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

Abstract

To provide a xylylene diisocyanate composition, a modified xylylene diisocyanate composition, and a polymerizable composition, which enable stable production of resin excellent in yellowing resistance and transparency, and to provide resin, a molded body, an optical element, and a lens.SOLUTION: Xylylene diisocyanate and a compound having retention time of 14.0-14.6 min when measured by gas chromatography mass spectrometry under specific measurement conditions are contained in a xylylene diisocyanate composition, and the content ratio of the compound is adjusted to 2,000 ppm or less.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art Conventionally, xylylene diisocyanate compositions have been known as raw materials for poly(thio)urethane resins used in various industrial products (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-24453 A Summary of the Invention [Problem to be solved by the invention]

[0004] The xylylene diisocyanate composition described in Patent Document 1 may contain, in addition to xylylene diisocyanate, a compound other than xylylene diisocyanate.

[0005] Therefore, resins are required to have excellent yellowing resistance and transparency depending on the purpose and application. However, if a xylylene diisocyanate composition contains a specific compound, the yellowing resistance and transparency of a resin produced from the xylylene diisocyanate composition may be significantly reduced.

[0006] Therefore, the present invention provides a xylylene diisocyanate composition, a xylylene diisocyanate-modified composition, a polymerizable composition, a resin, a molded article, an optical element, and a lens that can stably produce a resin having excellent yellowing resistance and transparency. [Means for solving the problem]

[0007] The present invention [1] is a xylylene diisocyanate composition comprising: xylylene diisocyanate; and a compound having a retention time of 14.0 minutes to 14.6 minutes when the xylylene diisocyanate composition is measured by gas chromatography mass spectrometry under the following measurement conditions, and the content of the compound is 2000 ppm or less.

[0008] (Gas chromatography mass spectrometry measurement conditions) Column: HP19091L-433 HP-50+ (inner diameter 0.25 mm × length 30 m, film 0.25 μm), Oven temperature: 50°C for 1 minute, heated from 50°C to 280°C at 10.0°C / min, held at 280°C for 6 minutes. 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 in dichloromethane Injection temperature: 200℃, Interface temperature: 280℃; Quadrupole temperature: 150℃, Ion source temperature: 230°C; Detection method: Scan method (m / z: 10-500).

[0009] The present invention [2] includes the xylylene diisocyanate composition of [1] above, in which the content of the compound exceeds 100 ppm. The present invention [3] includes the xylylene diisocyanate composition according to [1] above, in which the content of the compound is 10 ppm or more.

[0010] The present invention [4] includes the xylylene diisocyanate composition according to any one of the above [1] to [3], wherein the molecular weight of the compound is 161.

[0011] The present invention [5] includes the xylylene diisocyanate composition according to any one of the above [1] to [4], wherein the compound is represented by the following general formula (1).

[0012] [ka] (In the general formula (1), R 1 R represents a hydrogen atom, a methyl group, or an ethyl group. 2 represents a hydrogen atom, a methyl group, an ethyl group, or a formyl group; and m represents an integer of 0 to 2. The present invention [6] includes the xylylene diisocyanate composition according to the above [5], wherein the compound comprises a formyl group-containing isocyanate represented by the following chemical formula (2) and / or an ethyl group-containing isocyanate represented by the following chemical formula (3).

[0013] [ka]

[0014] [ka] The present invention [7] includes a xylylene diisocyanate composition comprising xylylene diisocyanate and a compound represented by the following general formula (1) and having a molecular weight of 161, wherein the content of the compound is 2000 ppm or less.

[0015] [ka] (In the general formula (1), R 1 R represents a hydrogen atom, a methyl group, or an ethyl group. 2 represents a hydrogen atom, a methyl group, an ethyl group, or a formyl group; and m represents an integer of 0 to 2. The present invention [8] includes the xylylene diisocyanate composition according to [7] above, in which the content of the compound exceeds 100 ppm. The present invention [9] includes the xylylene diisocyanate composition according to [7] above, in which the content of the compound is 10 ppm or more.

[0016] The present invention

[10] comprises the xylylene diisocyanate composition according to any one of the above [7] to [9], wherein the compound comprises a formyl group-containing isocyanate represented by the following chemical formula (2) and / or an ethyl group-containing isocyanate represented by the following chemical formula (3).

[0017] [ka]

[0018] [ka] The present invention

[11] includes the xylylene diisocyanate composition according to any one of the above [1] to

[10] , further comprising chloromethyl benzyl isocyanate, and the content of the chloromethyl benzyl isocyanate is 0.2 ppm or more and 3000 ppm or less.

