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

Abstract

To provide a xylylene diisocyanate composition, a polymerizable composition, a resin, a molded article, an optical element, and a lens capable of improving hue and transparency of resin.SOLUTION: A xylylene diisocyanate composition includes xylylene diisocyanate and 4-methylbenzenesulfonyl isocyanate.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Conventionally, a xylylene diisocyanate composition has been known as a raw material for resins used in various industrial products.

[0003] For example, a xylylene diisocyanate composition containing xylylene diisocyanate and dichloromethylbenzyl isocyanate and having a content ratio of dichloromethylbenzyl isocyanate of 0.6 ppm or more and 60 ppm or less has been proposed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Regarding the resin produced from the xylylene diisocyanate composition described in Patent Document 1, improvement in hue and transparency may be required depending on the purpose and application.

[0006] [[ID=|42]] The present invention provides a xylylene diisocyanate composition, a polymerizable composition, a resin, a molded body, an optical element, and a lens that can improve the hue and transparency of the resin.

Means for Solving the Problems

[0007] The present invention [1] includes a xylylene diisocyanate composition comprising xylylene diisocyanate and 4-methylbenzenesulfonyl isocyanate.

[0008] The present invention [2] includes the xylylene diisocyanate composition described in [1] above, wherein the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is 15,000 ppm or less by mass.

[0009] The present invention [3] comprises the xylylene diisocyanate composition described in [1] or [2] above, which is for optical purposes.

[0010] The present invention [4] includes a polymerizable composition comprising one of the xylylene diisocyanate compositions described in [1] to [3] above and an active hydrogen group-containing component.

[0011] The present invention [5] includes the polymerizable composition of [4] above, wherein the active hydrogen group-containing component contains a polythiol.

[0012] The present invention [6] relates to a polythiol comprising 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), and 2,5-bis(mercaptomethyl)-1,4-dithian The polymerizable composition [5] described above is at least one selected from the group consisting of bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0013] The present invention [7] comprises a resin which is a cured product of any one of the polymerizable compositions [4] to [6] described above.

[0014] The present invention [8] includes a molded article made of the resin described in [7] above.

[0015] The present invention [9] includes an optical element which is a molded body as described in [8] above.

[0016] The present invention

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

[0017] The xylylene diisocyanate composition of the present invention contains 4-methylbenzenesulfonyl isocyanate. Therefore, the resin produced from the above-described xylylene diisocyanate composition exhibits excellent hue and transparency.

[0018] The polymerizable composition of the present invention contains the above-described xylylene diisocyanate composition. Therefore, the resin produced from the above-described polymerizable composition is excellent in hue and transparency.

[0019] The resin of the present invention is a cured product of the above-described polymerizable composition. Therefore, the resin is excellent in hue and transparency.

[0020] The molded article of the present invention is made of the above-described resin. Therefore, the molded article is excellent in hue and transparency.

[0021] The optical element of the present invention is the above-described molded article. Therefore, the optical element is excellent in hue and transparency.

[0022] The lens of the present invention is the above-described optical element. Therefore, the lens is excellent in hue and transparency.

Embodiments for Carrying Out the Invention

[0023] 1. Xylylene Diisocyanate Composition The xylylene diisocyanate composition (XDI composition) contains xylylene diisocyanate (XDI) as a main component.

[0024] Examples of XDI include 1,2-XDI (o-XDI), 1,3-XDI (m-XDI), and 1,4-XDI (p-XDI).

[0025] Such XDI may be contained in the XDI composition in one kind or two or more kinds.

[0026] Preferably, 1,3-XDI (m-XDI) is mentioned as XDI. <00​The XDI content (purity) is, for example, 98.00% by mass or more, preferably 99.00% by mass or more, more preferably 99.30% by mass or more, even more preferably 99.60% by mass or more, and for example, 99.95% by mass or less, relative to the total mass of the XDI composition. In other words, the XDI composition consists almost entirely of XDI. The XDI content can be measured by the method described in paragraph

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

[0028] The XDI composition contains 4-methylbenzenesulfonyl isocyanate (PTSI, also known as p-toluenesulfonyl isocyanate) as a minor component.

