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

Abstract

The xylylene diisocyanate composition contains a xylylene diisocyanate and a specific compound. When the xylylene diisocyanate composition is mixed with deuterated chloroform and the mixture is subjected to 1H-NMR measurement, the specific compound has a peak in a chemical shift value range of 2.44 ppm to 2.46 ppm based on chloroform in the deuterated chloroform.

Description

Technical Field

[0001] This invention relates to phthalamide diisocyanate compositions, polymerizable compositions, resins, molded articles, optical elements, and lenses. Background Technology

[0002] Previously, it was known to react phenylene diisocyanate compositions with polythiols to produce resins that could be used in optical elements such as lenses (see Patent Document 1 below).

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2018 / 190290 Summary of the Invention

[0004] The problem that the invention aims to solve In the manufacture of the resin described in Patent Document 1, it is sometimes desirable to further improve its heat resistance.

[0005] The present invention provides phenylene diisocyanate compositions and polymerizable compositions capable of manufacturing resins with excellent heat resistance, as well as resins with excellent heat resistance, molded articles, optical elements and lenses.

[0006] Methods for solving problems The present invention [1] is a phenylene diisocyanate composition containing: phenylene diisocyanate; and a specific compound, wherein the aforementioned phenylene diisocyanate composition is mixed with deuterated chloroform and subjected to... 1 When measured by H-NMR, the specific compound has a peak in the range of 2.44 ppm to 2.46 ppm based on chloroform in the aforementioned deuterated chloroform.

[0007] The present invention [2] includes the phenylene diisocyanate composition of [1] above, wherein the proportion of the aforementioned specific compound is 100 ppm or more by mass.

[0008] The present invention [3] includes the phenylene diisocyanate composition of [1] or [2] above, wherein the proportion of the aforementioned specific compound is less than 10,000 ppm by mass.

[0009] The present invention [4] includes the phenylene diisocyanate composition of [1] or [2] above, wherein the proportion of the aforementioned specific compound is less than 3000 ppm by mass.

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

[0011] Chemical formula (1): [Chemical Formula 1] Chemical formula (2): [Chemical Formula 2] The present invention [6] includes the phenylene diisocyanate composition of any one of [1] to [5] above, which further contains at least one of 4-methylbenzenesulfonamide and 4-methylbenzenesulfonyl isocyanate.

[0012] The present invention [7] includes the phenylene diisocyanate composition of [6] above, wherein the sum of the proportion of the aforementioned 4-methylbenzenesulfonamide in the aforementioned phenylene diisocyanate composition and the proportion of the aforementioned 4-methylbenzenesulfonyl isocyanate in the aforementioned phenylene diisocyanate composition is less than 2000 ppm by mass.

[0013] The present invention [8] includes the phenylene diisocyanate composition of any one of [1] to [7] above, which further contains at least one of monochloromethyl benzyl isocyanate and dichloromethyl benzyl isocyanate.

[0014] The present invention [9] includes a phenylene diisocyanate composition of any one of [1] to [8] above, wherein the aforementioned phenylene diisocyanate is obtained by the reaction of phenylene dimethylamine with carbonyl dichloride or by the reaction of phenylene dimethylamine hydrochloride with carbonyl dichloride.

[0015] The present invention

[10] includes a polymerizable composition comprising: a phenylene diisocyanate composition of any one of [1] to [9] above; and a component containing an active hydrogen group.

[0016] The present invention

[11] includes the polymerizable composition of

[10] above, wherein the aforementioned active hydrogen-containing component comprises selected from 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, At least one polythiol from the group consisting of 5-bis(mercaptomethyl)-1,4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0017] The present invention

[12] includes a resin, which is a cured product of the polymeric composition of

[10] or

[11] described above.

[0018] The present invention

[13] includes a molded body formed from the resin described above

[12] .

[0019] The present invention

[14] includes an optical element, which is a molded body of

[13] described above.

[0020] The present invention

[15] includes a lens, which is the optical element described in

[14] above.

[0021] Invention Effects The phenylene diisocyanate composition and polymerizable composition of the present invention contain specific compounds. The phenylene diisocyanate composition is mixed with deuterated chloroform and subjected to... 1 Under H-NMR determination, the specific compound has a peak in the range of 2.44 ppm to 2.46 ppm based on chloroform in deuterated chloroform.

[0022] By using a phenylene diisocyanate composition containing specific compounds and a polymerizable composition as raw materials, it is possible to manufacture a resin with excellent heat resistance.

[0023] The resin of the present invention is a cured product of a polymeric composition containing the above-mentioned diphenylene diisocyanate composition.

[0024] Furthermore, the molded body, optical element, and lens of the present invention are formed from the above-mentioned resin.

[0025] Therefore, the resin, molded body, optical element and lens of the present invention have excellent heat resistance. Detailed Implementation

[0026] 1. Phenylene diisocyanate composition The phenylene diisocyanate composition (XDI composition) contains phenylene diisocyanate (XDI) as the main component. It should be noted that the "XDI composition" described here refers to the "second XDI composition" obtained by the "method of manufacturing XDI composition" described later.

[0027] Examples of XDIs include 1,2-XDI (adjacent XDI), 1,3-XDI (intermediate XDI), and 1,4-XDI (paired XDI).

[0028] As an XDI, 1,3-XDI (inter-XDI) is a preferred example.

[0029] An XDI composition may contain two or more types of XDI.

