Polyisocyanate composition, polymerizable composition, resin, molded article, optical element and lens

Abstract

The polyisocyanate composition contains xylylene diisocyanate, an aromatic polyisocyanate, and a chain aliphatic polyisocyanate, and the proportion of xylylene diisocyanate in the polyisocyanate composition is 20% by mass or more.

Description

Technical Field

[0001] This invention relates to polyisocyanate 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, for example, Patent Document 1).

[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, depending on the application of the optical element, it is sometimes desirable to suppress the decrease in heat resistance and adjust the refractive index.

[0005] The present invention provides a polyisocyanate composition, a polymerizable composition, a resin, a molded article, an optical element, and a lens capable of suppressing the reduction of the heat resistance of the obtained resin and adjusting the refractive index of the obtained resin to a desired refractive index.

[0006] Methods for solving problems The present invention [1] includes a polyisocyanate composition containing phenylene diisocyanate, aromatic polyisocyanate and chain aliphatic polyisocyanate, wherein the proportion of the aforementioned phenylene diisocyanate in the aforementioned polyisocyanate composition is 20% by mass or more.

[0007] The present invention [2] includes the polyisocyanate composition of [1] above, wherein the aforementioned aromatic polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate and phenyl diisocyanate.

[0008] The present invention [3] includes the polyisocyanate composition of [1] above, wherein the aforementioned chain aliphatic polyisocyanate is selected from at least one of hexamethylene diisocyanate and pentamethylene diisocyanate.

[0009] The present invention [4] includes a polymerizable composition comprising a polyisocyanate composition of any one of [1] to [3] above, and a component containing an active hydrogen group.

[0010] The present invention [5] includes the polymerizable composition of [4] 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), 2,5 At least one polythiol from the group consisting of 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).

[0011] The present invention [6] includes a resin, which is a cured product of the polymeric composition of [4] or [5] described above.

[0012] The present invention [7] includes a molded body formed from the resin described above [6].

[0013] The present invention [8] includes an optical element, which is a molded body of the above [7].

[0014] The present invention [9] includes a lens, which is the optical element described above [8].

[0015] Invention Effects The polyisocyanate composition of the present invention contains, in addition to 20% by mass or more of phenylene diisocyanate, aromatic polyisocyanates and chain aliphatic polyisocyanates.

[0016] Therefore, it is possible to suppress the decrease in the heat resistance of the obtained resin and adjust the refractive index of the obtained resin to the desired refractive index.

[0017] Furthermore, as a cured product of a polymeric composition containing such a polyisocyanate composition, the resin, molded body, optical element, and lens can have sufficient heat resistance and obtain the desired refractive index. Detailed Implementation

[0018] 1. Polyisocyanate composition The polyisocyanate composition contains phenylene diisocyanate (XDI), aromatic polyisocyanate, and aliphatic polyisocyanate as main components.

[0019] Examples of XDIs include 1,2-XDI (adjacent XDI), 1,3-XDI (intermediate XDI), and 1,4-XDI (paired XDI).

[0020] The polyisocyanate composition may contain two or more types of XDI.

[0021] As an XDI, 1,3-XDI (inter-XDI) is a preferred example.

[0022] The proportion of XDI in the polyisocyanate composition is, for example, 20.00% by mass or more, preferably 30.00% by mass or more, more preferably 40.00% by mass or more, more preferably 45.00% by mass or more, more preferably 50.00% by mass or more, more preferably 55.00% by mass or more, more preferably 60.00% by mass or more, more preferably 65.0% by mass or more, and more preferably 70.00% by mass or more.

[0023] If the proportion of XDI in the polyisocyanate composition is above the lower limit mentioned above, the YI value of the obtained resin can be reduced.

[0024] As long as aromatic and aliphatic polyisocyanates can be incorporated into the polyisocyanate composition, there is no upper limit to the proportion of XDI in the polyisocyanate composition. For example, the upper limit of the proportion of XDI in the polyisocyanate composition is 90.00% by mass or less. The proportion of XDI in the polyisocyanate composition can also be 85.00% by mass or less.