[0029] The proportion of PTSI in the XDI composition is 15,000 ppm or less by mass, preferably 12,000 ppm or less, more preferably 10,000 ppm or less, more preferably 8,000 ppm or less, more preferably 5,000 ppm or less, more preferably 2,000 ppm or less, more preferably 1,000 ppm or less, more preferably 500 ppm or less, and more preferably 100 ppm or less.

[0030] If the proportion of PTSI in the XDI composition is below the above upper limit, the hue and transparency of the resin produced from the XDI composition can be improved. In particular, if the proportion of PTSI in the XDI composition is 8000 ppm or less, the hue of the resin produced from the XDI composition can be further improved.

[0031] The hue can be evaluated using the yellow index described in the examples below. Transparency can be evaluated using the devitrification degree described in the examples below.

[0032] Furthermore, the proportion of PTSI in the XDI composition is, on a mass basis, for example, greater than 0 ppm, preferably 1 ppm or more, more preferably 5 ppm or more, more preferably 10 ppm or more, more preferably 20 ppm or more, and more preferably 40 ppm or more.

[0033] If the PTSI content is above the lower limit mentioned above, the hue and transparency of the resin produced from the XDI composition can be improved.

[0034] Furthermore, the upper and lower limits of the PTSI content percentage described above can be appropriately combined to set a range for the PTSI content percentage.

[0035] To measure the PTSI content, first, 100 mg of an XDI composition containing PTSI and 0.5 mg of methylnaphthalene as an internal standard are mixed, and the resulting mixture is diluted to a volume of 10 mL to obtain a sample. Next, the obtained sample is subjected to gas chromatography-mass spectrometry under the following measurement conditions. The PTSI content is calculated from the area ratio between the peak of the internal standard that appears at a retention time of 12.1 minutes and the peak of PTSI that appears from a retention time of 13.2 minutes to 13.9 minutes. (Measurement conditions for gas chromatography-mass spectrometry) Column; HP19091L-433 HP-50+ (inner diameter 0.25 mm x length 30 m, film 0.25 μm) Oven temperature: Hold at 50°C for 1 minute, increase temperature from 50°C to 280°C at a rate of 10.0°C / min, hold at 280°C for 6 minutes after reaching 280°C. Carrier gas: He 1.0 ml / min constant flow mode. Injection method: Pulsed splitless method (150kPa at 0.5min) Injection volume; 1.0μL, 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).

[0036] Furthermore, the XDI composition may contain other minor components besides PTSI.

[0037] Other minor components include, for example, 4-methylbenzenesulfonamide (PTSA, also known as p-toluenesulfonamide), dichloromethylbenzyl diisocyanate (DCI) as described in paragraphs

[0028] to

[0030] of International Publication No. 2018 / 190290, and monochloromethylbenzyl isocyanate (CBI) as described in paragraphs

[0039] to

[0041] of International Publication No. 2018 / 190290.

[0038] The proportion of PTSA in the XDI composition is, for example, 3000 ppm or less, preferably 2000 ppm or less.

[0039] If the PTSA content is within the above range, yellowing and clouding of the resin produced from the XDI composition can be suppressed.

[0040] The proportion of DCI in the XDI composition is, for example, 0.1 ppm or more, preferably 0.3 ppm or more, more preferably 0.6 ppm or more, more preferably 1.0 ppm or more, and for example, 60 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, and more preferably 20 ppm or less.

[0041] If the proportion of DCI in the XDI composition is within the above range, yellowing and clouding of the resin produced from the XDI composition can be suppressed.

[0042] The proportion of CBI in the XDI composition is, for example, 0.2 ppm or more, preferably 6 ppm or more, more preferably 100 ppm or more, for example 5000 ppm or less, preferably 4000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1600 ppm or less, and especially preferably 1000 ppm or less.

[0043] Furthermore, the CBI content is, for example, 2 times or more, preferably 10 times or more, more preferably 20 times or more, for example, 800 times or less, preferably 300 times or less, and more preferably 50 times or less, relative to the DCI content.

[0044] If the CBI content is within the above range, yellowing of the resin can be suppressed. In particular, if the CBI content is below the above upper limit, yellowing of the resin can be suppressed, and the urethane reaction during resin manufacturing can proceed smoothly, thereby reliably improving the mechanical properties of the resin.

[0045] The DCI content and the CBI content can be measured by the method described in the examples of International Publication No. 2018 / 190290.