[0019] The present invention

[12] relates to a modified composition obtained by modifying the xylylene diisocyanate composition according to any one of the above [1] to

[11] , and includes a modified xylylene diisocyanate composition containing at least one of the following functional groups (a) to (i): (a) an isocyanurate group, (b) an allophanate group; (c) a biuret group, (d) a urethane group, (e) a urea group, (f) an iminooxadiazinedione group, (g) a uretdione group, (h) a uretonimine group, (i) A carbodiimide group.

[0020] The present invention

[13] includes a polymerizable composition comprising an isocyanate component containing the xylylene diisocyanate composition of any one of [1] to

[11] above and / or the xylylene diisocyanate modified composition of

[12] above, and an active hydrogen group-containing component.

[0021] The present invention

[14] includes a resin which is a cured product of the polymerizable composition according to the above

[13] .

[0022] The present invention

[15] includes a molded article containing the resin according to

[14] above.

[0023] The present invention

[16] includes an optical element comprising the molded article according to the above

[15] .

[0024] The present invention

[17] includes a lens including the optical element according to

[16] above. Effect of the Invention

[0025] The xylylene diisocyanate composition of the present invention contains xylylene diisocyanate and the above-mentioned compound, and the content ratio of the above-mentioned compound is not more than the above-mentioned upper limit. Therefore, a resin produced from the above-mentioned xylylene diisocyanate composition has excellent yellowing resistance and transparency.

[0026] The xylylene diisocyanate modified composition of the present invention is obtained by modifying the above-mentioned xylylene diisocyanate composition. Therefore, a resin produced from the above-mentioned xylylene diisocyanate modified composition has excellent yellowing resistance and transparency.

[0027] The polymerizable composition of the present invention contains the above-mentioned xylylene diisocyanate composition and / or the above-mentioned xylylene diisocyanate modified composition as an isocyanate component, and therefore the resin produced from the above-mentioned polymerizable composition has excellent yellowing resistance and transparency.

[0028] The resin, molded article, optical element, and lens of the present invention contain a cured product of the above-mentioned polymerizable composition, and therefore the resin, molded article, optical element, and lens have excellent yellowing resistance and transparency. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] 1. Xylylene diisocyanate composition The xylylene diisocyanate composition of the present invention is substantially a single compound (i.e., xylylene diisocyanate) containing 99% by mass or more of xylylene diisocyanate as the main component, but contains a specific compound (more specifically, a specific isocyanate compound) described below as a secondary component, and is therefore defined as a xylylene diisocyanate composition.

[0030] That is, the xylylene diisocyanate composition of the present invention contains, as essential components, xylylene diisocyanate and the specific compound described below.

[0031] In the following, the xylylene diisocyanate composition is referred to as the XDI composition, and xylylene diisocyanate is referred to as XDI.

[0032] Examples of XDI include 1,2-XDI (o-XDI), 1,3-XDI (m-XDI), and 1,4-XDI (p-XDI).

[0033] These XDIs can be used alone or in combination of two or more types.

[0034] Of the XDIs, 1,3-XDI (m-XDI) is preferable.

[0035] XDI can be produced, for example, by a known hydrochloride method. Specifically, XDI can be produced by reacting xylylenediamine hydrochloride with phosgene under normal pressure (0.1 MPa). If necessary, XDI can be purified, for example, by a known purification method. Examples of the purification method include rectification (distillation) and extraction.

[0036] The content (purity) of XDI is, for example, 99.00 mass% or more, preferably 99.50 mass% or more, more preferably 99.60 mass% or more, even more preferably 99.80 mass% or more, and for example, 99.95 mass% or less, based on the total mass of the XDI composition. The content of XDI can be measured in accordance with the method described in paragraph

[0377] of Japanese Patent No. 6373536.

[0037] The specific compound is included in the XDI composition by, for example, being added to XDI. Note that the specific compound may be a by-product in the above-mentioned production of XDI and included in the XDI composition. When the specific compound is a by-product in the production of XDI and is contained in the XDI composition, the method for adjusting the content ratio of the specific compound contained in the XDI composition is not limited. The content ratio of the specific compound contained in the XDI composition can be adjusted by a known method such as distillation or column purification.

[0038] When the XDI composition is measured by gas chromatography mass spectrometry under the following measurement conditions, the retention time of the specific compound is 14.0 minutes to 14.6 minutes. (Gas chromatography mass spectrometry measurement conditions) Column: HP19091L-433 HP-50+ (inner diameter 0.25 mm × length 30 m, film 0.25 μm), Oven temperature: 50°C for 1 minute, heated from 50°C to 280°C at 10.0°C / min, held at 280°C for 6 minutes. 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 in dichloromethane solution Injection temperature: 200℃, Interface temperature: 280℃; Quadrupole temperature: 150℃, Ion source temperature: 230°C; Detection method: Scan method (m / z: 10-500).

