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

Abstract

The xylylene diisocyanate composition contains xylylene diisocyanate and methyl isocyanate benzoyl chloride, and is characterized in that the xylylene diisocyanate composition contains xylylene diisocyanate and methyl isocyanate benzoyl chloride.

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 suppress the decline in lightfastness and further improve heat resistance.

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

[0006] Methods for solving problems The present invention [1] comprises a phenylene diisocyanate composition containing phenylene diisocyanate and methyl isocyanate benzoyl chloride.

[0007] The present invention [2] includes the phenylene diisocyanate composition of [1] above, wherein the proportion of methyl isocyanate benzoyl chloride in the aforementioned phenylene diisocyanate composition is more than 1 ppm by mass.

[0008] The present invention [3] includes the phenylene diisocyanate composition of [1] or [2] above, wherein the proportion of methyl isocyanate benzoyl chloride in the aforementioned phenylene diisocyanate composition is less than 2000 ppm by mass.

[0009] The present invention [4] includes any of the above [1] to [3] phenylene diisocyanate compositions, which further contain methyl isocyanate benzoic acid.

[0010] The present invention [5] includes a polymerizable composition comprising any one of the above [1] to [4] phenylene diisocyanate compositions and a component containing an active hydrogen group.

[0011] The present invention [6] includes the polymerizable composition of [5] above, wherein the aforementioned active hydrogen group-containing component comprises a composition 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).

[0012] The present invention [7] includes a resin, which is a cured product of the polymeric composition described above [5] or [6].

[0013] The present invention [8] includes a molded body formed from the resin described above [7].

[0014] The present invention [9] includes an optical element, which is a molded body of [8] described above.

[0015] The present invention

[10] includes a lens, which is the optical element described above [9].

[0016] Invention Effects The phenylene diisocyanate composition and polymerizable composition of the present invention contain methyl isocyanate-based benzoyl chloride.

[0017] By using a phenylene diisocyanate composition containing methyl isocyanate benzoyl chloride and a polymerizable composition as raw materials, it is possible to manufacture resins with excellent light and heat resistance.

[0018] The resin of the present invention is a cured product of a polymeric composition containing the above-mentioned diphenylene diisocyanate composition.

[0019] Furthermore, the molded body, optical element, and lens of the present invention are formed from the above-mentioned resin.

[0020] Therefore, the resin, molded body, optical element and lens of the present invention have excellent light resistance and heat resistance. Detailed Implementation

[0021] 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.

[0022] Examples of XDIs include 1,2-XDI (adjacent XDI), 1,3-XDI (intermediate XDI), and 1,4-XDI (paired XDI).

[0023] As an XDI, 1,3-XDI (inter-XDI) is a preferred example.

[0024] An XDI composition may contain two or more types of XDI.

[0025] The proportion (purity) of XDI in the XDI composition is, for example, 98.00% by mass or more, 99.00% by mass or more, 99.30% by mass or more, or 99.60% by mass or more.

[0026] The proportion of XDI in the XDI composition is, for example, 99.95% by mass or less.

[0027] The range of XDI content in the XDI composition can be set by combining the upper and lower limits of the XDI content. The XDI content in the XDI composition is 98.00% to 99.95% by mass, 99.00% to 99.95% by mass, 99.30% to 99.95% by mass, or 99.60% to 99.95% by mass.

[0028] The proportion of XDI in the XDI composition can be determined using the methods described in the examples below.

[0029] The XDI composition contains methyl isocyanate-based benzoyl chloride as a byproduct.

[0030] Examples of methyl isocyanate-based benzoyl chlorides include 2-methyl isocyanate-based benzoyl chloride (o-methyl isocyanate-based benzoyl chloride), 3-methyl isocyanate-based benzoyl chloride (m-methyl isocyanate-based benzoyl chloride), and 4-methyl isocyanate-based benzoyl chloride (p-methyl isocyanate-based benzoyl chloride).

[0031] As a methyl isocyanate-based benzoyl chloride, 3-methyl isocyanate-based benzoyl chloride (m-methyl isocyanate-based benzoyl chloride) is a preferred example.

[0032] XDI compositions may contain two or more methyl isocyanate-based benzoyl chlorides.