[0025] The range of the XDI ratio in the polyisocyanate composition can be set by combining any one of the aforementioned upper limits of the XDI ratio in the polyisocyanate composition with any one of the aforementioned lower limits of the XDI ratio in the polyisocyanate composition. For example, the XDI ratio in the polyisocyanate composition is 20.00% by mass to 90.00% by mass, preferably 30.00% by mass to 85.00% by mass, more preferably 40.00% by mass to 85.00% by mass, more preferably 45.00% by mass to 85.00% by mass, more preferably 50.00% by mass to 85.00% by mass, more preferably 55.00% by mass to 85.00% by mass, more preferably 60.00% by mass to 85.00% by mass, more preferably 65.00% by mass to 85.00% by mass, and more preferably 70.00% by mass to 85.00% by mass.

[0026] The proportion of XDI in the polyisocyanate composition can be determined using the method described in paragraph

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

[0027] Aromatic polyisocyanates have an aromatic ring and multiple isocyanate groups. All the isocyanate groups in an aromatic polyisocyanate are bonded to the aromatic ring. Examples of aromatic polyisocyanates include aromatic diisocyanates. Examples of aromatic diisocyanates include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and phenyl diisocyanate.

[0028] The polyisocyanate composition may contain two or more aromatic polyisocyanates.

[0029] TDI is a preferred aromatic polyisocyanate.

[0030] The proportion of aromatic polyisocyanates in the polyisocyanate composition is, for example, 45.00% by mass or less, preferably 35.00% by mass or less, and more preferably 34.00% by mass or less. When the proportion of XDI in the polyisocyanate composition is 65.00% by mass or more, the proportion of aromatic polyisocyanates in the polyisocyanate composition is more preferably 30.00% by mass or less, more preferably 27.00% by mass or less, and more preferably 24.00% by mass or less.

[0031] If the proportion of aromatic polyisocyanates in the polyisocyanate composition is below the above-mentioned upper limit, the YI value of the obtained resin can be reduced.

[0032] The proportion of aromatic polyisocyanates in the polyisocyanate composition is, for example, 5.00% by mass or more, preferably 10% by mass or more, more preferably 16% by mass or more, and even more preferably 20% by mass or more. When the proportion of XDI in the polyisocyanate composition is 55.00% by mass or more and less than 65.00% by mass, the proportion of aromatic polyisocyanates in the polyisocyanate composition is more preferably 21.00% by mass or more, and even more preferably 26.00% by mass or more.

[0033] The refractive index of the obtained resin can be increased by increasing the proportion of aromatic polyisocyanates in the polyisocyanate composition.

[0034] The range of the proportion of aromatic polyisocyanates in the polyisocyanate composition can be set by combining any one of the aforementioned upper limits of the proportion of aromatic polyisocyanates in the polyisocyanate composition with any one of the aforementioned lower limits of the proportion of aromatic polyisocyanates in the polyisocyanate composition. For example, the proportion of aromatic polyisocyanates in the polyisocyanate composition is 5.00% by mass to 45.00% by mass, preferably 10.00% by mass to 35.00% by mass, more preferably 16.00% by mass to 34.00% by mass, and even more preferably 20.00% by mass to 34.00% by mass. When the proportion of XDI in the polyisocyanate composition is 65.00% by mass or more, the proportion of aromatic polyisocyanates in the polyisocyanate composition is more preferably 20.00% by mass to 30.00% by mass, more preferably 20.00% by mass to 27.00% by mass, and even more preferably 20.00% by mass to 24.00% by mass. When the proportion of XDI in the polyisocyanate composition is 55% by mass or more and less than 65% by mass, the proportion of aromatic polyisocyanate in the polyisocyanate composition is more preferably 21.00% by mass to 34.00% by mass, and more preferably 26.00% by mass to 34.00% by mass.

[0035] The proportion of aromatic polyisocyanates in the polyisocyanate composition can be determined by a method identical to the method for determining the proportion of XDI in the polyisocyanate composition described above, except that aromatic polyisocyanates are the analyte, or by nuclear magnetic resonance (NMR) analysis. In NMR analysis, an ECX-400P NMR apparatus (manufactured by NEC Corporation) is used, and the proportion of aromatic polyisocyanates in the polyisocyanate composition is determined by 1H-NMR under the following conditions: H (400 Hz) observed nucleus, 15 ppm observation range, and 64 cumulative measurements.