[0046] 2. Method for producing XDI composition Next, a method for producing the XDI composition will be described.

[0047] A method for producing an XDI composition includes, for example, the steps of producing a reaction mass (pre-purification composition) by the method for producing an XDI composition described in paragraphs

[0054] to

[0110] of International Publication No. 2018 / 190290, purifying the reaction mass, and adjusting the PTSI content.

[0048] To produce the reaction mass, for example, xylylenediamine and hydrogen chloride are mixed to produce xylylenediamine hydrochloride, and then the hydrochloride is reacted with carbonyl chloride (phosgene) (phosgenation method of amine hydrochloride).

[0049] In the following, xylylenediamine is referred to as XDA. Examples of XDA include 1,2-XDA(o-XDA), 1,3-XDA(m-XDA), and 1,4-XDA(p-XDA), with 1,3-XDA(m-XDA) being preferred.

[0050] In the salt production process for XDA hydrochloride, for example, XDA and hydrogen chloride are mixed in the presence of an inert solvent to produce XDA hydrochloride (salt production).

[0051] Examples of inert solvents include those described in paragraph

[0059] of International Publication No. 2018 / 190290. Inert solvents can be used alone or in combination of two or more. Among the inert solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are preferred.

[0052] Then, while stirring the solution in which XDA is dissolved in an inert solvent, hydrogen chloride gas is supplied and mixed.

[0053] The mass ratio of XDA (total amine concentration) to the total mass of XDA and the inert solvent is, for example, 3% by mass or more, preferably 5% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0054] The supply ratio of hydrogen chloride is, for example, 2 moles or more, and for example, 10 moles or less, preferably 6 moles or less, and more preferably 4 moles or less, per mole of XDA.

[0055] The salt production temperature in the salt production process is, for example, 30°C or higher, preferably 50°C or higher, and for example, 160°C or lower, preferably 150°C or lower. The salt production pressure (gauge pressure) in the salt production process is, for example, atmospheric pressure (0 MPaG) or higher, preferably 0.01 MPaG or higher, and for example, 1.0 MPaG or lower, preferably 0.5 MPaG or lower.

[0056] This process generates XDA hydrochloride from XDA and hydrogen chloride (hydrochloride conversion reaction), and a slurry containing XDA hydrochloride is produced.

[0057] Next, carbonyl dichloride is supplied to the slurry containing XDA hydrochloride, and the XDA hydrochloride and carbonyl dichloride are reacted while removing the by-product hydrogen chloride gas (isocyanate reaction, phosgenation).

[0058] The supply ratio of carbonyl dichloride is, for example, 4 moles or more, preferably 5 moles or more, more preferably 6 moles or more, and for example, 50 moles or less, preferably 40 moles or less, more preferably 30 moles or less, per mole of XDA hydrochloride.

[0059] The reaction time for the isocyanation step is, for example, 4 hours or more, preferably 6 hours or more, and for example, 25 hours or less, preferably 20 hours or less, and more preferably 15 hours or less.

[0060] The reaction temperature in the isocyanation step is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and also, for example, 190°C or lower, preferably 180°C or lower, more preferably 160°C or lower.

[0061] The reaction pressure (gauge pressure) in the isocyanate step is, for example, greater than atmospheric pressure (0 MPaG), preferably 0.0005 MPaG or higher, more preferably 0.001 MPaG or higher, even more preferably 0.003 MPaG or higher, particularly preferably 0.01 MPaG (10 kPaG) or higher, especially preferably 0.02 MPaG (20 kPaG) or higher, most preferably 0.03 MPaG (30 kPaG) or higher, and also, for example, 0.6 MPaG or lower, preferably 0.4 MPaG or lower, more preferably 0.2 MPaG or lower.

[0062] The isocyanation process is preferably carried out in a continuous manner. That is, the slurry (XDA hydrochloride) generated in the stirred tank is continuously transferred from the stirred tank to a separate reaction tank, where the XDA hydrochloride reacts with carbonyl dichloride, while the reaction solution (reaction mass) is continuously withdrawn from the reaction tank.

[0063] This causes XDA hydrochloride to react with carbonyl dichloride, producing XDI as the main component.