[0033] The proportion of methyl isocyanate benzoyl chloride in the XDI composition, on a mass basis, is, for example, 1 ppm or more, 3 ppm or more, 5 ppm or more, 7 ppm or more, 10 ppm or more, 15 ppm or more, 20 ppm or more, 25 ppm or more, 30 ppm or more, 35 ppm or more, 40 ppm or more, 45 ppm or more, or 50 ppm or more.

[0034] If the proportion of methyl isocyanate benzoyl chloride in the XDI composition is above the lower limit mentioned above, the heat resistance of the resin manufactured using the XDI composition can be improved.

[0035] The proportion of methyl isocyanate benzoyl chloride in the XDI composition, on a mass basis, is, for example, less than 5000 ppm, less than 2000 ppm, less than 1900 ppm, less than 1500 ppm, less than 1000 ppm, less than 800 ppm, less than 500 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 90 ppm, or less than 70 ppm.

[0036] If the proportion of methyl isocyanate benzoyl chloride in the XDI composition is below the above-mentioned upper limit, the decrease in lightfastness of the resin manufactured using the XDI composition can be suppressed.

[0037] The range of the proportion of methyl isocyanate-based benzoyl chloride in the XDI composition can be set by combining the upper and lower limits of the proportion. The proportion of methyl isocyanate-based benzoyl chloride in the XDI composition, based on mass, can be 1 ppm to 5000 ppm, 3 ppm to 2000 ppm, 5 ppm to 1900 ppm, 7 ppm to 1500 ppm, 10 ppm to 1000 ppm, 15 ppm to 800 ppm, 20 ppm to 500 ppm, 25 ppm to 300 ppm, 30 ppm to 200 ppm, 35 ppm to 100 ppm, 40 ppm to 90 ppm, 45 ppm to 70 ppm, or 50 ppm to 70 ppm.

[0038] The proportion of methyl isocyanate benzoyl chloride in the XDI composition can be determined using the methods described in the examples below.

[0039] XDI compositions may also contain methyl isocyanate benzoic acid as a by-product.

[0040] The proportion of methyl isocyanate benzoic acid in the XDI composition, on a mass basis, is, for example, 0.1 ppm or more, 0.3 ppm or more, 0.5 ppm or more, 0.7 ppm or more, 1.0 ppm or more, 1.5 ppm or more, 2.0 ppm or more, 2.5 ppm or more, 3.0 ppm or more, 3.5 ppm or more, 4.0 ppm or more, 4.5 ppm or more, or 5.0 ppm or more.

[0041] If the proportion of methyl isocyanate benzoic acid in the XDI composition is above the lower limit mentioned above, the heat resistance of the resin manufactured using the XDI composition can be improved.

[0042] The proportion of methyl isocyanate benzoic acid in the XDI composition, on a mass basis, is, for example, less than 100.0 ppm, less than 80.0 ppm, less than 50.0 ppm, less than 30.0 ppm, less than 20.0 ppm, less than 10.0 ppm, less than 9.0 ppm, or less than 7.0 ppm.

[0043] If the proportion of methyl isocyanate benzoic acid in the XDI composition is below the above-mentioned upper limit, the decrease in lightfastness of the resin manufactured using the XDI composition can be suppressed.

[0044] The range of the proportion of methyl isocyanate-based benzoic acid in the XDI composition can be set by combining the upper and lower limits of the proportion. The proportion of methyl isocyanate-based benzoic acid in the XDI composition, based on mass, can be 0.1ppm~100.0ppm, 0.3ppm~80.0ppm, 0.5ppm~50.0ppm, 0.7ppm~30.0ppm, 1.0ppm~20.0ppm, 1.5ppm~10.0ppm, 2.0ppm~9.0ppm, 2.5ppm~7.0ppm, 3.0ppm~7.0ppm, 3.5ppm~7.0ppm, 4.0ppm~7.0ppm, 4.5ppm~7.0ppm, or 5.0ppm~7.0ppm.

[0045] The proportion of methyl isocyanate-benzoic acid in the XDI composition was determined by gas chromatography-mass spectrometry and gas chromatography under the same determination conditions as the methyl isocyanate-benzoyl chloride described above.