[0036] Chain-like aliphatic polyisocyanates have a backbone formed by a straight-chain or branched chain hydrocarbon having 4 to 8 carbon atoms, and multiple isocyanate groups bonded to the backbone. Examples of chain-like aliphatic polyisocyanates include chain-like aliphatic diisocyanates. Examples of chain-like aliphatic diisocyanates include hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI).

[0037] The polyisocyanate composition may contain two or more chain-like aliphatic polyisocyanates.

[0038] HDI is a preferred example of a chain-like aliphatic polyisocyanate.

[0039] The proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is, for example, 30.00% by mass or less, preferably 25.00% by mass or less, more preferably 20.00% by mass or less, more preferably 17.00% by mass or less, and even more preferably 14.00% by mass or less. When the proportion of XDI in the polyisocyanate composition is 65.00% by mass or more, the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is more preferably 10.00% by mass or less, and even more preferably 9.00% by mass or less.

[0040] If the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is below the above-mentioned upper limit, the decrease in the refractive index of the obtained resin and the decrease in the heat resistance of the obtained resin can be suppressed.

[0041] The proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is, for example, 1.00% by mass or more, preferably 3.00% by mass or more, more preferably 4.00% by mass or more, and even more preferably 6.00% by mass or more. When the proportion of XDI in the polyisocyanate composition is 55.00% by mass or more and less than 65.00% by mass, the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is more preferably 8.00% by mass or more.

[0042] If the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is above the lower limit mentioned above, the YI value of the obtained resin can be reduced, and the flexural strength of the obtained resin can be increased.

[0043] The range of the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition can be set by combining any one of the aforementioned upper limits of the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition with any one of the aforementioned lower limits of the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition. The proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is, for example, 1.00% by mass to 30.00% by mass, preferably 3.00% by mass to 25.00% by mass, more preferably 4.00% by mass to 20.00% by mass, more preferably 6.00% by mass to 17.00% by mass, and even more preferably 6.00% by mass to 14.00% by mass. When the proportion of XDI in the polyisocyanate composition is 65.00% by mass or more, the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is more preferably 6.00% by mass to 10.00% by mass, and even more preferably 6.00% by mass to 9.00% by mass. When the proportion of XDI in the polyisocyanate composition is 55.00% by mass or more and less than 65.00% by mass, the proportion of chain aliphatic polyisocyanate in the polyisocyanate composition is more preferably 8.00% by mass to 14.00% by mass.

[0044] The proportion of chain aliphatic polyisocyanates in the polyisocyanate composition can be determined by a method identical to the method for determining the proportion of XDI in the polyisocyanate composition described above, except that the chain aliphatic polyisocyanates are the target of measurement, or by nuclear magnetic resonance (NMR) analysis. In NMR analysis, an ECX-400P NMR apparatus (manufactured by NEC Corporation) is used, and the proportion of chain aliphatic polyisocyanates in the polyisocyanate composition is determined by 1H-NMR under the following conditions: H (400 Hz) observed nucleus, 15 ppm observation range, and 64 cumulative measurements.

[0045] The mass ratio of the aliphatic polyisocyanate to the aromatic polyisocyanate (mass of the aliphatic polyisocyanate / mass of the aromatic polyisocyanate) is, for example, 0.050 or more, preferably 0.100 or more, more preferably 0.150 or more, more preferably 0.200 or more, more preferably 0.250 or more, for example, 1.000 or less, preferably 0.800 or less, more preferably 0.700 or less, more preferably 0.500 or less, more preferably 0.400 or less. The mass ratio of the aliphatic polyisocyanate to the aromatic polyisocyanate (mass of the aliphatic polyisocyanate / mass of the aromatic polyisocyanate) is, for example, 0.050 to 1.000, preferably 0.100 to 0.800, more preferably 0.150 to 0.700, more preferably 0.200 to 0.500, more preferably 0.250 to 0.400.

[0046] By increasing the mass ratio of chain aliphatic polyisocyanates to aromatic polyisocyanates, the YI value of the obtained resin can be reduced, and the flexural strength of the obtained resin can also be increased.

[0047] By reducing the mass ratio of chain aliphatic polyisocyanates to aromatic polyisocyanates, the decrease in the refractive index and the decrease in the heat resistance of the obtained resin can be suppressed.