[0064] Next, if necessary, a degassing step, a solvent removal step, and a tar removal step are carried out on the reaction solution (reaction mixture). In the degassing step, excess carbonyl chloride and by-product hydrogen chloride gases are removed from the reaction solution (reaction mixture) using a known degassing column. In the solvent removal step, the inert solvent is distilled off from the reaction solution using a known distillation column. In the tar removal step, tar components are removed from the reaction solution using a known tar remover.

[0065] The above process produces a reaction mass containing XDI.

[0066] The XDI content in the reaction mass is, for example, 80.0% by mass or more, preferably 90.0% by mass or more, more preferably 95.0% by mass or more, and also, for example, 99.0% by mass or less, preferably 98.5% by mass or less, more preferably 98.0% by mass or less.

[0067] Next, the reaction mass is purified.

[0068] One method for purifying the reaction mass is distillation. To purify the reaction mass by distillation, for example, low-boiling components are removed from the reaction mass by distillation, and then the de-boiling mass, which is the reaction mass after de-boiling, is rectified.

[0069] In the low-boiling step, for example, the reaction mass is distilled using a low-boiling column to remove low-boiling substances.

[0070] Examples of low-boiling towers include tray towers and packed towers, with packed towers being preferred. The theoretical number of stages in a low-boiling tower is, for example, 3 or more stages, preferably 5 or more stages, more preferably 7 or more stages, and also, for example, 40 stages or less, preferably 20 stages or less, more preferably 15 stages or less.

[0071] The bottom temperature of the de-boiling column is, for example, 130°C or higher, preferably 140°C or higher, more preferably 150°C or higher, and also, for example, 200°C or lower, preferably 190°C or lower, more preferably 180°C or lower.

[0072] The top temperature of the de-boiling column is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and also, for example, 160°C or lower, preferably 150°C or lower, more preferably 140°C or lower.

[0073] The top pressure of the de-boiling column is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, and also, for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0074] The top reflux ratio of the low-boiling column is, for example, 1 or more, preferably 5 or more, more preferably 10 or more, and also, for example, 80 or less, preferably 60 or less, more preferably 50 or less.

[0075] The residence time in the de-boiling column is, for example, 0.1 hours or more, preferably 0.2 hours or more, more preferably 0.3 hours or more, and also, for example, 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

[0076] From this, the low-boiling components are removed by distillation to obtain the de-low-boiling mass as the bottom liquid.

[0077] Next, in the rectification process, for example, the de-low boiling mass is distilled in a rectification column to obtain the fraction.

[0078] Examples of rectification columns include tray columns and packed columns, with packed columns being preferred. The theoretical number of stages in the rectification column is, for example, one or more stages, and for example, 20 stages or less, preferably 10 stages or less, and more preferably 5 stages or less.

[0079] The bottom temperature of the rectification column is, for example, 120°C or higher, preferably 130°C or higher, more preferably 140°C or higher, and also, for example, 190°C or lower, preferably 180°C or lower, more preferably 170°C or lower.

[0080] The top temperature of the rectification column is, for example, 90°C or higher, preferably 110°C or higher, more preferably 130°C or higher, and also, for example, 180°C or lower, preferably 170°C or lower, more preferably 160°C or lower.

[0081] The top pressure of the rectification column is, for example, 0.05 kPa or more, preferably 0.1 kPa or more, more preferably 0.2 kPa or more, and also, for example, 3.0 kPa or less, preferably 2.0 kPa or less, more preferably 1.0 kPa or less.

[0082] The reflux ratio at the top of the rectification column is, for example, 0.1 or higher, preferably 0.2 or higher, more preferably 0.3 or higher, and also, for example, 50 or lower, preferably 20 or lower, more preferably 10 or lower.

[0083] The residence time in the rectification column is, for example, 0.2 hours or more, preferably 0.5 hours or more, more preferably 1.0 hour or more, and also, for example, 20 hours or less, preferably 10 hours or less.

[0084] As a result, a fraction mainly composed of XDI is isolated. The isolated fraction contains DCI and CBI within the ranges described above.

[0085] Next, adjust the proportion of PTSI.

[0086] To adjust the PTSI content, PTSI is mixed into the extracted fraction so that the PTSI content falls within the range specified above.

[0087] The method for adjusting the PTSI content is not limited. If PTSI is included in the XDI composition, the PTSI content may be adjusted by known methods such as distillation or column purification.