[0046] The XDI composition may also contain at least one of monochloromethyl benzyl isocyanate (CBI), dichloromethyl benzyl isocyanate (DCI), and dichloromethane iminomethyl benzyl isocyanate (dichloroimino) as shown in the following chemical formula (1) as an auxiliary component.

[0047] Chemical formula (1): [Compound 1] Examples of DCIs include 2-(dichloromethyl)benzyl isocyanate (ortho-DCI), 3-(dichloromethyl)benzyl isocyanate (meta-DCI), and 4-(dichloromethyl)benzyl isocyanate (para-DCI).

[0048] As a DCI, 3-(dichloromethyl)benzyl isocyanate (m-DCI) is a preferred example.

[0049] XDI compositions may contain two or more DCIs.

[0050] The proportion of DCI in the XDI composition, on a mass basis, is, for example, 0.1 ppm or more, 0.3 ppm or more, 0.6 ppm or more, or 1.0 ppm or more.

[0051] The proportion of DCI in the XDI composition is, for example, less than 60 ppm, less than 50 ppm, less than 30 ppm, or less than 20 ppm by mass.

[0052] The range of DCI proportion in the XDI composition can be set by combining the upper and lower limits of the above-mentioned DCI proportion. The proportion of DCI in the XDI composition, based on mass, can be 0.1ppm~60ppm, 0.3ppm~50ppm, 0.6ppm~30ppm, or 1.0ppm~20ppm.

[0053] If the proportion of DCI in the XDI composition is within the above range, the yellowness of the resin manufactured from the XDI composition can be reduced.

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

[0055] Examples of CBIs include 2-(monochloromethyl)benzyl isocyanate (ortho-CBI), 3-(monochloromethyl)benzyl isocyanate (meta-CBI), and 4-(monochloromethyl)benzyl isocyanate (para-CBI).

[0056] As a CBI, 3-(monochloromethyl)benzyl isocyanate (me-CBI) is a preferred example.

[0057] XDI compositions may contain two or more CBIs.

[0058] The proportion of CBI in the XDI composition, on a mass basis, is, for example, 0.2 ppm or more, 6 ppm or more, or 100 ppm or more.

[0059] The proportion of CBI in the XDI composition, on a mass basis, is, for example, less than 5000 ppm, less than 4000 ppm, less than 3000 ppm, less than 1600 ppm, or less than 1000 ppm.

[0060] The range of CBI proportion in the XDI composition can be set by combining the upper and lower limits of the above-mentioned CBI proportion. The CBI proportion in the XDI composition, based on mass, can be 0.2ppm~5000ppm, 6ppm~4000ppm, 100ppm~3000ppm, 100ppm~1600ppm, or 100ppm~1000ppm.

[0061] 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 in the XDI composition is below the above-mentioned upper limit, 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.

[0062] In addition, the content ratio of CBI relative to DCI is, for example, more than 2 times, more than 10 times, or more than 20 times. The content ratio of CBI relative to DCI is, for example, less than 800 times, less than 300 times, or less than 50 times. The content ratio of CBI relative to DCI can be 2 times to 800 times, 10 times to 300 times, or 20 times to 50 times.

[0063] The proportion of CBI in the XDI composition can be determined using the methods described in the examples below.

[0064] Examples of dichloroimino derivatives include 2-(dichloromethaneiminomethyl)benzyl isocyanate, 3-(dichloromethaneiminomethyl)benzyl isocyanate, and 4-(dichloromethaneiminomethyl)benzyl isocyanate.

[0065] As a dichloroimine, 3-(dichloromethaneiminomethyl)benzyl isocyanate is a preferred example.

[0066] XDI compositions may contain two or more dichloroimines.

[0067] The proportion of dichloroimine in the XDI composition, on a mass basis, is, for example, 0.1 ppm or more, 0.2 ppm or more, 0.5 ppm or more, 1.0 ppm or more, or 2.0 ppm or more.

[0068] The proportion of dichloroimine in the XDI composition, on a mass basis, is, for example, less than 200 ppm, less than 150 ppm, less than 100 ppm, less than 80 ppm, or less than 60 ppm.

[0069] The range of the proportion of dichloroimine in the XDI composition can be set by combining the upper and lower limits of the proportion. The proportion of dichloroimine in the XDI composition, based on mass, can be 0.1ppm~200ppm, 0.2ppm~150ppm, 0.5ppm~100ppm, 1.0ppm~80ppm, or 2.0~60ppm.

