group consisting of 1,3-dimethyl-2,4-dithiapentane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0136] The polythiol composition may contain minor components.

[0137] Examples of the secondary component include a compound in which at least one of the multiple mercapto groups of the above-mentioned polythiol is substituted with a functional group represented by the following chemical formula (3) (hereinafter referred to as compound A).

[0138] Chemical formula (3):

[0139]

[0140] When the polythiol composition contains compound A, in high performance liquid chromatography measurement of the polythiol composition, the peak area (R1) of compound A relative to 100 of the peak area of ​​the polythiol is, for example, 3.0 or less, preferably 1.5 or less, more preferably 0.50 or less, and for example, 0.01 or more.

[0141] The "peak area (R1) of compound A relative to 100 of the peak area of ​​polythiol" refers to the peak area (P ｔｈｉｏｌ ) is set to 100, the peak area of ​​compound A (P Ａ ) and is calculated by the following formula (1).

[0142] Formula (1): R1=(P Ａ / P ｔｈｉｏｌ ) × 100 When determining the "peak area (R1) of compound A relative to 100 of the peak area of ​​polythiol," high performance liquid chromatography measurement is performed under the measurement conditions described in paragraph

[0041] of WO 2022 / 102625.

[0143] When the peak area (R1) of compound A relative to 100 of the peak area of ​​the polythiol is equal to or greater than the above-mentioned lower limit and equal to or less than the above-mentioned upper limit, the pot life of the polymerizable composition obtained from the polythiol composition and the polyisocyanate composition can be maintained at a good level, and further, by curing the polymerizable composition, a plastic lens made of a polythiourethane resin excellent in quality such as hue, transparency, and striae can be obtained.

[0144] Furthermore, when the polythiol composition contains at least one polythiol selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, the polythiol composition may further contain a compound represented by the following chemical formula (4) (hereinafter referred to as compound B) as a minor component.

[0145] Chemical formula (4):

[0146]

[0147] (In general formula (1), m and n each independently represent 0 or 1, and m + n = 1.) When the polythiol composition contains compound B, in high performance liquid chromatography measurement of the polythiol composition, the peak area (R2) of compound B relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is, for example, 10.0 or less, preferably 9.0 or less, more preferably 8.0 or less, more preferably 7.0 or less, more preferably 6.0 or less, and is, for example, greater than 0, preferably 0.02 or more, more preferably 0.04 or more, more preferably 1.0 or more, more preferably 2.0 or more, more preferably 3.0 or more, and more preferably 4.0 or more.

[0148] The "peak area (R2) of compound B relative to the total peak area of ​​the compounds contained in the polythiol composition (100)" is the total peak area (P ｓｕｍ ) is set to 100, the peak area of ​​compound B (P Ｂ The total peak area (P ｓｕｍ ) is the sum of the peak areas of all peaks detected in high performance liquid chromatography measurement of the polythiol composition.

[0149] Formula (2): R2=(P Ｂ / P ｓｕｍ ) × 100 When determining the "peak area (R2) of compound B relative to the total peak area of ​​the compounds contained in the polythiol composition (100)," the high performance liquid chromatography measurement is carried out under the measurement conditions described in paragraph

[0049] of WO 2022 / 138865.

[0150] When the peak area (R2) of compound B relative to the total peak area 100 of the compounds contained in the polythiol composition is the upper limit or less, the light resistance of the resin produced from the polythiol composition can be improved. Furthermore, when the peak area (R2) of compound B relative to the total peak area 100 of the compounds contained in the polythiol composition is the lower limit or more, the dyeability of the resin produced from the polythiol composition can be improved.

[0151] For example, the resin is produced by cast molding. In cast molding, an isocyanate component and an active hydrogen group-containing component are first mixed in a ratio such that the ratio of active hydrogen groups (amino groups, thiol groups, or hydroxyl groups) in the active hydrogen group-containing component to isocyanate groups in the isocyanate component is 0.8 to 1.2. The resulting mixture is a polymerizable composition containing the isocyanate component and the active hydrogen group-containing component.

[0152] The polymerizable composition may contain known additives, such as curing catalysts, stabilizers (acidic phosphate esters), and ultraviolet absorbers.