[0030] The proportion (purity) of XDI in the XDI composition is, for example, 98.00% by mass or more, preferably 99.00% by mass or more, more preferably 99.30% by mass or more, even more preferably 99.60% by mass or more, and, for example, 99.95% by mass or less.

[0031] The proportion of XDI in the XDI composition can be determined using the methods described in the examples below.

[0032] The XDI composition contains specific compounds as by-products. This involves mixing the phenylene diisocyanate composition with deuterated chloroform and then... 1 Under H-NMR determination, the specific compound has a peak in the range of 2.44 ppm to 2.46 ppm based on chloroform in deuterated chloroform.

[0033] 1 H-NMR can be performed under the measurement conditions described in the examples described later.

[0034] The XDI composition contains at least one of the following urea compounds: the urea compound represented by chemical formula (1) and the urea compound represented by chemical formula (2) as a specific compound.

[0035] Chemical formula (1): [Chemical Formula 1] Chemical formula (2): [Chemical Formula 2] Additionally, the XDI composition may contain a specific compound derived from XDI and 4-methylbenzenesulfonyl isocyanate (PTSI, also known as p-toluenesulfonyl isocyanate). Examples of such derivatives include isocyanurate bodies, urea-formate bodies, biuret bodies, urea-ketone imine bodies, carbodiimine bodies, and urea-diketone bodies.

[0036] When the specific compound is at least one of the urea compound shown in chemical formula (1) and the urea compound shown in chemical formula (2) above, the proportion of the specific compound in the XDI composition, on a mass basis, 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.

[0037] If the proportion of a specific compound in the XDI composition is above the aforementioned lower limit, the heat resistance of the resin manufactured using the XDI composition can be improved.

[0038] When the specific compound is at least one of the urea compound represented by chemical formula (1) and the urea compound represented by chemical formula (2) above, the proportion of the specific compound in the XDI composition, on a mass basis, 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.

[0039] If the proportion of a specific compound in the XDI composition is below the above-mentioned upper limit, the yellowness (YI value) of the resin manufactured using the XDI composition can be reduced.

[0040] It should be noted that the range of the proportion of a specific compound in the XDI composition can be set by combining any one of the upper limits of the proportion of a specific compound in the XDI composition with any one of the lower limits of the proportion of a specific compound in the XDI composition.

[0041] The proportion of specific compounds in the XDI composition can be determined using the methods described in the examples below.

[0042] The XDI composition may also contain at least one of PTSI and 4-methylbenzenesulfonamide (PTSA, also known as p-toluenesulfonamide) as an auxiliary component.

[0043] The proportion of PTSI in the XDI composition, on a mass basis, is, 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.

[0044] If the proportion of PTSI in the XDI composition is below the above-mentioned upper limit, the yellowness of the resin made from the XDI composition can be reduced.

[0045] In addition, the proportion of PTSI in the XDI composition, on a mass basis, is, for example, higher 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.

[0046] If the proportion of PTSI in the XDI composition is above the lower limit mentioned above, the storage stability of the XDI composition can be improved.

[0047] It should be noted that the range of PTSI ratio in the XDI composition can be set by combining any one of the upper limit values ​​of the PTSI ratio in the XDI composition and any one of the lower limit values ​​of the PTSI ratio in the XDI composition.

[0048] The proportion of PTSI in the XDI composition can be determined using the methods described in the examples below.

[0049] The proportion of PTSA in the XDI composition, on a mass basis, is, 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.

[0050] If the proportion of PTSA in the XDI composition is below the above-mentioned upper limit, it is possible to suppress the increase in yellowness of the resin made from the XDI composition due to the specific compound.

[0051] In addition, the proportion of PTSA in the XDI composition, on a mass basis, is, for example, higher 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.

[0052] If the proportion of PTSA in the XDI composition is above the lower limit mentioned above, the storage stability of the XDI composition can be improved.

[0053] It should be noted that the range of the PTSA ratio in the XDI composition can be set by combining any one of the upper limit values ​​of the PTSA ratio in the XDI composition and any one of the lower limit values ​​of the PTSA ratio in the XDI composition.

[0054] The proportion of PTSA in the XDI composition can be determined using the methods described in the examples below.

[0055] The sum of the proportion of 4-methylbenzenesulfonamide in the phenylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the phenylene diisocyanate composition, on a mass basis, is, 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.

[0056] If the sum of the proportion of 4-methylbenzenesulfonamide in the phenylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the phenylene diisocyanate composition is below the above-mentioned upper limit, the yellowness of the resin made from the XDI composition can be reduced, and the heat resistance of the resin made using the XDI composition can be improved.

[0057] The sum of the proportion of 4-methylbenzenesulfonamide in the phenylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the phenylene diisocyanate composition, on a mass basis, 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, 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.

[0058] If the sum of the proportion of 4-methylbenzenesulfonamide in the phenylene diisocyanate composition and the proportion of 4-methylbenzenesulfonyl isocyanate in the phenylene diisocyanate composition is above the lower limit mentioned above, the storage stability of the XDI composition can be improved.

[0059] The XDI composition may also contain at least one of monochloromethyl benzyl isocyanate (CBI) and dichloromethyl benzyl isocyanate (DCI) as an auxiliary component.

[0060] The proportion of DCI in the XDI composition, on a mass basis, is, 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, for example, 60 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, and more preferably 20 ppm or less.