[0070] The proportion of dichloroimine in the XDI composition can be determined using the methods described in the examples below.

[0071] 2. Method for manufacturing XDI composition The method for manufacturing the XDI composition is described.

[0072] Methods for manufacturing XDI compositions include, for example, synthesis steps, purification steps, and generation steps.

[0073] 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.

[0074] In the salt-making process, phenylenediamine (XDA) is mixed with hydrogen chloride to produce phenylenediamine hydrochloride (XDA hydrochloride).

[0075] 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.

[0076] 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.

[0077] 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.

[0078] The proportion of XDA (total amine concentration) relative to the total mass of XDA and inactive solvent is, for example, 3% to 30% by mass, 5% to 20% by mass, or 5% to 15% by mass.

[0079] The supply ratio of hydrogen chloride relative to 1 mole of XDA is, for example, 2 to 10 moles, 2 to 6 moles, or 2 to 4 moles.

[0080] The reaction temperature in the salt-making process is, for example, 30℃~160℃, 50℃~150℃, or 50℃~140℃.

[0081] The reaction pressure (gauge pressure) in the salt-making process is, for example, 0 MPaG (atmospheric pressure) ~ 1.0 MPaG, or 0.01 MPaG ~ 0.5 MPaG.

[0082] XDA is reacted with hydrogen chloride to generate XDA hydrochloride, thus obtaining a slurry containing XDA hydrochloride.

[0083] 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 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.

[0084] The supply ratio of carbonyl dichloride relative to 1 mole of XDA hydrochloride is, for example, 4 to 50 moles, 5 to 40 moles, or 6 to 30 moles.

[0085] The reaction time for the isocyanate esterification process is, for example, 4 hours to 25 hours, 6 hours to 20 hours, or 6 hours to 15 hours.

[0086] The reaction temperature in the isocyanate esterification process is, for example, 90℃~190℃, 100℃~180℃, or 110~160℃.

[0087] The reaction pressure (gauge pressure) in the isocyanate esterification process is, for example, 0 MPaG~0.6 MPaG, 0.0005 MPaG~0.4 MPaG, 0.001 MPaG~0.2 MPaG, 0.003 MPaG~0.2 MPaG, 0.01 MPaG~0.2 MPaG, 0.02 MPaG~0.2 MPaG, or 0.03 MPaG~0.2 MPaG. The reaction pressure (gauge pressure) in the isocyanate esterification process is preferably greater than 0 MPaG (atmospheric pressure).

[0088] 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.

[0089] Next, gaseous components, inactive solvents, and tar components are removed from the reactants.

[0090] 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.

[0091] Inactive solvents can be removed from the reactants by distillation using, for example, known distillation columns.

[0092] Tar components can be removed from the reactants using, for example, known tar removers.

[0093] After removing gaseous components, inactive solvents, and tar components, the proportion of XDI in the reactants is, for example, 80.0% to 99.0% by mass, 90.0% to 98.5% by mass, or 95.0% to 98.0% by mass.

[0094] 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.

[0095] 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.

[0096] 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 to 40, 5 to 20, or 7 to 15.

[0097] The bottom temperature of the deboiling tower is, for example, 130℃~200℃, 140℃~190℃, or 150℃~180℃.

[0098] The top temperature of the deboiling tower is, for example, 90℃~160℃, 100℃~150℃, or 110℃~140℃.

[0099] The top pressure of the deboiling tower is, for example, 0.05 kPa to 3.0 kPa, 0.1 kPa to 2.0 kPa, or 0.2 kPa to 1.0 kPa.

[0100] The reflux ratio at the top of the deboiling column is, for example, 1~80, 5~60, or 10~50.

[0101] The residence time of the deboiling tower is, for example, 0.1 hours to 10 hours, 0.2 hours to 5 hours, or 0.3 hours to 3 hours.

[0102] The reaction material after removing low-boiling-point components by distillation was obtained by using a de-boiling column as the bottom liquid.

[0103] Next, in the distillation process, a distillation column is used to further distill (distill) the reaction material after the low-boiling point removal process.

[0104] 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, 1 to 20, 1 to 10, or 1 to 5.