[0153] Next, the polymerizable composition is poured into a mold and then heated and cured, thereby obtaining a molded article made of resin. In other words, the resin is a cured product of the polymerizable composition.

[0154] When the active hydrogen group-containing component contains a polythiol, the resulting molded article has excellent transparency.

[0155] Furthermore, since the polyisocyanate composition contains XDI and a specific compound, the resulting molded article has a high refractive index and excellent heat resistance.

[0156] Specifically, the refractive index (ne) of the obtained molded body is, for example, 1.650 or more, preferably 1.660 or more, and for example, 1.670 or less.

[0157] The obtained molded body has an Abbe number (νe) of, for example, 30 or more, or preferably 31 or more, and for example, 35 or less, or preferably 33 or less.

[0158] The glass transition temperature (Tg) of the obtained molded body is, for example, 80°C or more, preferably 85°C or more, and for example, 95°C or less.

[0159] The obtained molded article also has a low YI value. Specifically, the YI value of the obtained molded article is, for example, 2.00 or less, preferably 1.50 or less, more preferably 1.20 or less, more preferably 1.10 or less, more preferably 1.05, and for example, 1.00 or more.

[0160] When the molded article has the above-mentioned physical properties, it is suitable as an optical element.

[0161] Examples of the optical element include a lens, a sheet, and a film, and preferably a lens.

[0162] Examples of lenses include clear lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0163] The uses of the XDI composition are not limited to the optical materials described above. Examples of uses of the XDI composition include inks, transfer foils, pressure sensitive adhesives, binders, gels, elastomers, foams, adhesives, one-component curing sealants, RIM molded products, micro-foamed polyurethanes, various microcapsules, aqueous resins, thermosetting resins, active energy ray (e.g., electron beams, ultraviolet rays, etc.) curable resins, artificial and synthetic leathers, slush powders, robot components, mobility components, healthcare materials, base resins for carbon fiber reinforced plastics (CFRP), transparent rubbers, transparent hard resins, Examples of applications include waterproof materials, films, sheets, tubes, blades, speakers, sensors, organic electroluminescent (EL) components, solar power generation components, android components, wearable components, sporting goods, leisure goods, medical supplies, nursing care products, housing components, acoustic components, lighting components, chandeliers, outdoor lights, packing, vibration-proofing, vibration-damping and seismic isolation components, soundproofing components, daily necessities, miscellaneous goods, cushions, bedding, stress absorbing materials, stress relaxation materials, interior and exterior parts of automobiles, transportation equipment components, office automation equipment components, surface protection components for miscellaneous goods, self-repairing materials, and health equipment.

[0164] Preferred applications of the XDI composition include the above-mentioned optical materials, elastomers, foams, and one-component curing sealants.

[0165] 4. Effects and Effects The xylylene diisocyanate composition and polymerizable composition of the present invention contain the specific compound described above.

[0166] Therefore, by using the xylylene diisocyanate composition and the polymerizable composition as raw materials, a resin having excellent heat resistance can be produced.

[0167] The resin of the present invention is a cured product of a polymerizable composition containing the xylylene diisocyanate composition.

[0168] The molded article, optical element, and lens of the present invention are made of the above resin.

[0169] Therefore, the resin, molded article, optical element, and lens of the present invention have excellent heat resistance.

[0170] 5. Variations (1) The synthesis method of XDI is not limited to the hydrochloride method described above. Examples of the synthesis method of XDI include a gas-phase method in which evaporated XDA is reacted with carbonyl dichloride, a one-stage method in which XDA is directly reacted with carbonyl dichloride in one stage, and a cold-hot two-stage method in which XDA is reacted with carbonyl dichloride at a low temperature and then subsequently reacted at a high temperature. In these methods, XDI is obtained by the reaction of XDA with carbonyl dichloride. Another example of the synthesis method of XDI is a non-phosgene method in which XDI is obtained by thermal decomposition of xylylene dicarbamate.

[0171] (2) The production of the XDI composition does not have to be carried out continuously in the same plant. For example, a first XDI composition produced in a first plant can be used to carry out the purification step in a second plant.