[0061] If the proportion of DCI in the XDI composition is within the above range, the yellowness of the resin made from the XDI composition can be reduced.

[0062] The proportion of CBI in the XDI composition, on a mass basis, is, for example, 0.2 ppm or more, preferably 6 ppm or more, more preferably 100 ppm or more, for example, 5000 ppm or less, preferably 4000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1600 ppm or less, and especially preferably 1000 ppm or less.

[0063] In addition, the proportion of CBI relative to the proportion of DCI is, for example, more than 2 times, preferably more than 10 times, more preferably more than 20 times, for example, less than 800 times, preferably less than 300 times, and more preferably less than 50 times.

[0064] If the proportion of CBI in the XDI composition is within the above-mentioned range, the yellowness of the resin manufactured from the XDI composition can be reduced. In particular, if the proportion of CBI is below the upper limit mentioned above, yellowing of the resin can be suppressed, and the urethane esterification reaction during resin manufacturing can proceed smoothly, thereby reliably improving the mechanical properties of the resin.

[0065] The proportions of DCI and CBI in the XDI composition can be determined using the methods described in the examples below.

[0066] 2. Method for manufacturing XDI composition The method for manufacturing the XDI composition is described.

[0067] Methods for manufacturing XDI compositions include, for example, synthesis steps, purification steps, and generation steps.

[0068] In the synthesis process, XDI is synthesized. For example, XDI is synthesized using the hydrochloride method. When using the hydrochloride method, the synthesis process includes a salt-making process and an isocyanate esterification process.

[0069] In the salt-making process, phenylenediamine (XDA) is mixed with hydrogen chloride to produce phenylenediamine hydrochloride (XDA hydrochloride).

[0070] Examples of XDAs include 1,2-XDA (o-XDA), 1,3-XDA (m-XDA), and 1,4-XDA (p-XDA), with 1,3-XDA (m-XDA) being the most preferred.

[0071] In the salt-making process, for example, XDA is reacted with hydrogen chloride in the presence of an inert solvent. Specifically, hydrogen chloride gas is mixed into a solution obtained by dissolving XDA in an inert solvent, thereby causing XDA to react with hydrogen chloride.

[0072] Examples of inactive solvents include those described in paragraph

[0059] of International Publication No. 2018 / 190290. Inactive solvents can be used alone or in combination of two or more. Halogenated aromatic hydrocarbons are preferred among inactive solvents, and chlorobenzene and dichlorobenzene are more preferred.

[0073] The mass percentage (total amine concentration) of XDA relative to the total mass of XDA and inactive solvent is, for example, 3% by mass or more, preferably 5% by mass or more, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0074] The supply ratio of hydrogen chloride relative to 1 mole of XDA is, for example, 2 moles or more, for example, 10 moles or less, preferably 6 moles or less, and more preferably 4 moles or less.

[0075] The reaction temperature in the salt-making process is, for example, above 30°C, preferably above 50°C, for example below 160°C, preferably below 150°C, and more preferably below 140°C.

[0076] The reaction pressure (gauge pressure) in the salt-making process is, for example, atmospheric pressure (0 MPaG) or higher, preferably 0.01 MPaG or higher, for example, 1.0 MPaG or lower, and preferably 0.5 MPaG or lower.

[0077] XDA is reacted with hydrogen chloride to generate XDA hydrochloride, thus obtaining a slurry containing XDA hydrochloride.

[0078] Next, in the isocyanate esterification process, XDA hydrochloride is reacted with carbonyl dichloride to produce a reactant containing XDI. In the isocyanate esterification process, carbonyl dichloride is mixed into a slurry containing XDA hydrochloride while removing hydrogen chloride gas generated in the side reaction, and the XDA hydrochloride reacts with the carbonyl dichloride. XDI is generated through the reaction of XDA hydrochloride with carbonyl dichloride. That is, XDI is obtained through the reaction of XDA hydrochloride with carbonyl dichloride.

[0079] The supply ratio of carbodichloro is, for example, 4 moles or more, preferably 5 moles or more, more preferably 6 moles or more, for example, 50 moles or less, preferably 40 moles or less, more preferably 30 moles or less, relative to 1 mole of XDA hydrochloride.

[0080] The reaction time for the isocyanate esterification process is, for example, 4 hours or more, preferably 6 hours or more, for example, 25 hours or less, preferably 20 hours or less, and more preferably 15 hours or less.

[0081] The reaction temperature in the isocyanate esterification process is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, for example, 190°C or lower, preferably 180°C or lower, more preferably 160°C or lower.

[0082] The reaction pressure (gauge pressure) in the isocyanate esterification process is, for example, higher than atmospheric pressure (0 MPaG), 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, for example, 0.6 MPaG or less, preferably 0.4 MPaG or less, more preferably 0.2 MPaG or less.

[0083] The isocyanate esterification process is preferably carried out continuously. That is, a slurry containing XDA hydrochloride is continuously fed into the reaction tank used in the isocyanate esterification process, and the XDA hydrochloride reacts with carbonyl dichloride in the reaction tank while the reactant is continuously removed from the reaction tank.

[0084] Next, gaseous components, inactive solvents, and tar components are removed from the reactants.

[0085] The gaseous components contain carbonyl dichloride that remains in the reactants due to its non-reaction with XDA hydrochloride during the isocyanate esterification process, and hydrogen chloride gas generated as a byproduct of the isocyanate esterification process. These gaseous components can be removed from the reactants using, for example, a known degassing tower.