[0048] The polyisocyanate composition can be manufactured by mixing XDI, aromatic polyisocyanate, and aliphatic polyisocyanate in the above proportions.

[0049] In addition, the polyisocyanate composition may also contain at least one of the group consisting of monochloromethyl benzyl isocyanate (CBI), dichloromethyl benzyl isocyanate (DCI), and cyanobenzyl isocyanate (MCN) as a secondary component.

[0050] Examples of CBIs include 2-(monochloromethyl)benzyl isocyanate (ortho-CBI), 3-(monochloromethyl)benzyl isocyanate (meta-CBI), and 4-(monochloromethyl)benzyl isocyanate (para-CBI).

[0051] Polyisocyanate compositions may contain two or more CBIs.

[0052] The proportion of CBI in the polyisocyanate composition can be determined using the method described in paragraph

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

[0053] Furthermore, in the gas chromatography of the polyisocyanate composition under the following condition 1, the peak area of ​​CBI relative to the peak area of ​​XDI is, for example, 5.0 ppm or more, preferably 50 ppm or more, more preferably 100 ppm or more, for example, 4000 ppm or less, preferably 3000 ppm or less, more preferably 2000 ppm or less, more preferably 1500 ppm or less, and more preferably 1000 ppm or less.

[0054] <Condition 1> Filler: DB-1 (film thickness) 1.5μm Column: Inner diameter 0.53mm × length 60m (manufactured by Agilent Technologies) 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℃.

[0055] Shunt ratio: Pulse shunt method Inlet temperature: 280℃ Detector temperature: 300℃ Carrier gas: N2 158kPa, H2 55kPa, air 45kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID Examples of DCIs include 2-(dichloromethyl)benzyl isocyanate (ortho-DCI), 3-(dichloromethyl)benzyl isocyanate (meta-DCI), and 4-(dichloromethyl)benzyl isocyanate (para-DCI).

[0056] Polyisocyanate compositions may contain two or more DCIs.

[0057] The proportion of DCI in the polyisocyanate composition can be determined using the method described in paragraphs

[0375] to

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

[0058] Furthermore, in the gas chromatography of the polyisocyanate composition under the following condition 2, the peak area of ​​DCI relative to the peak area of ​​XDI is, for example, 0.05 ppm or more, preferably 0.1 ppm or more, more preferably 0.3 ppm or more, more preferably 0.6 ppm or more, for example, 200 ppm or less, preferably 150 ppm or less, more preferably 100 ppm or less, more preferably 80 ppm or less, more preferably 70 ppm or less, more preferably 60 ppm or less.

[0059] <Condition 2> Column: HP-50+, inner diameter 0.25mm × length 30m × film thickness 0.25μm (manufactured by Hewlett-Packard Company) Column oven temperature: Increase from 50℃ to 280℃ at a rate of 10℃ / min, and hold at 280℃ for 6 minutes.

[0060] Shunt ratio: Pulse shunt method Inlet temperature: 200℃ Detector temperature: 280℃ Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume: 1.0 μL Detection method: SIM (monitoring ions: m / z 180, 215) Examples of MCNs include 2-cyanobenzyl isocyanate (ortho-MCN), 3-cyanobenzyl isocyanate (meta-MCN), and 4-cyanobenzyl isocyanate (para-MCN).

[0061] The polyisocyanate composition may contain two or more MCNs.

[0062] The proportion of MCN in the polyisocyanate composition can be determined using the method described in paragraph

[0378] of International Publication No. 2018 / 190290.

[0063] Furthermore, in the gas chromatography of the polyisocyanate composition under condition 1 above, the peak area of ​​MCN relative to the peak area of ​​XDI is, for example, 0.1 ppm or more, preferably 3.0 ppm or more, more preferably 5.0 ppm or more, for example, 1000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less, and more preferably 75 ppm or less.

[0064] The acid content of the polyisocyanate composition is, for example, 3000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less, more preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 30 ppm or less, and more preferably less than 15 ppm.

[0065] There is no lower limit for the acid content of the polyisocyanate composition. For example, the lower limit for the acid content of the polyisocyanate composition is 1 ppm.