[0039] The molecular weight of the specific compound is 161. Specific examples of the specific compound include isocyanate compounds represented by the following general formula (1).

[0040] General formula (1) [ka] (In the general formula (1), R 1 R represents a hydrogen atom, a methyl group, or an ethyl group. 2 represents a hydrogen atom, a methyl group, an ethyl group, or a formyl group; and m represents an integer of 0 to 2. In the general formula (1), R 1 preferably represents a hydrogen atom.

[0041] In the general formula (1), R 2 preferably represents an ethyl group or a formyl group.

[0042] In the general formula (1), m is preferably 1.

[0043] The isocyanate compound represented by the above general formula (1) preferably contains a formyl group-containing isocyanate represented by the following chemical formula (2) and / or an ethyl group-containing isocyanate represented by the following chemical formula (3), and more preferably contains a formyl group-containing isocyanate represented by the following chemical formula (2).

[0044] Chemical formula (2) [ka]

[0045] Chemical formula (3) [ka] The content ratio of the specific compound is, for example, 0.1 ppm, preferably 1 ppm or more, more preferably 10 ppm or more, even more preferably more than 100 ppm, and 2000 ppm or less, preferably 1700 ppm or less, more preferably 1500 ppm or less, even more preferably 1200 ppm or less, and particularly preferably 1000 ppm or less, based on the total mass of the XDI composition. The content ratio of the specific compound can be calculated in accordance with the method described in the examples below. The upper limit and the lower limit can be combined as appropriate.

[0046] If the content ratio of the specific compound is equal to or greater than the lower limit, the dyeability of the resin produced from the XDI composition can be improved. If the content ratio of the specific compound is equal to or greater than the lower limit, the storage stability of the XDI composition can be prevented from decreasing. If the content ratio of the specific compound is equal to or greater than the lower limit, the specific compound can be easily reduced, and the productivity of the XDI composition can be prevented from decreasing. If the content ratio of the specific compound is equal to or less than the upper limit, the yellowing resistance and transparency of the resin produced from the XDI composition can be improved.

[0047] The XDI composition may contain chloromethylbenzyl isocyanate (monochloromethylbenzyl isocyanate) represented by the following chemical formula (4): Hereinafter, chloromethylbenzyl isocyanate is referred to as CBI.

[0048] Chemical formula (4) [ka] CBI is a chlorine compound produced as a by-product in the production of XDI. In other words, CBI may be produced as a by-product in the production of XDI. The structural isomer of CBI produced as a by-product in the production of XDI corresponds to the structural isomer of XDI produced.

[0049] CBIs include, for example, o-CBI, m-CBI and p-CBI.

[0050] The content of CBI is, for example, 0 ppm or more, preferably 0.2 ppm or more, preferably 6 ppm or more, more preferably 100 ppm or more, and, for example, 5000 ppm or less, preferably 4000 ppm or less, more preferably 3000 ppm or less, particularly preferably 1600 ppm or less, and particularly preferably 1000 ppm or less, based on the total mass of the XDI composition. The content of CBI can be measured according to the method described in paragraph

[0377] of Japanese Patent No. 6373536.

[0051] If the CBI content is within the above range, the yellowing resistance of the resin produced from the XDI composition can be reliably improved. In particular, if the CBI content is equal to or less than the upper limit, the yellowing resistance of the resin produced from the XDI composition can be reliably improved, and the mechanical properties of the resin can be improved. The XDI composition may also contain dichloromethylbenzyl isocyanate, hereinafter referred to as DCI. The DCI content 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, more preferably 20 ppm or less, relative to the total mass of the XDI composition. When the content of DCI is within the above range, yellowing and / or clouding of the resin produced from the XDI composition can be suppressed. The DCI content can be measured in accordance with the method described in paragraph

[0376] of Japanese Patent No. 6373536.

[0052] The XDI composition may also contain other ingredients, such as dichloromethaneimino-methylbenzyl isocyanate, xylylene dichloride, and cyanobenzyl isocyanate.

[0053] The XDI composition may contain only one type of the other components, or may contain two or more types.

[0054] The content ratio of other components relative to the total mass of the XDI composition is, for example, 0 ppm or more and, for example, 0.2 ppm or less, preferably 300 ppm or less.