[0088] Furthermore, when PTSA is incorporated into the XDI composition, the PTSA is mixed into the extracted fraction so that the PTSA content falls within the range described above.

[0089] The XDI composition is obtained as described above.

[0090] <Effects and Effects> The XDI composition of the present invention contains PTSI.

[0091] Therefore, resins produced from XDI compositions exhibit excellent hue and transparency.

[0092] When the proportion of PTSI in the XDI composition is 15,000 ppm or less by mass, the hue and transparency of the resin produced from the XDI composition can be improved.

[0093] 3. Polymerizable composition The polymerizable composition contains an isocyanate component and an active hydrogen group-containing component. The isocyanate component contains an XDI composition. In other words, the polymerizable composition contains an XDI composition. Preferably, the isocyanate component consists of an XDI composition.

[0094] Examples of active hydrogen group-containing components include polyols, polythiols, and polyamines.

[0095] The active hydrogen group-containing components can be used alone or in combination of two or more types.

[0096] From the viewpoint of optical properties, the active hydrogen group-containing component preferably contains a polythiol. More preferably, the active hydrogen group-containing component consists of a polythiol.

[0097] Examples of polythiols include aliphatic polythiols, aromatic polythiols, and heterocyclic polythiols.

[0098] Examples of aliphatic polythiols include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), and trimethylolpropanetris(2-mercaptoacetate). ), trimethylolpropanetris(3-mercaptopropionate), trimethylolethanetris(2-mercaptoacetate), trimethylolethanetris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide, bis (mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7 -Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Tetrakis(mercaptomethylthiomethyl)methane, Tetrakis(2-mercaptoethylthiomethyl)methane, Tetrakis(3-mercaptopropylthiomethyl)methane, Bis(2,3-Dimercaptopropyl)sulfide, 2,5-Dimercaptomethyl-1,4-Dithiane, 2,5-Dimercapto-1,4-Dithiane, 2,5-Dimercaptomethyl-2,5-dimethyl-1,4-Dithiane, and esters thereof of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercapto Examples include propinate, bis(2-mercaptoethyl ester) thiodiglycolate, bis(2-mercaptoethyl ester) thiodipropionate, bis(2-mercaptoethyl ester) dithiodiglycolate, bis(2-mercaptoethyl ester) dithiodipropionate, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane.

[0099] Examples of aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol.

[0100] Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, and bismuthiol.

[0101] Such polythiols can be used alone or in combination of two or more types.

[0102] Furthermore, as polythiols, preferably, are 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptomethyl) At least one selected from the group consisting of captoethyl sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0103] 3. Resin The resin is a cured product of a polymerizable composition. In other words, the XDI composition is used as a raw material for resin. More specifically, the resin is produced by reacting the above-mentioned isocyanate component with the above-mentioned active hydrogen group-containing component. When the active hydrogen group-containing component contains polythiol, the resin exhibits excellent transparency. Therefore, the resin is suitable as an optical material. In other words, the XDI composition is preferably for optical applications. To put it another way, the XDI composition is a raw material for optical materials.

[0104] The yellow index (YI value) of the resin is, for example, 1.10 or less, preferably 1.05 or less, more preferably 1.03 or less, and more preferably 1.00 or less. When the YI value is below the above upper limit, the hue is excellent.

[0105] Furthermore, there is no lower limit to the YI value of the resin. The YI value of the resin is, for example, 0.95 or higher.

[0106] The devitrification of the resin is, for example, 18 or less, preferably 16 or less, and more preferably 15 or less. When the devitrification is below the above upper limit, the resin has excellent transparency.

[0107] The lower limit of the devitrification degree of the resin is not limited. For example, the devitrification degree of the resin is 10 or higher.

[0108] The resin is preferably molded by a known molding method. The resin is preferably cast. In casting, an isocyanate component and an active hydrogen group-containing component are mixed in a ratio such that the isocyanate groups in the isocyanate component are 0.8 to 1.2 times the active hydrogen groups (amino groups, thiol groups, or hydroxyl groups) in the active hydrogen group-containing component. The resulting mixture is poured into a mold and then heat-cured. This yields a molded article as a cast article. In other words, the molded article is made of resin. The molded article is suitable as an optical component. Examples of molded articles made of resin include optical elements.