[0105] The bottom temperature of a distillation column is, for example, 120℃~190℃, 130℃~180℃, or 140℃~170℃.

[0106] The top temperature of a distillation column is, for example, 90℃~180℃, 110℃~170℃, or 130℃~160℃.

[0107] The top pressure of the distillation column is, for example, 0.05 kPa to 3.0 kPa, 0.1 kPa to 2.0 kPa, or 0.2 kPa to 1.0 kPa.

[0108] The reflux ratio at the top of the distillation column is, for example, 0.1~50, 0.2~20, or 0.3~10.

[0109] The residence time of the distillation column is, for example, 0.2 hours to 20 hours, 0.5 hours to 10 hours, or 1.0 hour to 10 hours.

[0110] The fraction containing XDI (first XDI composition) is obtained through a distillation process. The first XDI composition contains DCI, CBI, and dichloroimine.

[0111] Next, in the production process, methyl isocyanate-based benzoic acid and methyl isocyanate-based benzoyl chloride are generated.

[0112] In detail, during the production process, compressed air is blown into the first XDI composition.

[0113] The temperature of the first XDI composition in the production process is, for example, 10°C to 80°C, 15°C to 70°C, 20°C to 50°C, or 20°C to 30°C.

[0114] The flow rate of compressed air relative to 100g of the first XDI composition is, for example, 10ml / min to 30ml / min, or 15ml / min to 25ml / min.

[0115] The time for blowing in compressed air is, for example, 10 minutes to 20 hours, 1 hour to 15 hours, 2 hours to 10 hours, or 5 hours to 10 hours.

[0116] Through a production process, methyl isocyanate-based benzoic acid and methyl isocyanate-based benzoyl chloride are generated. Specifically, it is believed that by blowing compressed air into the first XDI composition, a byproduct in the first XDI composition reacts with oxygen to generate methyl isocyanate-based benzoic acid. Furthermore, it is believed that the generated methyl isocyanate-based benzoic acid reacts with hydrolyzable chlorine in the first XDI composition to generate methyl isocyanate-based benzoyl chloride.

[0117] The above-mentioned XDI composition (second XDI composition) is obtained through the production process.

[0118] It should be noted that the manufacturing method of the XDI composition may also exclude the generation process, but include, for example, a salt formation process, an isocyanate esterification process, a purification process, and a mixing process.

[0119] In the mixing process, methyl isocyanate-based benzoic acid or methyl isocyanate-based benzoyl chloride is added to the first XDI composition and mixed.

[0120] The above-mentioned XDI composition can also be obtained using this method.

[0121] 3. Uses of XDI compositions The above-mentioned 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 the component containing an active hydrogen group of a compound.

[0122] Compounds containing active hydrogen groups contain active hydrogen groups. An active hydrogen group is a functional group that can generate active hydrogen. Examples of active hydrogen groups include hydroxyl, mercapto, and amino groups. Examples of compounds containing active hydrogen groups include polyols, polythiols, and polyamines.

[0123] Compounds containing active hydrogen groups can be used alone or in combination of two or more.

[0124] From an optical property point of view, compounds containing active hydrogen groups are preferably polythiols. The active hydrogen group-containing component is preferably a polythiol group containing polythiols as the main component.

[0125] The proportion of polythiols in the polythiols composition is, for example, 50% or more by mass, 60% or more by mass, 70% or more by mass, or 80% or more by mass.

[0126] The proportion of polythiols in a polythiols composition can be determined using, for example, high performance liquid chromatography.

[0127] Polythiols contain multiple thiol groups. Polythiols do not contain the byproducts described later. Examples of polythiols include aliphatic polythiols, aromatic polythiols, and heterocyclic polythiols.

[0128] 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-mercaptopropyl)sulfide Acetate), 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), thionidodiacetic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiacetic acid bis(2-mercaptoethyl ester), dithiodipropionic acid 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.

[0129] 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.

[0130] Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-triazine, 3,4-thiophene dithiol, and bismuth reagents.

[0131] Polythiols can be used alone or in combination of two or more.

[0132] 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).

[0133] Polythiol compositions may contain byproducts.

[0134] As a byproduct, a compound (hereinafter referred to as compound A) can be obtained by replacing at least one of the thiol groups of the above-mentioned polythiol with the functional group shown in the following chemical formula (2).