[0055] The concentration of hydrolyzable chlorine (HC) in the XDI composition is, for example, 10 ppm or more, preferably 20 ppm or more, more preferably 30 ppm or more, and for example, 1000 ppm or less, preferably 500 ppm or less, more preferably 200 ppm or less. The concentration of hydrolyzable chlorine (HC) is measured in accordance with the method for determining hydrolyzable chlorine described in JIS K-1603-3 (2007).

[0056] 2. Xylylene diisocyanate modified composition The above-mentioned XDI composition may be modified, if necessary, by a known method.

[0057] The 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) an isocyanurate group, (b) an allophanate group; (c) a biuret group, (d) a urethane group, (e) a urea group, (f) an iminooxadiazinedione group, (g) a uretdione group, (h) a uretonimine group, (i) A carbodiimide group.

[0058] More specifically, the XDI modified composition containing the functional group (a) (isocyanurate group) contains a trimer of XDI and can be obtained, for example, by reacting the XDI composition in the presence of a known isocyanurate catalyst to isocyanurate (e.g., trimerize) the XDI.

[0059] The XDI modified composition containing the functional group (allophanate group) described above (b) contains an allophanate modified XDI, and can be obtained, for example, by reacting an XDI composition with a monohydric alcohol or a dihydric alcohol, and then further reacting the resulting mixture in the presence of a known allophanate catalyst.

[0060] The XDI modified composition containing the functional group (c) (biuret group) contains a biuret modified XDI and can be obtained, for example, by reacting an XDI composition with water or a secondary amine, and then further reacting it in the presence of a known biuretization catalyst.

[0061] The XDI modified composition containing the functional group (urethane group) described above (d) contains a polyol modified XDI, and can be obtained, for example, by reacting the XDI composition with a low molecular weight polyol (e.g., trimethylolpropane).

[0062] The XDI modified composition containing the functional group (urea group) of (e) above contains a polyamine modified XDI, and can be obtained, for example, by reacting an XDI composition with a polyamine.

[0063] The XDI modified composition containing the functional group (f) (iminooxadiazinedione group) contains an iminooxadiazinedione modified XDI (asymmetric trimer) and can be obtained, for example, by reacting the XDI composition in the presence of a known iminooxadiazinedione conversion catalyst to convert XDI into iminooxadiazinedione (e.g., trimerization).

[0064] The XDI modified composition containing the functional group (uretdione group) described above (g) contains a uretdione modified XDI, and can be obtained, for example, by reacting the XDI composition in the presence of a known uretdione conversion catalyst to convert the XDI into a uretdione (e.g., dimerize it).

[0065] The XDI modified composition containing the functional group (uretonimine group) described above (h) contains a uretonimine modified form of XDI, and can be obtained, for example, by reacting the XDI composition in the presence of a known carbodiimide catalyst to form a carbodiimide group, and then adding XDI to the carbodiimide group.

[0066] The XDI modified composition containing the functional group (carbodiimide group) described above (i) contains a carbodiimide modified XDI, and can be obtained, for example, by reacting the XDI composition in the presence of a known carbodiimide catalyst.

[0067] The XDI modified composition may contain at least one of the functional groups (a) to (i) above, and may contain two or more of them. Such a XDI modified composition is produced by appropriately combining the above reactions.

[0068] The XDI modified compositions may be used alone or in combination of two or more kinds.

[0069] <Action and effect> The XDI composition described above contains XDI and the specific compound described above, and the content ratio of the specific compound described above is equal to or less than the upper limit described above. The XDI modified composition described above is obtained by modifying the XDI composition described above.

[0070] Therefore, a resin produced from the above-mentioned XDI composition and / or the above-mentioned modified XDI composition has excellent yellowing resistance and transparency.

[0071] In the above embodiment, the specific compound is a compound represented by the general formula (1), specifically, a formyl group-containing isocyanate represented by the chemical formula (2) and an ethyl group-containing isocyanate represented by the chemical formula (3). However, the specific compound is not limited thereto.

[0072] When the XDI composition is measured by gas chromatography mass spectrometry under the above measurement conditions, the specific compound does not necessarily have to be included in the above general formula (1) as long as it is a compound that has a retention time of 14.0 minutes to 14.6 minutes.

[0073] Furthermore, as long as the specific compound is a compound included in the above general formula (1) and has a molecular weight of 161, the retention time of the specific compound may be outside the range of 14.0 minutes to 14.6 minutes when the XDI composition is measured by gas chromatography mass spectrometry under the above measurement conditions.