[0172] The present invention will be described in more detail below with reference to examples, but is not limited thereto. The specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Form for Carrying Out the Invention." The "ratio" of each component is based on mass.

[0173] 1. Production of XDI Composition (1) Example 1 An XDI composition (first XDI composition) was produced by the production method described in International Publication No. 2018-190290.

[0174] 50 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of the obtained XDI composition, and the mixture was stirred at 60° C. for 6 hours. Thereafter, 10 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and mixed uniformly. This gave an XDI composition (second XDI composition).

[0175] (2) Example 2 80 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of an XDI composition (first XDI composition) obtained by the production method described in International Publication No. 2018-190290, and the mixture was stirred at 60° C. for 10 hours. This gave an XDI composition (second XDI composition).

[0176] (3) Example 3 150 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of an XDI composition (first XDI composition) obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 60°C for 10 hours. Thereafter, 60 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and mixed uniformly. This gave an XDI composition (second XDI composition).

[0177] (4) Example 4 An XDI composition (second XDI composition) obtained by the same production method as in Example 1 was stirred at 100°C for 2 hours, and then 40 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed uniformly at room temperature to obtain an XDI composition (second XDI composition).

[0178] (5) Example 5 300 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of an XDI composition (first XDI composition) obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 80°C for 5 hours. Thereafter, 80 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and mixed uniformly. This gave an XDI composition (second XDI composition).

[0179] (6) Example 6 300 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of an XDI composition (first XDI composition) obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 80°C for 6 hours. Thereafter, 100 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and mixed uniformly. This gave an XDI composition (second XDI composition).

[0180] (7) Example 7 200 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of an XDI composition (first XDI composition) obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 100°C for 4 hours. Thereafter, 50 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and mixed uniformly. This gave an XDI composition (second XDI composition).

[0181] (8) Example 8 200 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of an XDI composition (first XDI composition) obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 100 ° C. for 4 hours. Thereafter, 300 mg of PTSA and 300 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) were added at room temperature and mixed uniformly. This gave an XDI composition (second XDI composition).

[0182] (9) Comparative Example 1 150 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 100 g of the XDI composition obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was mixed uniformly at room temperature to obtain an XDI composition.

[0183] (10) Comparative Example 2 100 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 g of the XDI composition obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was mixed uniformly at room temperature to obtain an XDI composition.

[0184] (11) Comparative Example 3 50 mg of PTSA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 50 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 100 g of an XDI composition obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was mixed uniformly at room temperature to obtain an XDI composition.

[0185] 2. Measurement of component amounts of XDI compositions The proportions of XDI, PTSA, PTSI, urea compound, DCI, and CBI in the XDI compositions obtained in each Example and Comparative Example were measured by the following method. The results are shown in Tables 1 and 2.

[0186] (1) Ratio of XDI, PTSA, and PTSI in the XDI composition 100 mg of the XDI composition was mixed with 100 mg of 1,2,4,5-tetrachlorobenzene as an internal standard. The resulting mixture was then diluted with dichloromethane to a constant volume of 10 mL to obtain a sample. The resulting sample was then analyzed by gas chromatography under the following measurement conditions.

[0187] (Measurement conditions) Apparatus: SHIMADZU 2014 (Shimadzu Corporation) Packing material: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm × length 60 m (Shimadzu Corporation) Oven temperature: heated from 130°C to 220°C at 3°C / min, and after reaching 220°C, heated to 300°C at 10°C / min.

[0188] Split ratio: Pulsed splitless method Injection port temperature: 280°C Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55 kPa, Air 45 kPa (constant pressure control) Injection volume: 2 μL Detection method: FID The proportion of XDI in the XDI composition was calculated from the area ratio between the peak of the internal standard appearing at a retention time of 8.8 minutes and the peak of XDI appearing at a retention time of 13.8 minutes.

[0189] The proportion of PTSA in the XDI composition was calculated from the area ratio between the peak of the internal standard and the peak of PTSA appearing at a retention time of 15.0 minutes.

[0190] The proportion of PTSI in the XDI composition was calculated from the area ratio between the peak of the internal standard and the peak of PTSI appearing at a retention time of 9.1 minutes.