[0086] Inactive solvents can be removed from the reactants by distillation using, for example, known distillation columns.

[0087] Tar components can be removed from the reactants using, for example, known tar removers.

[0088] After removing gaseous components, inactive solvents, and tar components, the proportion of XDI in the reactants is, for example, 80.0% by mass or more, preferably 90.0% by mass or more, more preferably 95.0% by mass or more, and for example, 99.0% by mass or less, preferably 98.5% by mass or less, more preferably 98.0% by mass or less.

[0089] Next, in the purification process, the reactants are purified. The purification process includes, for example, a low-boiling-point removal process and a distillation process.

[0090] In the low-boiling-point removal process, low-boiling-point components are removed from the reactants. These components have boiling points lower than that of XDI. The low-boiling-point removal process may involve, for example, distilling the reactants using a low-boiling-point removal tower to remove these components.

[0091] Examples of low-boiling-point removal towers include, for example, plate towers and packed towers, with packed towers being preferred. The theoretical number of plates in a low-boiling-point removal tower is, for example, 3 or more, preferably 5 or more, more preferably 7 or more, for example, 40 or less, preferably 20 or less, and more preferably 15 or less.

[0092] The bottom temperature of the deboiling tower is, for example, above 130°C, preferably above 140°C, more preferably above 150°C, for example below 200°C, preferably below 190°C, more preferably below 180°C.

[0093] The top temperature of the deboiling tower is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, for example, 160°C or lower, preferably 150°C or lower, more preferably 140°C or lower.

[0094] The top pressure of the deboiling column is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0095] The reflux ratio at the top of the deboiling column is, for example, 1 or more, preferably 5 or more, more preferably 10 or more, for example, 80 or less, preferably 60 or less, more preferably 50 or less.

[0096] The residence time of the deboiling tower is, for example, 0.1 hours or more, preferably 0.2 hours or more, more preferably 0.3 hours or more, for example, 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

[0097] The reaction material after removing low-boiling-point components by distillation was obtained by using a de-boiling column as the bottom liquid.

[0098] Next, in the distillation process, a distillation column is used to further distill (distill) the reaction material after the low-boiling point removal process.

[0099] Examples of distillation columns include, for example, plate columns and packed columns, with packed columns being preferred. The theoretical number of plates in a distillation column is, for example, one or more, for example, 20 or less, preferably 10 or less, and more preferably 5 or less.

[0100] The bottom temperature of the distillation column is, for example, above 120°C, preferably above 130°C, more preferably above 140°C, for example below 190°C, preferably below 180°C, more preferably below 170°C.

[0101] The top temperature of the distillation column is, for example, above 90°C, preferably above 110°C, more preferably above 130°C, for example below 180°C, preferably below 170°C, more preferably below 160°C.

[0102] The pressure at the top of the distillation column is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0103] The reflux ratio at the top of the distillation column is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, for example, 50 or less, preferably 20 or less, more preferably 10 or less.

[0104] The residence time of the distillation column is, for example, 0.2 hours or more, preferably 0.5 hours or more, more preferably 1.0 hour or more, for example, 20 hours or less, and preferably 10 hours or less.

[0105] The fraction containing XDI (first XDI composition) is obtained through a distillation process. The first XDI composition contains DCI and CBI.

[0106] Next, in the production process, the aforementioned urea compound is generated.

[0107] To generate urea compounds, for example, PTSA is added to the first XDI composition while heating and stirring.

[0108] The heating temperature in the production process is, for example, 40°C or above, preferably 50°C or above, more preferably 60°C or above, for example, 120°C or below, preferably 100°C or below, more preferably 80°C or below.

[0109] The heating time in the production process is, for example, more than 1 hour, preferably more than 3 hours, more preferably more than 5 hours, more preferably more than 8 hours, for example, less than 48 hours, preferably less than 36 hours, more preferably less than 24 hours, and more preferably less than 12 hours.

[0110] In the production process, PTSA reacts with XDI to generate the aforementioned urea compound. This yields the aforementioned XDI composition (the second XDI composition).

[0111] It should be noted that PTSI can also be added to the obtained XDI composition (second XDI composition) as needed for mixing.

[0112] Alternatively, the method for manufacturing the XDI composition may exclude the generation step, but include, for example, a salt-making step, an isocyanate esterification step, a purification step, and a mixing step.

[0113] In the mixing process, the aforementioned urea compound, and PTSA and PTSI as needed, are added to the first XDI composition and mixed.

[0114] The above-mentioned XDI composition can also be obtained using this method.

[0115] 3. Uses of XDI compositions The above-described XDI composition can be used as a raw material for resins. Resins can be manufactured by reacting the isocyanate component containing the XDI composition with a component containing active hydrogen groups.

[0116] Components containing active hydrogen groups contain compounds containing active hydrogen groups.

[0117] Examples of compounds containing active hydrogen groups include polyols, polythiols, and polyamines.

[0118] Compounds containing active hydrogen groups can be used alone or in combination of two or more.

[0119] From an optical property point of view, compounds containing active hydrogen groups are preferably polythiols. The active hydrogen group-containing component is preferably a polythiolactic acid composition containing polythiols as the main component.

[0120] The proportion of polythiols in the polythiols composition is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0121] The proportion of polythiols in a polythiols composition can be determined using, for example, high performance liquid chromatography.