[0109] Examples of optical elements include lenses, sheets, and films, with lenses being preferred.

[0110] The lenses are manufactured, for example, by the reaction of an XDI composition with a polythiol. In lens manufacturing, for example, a casting method can be employed.

[0111] Examples of lenses include clear lenses, sunglass lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0112] <Effects and Effects> The resin, molded articles, optical elements, and lenses contain cured products of polymerizable compositions. Therefore, the resin, molded articles, optical elements, and lenses exhibit excellent hue and transparency.

[0113] Furthermore, the XDI composition can also be used as a raw material for coating agents (e.g., paints and adhesives). In this case, the XDI composition is modified as necessary by known methods and included as an isocyanate component in the polymerizable composition for coatings.

[0114] A xylylene diisocyanate modified composition (hereinafter referred to as the XDI modified composition) is produced by modifying the above-mentioned XDI composition and contains at least one of the following functional groups (a) to (i). (a) isocyanurate group, (b) Allophanate group, (c) Biuret group, (d) Urethane group, (e) Urea group, (f) Iminooxadiazine group, (g) Uretidione group, (h) Uretonimine group, (i) Carbodiimide group.

[0115] More specifically, the XDI modified composition containing the functional group (isocyanurate group) described in (a) above contains a trimer of XDI and can be obtained, for example, by adding a known isocyanuration catalyst to an XDI monomer composition and reacting it to isocyanurate (e.g., trimerize) XDI.

[0116] The XDI modified composition containing the functional group (allophanate group) described in (b) above contains an allophanate modified form of XDI, and can be obtained, for example, by reacting an XDI monomer composition with a monohydric alcohol or a dihydric alcohol, and then adding a known allophanate catalyst and reacting further.

[0117] The XDI modified composition containing the functional group (biuret group) described in (c) above contains a biuret modified form of XDI and can be obtained, for example, by reacting an XDI monomer composition with water or a secondary amine, followed by adding a known biuretization catalyst and continuing the reaction.

[0118] The XDI modified composition containing the functional group (urethane group) described in (d) above contains a polyol modified form of XDI and can be obtained, for example, by the reaction of an XDI monomer composition with a low molecular weight polyol (e.g., trimethylolpropane).

[0119] The XDI-modified composition containing the functional group (urea group) described in (e) above contains a polyamine-modified form of XDI, and can be obtained, for example, by the reaction of an XDI monomer composition with a polyamine.

[0120] The XDI modified composition containing the functional group (iminooxadiazinedione group) described in (f) above contains an iminooxadiazinedione modified form (asymmetric trimer) of XDI, and can be obtained, for example, by reacting an XDI composition in the presence of a known iminooxadiazinedione catalyst to iminooxadiazinedione (e.g., trimerize) XDI.

[0121] The XDI modified composition containing the functional group (uretdione group) described in (g) above contains a uretdione modified form of XDI, and can be obtained, for example, by heating the XDI composition to about 90°C to 200°C, or by reacting it in the presence of a known uretdione catalyst to uretdione (e.g., dimerize) XDI.

[0122] The XDI modified composition containing the functional group (uretonimine group) described in (h) above contains a uretonimine modified form of XDI, and can be obtained, for example, by reacting an XDI composition in the presence of a known carbodiimide catalyst to form a carbodiimide group, and then adding XDI to that carbodiimide group.

[0123] The XDI modified composition containing the functional group (carbodiimide group) described in (i) above contains a carbodiimide modified form of XDI and can be obtained, for example, by reacting an XDI composition in the presence of a known carbodiimide catalyst.

[0124] Furthermore, the XDI-modified composition only needs to contain at least one of the functional groups described in (a) to (i) above, and may contain two or more. The XDI-modified composition can also be used alone or in combination of two or more.

[0125] A polymerizable composition for coating is, for example, a two-component curing type, comprising agent A as a curing agent and agent B as a main component. Agent A contains an isocyanate component. Agent A preferably contains an XDI modified composition. Agent B contains an active hydrogen group-containing component. Agent B preferably contains a polyol. [Examples]

[0126] The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than or equal to" or "greater than or equal to") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above. Note that "parts" and "%" refer to mass unless otherwise specified.

[0127] 1. Manufacturing of XDI composition An XDI composition was prepared by the method described in International Publication No. 2018-190290.