[0135] Chemical formula (2): [Compound 2] 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, 0.01~3.0, 0.01~1.5, or 0.01~0.5.

[0136] 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).

[0137] 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.

[0138] If the peak area (R1) of compound A relative to the peak area 100 of the polythiol is within the above range, 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.

[0139] 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 (3) (hereinafter referred to as compound B) as a by-product.

[0140] Chemical formula (3): [Compound 3] (In chemical formula (3), 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, greater than 0 and less than 10.0, 0.02 to 9.0, 0.04 to 8.0, 1.0 to 7.0, 2.0 to 6.0, 3.0 to 6.0, or 4.0 to 6.0.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] For example, the resin can be manufactured by casting. In casting, the isocyanate component and the active hydrogen group component are preferably 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 polymerizable composition containing the XDI composition and the active hydrogen group component.

[0145] 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.

[0146] 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.

[0147] When the active hydrogen group component contains polythiols, the resulting molded body exhibits excellent transparency.

[0148] Furthermore, since the above-mentioned XDI composition contains XDI and methyl isocyanate benzoyl chloride, the resulting molded articles have low yellowness and excellent heat resistance.

[0149] Specifically, the glass transition temperature (Tg) of the obtained molded article is, for example, 85.0°C or higher, 87.0°C or higher, or 87.5°C or higher. The glass transition temperature (Tg) of the obtained molded article is, for example, 90.0°C or lower, or 88.0°C or lower. The glass transition temperature (Tg) of the obtained molded article may also be 85.0°C to 90.0°C, 87.0°C to 88.0°C, or 87.5°C to 88.0°C.

[0150] The YI value of the obtained molded body is, for example, 5.85 or less, 5.65 or less, 5.60 or less, 5.55 or less, 5.50 or less, 5.45 or less, or 5.43 or less. The YI value of the obtained molded body is, for example, 5.40 or more. The YI value of the obtained molded body can also be 5.40 to 5.85, 5.40 to 5.65, 5.40 to 5.55, 5.40 to 5.50, 5.40 to 5.45, or 5.40 to 5.43.

[0151] The resulting molded body also has a high refractive index. The refractive index (ne) of the resulting molded body is, for example, 1.650 or higher, or 1.660 or higher. The refractive index (ne) of the resulting molded body is, for example, 1.670 or lower. The refractive index (ne) of the resulting molded body may also be 1.650 to 1.670, or 1.660 to 1.670.

[0152] The Abbe number (νe) of the resulting molded body is, for example, 30 or more, or 31 or more. The Abbe number (νe) of the resulting molded body is, for example, 35 or less, or 33 or less. The Abbe number (νe) of the resulting molded body can also be 30 to 35, or 31 to 33.

[0153] With the above-mentioned physical properties, the resulting molded body is suitable as an optical element.

[0154] Examples of optical elements include lenses, sheets, and films, with lenses being a preferred choice.

[0155] Examples of lenses include transparent lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0156] 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.

[0157] Examples of preferred uses for XDI compositions include the aforementioned optical materials, elastomers, foams, and one-component curing sealants.

[0158] 4. Effects The phenylene diisocyanate composition and polymerizable composition of the present invention contain methyl isocyanate-based benzoyl chloride.

[0159] By using a phenylene diisocyanate composition containing methyl isocyanate benzoyl chloride and a polymerizable composition as raw materials, it is possible to manufacture resins with excellent light and heat resistance.

[0160] The resin of the present invention is a cured product of a polymeric composition containing the above-mentioned diphenylene diisocyanate composition.

[0161] Furthermore, the molded body, optical element, and lens of the present invention are formed from the above-mentioned resin.

[0162] Therefore, the resin, molded body, optical element and lens of the present invention have excellent light resistance and heat resistance.

[0163] 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 vaporized 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 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.

[0164] (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.

[0165] 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.

[0166] 1. Manufacturing of XDI compositions (1) Example 1 A dropwise solution was prepared by mixing 136 g (1.0 mol) of m-phenylenediamine (manufactured by Fujifilm and Koichi Chemical Co., Ltd.) and 621 g of o-dichlorobenzene (ODCB) in an Erlenmeyer flask.

[0167] Next, 845g of ODCB was added to a 1L flask equipped with a reflux condenser, thermometer, and gas inlet tube.