[0122] Polythiols contain multiple thiol groups. Polythiols do not contain the byproducts described later. Examples of polythiols include aliphatic polythiols, aromatic polythiols, and heterocyclic polythiols.

[0123] Examples of aliphatic polythiols include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, tetra(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tri(2-mercaptoacetate), trimethylolpropane tri(3-mercaptopropionate), trimethylolethane tri(2-mercaptoacetate), trimethylolethane tri(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(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, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiacyclohexane, 2,5-dimercapto-1,4-dithiacyclohexane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiacyclohexane, and their thioglycolic acid esters and thiopropionates, hydroxymethyl sulfide bis(2-mercaptoacetic acid ester), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoethyl)sulfide Hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), thionyl diacetate bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), thionyl diacetate bis(2-mercaptoethyl ester), dithiodipropionate bis(2-mercaptoethyl ester), 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-Dithicyclobutane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithicyclopentane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane.

[0124] 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(mercaptomethyloxy)benzene, 1,3,5-tris(mercaptoethyloxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol.

[0125] Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-triazine, 3,4-thiophene dithiol, and bismuth reagents.

[0126] Polythiols can be used alone or in combination of two or more.

[0127] In addition, preferred polythiols 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 tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), and 2,5-bis(mercaptomethyl)-1,4-dithio At least one of the following groups: heterocyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithionecyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithionecyclobutane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithionepentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0128] Polythiol compositions may contain byproducts.

[0129] As a byproduct, a compound (hereinafter referred to as compound A) can be obtained by replacing at least one of the multiple thiol groups of the above-mentioned polythiol with the functional group shown in the following chemical formula (3).

[0130] Chemical formula (3): [Chemical Formula 3] When the polythiol composition contains compound A, in the high performance liquid chromatography determination of the polythiol composition, the peak area (R1) of compound A relative to the peak area 100 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.

[0131] The term "peak area (R1) of compound A relative to the peak area of ​​polythiols (100)" refers to the peak area (P) of polythiols (including structural isomers of polythiols). thiol The peak area (P) of compound A when the value is 100. A The relative value (proportion) of ) is calculated by the following formula (1).

[0132] Equation (1): R1 = (P A / P thiol )×100 Once the peak area (R1) of compound A relative to the peak area 100 of the polythiol is determined, the high performance liquid chromatography determination can be performed under the determination conditions described in paragraph

[0041] of International Publication No. 2022 / 102625.

[0133] If the peak area (R1) of compound A relative to the peak area 100 of the polythiol is above the lower limit and below the upper limit, the pot life of the polymerizable composition obtained from the polythiol composition and the polyisocyanate composition can be well guaranteed. By further curing the polymerizable composition, a plastic lens formed from polysulfururate resin with excellent hue, transparency, and corrugation can be obtained.

[0134] In addition, 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 also contain a compound represented by the following chemical formula (4) (hereinafter referred to as compound B) as a by-product.

[0135] Chemical formula (4): [Chemical Formula 4] (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 the high performance liquid chromatography determination of the polythiol composition, the peak area (R2) of compound B relative to the total peak area 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, 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, more preferably 4.0 or more.

[0136] The term "peak area (R2) of compound B relative to the total peak area 100 of the compounds contained in the polythiol composition" refers to the total peak area (P) of the compounds contained in the polythiol composition. sum The peak area (P) of compound B under the condition of 100. B The relative value (proportion) of the compounds contained in the polythiol composition is calculated by the following formula (2). sum "" is the sum of the peak areas of all peaks detected in the high performance liquid chromatography determination of polythiol compositions.

[0137] Equation (2): R2 = (P B / P sum )×100 When determining the peak area (R2) of compound B relative to the total peak area 100 of the compounds contained in the polythiol composition, the high performance liquid chromatography determination can be performed under the determination conditions described in paragraph

[0049] of International Publication No. 2022 / 138865.

[0138] If the peak area (R2) of compound B relative to the total peak area 100 of the compounds contained in the polythiol composition is below the aforementioned upper limit, the lightfastness of the resin manufactured from the polythiol composition can be improved. Furthermore, if the peak area (R2) of compound B relative to the total peak area 100 of the compounds contained in the polythiol composition is above the aforementioned lower limit, the dyeability of the resin manufactured from the polythiol composition can be improved.

[0139] For example, the resin can be manufactured by casting. In casting, firstly, the isocyanate component and the active hydrogen group component are mixed in a ratio of 0.8 to 1.2 of isocyanate groups in the isocyanate component to active hydrogen groups (amino, thiol, or hydroxyl) in the active hydrogen group component. The resulting mixture is a polymeric composition containing the isocyanate component and the active hydrogen group component.

[0140] It should be noted that known additives can be mixed into the polymerizable composition. Examples of additives include curing catalysts, stabilizers (acidic phosphate esters), and ultraviolet absorbers.

[0141] Next, the polymeric composition is injected into a mold and then heated to cure. This yields a molded body formed from the resin. In other words, the resin is a cured product of the polymeric composition.

[0142] When the active hydrogen group component contains polythiols, the resulting molded body exhibits excellent transparency.

[0143] Furthermore, since the above-mentioned polyisocyanate composition contains XDI and specific compounds, the resulting molded article has a high refractive index and excellent heat resistance.

[0144] In detail, the refractive index (ne) of the resulting molded article is, for example, 1.650 or more, preferably 1.660 or more, and for example, 1.670 or less.