[0074] 3. Polymerizable composition The above-mentioned XDI composition and / or XDI modified composition are preferably used as a raw material for resin. More specifically, the XDI composition and / or XDI modified composition is contained as an isocyanate component in a polymerizable composition that is a raw material for resin.

[0075] The polymerizable composition includes an isocyanate component and an active hydrogen group-containing component.

[0076] The isocyanate component contains an XDI composition and / or an XDI modified composition, and preferably consists of an XDI composition and / or an XDI modified composition.

[0077] Examples of the active hydrogen group-containing component include a polyol component, a polythiol component, and a polyamine component.

[0078] The active hydrogen group-containing component can be used alone or in combination of two or more kinds.

[0079] Of the active hydrogen group-containing components, preferred are polyol components and polythiol components.

[0080] The polyol component includes, for example, a low molecular weight polyol and a high molecular weight polyol.

[0081] The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400, preferably 300 or less. Examples of the low molecular weight polyol include dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, hexahydric alcohols, heptahydric alcohols, and octahydric alcohols. Among the low molecular weight polyols, dihydric alcohols and trihydric alcohols are preferable.

[0082] Examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane(7-22)diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol (C (number of carbon atoms, the same applies below) 17-20), isosorbide, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, and bisphenol A.

[0083] Examples of trihydric alcohols include glycerin and trimethylolpropane.

[0084] In addition, the low molecular weight polyol may be a polyalkylene oxide having a number average molecular weight of 60 or more and less than 400. The polyalkylene oxide may be a random and / or block copolymer of two or more alkylene oxides. The polyalkylene oxide may be obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide) to the above alcohol as an initiator.

[0085] The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, preferably 500 or more, and for example, 10,000 or less, preferably 5,000 or less.

[0086] Examples of high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, silicone polyols, fluorine polyols, and vinyl monomer modified polyols.

[0087] Such polyol components can be used alone or in combination of two or more kinds.

[0088] The hydroxyl value of the polyol component is, for example, 5 mgKOH / g or more, preferably 10 mgKOH / g or more, and, for example, 300 mgKOH / g or less, preferably 250 mgKOH / g or less. The hydroxyl value can be measured by the acetylation method or the phthalation method according to the JIS K1557-1 method A or B.

[0089] The number average molecular weight of the polyol component is, in terms of standard polystyrene measured by gel permeation chromatography (GPC), for example, 2000 or more, preferably 5000 or more, and for example, 100000 or less, preferably 50000 or less.

[0090] Examples of polythiol components 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 trimethylolpropane tris(2-mercaptoacetate). , trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis( mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7- Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-Dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercapto Aliphatic polythiol compounds such as tris(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, and 2,5-bis(mercaptomethyl)-1,4-dithiane; Aromatic polythiol compounds such as 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; Examples of the heterocyclic polythiol compounds include 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, and bismuthiol.

[0091] Such polythiol components can be used alone or in combination of two or more kinds.

[0092] In addition, examples of the polythiol component include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)-1,4-dithiane, and bis(mercaptoethyl)-1,4-dithiane.

[0043] It is preferable that the mercaptomethylthio compound is at least one selected from the group consisting of 1,2,3-dimethyl-2,4-phenylenediamine, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0093] <Action and effect> The polymerizable composition contains the XDI composition and / or the XDI modified composition as an isocyanate component, and therefore the resin produced from the polymerizable composition has excellent yellowing resistance and transparency.

[0094] 4. Resin The resin is produced by reacting the above-mentioned isocyanate component with the above-mentioned active hydrogen group-containing component. In other words, the resin is a cured product of the polymerizable composition. The resin is preferably molded by a known molding method. In other words, the molded product includes the resin.

[0095] An example of a resin molded article is an optical element.

[0096] The optical element includes, for example, a lens, a sheet, and a film, and preferably includes a lens.

[0097] The lens is produced, for example, by reacting the above-mentioned XDI composition with the above-mentioned polythiol component. In producing the lens, for example, a casting method can be used.

[0098] Examples of lenses include clear lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0099] The polymerizable composition can also be prepared as a two-component curable resin raw material.

[0100] The two-component curing resin raw material contains component A as a curing agent and component B as a base component.

[0101] The agent A includes, for example, the above-mentioned XDI modified composition, and the agent B includes, for example, the above-mentioned polyol component.

[0102] Examples of the two-component curing resin raw material include two-component curing coating raw materials. Examples of the coating include paints and adhesives.