[0168] The ODCB was heated to 100°C, and while stirring, the above-mentioned solution was added dropwise over 3 hours at a flow rate of 2 mL per minute using a feed pump (HPLC pump PU-980 manufactured by Japan Spectroscopy Corporation). Simultaneously with the dropwise addition of the solution, 230 g of hydrochloric acid gas was blown in over 3 hours.

[0169] Next, stop blowing in hydrochloric acid gas and heat and stir for 30 minutes. This yields a slurry of m-phenylenediamine hydrochloride (salt-making process).

[0170] Next, nitrogen gas is blown into the slurry for 1 hour to remove unreacted hydrochloric acid gas.

[0171] Next, the slurry is heated to 160°C, and 1200g of carbonyl dichloride gas is blown into the slurry over 6 hours. This causes m-phenylenediamine hydrochloride to react with carbonyl dichloride, yielding a reactant containing m-XDI (isocyanate esterification process).

[0172] Next, nitrogen gas is blown into the reactants for 1 hour to remove unreacted carbonyl dichloride from the reactants.

[0173] Next, the reactants are filtered under reduced pressure to remove precipitates.

[0174] Next, the reactants after the precipitates have been removed are desolventized, and the ODCB in the reactants is removed by distillation (desolventization process).

[0175] Next, the reactants were subjected to vacuum distillation (0.5 to 1.0 Torr) using a distillation column with a packing equivalent to 4 theoretical plates, and 158 g of the first XDI composition containing meta-XDI was obtained from the reactants as a fraction (purification step).

[0176] Next, 100g of the first XDI composition is loaded into a 200ml round-bottom bottle, and compressed air is blown into the first XDI composition (temperature of the first XDI composition: 25°C, flow rate of compressed air: 20ml / min, blowing time: 20min) (production process).

[0177] Then, the mixture was filtered using a 1μm Teflon (registered trademark) filter, and 75mg of phenol (stabilizer) was added to prepare the XDI composition (the second XDI composition).

[0178] (2) Example 2 In the production process, compressed air is blown in for 2 hours. Otherwise, the XDI composition is prepared using the same method as in Example 1.

[0179] (3) Example 3 In the production process, compressed air is blown in for 6 hours. Otherwise, the XDI composition is prepared using the same method as in Example 1.

[0180] (4) Example 4 In the production process, compressed air is blown in for 15 hours. Otherwise, the XDI composition is prepared using the same method as in Example 1.

[0181] (5) Example 5 In the production process, the first XDI composition is heated to 60°C and compressed air is blown in for 5 hours. Otherwise, the XDI composition is prepared using the same method as in Example 1.

[0182] (6) Example 6 In the production process, the first XDI composition is heated to 60°C and compressed air is blown in for 10 hours. Otherwise, the XDI composition is prepared using the same method as in Example 1.

[0183] (7) Comparative example In the production process, hydrochloric acid gas equivalent to 20 ppm is blown in instead of compressed air. Otherwise, the XDI composition is prepared using the same method as in Example 1.

[0184] 2. Determination of the compositional content of the XDI composition The proportions of XDI, methyl isocyanate benzoyl chloride (acyl chloride), dichloroimide, 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 Table 1.

[0185] (1) Identification of methyl isocyanate benzoyl chloride The XDI composition obtained in Example 1 was subjected to gas chromatography-mass spectrometry analysis under the following conditions.

[0186] (Measurement conditions) Device: Agilent 6890 / 5973N Column: HP19091L-433 HP-50+ (inner diameter 0.25mm × length 30m, membrane 0.25μm) Column oven temperature: Hold at 50℃ for 1 minute, then increase from 50℃ to 280℃ at a rate of 10℃ / minute, and hold at 280℃ for 10 minutes. Carrier gas: constant flow mode, He, 1.0 mL / min Injection method: Pulse-without-shunt method (150 kPa, for 0.5 minutes) Injection volume: 1.0 μL Sample concentration: 1.0% by mass dichloromethane solution Injection temperature: 200℃ Interface temperature: 280℃ Quadrupole temperature: 150℃ Ion source temperature: 230℃ Detection method: Scan method (m / z: 10~500) The mass spectrum of the peak appearing at the retention time of 19.87 minutes in the obtained total ion chromatogram was compared with the spectral library data.