[0145] It should be noted that the Abbe number (νe) of the obtained molded body is, for example, 30 or more, preferably 31 or more, for example, 35 or less, preferably 33 or less.

[0146] In addition, the glass transition temperature (Tg) of the obtained molded article is, for example, 80°C or higher, preferably 85°C or higher, and for example, 95°C or lower.

[0147] Furthermore, the resulting molded article also has a low YI value. Specifically, the YI value of the resulting 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.

[0148] With the aforementioned physical properties, the resulting molded body is suitable as an optical element.

[0149] Examples of optical elements include lenses, sheets, and films, with lenses being a preferred choice.

[0150] Examples of lenses include transparent lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0151] It should be noted that the uses of XDI compositions are not limited to the aforementioned optical materials. Examples of uses for XDI compositions include, for example, inks, transfer foils, adhesives, binders, gels, elastomers, foams, bonding agents, one-component curable sealants, RIM molded products, microfoamed polyurethane, various microcapsules, water-based resins, thermosetting resins, active energy radiation (e.g., electron beams, ultraviolet rays) curable resins, artificial and synthetic leather, slush molding powders, robot components, movable components, health care materials, carbon fiber reinforced plastic (CFRP) base resins, transparent rubbers, transparent rigid resins, waterproof materials, and films. Sheets, tubes, blades, speakers, sensors, organic EL components, solar power generation components, humanoid robot components, wearable components, sporting goods, leisure goods, medical supplies, nursing supplies, residential components, audio components, lighting components, chandeliers, streetlights, padding, vibration damping and isolation components, sound insulation components, daily necessities, general merchandise, cushioning pads, bedding, stress-absorbing materials, stress-relieving materials, automotive interior and exterior trim parts, transportation machinery components, OA equipment components, general merchandise surface protection components, self-healing materials, and health equipment.

[0152] Examples of preferred uses for XDI compositions include the aforementioned optical materials, elastomers, foams, and one-component curing sealants.

[0153] 4. Effects The phthalene diisocyanate composition and polymerizable composition according to the present invention contain the specific compounds described above.

[0154] Therefore, by using phenylene diisocyanate compositions and polymerizable compositions as raw materials, it is possible to manufacture resins with excellent heat resistance.

[0155] The resin of the present invention is a cured product of a polymeric composition containing the above-mentioned diphenylene diisocyanate composition.

[0156] Furthermore, the molded body, optical element, and lens of the present invention are formed from the above-mentioned resin.

[0157] Therefore, the resin, molded body, optical element and lens of the present invention have excellent heat resistance.

[0158] 5. Variations (1) The synthesis method of XDI is not limited to the hydrochloride method described above. Examples of XDI synthesis methods include: a gas-phase method in which evaporated XDA is reacted with carbonyl dichloride; a one-step method in which XDA and carbonyl dichloride are reacted directly in one step; and a two-step method of hot and cold reaction in which XDA and carbonyl dichloride are reacted at low temperature and then at high temperature. In these methods, XDI is obtained by the reaction of XDA with carbonyl dichloride. In addition, examples of XDI synthesis methods include the non-phosgene method, which obtains XDI by thermal decomposition of p-phenylene dicarboxylate.

[0159] (2) The manufacture of the XDI composition may not be carried out continuously in the same equipment. For example, the first XDI composition manufactured in the first equipment may be used, and the production process may be carried out in the second equipment.

[0160] Example The following examples illustrate the invention in more detail, but the invention is not limited thereto. The specific values ​​of proportions (including ratios), physical properties, parameters, etc., used in the following description can be replaced by the corresponding upper limit values ​​(defined as "below" or "less than") or lower limit values ​​(defined as "above" or "more than") of the proportions (including ratios), physical properties, parameters, etc., described in the "Specific Embodiments" above. It should be noted that the "proportion" of each component is based on mass.

[0161] 1. Manufacturing of XDI compositions (1) Example 1 An XDI composition (the first XDI composition) was manufactured using the manufacturing method described in International Publication No. 2018-190290.

[0162] Add 50 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) to 100 g of the obtained XDI composition and stir at 60°C for 6 hours. Then, add 10 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) at room temperature and mix thoroughly. Thus, the XDI composition (second XDI composition) is obtained.

[0163] (2) Example 2 80 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) 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. This yielded an XDI composition (second XDI composition).

[0164] (3) Example 3 150 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 100 g of an XDI composition (first XDI composition) obtained using the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 60°C for 10 hours. Then, 60 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature, and the mixture was thoroughly mixed. This yielded an XDI composition (second XDI composition).

[0165] (4) Example 4 After stirring the XDI composition (second XDI composition) obtained using the same manufacturing method as in Example 1 at 100°C for 2 hours, 40 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and mixed evenly. Thus, the XDI composition (second XDI composition) was obtained.

[0166] (5) Example 5 300 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 100 g of an XDI composition (first XDI composition) obtained using the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 80°C for 5 hours. Then, 80 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature, and the mixture was thoroughly mixed. This yielded an XDI composition (second XDI composition).

[0167] (6) Example 6 300 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 100 g of an XDI composition (first XDI composition) obtained using the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 80°C for 6 hours. Then, 100 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature, and the mixture was thoroughly mixed. This yielded an XDI composition (second XDI composition).