[0103] <Action and effect> The above-mentioned resin, molded article, optical element, lens and coating contain a cured product of the above-mentioned polymerizable composition, and therefore the resin, molded article, optical element, lens and coating have excellent yellowing resistance and transparency. EXAMPLES

[0104] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numerical values ​​defined as "less than or equal to" or "less than") or lower limit values ​​(numerical values ​​defined as "more than or equal to" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention". In addition, "parts" and "%" are based on mass unless otherwise specified.

[0105] <Evaluation method> In the examples, the physical properties of the plastic lenses were evaluated as follows.

[0106] <Refractive index (ne), Abbe number (νe)> Using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive indices (ne, nF', nC') at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line) were measured, and the refractive index (ne) and Abbe number (νe) were calculated.

[0107] <Heat resistance> The glass transition temperature Tg was measured by the TMA penetration method (load 50 g, pin tip 0.5 mmφ, heating rate 10° C. / min) using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, and used as an index of heat resistance.

[0108] <Calculation of Yellow Index Value (YI Value) of Plastic Lens (Resin)> The resin was formed into a circular flat plastic lens having a thickness of 9 mm and a diameter of 75 mm, and the YI value was determined using a spectrophotometer CM-5 manufactured by Konica Minolta.

[0109] In addition, there is a correlation between a smaller YI value, the better the hue of the plastic lens, and a larger YI value, the worse the hue.

[0110] <Devitrification of plastic lenses (resin)> The resin was made into a circular flat plastic lens with a thickness of 9 mm and a diameter of 75 mm, and light from a light source (Luminar Ace LA-150A manufactured by Hayashi Repic) was transmitted through the flat lens. An image of the light transmitted through the flat lens was captured into an image processing device (manufactured by Ube Information Systems Co., Ltd.), and the captured image was subjected to shading processing. The degree of shading of the processed image was quantified for each pixel, and the average value of the numerical value of the degree of shading of each pixel was obtained, and the devitrification degree of the flat lens was calculated.

[0111] The smaller the devitrification degree, the less the transparency of the resin (here, the flat lens) is impaired (that is, the resin has excellent transparency).

[0112] 2. Preparation Example 1: Preparation of XDI An autoclave with a reflux condenser, stirring blade, thermometer, hydrogen chloride gas inlet pipe, phosgene inlet pipe, raw material tank, raw material charging pump, and pressure regulator (internal volume 2 m) 3 Into this reactor, 846 kg of orthodichlorobenzene was charged as an inert solvent, and in the raw material tank, 136.2 kg (1.0 kmol) of m-xylylenediamine and 621 kg of orthodichlorobenzene were charged (total amine concentration 8.5% by mass).

[0113] Next, the temperature inside the reactor was raised to 120°C, and the internal pressure was adjusted to 0.01 MPa higher than atmospheric pressure. Then, hydrogen chloride gas was started to be charged into the reactor from the hydrogen chloride gas inlet tube at a rate of 43.8 kg / hr, and at the same time, m-xylylenediamine diluted with an inert solvent was started to be charged from the raw material tank at a rate of 379 kg / hr using the raw material charging pump, and the entire amount was charged over 2 hours. After that, the mixture was aged for 1 hour while hydrogen chloride gas was further charged at 20 kg / hr.

[0114] Next, the reaction liquid (hydrochloride slurry) in the reactor was heated to 160°C, and phosgene was introduced from the phosgene inlet tube at 100 kg / hr (1.0 kmol / hr) and reacted for 8 hours while maintaining the temperature. After the reaction was completed, unreacted phosgene and hydrogen chloride gas were removed by purging nitrogen into the reactor. Then, the reaction liquid was filtered to remove 0.8 kg (dry weight) of unreacted hydrochloride. The obtained filtrate was desolvated to obtain 188.6 kg of reaction mass with m-XDI purity of 98.10%.

[0115] The resulting reaction mass was then rectified to obtain m-XDI with an m-XDI purity of 99.99% by mass.

[0116] 3. Preparation Example 2: Preparation of formyl group-containing isocyanate A 500 ml-scale pressure-resistant autoclave was charged with 10 g (0.078 mol) of 1,3-dicyanobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 16.6 g (0.0078 mol of palladium) of a 5 mass% palladium-supported carbon catalyst (manufactured by NE Chemcat Corporation, NX type, 49 mass% water content), and 100 g of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a reaction solvent.

[0117] Next, nitrogen was supplied into the autoclave to increase the pressure inside the autoclave to 3.1 MPa (absolute pressure), and then the nitrogen was discharged from the autoclave to reduce the pressure inside the autoclave to 0.2 MPa (absolute pressure). This operation was repeated four times to replace the inside of the autoclave with nitrogen.