[0066] The acid content of the polyisocyanate composition can be determined using the method described in paragraph

[0091] of International Publication No. 2021 / 256417.

[0067] In addition, the polyisocyanate composition may also contain a stabilizer. Examples of stabilizers include 4-methylbenzenesulfonamide.

[0068] 2. Uses of polyisocyanate compositions Polyisocyanate compositions can be used as raw materials for resins. Specifically, resins can be manufactured by reacting the isocyanate component with a component containing active hydrogen groups. The isocyanate component contains the polyisocyanate composition.

[0069] Components containing active hydrogen groups contain compounds containing active hydrogen groups.

[0070] Examples of compounds containing active hydrogen groups include polyols, polythiols, and polyamines.

[0071] Compounds containing active hydrogen groups can be used alone or in combination of two or more.

[0072] 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.

[0073] 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.

[0074] The proportion of polythiols in a polythiols composition can be determined using, for example, high performance liquid chromatography.

[0075] Polythiols contain multiple thiol groups. Polythiols do not contain the byproducts described later. Examples of polythiols include aliphatic polythiols, aromatic polythiols, and heterocyclic polythiols.

[0076] 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, and bis(mercaptomethyl) sulfide. 1,2-Di(mercaptoethyl) thioether, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) thioether, 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 (GST), 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 (DMMD), 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- 2-mercaptoacetic acid ester), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetic acid ester), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetic acid ester), hydroxyethyl disulfide bis(3-mercaptopropionate), thionyl diacetic acid bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), thionyl diacetic acid 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.

[0077] 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.

[0078] Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-triazine, 3,4-thiophene dithiol, and bismuth reagents.

[0079] Polythiols can be used alone or in combination of two or more.

[0080] 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).

[0081] Polythiol compositions may contain byproducts.

[0082] 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 (1).

[0083] Chemical formula (1): [Chemical Formula 1] 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.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] 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 (2) (hereinafter referred to as compound B) as a by-product.

[0088] Chemical formula (2): [Chemical Formula 2] (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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] The resin is preferably molded using known molding methods. Casting is the preferred method for molding the resin. In casting, firstly, the isocyanate component and the active hydrogen group component are mixed at a ratio of 0.8 to 1.2 of the isocyanate groups in the isocyanate component to the 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.

[0093] 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.

[0094] 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.

[0095] When the active hydrogen group component contains polythiols, the resulting molded body exhibits excellent transparency.

[0096] Furthermore, since the above-mentioned polyisocyanate composition contains XDI, aromatic polyisocyanates and chain aliphatic polyisocyanates, the resulting molded articles have high refractive index and excellent heat resistance.

[0097] 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.

[0098] 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.

[0099] In addition, the glass transition temperature (Tg) of the obtained molded article is, for example, 70°C or higher, preferably 75°C or higher, and for example, 90°C or lower.

[0100] Furthermore, the resulting molded article also exhibits high flexural strength. Specifically, the flexural strength of the resulting molded article is, for example, 170 N / mm². 2 The preferred value is 180 N / mm. 2 The above, for example, is 250 N / mm. 2 the following.

[0101] Furthermore, the resulting molded article also has a low YI value. Specifically, the YI value of the resulting molded article is, for example, 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less, and for example, 1.5 or more.

[0102] With the aforementioned physical properties, the resulting molded body is suitable as an optical element.

[0103] Examples of optical elements include lenses, sheets, and films, with lenses being a preferred choice.

[0104] Examples of lenses include transparent lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0105] It should be noted that the uses of polyisocyanate compositions are not limited to the aforementioned optical materials. Examples of uses for polyisocyanate compositions include, for example, inks, transfer foils, adhesives, binders, gels, elastomers, foams, bonding agents, one-component curable sealants, RIM molded articles, microfoamed polyurethane, various microcapsules, waterborne 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, and waterproof materials. Membranes, sheets, tubes, blades, loudspeakers, 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.

[0106] Examples of preferred uses for polyisocyanate compositions include optical materials, elastomers, foams, and one-component curing sealants.

[0107] 3. Effects The polyisocyanate composition of the present invention contains, in addition to 20% by mass or more of phenylene diisocyanate, aromatic polyisocyanates and aliphatic polyisocyanates.

[0108] Therefore, it is possible to suppress the reduction of the obtained resin and adjust the refractive index of the obtained resin to the desired refractive index.