[0168] (7) Example 7 200 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 100 g of an XDI composition (first XDI composition) obtained using the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 100°C for 4 hours. Then, 50 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature, and the mixture was thoroughly mixed. This yielded an XDI composition (second XDI composition).

[0169] (8) Example 8 200 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 100 g of an XDI composition (first XDI composition) obtained using the manufacturing method described in International Publication No. 2018-190290, and the mixture was stirred at 100°C for 4 hours. Then, 300 mg of PTSA and 300 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) were added at room temperature and mixed evenly. Thus, an XDI composition (second XDI composition) was obtained.

[0170] (9) Comparative Example 1 150 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added to 100 g of an XDI composition obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was uniformly mixed at room temperature. Thus, the XDI composition was obtained.

[0171] (10) Comparative Example 2 100 mg of PTSI (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 g of an XDI composition obtained by the manufacturing method described in International Publication No. 2018-190290, and the mixture was uniformly mixed at room temperature. Thus, the XDI composition was obtained.

[0172] (11) Comparative Example 3 50 mg of PTSA (manufactured by FUJIFILM Wako Pure Chemical Corporation) 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 uniformly mixed at room temperature. Thus, the XDI composition was obtained.

[0173] 2. Determination of the compositional content of the XDI composition The proportions of XDI, PTSA, PTSI, urea compounds, DCI, and CBI in the XDI compositions obtained in each example and comparative example were determined using the following methods. The results are shown in Tables 1 and 2.

[0174] (1) The 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 final volume of 10 mL to obtain the sample. The sample was then analyzed by gas chromatography under the following assay conditions.

[0175] (Measurement conditions) Device: SHIMADZU 2014 (Made by Shimadzu Corporation) Filler: DB-1 (film thickness) 1.5μm, Column: Inner diameter 0.53mm × length 60m (Shimadzu Corporation) Column oven temperature: Increase from 130℃ to 220℃ at a rate of 3℃ / min, and then increase to 300℃ at a rate of 10℃ / min after reaching 220℃.

[0176] Shunt ratio: Pulse shunt method Inlet temperature: 280℃ Detector temperature: 300℃ Carrier gas: N2 158kPa, H2 55kPa, air 45kPa (constant pressure control) Injection volume: 2μL Detection method: FID The proportion of XDI in the XDI composition was calculated by the ratio of the area of ​​the internal standard peak appearing at retention time 8.8 minutes to the area of ​​the XDI peak appearing at retention time 13.8 minutes.

[0177] In addition, the proportion of PTSA in the XDI composition was calculated by the ratio of the area of ​​the internal standard peak to the area of ​​the PTSA peak appearing at a retention time of 15.0 minutes.

[0178] In addition, the proportion of PTSI in the XDI composition was calculated by the ratio of the area of ​​the internal standard peak to the area of ​​the PTSI peak appearing at a retention time of 9.1 minutes.

[0179] (2) The proportion of specific compounds in the XDI composition The infrared spectrum of the XDI composition was measured using an FTIR spectrophotometer (trade name: IRSpirit, manufactured by Shimadzu Corporation).

[0180] In the infrared spectra of the XDI compositions of Examples 1-8, at 1500 cm⁻¹ -1 Up to 1650cm -1 A peak believed to originate from urea bonds was observed at [location missing]. On the other hand, in the infrared spectra of the XDI compositions of Comparative Examples 1-3, a peak was observed at 1500 cm⁻¹. -1 Up to 1650cm -1No peaks that were thought to originate from urea bonds were observed at that location.

[0181] In addition, for XDI compositions 1 The measurements were performed using H-NMR.

[0182] Specifically, 35 mg of the XDI composition, 0.7 mL of deuterated chloroform, and 25 mg of p-xylene (manufactured by FUJIFILM Wako Pure Chemical Corporation) as an internal standard were mixed to obtain the sample for determination.

[0183] For the obtained samples, an NMR device (ECX-400P, manufactured by JEOL Ltd.) was used, with the observation nucleus set to H (400MHz), the observation range set to 15ppm, and the cumulative number of iterations set to 64. 1 H-NMR determination.

[0184] The XDI compositions in Examples 1-8 1 In the 1H-NMR spectrum, using chloroform in deuterated chloroform as a reference, multiple peaks were observed at chemical shifts of 2.44–2.46 ppm. On the other hand, in the XDI compositions of Comparative Examples 1–3… 1 In the H-NMR spectrum, no peak with chemical shift values ​​of 2.44~2.46 ppm was observed.

[0185] Based on infrared spectrum and 1 Comparison of H-NMR spectra suggests that multiple peaks with chemical shift values ​​of 2.44~2.46 ppm represent the urea compound shown in chemical formula (1), the urea compound shown in chemical formula (2), and derivatives obtained from XDI and PTSI.

[0186] It should be noted that the peak of the internal standard was observed at a chemical shift value of 2.30 ppm.

[0187] Next, the proportion of urea compounds in the XDI composition is calculated when the multiple peaks with chemical shift values ​​of 2.44 to 2.46 ppm are at least one of the urea compounds shown in chemical formula (1) and chemical formula (2).

[0188] In detail, the mass ratio of urea compound to internal standard is calculated by summing the peak areas of multiple peaks with chemical shift values ​​of 2.44~2.46 ppm and the peak area of ​​internal standard.

[0189] The proportion of urea compounds in the XDI composition is calculated from the obtained mass ratio and the proportion of internal standard in the sample.