[0118] Next, hydrogen was supplied into the autoclave to increase the pressure inside the autoclave to 2.1 MPa (absolute pressure), and then hydrogen was discharged from the autoclave to reduce the pressure inside the autoclave to 0.2 MPa (absolute pressure). This operation was repeated four times to replace the inside of the autoclave with hydrogen.

[0119] Next, hydrogen was supplied into the autoclave using a pressure accumulator to increase the pressure inside the autoclave to 1.0 MPa (absolute pressure). Then, while maintaining the pressure inside the autoclave, the contents inside the autoclave were stirred to hydrogenate 1,3-dicyanobenzene.

[0120] When hydrogen absorption reached about 75% of the theoretical amount, the atmosphere in the autoclave was replaced with nitrogen to remove hydrogen from the autoclave.

[0121] The reaction solution was then filtered through filter paper to remove the palladium-supported carbon catalyst from the reaction solution. The filtrate was then concentrated using a rotary evaporator. Low boiling components were then removed from the concentrated filtrate using a vacuum pump.

[0122] This resulted in a composition containing 1-iminomethyl-3-(aminomethyl)benzene as the main component, which was then hydrolyzed to obtain a composition containing 3-(aminomethyl)benzaldehyde as the main component.

[0123] Next, the composition mainly composed of 3-(aminomethyl)benzaldehyde was reacted with triphosgene in toluene to prepare the formyl group-containing isocyanate (3-(isocyanatomethyl)benzaldehyde) represented by the above chemical formula (2). After the toluene was distilled off from the reaction solution, the formyl group-containing isocyanate was obtained by vacuum distillation.

[0124] When the obtained formyl group-containing isocyanate was analyzed under the above-mentioned gas chromatography mass spectrometry conditions, a peak was confirmed at a retention time of 14.0 minutes to 14.6 minutes.

[0125] 4. Examples 1 to 4 and Comparative Example 1 The XDI obtained in Preparation Example 1 and the formyl group-containing isocyanate obtained in Preparation Example 2 were mixed so that the content ratio of the formyl group-containing isocyanate in the XDI composition was the value shown in Table 1. In this way, an XDI composition was obtained.

[0126] The content ratio of the formyl group-containing isocyanate in the XDI composition was calculated by adding the following internal standard substance to the obtained XDI composition, analyzing it under the above-mentioned gas chromatography mass spectrometry measurement conditions, and calculating it from the area ratio of the internal standard substance appearing at a retention time of 12.1 minutes and the formyl group-containing isocyanate appearing at a retention time of 14.0 minutes to 14.6 minutes. The results are shown in Table 1.

[0127] Internal standard: 0.5 mg of methylnaphthalene was added to 100 mg of analytical sample to make the volume 10 mL.

[0128] 5. Manufacturing of plastic lenses 52 parts by mass of the XDI composition of each Example and Comparative Example, 0.01 parts by mass of dibutyltin 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) were mixed and dissolved at 20°C. 48 parts by mass of a polythiol component mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were charged and mixed to obtain a mixed homogeneous liquid. This homogeneous liquid was degassed at 600 Pa for 1 hour, filtered with a 1 μm Teflon (registered trademark) filter, and then poured into a mold consisting of a glass mold and tape. This mold was placed in an oven, gradually heated to 10°C to 120°C, and polymerized for 38 hours. After the polymerization was completed, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120°C for 1 hour to produce a plastic lens. The physical properties were determined based on the methods for evaluating the physical properties of plastic lenses described above. The results are shown in Table 1.

[0129] [Table 1] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial Applicability]

[0130] The xylylene diisocyanate composition, the xylylene diisocyanate-modified composition, the polymerizable composition, the resin and the molded article of the present invention are used for optical elements such as lenses, sheets and films.

Claims

1. A xylylene diisocyanate composition comprising: 99% by mass or more of xylylene diisocyanate; A compound having a retention time of 14.0 minutes to 14.6 minutes when the xylylene diisocyanate composition is measured by gas chromatography mass spectrometry under the following measurement conditions: Dichloromethylbenzylisocyanate and Including, The content of the compound is 2000 ppm or less, The xylylene diisocyanate composition, wherein the content of dichloromethyl benzyl isocyanate is 60 ppm or less. (Gas chromatography mass spectrometry measurement conditions) Column: HP19091L-433 HP-50+ (inner diameter 0.25 mm × length 30 m, film 0.25 μm), Oven temperature: held at 50°C for 1 minute, heated from 50°C to 280°C at 10.0°C / min, held at 280°C for 6 minutes Carrier gas: He 1.0 ml / min constant flow mode Injection method: pulsed splitless method (150 kPa at 0.5 min), Injection volume: 1.0 μL, Sample concentration: 1.0% by mass in dichloromethane Injection temperature: 200℃, Interface temperature: 280° C. Quadrupole temperature: 150℃, Ion source temperature: 230° C. Detection method: Scan method (m / z: 10 to 500).