[0109] Furthermore, as a cured product of a polymeric composition containing such a polyisocyanate composition, the resin, molded body, optical element, and lens can have sufficient heat resistance and obtain the desired refractive index.

[0110] 4. Variations The polyisocyanate composition may also contain modified forms obtained from phenylene diisocyanate, aromatic polyisocyanate, and chain aliphatic polyisocyanate. Examples of modified forms include isocyanate forms, urea-formate forms, biuret forms, urea-ketene imides, carbodiimides, and urea-diketone forms.

[0111] In the case where the polyisocyanate composition contains a modifier, in order to manufacture the polyisocyanate composition, a modifier of phenylene diisocyanate, a modifier of aromatic polyisocyanate, and a modifier of chain aliphatic polyisocyanate can be mixed, or a mixture of phenylene diisocyanate, aromatic polyisocyanate, and chain aliphatic polyisocyanate can be modified.

[0112] 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 property values, parameters, etc., used in the following description can be replaced by the corresponding upper limit values ​​(defined in the form of "below" or "lower") or lower limit values ​​(defined in the form of "above" or "higher") of the proportions (including ratios), physical property values, parameters, etc., described in the "Specific Embodiments" above. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

[0113] 1. Resin Manufacturing 52 parts by weight of the polyisocyanate composition with the components shown in Tables 1 to 3, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name: Stepan Company; acidic phosphate ester), and 0.05 parts by weight of BioSorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.; ultraviolet absorber) were mixed at 20°C and dissolved to obtain mixture 1.

[0114] Next, 48 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, as a polythiol, are uniformly mixed into mixture 1 to obtain mixture 2 (polymeric composition).

[0115] Mixture 2 was degassed at 600 Pa for 1 hour, and then filtered using a 1 μm Teflon (registered trademark) filter.

[0116] Next, the filtered mixture 2 is injected into a casting mold formed by a glass mold and tape.

[0117] Next, the casting mold containing the mixture 2 was placed in an oven and heated from 10°C to 120°C for 38 hours for polymerization.

[0118] After polymerization, the casting mold was removed from the oven, the polymer was demolded from the casting mold, and the resulting polymer was annealed at 120°C for 1 hour.

[0119] The resins of each embodiment are obtained through the above methods.

[0120] 2. Determination of resin properties For the resins obtained in each embodiment, the following physical properties were measured. The results are shown in Tables 1 to 3.

[0121] (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').

[0122] (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.

[0123] The smaller the YI value, the less yellow the resin; the larger the YI value, the more yellow the resin.

[0124] (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.

[0125] (4) Bending strength The obtained resin was used to make rectangular flat test pieces with a length of 65 mm, a width of 25 mm, and a thickness of 2.5 mm.

[0126] For the obtained test pieces, a 3-point bending test was carried out using the AUTOGRAPH AGS-J manufactured by Shimadzu Corporation. Based on the range of 20N~30N of force applied to the test pieces, the maximum stress (bending strength) of the test pieces was determined.

[0127] [Table 1] [Table 2] [Table 3] 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.

[0128] Industrial availability The polyisocyanate compositions, polymerizable compositions, resins, and molded articles of the present invention can be used in the manufacture of optical components such as lenses.

Claims

1. A polyisocyanate composition comprising: phenylene diisocyanate, Aromatic polyisocyanates, and Chain-like aliphatic polyisocyanates, The proportion of phenylene diisocyanate in the polyisocyanate composition is 20% by mass or more.

2. The polyisocyanate composition according to claim 1, wherein, The aromatic polyisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, and phenyl diisocyanate.

3. The polyisocyanate composition of claim 1, wherein, The chain-like aliphatic polyisocyanate is selected from at least one of hexamethylene diisocyanate and pentamethylene diisocyanate.

4. A polymerizable composition comprising: The polyisocyanate composition according to any one of claims 1 to 3, and It contains active hydrogen groups.

5. The polymerizable composition of claim 4, 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).

6. A resin, which is a cured product of the polymeric composition of claim 4 or 5.

7. A molded article formed from the resin of claim 6.

8. An optical element, which is the molded body as described in claim 7.

9. A lens, which is the optical element as described in claim 8.

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