[0190] (5) The proportion of DCI in the XDI composition The proportion of DCI in the XDI composition was determined using the method described in paragraphs

[0375] to

[0376] of International Publication No. 2018 / 190290.

[0191] (6) The proportion of CBI in the XDI composition The proportion of CBI in the XDI composition was determined using the method described in paragraphs

[0376] to

[0377] of International Publication No. 2018 / 190290.

[0192] [Table 1] [Table 2] 2. Manufacturing of molded parts To 50.8 parts by weight of the XDI composition shown in Table 1, 0.01 parts by weight of dimethyltin dichloride (as a curing catalyst), 0.10 parts by weight of ZELEC UN (trade name: Stepan Company; acidic phosphate), and 1.5 parts by weight of BioSorb583 (manufactured by Sakai CHEMICAL Company; ultraviolet absorber) were mixed at 20°C to dissolve them, resulting in mixture 1.

[0193] 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 are uniformly mixed into mixture 1 to obtain mixture 2 (polymeric composition).

[0194] Mixture 2 was degassed at 600 Pa for 1 hour, and then filtered using a 1 μm Teflon (registered trademark) filter.

[0195] Next, the filtered mixture 2 is injected into a mold formed by a glass mold and tape.

[0196] Next, the mold containing the mixture 2 was placed in an oven and heated from 25°C to 120°C for 24 hours to cure.

[0197] Then, remove the mold from the oven, demold the cured material from the mold, and anneal the resulting cured material at 120°C for 1 hour.

[0198] Through the above methods, the cured products (molded bodies) of each embodiment and comparative example are obtained.

[0199] 3. Evaluation of the physical properties of the molded part (1) Refractive index (ne) and Abbe number (νe) Test specimens with a length of 10 mm, a width of 10 mm, and a thickness of 2.5 mm were prepared from the obtained resin. Using a Shimadzu KPR-30 Purfrich refractometer, 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. The Abbe number (νe) was calculated based on the refractive indices (ne), (nF'), and (nC').

[0200] In all the embodiments and comparative examples, the refractive index (ne) was 1.665 and the Abbe number (νe) was 31.

[0201] (2) YI value A circular plate with a thickness of 2.5 mm and a diameter of 75 mm was made from the obtained resin. The YI value was determined using a CM-5 spectrophotometer manufactured by KONICA MINOLTAJAPAN, INC.

[0202] The smaller the YI value, the less yellow the resin; the larger the YI value, the more yellow the resin.

[0203] The YI values ​​of each embodiment are shown in Table 1, and the YI values ​​of each comparative example are shown in Table 2.

[0204] (3) Heat resistance Test specimens with a length of 10 mm, a width of 10 mm, and a thickness of 2.5 mm were prepared from the obtained resin. Using a Shimadzu TMA-60 thermomechanical analyzer, the TMA penetration test (50 g load, 0.5 mm needle tip) was performed. The glass transition temperature (Tg) was determined by heating at a rate of 10℃ / min. A higher glass transition temperature (Tg) indicates better heat resistance.

[0205] The glass transition temperatures (Tg) of each embodiment are shown in Table 1, and the glass transition temperatures (Tg) of each comparative example are shown in Table 2.

[0206] It should be noted that the above-described invention is provided as an illustrative embodiment of the present invention, but it is merely illustrative and not intended to be limiting. Modifications of the present invention that will be apparent to those skilled in the art are included in the appended claims.

[0207] Industrial availability The phthalamide diisocyanate composition, polymerizable composition, resin, and molded article of the present invention can be used in the manufacture of optical components such as lenses.

Claims

1. A phenylene diisocyanate composition comprising: phenylene diisocyanate; and A specific compound, in which the phenylene diisocyanate composition is mixed with deuterated chloroform and subjected to... 1 When measured by H-NMR, the specific compound has a peak in the range of 2.44 ppm to 2.46 ppm based on chloroform in the deuterated chloroform.

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

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

4. The phenylene diisocyanate composition of claim 1, wherein, The proportion of the specific compound is less than 3000 ppm by mass.

5. The phenylene diisocyanate composition of claim 1, wherein the urea compound of chemical formula (1) and the urea compound of chemical formula (2) are at least one of the specific compounds. Chemical formula (1): [Chemical Formula 1] Chemical formula (2): [Chemical Formula 2] 。 6. The phenylene diisocyanate composition of claim 1, further comprising at least one of 4-methylbenzenesulfonamide and 4-methylbenzenesulfonyl isocyanate.

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

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

9. The phenylene diisocyanate composition of claim 1, wherein, The phenylene diisocyanate is obtained by the reaction of phenylene dimethylamine with carbonyl dichloride, or by the reaction of phenylene dimethylamine hydrochloride with carbonyl dichloride.

10. A polymerizable composition comprising: The phenylene diisocyanate composition according to any one of claims 1 to 9; and It contains active hydrogen groups.

11. The polymerizable composition of claim 10, wherein, The active hydrogen-containing component comprises, selected from 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 tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), and 2,5-bis(mercaptomethyl)-1,4 - at least one polythiol from the group consisting of dithiocyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiocyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiocyclobutane, 1,1,2,2-tetra(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 polymeric composition of claim 11.

13. A molded article formed from the resin of claim 12.

14. An optical element, which is the molded body as described in claim 13.

15. A lens, which is the optical element as described in claim 14.

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