2. The xylylene diisocyanate composition according to claim 1, wherein the content of the compound exceeds 100 ppm.

3. The xylylene diisocyanate composition according to claim 1 , wherein the content of the compound is 10 ppm or more.

4. The xylylene diisocyanate composition according to any one of claims 1 to 3, wherein the compound has a molecular weight of 161.

5. The compound is represented by the following general formula (1), The xylylene diisocyanate composition according to any one of claims 1 to 3. 【Chemistry 1】 (In the general formula (1), R １ R represents a hydrogen atom, a methyl group, or an ethyl group. ２ represents a hydrogen atom, a methyl group, an ethyl group, or a formyl group; and m represents an integer of 0 to 2.

6. The xylylene diisocyanate composition according to claim 5, wherein the compound comprises a formyl group-containing isocyanate represented by the following chemical formula (2) and / or an ethyl group-containing isocyanate represented by the following chemical formula (3). 【Chemistry 2】 【Chemistry 3】

7. 99% by mass or more of xylylene diisocyanate; A compound represented by the following general formula (1), Dichloromethylbenzylisocyanate and Including, The content of the compound is 2000 ppm or less, The xylylene diisocyanate composition, wherein the content of dichloromethyl benzyl isocyanate is 60 ppm or less. 【Chemistry 1】 (In the general formula (1), R １ R represents a hydrogen atom, a methyl group, or an ethyl group. ２ represents a hydrogen atom, a methyl group, an ethyl group, or a formyl group; and m represents an integer of 0 to 2.

8. The xylylene diisocyanate composition according to claim 7, wherein the content of the compound exceeds 100 ppm.

9. The xylylene diisocyanate composition according to claim 7, wherein the content of the compound is 10 ppm or more.

10. The compound comprises a formyl group-containing isocyanate represented by the following chemical formula (2) and / or an ethyl group-containing isocyanate represented by the following chemical formula (3). The xylylene diisocyanate composition according to any one of claims 7 to 9. 【Chemistry 2】 【Chemistry 3】

11. The xylylene diisocyanate composition according to any one of claims 1 to 10, further comprising chloromethyl benzyl isocyanate, and the content of the chloromethyl benzyl isocyanate is 0.2 ppm or more and 3000 ppm or less.

12. The xylylene diisocyanate composition according to any one of claims 1 to 11 is a modified composition, A xylylene diisocyanate modified composition containing at least one of the following functional groups (a) to (i): (a) an isocyanurate group, (b) an allophanate group, (c) a biuret group, (d) a urethane group, (e) a urea group, (f) an iminooxadiazinedione group, (g) a uretdione group, (h) a uretonimine group, (i) Carbodiimide group

13. An isocyanate component containing the xylylene diisocyanate composition according to any one of claims 1 to 11 and / or the xylylene diisocyanate modified composition according to claim 12; and an active hydrogen group-containing component.

14. A resin which is a cured product of the polymerizable composition according to claim 13.

15. A molded article comprising the resin according to claim 14.

16. An optical element comprising the molded article according to claim 15.

17. A lens comprising the optical element of claim 16.

18. Use of the xylylene diisocyanate composition according to any one of claims 1 to 11 for the manufacture of lenses.

19. 99% by mass or more of xylylene diisocyanate; A formyl group-containing isocyanate represented by the following chemical formula: Chloromethylbenzylisocyanate and Including, The content of the formyl group-containing isocyanate is 2000 ppm or less, 2. Use of a xylylene diisocyanate composition, the xylylene diisocyanate content of which is 3000 ppm or less, for producing a lens. Chemical formula: 【Chemistry 1】

20. 20. Use of the xylylene diisocyanate composition according to claim 19 for the manufacture of lenses, wherein the content of the formyl group-containing isocyanate exceeds 100 ppm.

21. 20. Use of the xylylene diisocyanate composition according to claim 19 for producing a lens, wherein the content of the formyl group-containing isocyanate is 10 ppm or more.

22. Use of the xylylene diisocyanate composition according to any one of claims 19 to 21 for producing a lens, wherein the content of chloromethyl benzyl isocyanate is 0.2 ppm or more.

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