[0191] (2) Proportion of specific compounds in XDI composition The infrared spectrum of the XDI composition was measured using an FTIR spectrophotometer (trade name: IRSpirit, manufactured by Shimadzu Corporation).

[0192] Infrared spectra of the XDI compositions of Examples 1 to 8 show a peak at 1500 cm －１ From 1650 cm －１ On the other hand, in the infrared spectra of the XDI compositions of Comparative Examples 1 to 3, a peak was observed at 1500 cm －１ From 1650 cm －１ However, no peaks attributed to urea bonds were observed.

[0193] In addition, the XDI composition １ H-NMR was measured.

[0194] Specifically, 35 mg of the XDI composition, 0.7 mL of deuterated chloroform, and 25 mg of paraxylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an internal standard were mixed to obtain a sample for measurement.

[0195] The obtained sample was subjected to nuclear magnetic resonance (NMR) analysis using a nuclear magnetic resonance spectrometer (ECX-400P, manufactured by JEOL Ltd.) with the observation nucleus set to H (400 MHz), the observation range set to 15 ppm, and the number of accumulations set to 64. １ H-NMR measurement was carried out.

[0196] The XDI compositions of Examples 1 to 8 １ In the H-NMR spectrum, multiple peaks were observed at chemical shift values ​​of 2.44 to 2.46 ppm with chloroform in deuterated chloroform as the reference. １ In the H-NMR spectrum, no peaks at chemical shift values ​​of 2.44 to 2.46 ppm were observed.

[0197] Infrared spectrum and １ Comparison with the H-NMR spectrum reveals that the multiple peaks at chemical shift values ​​of 2.44 to 2.46 ppm are considered to represent the urea compound represented by the above chemical formula (1), the urea compound represented by the above chemical formula (2), and a derivative obtained from XDI and PTSI.

[0198] The peak of the internal standard was observed at a chemical shift value of 2.30 ppm.

[0199] Next, the proportion of the urea compound in the XDI composition was calculated when the multiple peaks in the chemical shift range of 2.44 to 2.46 ppm were at least one of the urea compound represented by the chemical formula (1) and the urea compound represented by the chemical formula (2).

[0200] Specifically, the mass ratio of the urea compound to the internal standard was calculated from the sum of the peak areas of a plurality of peaks with chemical shift values ​​of 2.44 to 2.46 ppm and the peak area of ​​the internal standard.

[0201] The proportion of the urea compound in the XDI composition was calculated from the obtained mass ratio and the proportion of the internal standard substance in the sample.

[0202] (5) Proportion of DCI in XDI Composition The proportion of DCI in the XDI composition was measured by the method described in paragraphs

[0375] to

[0376] of WO 2018 / 190290.

[0203] (6) Proportion of CBI in XDI Composition The proportion of CBI in the XDI composition was measured by the method described in paragraphs

[0376] to

[0377] of WO 2018 / 190290.

[0204]

[0205]

[0206] 2. Production of Molded Article 50.8 parts by mass of the XDI composition shown in Table 1 was mixed and dissolved at 20°C with 0.01 parts by mass of dimethyltin dichloride as a curing catalyst, 0.10 parts by mass of Zelec UN (trade name, manufactured by Stepan Corporation; acidic phosphate ester), and 1.5 parts by mass of Biosorb 583 (manufactured by Sakai Chemical Industry Co., Ltd.; ultraviolet absorber) to obtain Mixture 1.

[0207] Next, 49.2 parts by mass of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was uniformly mixed with mixed solution 1 to obtain mixed solution 2 (polymerizable composition).

[0208] Mixture 2 was degassed at 600 Pa for 1 hour, and then filtered through a 1 μm Teflon (registered trademark) filter.

[0209] Next, the filtered mixed solution 2 was poured into a mold consisting of a glass mold and tape.

[0210] Next, the mold into which the mixed liquid 2 had been poured was placed in an oven, the temperature was raised from 25°C to 120°C, and the mixture was cured at 120°C for 24 hours.