[0128] Next, a predetermined amount of PTSI (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was mixed with the obtained XDI composition to adjust the "proportion of PTSI in the XDI composition" to the proportions shown in Table 1.

[0129] This yielded the XDI compositions for each example and comparative example.

[0130] 2. Manufacturing of plastic lenses Mixture 1 was obtained by mixing 50.8 parts by mass of the XDI composition shown in Table 1 with 0.01 parts by mass of dimethyltin dichloride as a curing catalyst, 0.10 parts by mass of Zerec UN (product of Stepan Co., Ltd.; acidic phosphate ester), and 1.5 parts by mass of Biosorb 583 (manufactured by Sakai Chemical Co., Ltd.; ultraviolet absorber) at 20°C and dissolving them.

[0131] Next, 49.2 parts by mass of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was uniformly mixed into Mixture 1 to obtain Mixture 2 (polymerizable composition).

[0132] Mixture 2 was degassed at 600 Pa for 1 hour, and then filtered through a 1 μm Teflon® filter.

[0133] Next, the filtered mixture 2 was poured into a mold consisting of a glass mold and tape.

[0134] Next, the mold into which the mixture 2 was poured was placed in an oven, the temperature was raised from 25°C to 120°C, and it was cured at 120°C for 24 hours.

[0135] Afterward, the mold was removed from the oven, the hardened material was released from the mold, and the resulting hardened material was annealed at 120°C for 1 hour.

[0136] Based on the above, cured products (molded articles) of each example and comparative example were obtained.

[0137] 3.Measurement method (1) Yellow Index value (YI value) The cured products of each example and comparative example were molded into disc-shaped (9 mm thick, 75 mm in diameter) plastic lenses (optical elements).

[0138] The YI values ​​of the transmitted light from the obtained plastic lenses were measured using a spectrophotometer CM-5 (manufactured by Konica Minolta).

[0139] Furthermore, a smaller YI value indicates better hue for plastic lenses, while a larger YI value indicates poorer hue. The results are shown in Table 1.

[0140] (2)Device clarity The cured products of each example and comparative example were molded into disc-shaped (9 mm thick, 75 mm in diameter) plastic lenses (optical elements).

[0141] Next, light from a light source (Hayashi Repic Luminar Ace LA-150A) was transmitted through the lens.

[0142] The image of light transmitted through the disc lens was captured by an image processing device (manufactured by Ube Information Systems Co., Ltd.), and the captured image was subjected to grayscale processing.

[0143] The degree of grayscale in the processed image was quantified for each pixel, and the average value of the grayscale values ​​for each pixel was calculated. The resulting average value represents the devitrification of the lens. A lower devitrification indicates better lens transparency. The results are shown in Table 1.

[0144] [Table 1]

[0145] The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims below. [Industrial applicability]

[0146] The xylylene diisocyanate composition, xylylene diisocyanate modified composition, polymerizable composition, resin, and molded articles of the present invention are used in optical elements such as lenses, sheets, and films.

Claims

1. A xylylene diisocyanate composition, Xylylene diisocyanate and At least one selected from the group consisting of monochloromethylbenzyl isocyanate and dichloromethylbenzyl isocyanate, 4-methylbenzenesulfonyl isocyanate and It contains, An optical xylylene diisocyanate composition wherein the proportion of 4-methylbenzenesulfonyl isocyanate in the xylylene diisocyanate composition is 1 ppm or more and 15,000 ppm or less by mass.

2. The optical xylylene diisocyanate composition according to claim 1, further comprising 4-methylbenzenesulfonamide.

3. The optical xylylene diisocyanate composition according to claim 1 or claim 2, Active hydrogen group-containing components and A polymerizable composition containing [the specified substance].

4. The polymerizable composition according to claim 3, wherein the active hydrogen group-containing component contains a polythiol.

5. The aforementioned polythiols are 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis The polymerizable composition according to claim 4, which is at least one selected from the group consisting of (mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(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 polymerizable composition described in claim 3.

7. A molded article made of the resin described in claim 6.

8. An optical element which is a molded body according to claim 7.

9. A lens, which is an optical element according to claim 8.

10. Use of the optical xylylene diisocyanate composition according to claim 1 or claim 2 for the manufacture of optical materials.

Images