[0187] The mass spectrometer contains a fragment peak with a molecular weight of 195 as the largest peak, which has a matching degree of more than 70% with methyl isocyanate benzoyl chloride.

[0188] Therefore, the compound corresponding to the peak that appeared at a retention time of 19.87 minutes in the total ion chromatogram was identified as methyl isocyanate benzoyl chloride.

[0189] (2) The ratio of XDI, methyl isocyanate benzoyl chloride and dichloroimine 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.

[0190] (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℃.

[0191] 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.

[0192] In addition, the proportion of methyl isocyanate benzoyl chloride in the XDI composition was calculated by the ratio of the peak area of ​​the internal standard to the peak area of ​​methyl isocyanate benzoyl chloride that appeared at a retention time of 17.8 minutes.

[0193] In addition, the proportion of dichloroimine in the XDI composition was calculated by the ratio of the area of ​​the internal standard peak to the area of ​​the dichloroimine peak appearing at a retention time of 15.6 minutes.

[0194] (3) 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.

[0195] (4) 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.

[0196] [Table 1] 2. Manufacturing of molded parts To 52 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.

[0197] Next, 48 parts by mass of 4,8-dimercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (manufactured by Mitsui Chemicals) were uniformly mixed into mixture 1 to obtain mixture 2 (polymeric composition).

[0198] Mixture 2 was degassed at 600 Pa for 1 hour, and then filtered using a 1 μm Teflon (registered trademark) filter.

[0199] Next, the filtered mixture 2 is injected into a mold formed by a glass mold and tape.

[0200] Next, the mold filled with mixture 2 is placed in an oven and heated from 10°C to 120°C, where it is cured for 38 hours.

[0201] 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.

[0202] Through the above methods, the cured products (molded bodies) of each embodiment and comparative example are obtained.

[0203] 3. Evaluation of the physical properties of the molded part (1) Light resistance A 2mm thick plate was fabricated from the obtained molded body, and a QUV test was conducted using a Q-Lab accelerated weathering tester (light source: UVA-340, intensity: 0.50W / m). 2 Test conditions: 50℃ × 150 hours.

[0204] The yellowness (YI value) of the molded body before and after the QUV test is measured, and the difference between the yellowness of the molded body before and after the QUV test (the change in yellowness, ΔYI) is calculated. The smaller the ΔYI, the better the lightfastness.

[0205] The ΔYI values ​​for each embodiment and comparative example are shown in Table 1.

[0206] (2) Yellowness (YI value) A circular plate with a thickness of 9 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.

[0207] The smaller the YI value, the less yellow the resin; the larger the YI value, the more yellow the resin.

[0208] The YI values ​​of each embodiment and comparative example are shown in Table 1.

[0209] (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. The higher the glass transition temperature (Tg), the better the heat resistance.

[0210] The glass transition temperatures (Tg) of each embodiment and comparative example are shown in Table 1.

[0211] (4) 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').

[0212] In all the embodiments and comparative examples, the refractive index (ne) was 1.665 and the Abbe number (νe) was 31.

[0213] 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.

[0214] 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 Methyl isocyanate benzoyl chloride.

2. The phenylene diisocyanate composition according to claim 1, wherein, The proportion of methyl isocyanate benzoyl chloride in the phenylene diisocyanate composition is more than 1 ppm by mass.

3. The phenylene diisocyanate composition according to claim 1, wherein, The proportion of methyl isocyanate benzoyl chloride in the phenylene diisocyanate composition is less than 2000 ppm by mass.

4. The phenylene diisocyanate composition of claim 1, further comprising methyl isocyanate-based benzoic acid.

5. A polymerizable composition comprising: The phenylene diisocyanate composition according to any one of claims 1 to 4; and It contains active hydrogen groups.

6. The polymerizable composition of claim 5, wherein, The active hydrogen group-containing component contains, 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), 2,5-bis(mercaptomethyl)-1, At least one polythiol from the group consisting of 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).

7. A resin, which is a cured product of the polymeric composition of claim 5.

8. A molded article formed from the resin of claim 7.

9. An optical element, which is the molded body as described in claim 8.

10. A lens, which is the optical element as described in claim 9.

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