[0211] Thereafter, the mold was removed from the oven, the cured product was released from the mold, and the resulting cured product was annealed at 120° C. for 1 hour.

[0212] As a result of the above, cured products (molded articles) of the respective Examples and Comparative Examples were obtained.

[0213] 3. Evaluation of Physical Properties of Molded Articles (1) Refractive Index (ne) and Abbe Number (νe) Test pieces measuring 10 mm in length, 10 mm in width, and 2.5 mm in thickness were prepared from the obtained resin, and the refractive index (ne) at a wavelength of 546.1 nm (mercury e-line), the refractive index (nF') at a wavelength of 480.0 nm (Cd F'-line), and the refractive index (nC') at a wavelength of 643.9 nm (Cd C'-line) were measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation. The Abbe number (νe) was calculated based on the refractive index (ne), the refractive index (nF'), and the refractive index (nC').

[0214] In all of the examples and comparative examples, the refractive index (ne) was 1.665 and the Abbe number (νe) was 31. (2) YI Value A circular plate having a thickness of 2.5 mm and a diameter of 75 mm was prepared from the obtained resin, and the YI value was determined using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc.

[0215] The smaller the YI value, the less yellow the resin is, and the larger the YI value, the more yellow the resin is.

[0216] The YI value of each example is shown in Table 1, and the YI value of each comparative example is shown in Table 2. (3) Heat Resistance Test pieces 10 mm long, 10 mm wide, and 2.5 mm thick were prepared from the obtained resin, and the glass transition temperature (Tg) was measured by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10°C / min) using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation. The higher the glass transition temperature (Tg), the better the heat resistance.

[0217] The glass transition temperature (Tg) of each example is shown in Table 1, and the glass transition temperature (Tg) of each comparative example is shown in Table 2.

[0218] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims.

[0219] The xylylene diisocyanate composition, polymerizable composition, resin, and molded article of the present invention can be used, for example, in the production of optical elements such as lenses.

Claims

1. A xylylene diisocyanate composition comprising: xylylene diisocyanate; and mixing the xylylene diisocyanate composition with deuterated chloroform. １ A specific compound having a peak in a chemical shift range of 2.44 ppm to 2.46 ppm based on chloroform in the deuterated chloroform when measured by H-NMR.

2. The xylylene diisocyanate composition according to claim 1, wherein the proportion of the specific compound is 100 ppm or more by mass.

3. The xylylene diisocyanate composition according to claim 1, wherein the proportion of the specific compound is 10,000 ppm or less by mass.

4. The xylylene diisocyanate composition according to claim 1, wherein the proportion of the specific compound is 3,000 ppm or less on a mass basis.

5. The xylylene diisocyanate composition according to claim 1, containing at least one of a urea compound represented by the following chemical formula (1) and a urea compound represented by the following chemical formula (2) as the specific compound. Chemical formula (1): Chemical formula (2):

6. The xylylene diisocyanate composition according to claim 1, further comprising at least one of 4-methylbenzenesulfonamide and 4-methylbenzenesulfonyl isocyanate.

7. The xylylene diisocyanate composition according to claim 6, wherein the sum of the proportion of 4-methylbenzenesulfonamide in the xylylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is 2000 ppm or less on a mass basis.

8. The xylylene diisocyanate composition according to claim 1, further comprising at least one of monochloromethyl benzyl isocyanate and dichloromethyl benzyl isocyanate.

9. The xylylene diisocyanate composition according to claim 1, wherein the xylylene diisocyanate is obtained by reacting xylylene diamine with carbonyl dichloride or by reacting xylylene diamine hydrochloride with carbonyl dichloride.

10. A polymerizable composition comprising the xylylene diisocyanate composition according to any one of claims 1 to 9 and an active hydrogen group-containing component.

11. The active hydrogen-containing component is selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptomethyl)-1,4-dithiane, 11. The polymerizable composition of claim 10, comprising at least one polythiol selected from the group consisting of 1,2,3-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

12. A resin which is a cured product of the polymerizable composition according to claim 11.

13. A molded article made of the resin according to claim 12.

14. An optical element which is the molded article according to claim 13.

15. A lens, which is the optical element according to claim 14.

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