Xylene diisocyanate composition, xylene diisocyanate modified composition, polymerizable composition, resin, molded body, optical element, and lens

Abstract

A compound having a retention time of 14.0 minutes to 14.6 minutes when measured under specific measurement conditions using gas chromatography-mass spectrometry is contained in the xylylene diisocyanate composition, and the contained proportion of the compound is adjusted to 2000 ppm or less.

Description

[0001] This application is a divisional application of the invention patent application filed on June 14, 2021, with application number 202180006622.3 (PCT / JP2021 / 022484) and entitled "Phenylene diisocyanate composition, phenylene diisocyanate modified composition, polymerizable composition, resin, molded article, optical element and lens". Technical Field

[0002] This invention relates to phenylene diisocyanate compositions, phenylene diisocyanate modified compositions, polymerizable compositions, resins, molded articles, optical elements, and lenses. Background Technology

[0003] Phenylene diisocyanate compositions have long been known as raw materials for poly(sulfur)urethane resins that can be used in various industrial products (see, for example, Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2020-24453 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The phenylene diisocyanate composition described in Patent Document 1 contains compounds other than phenylene diisocyanate in addition to phenylene diisocyanate.

[0009] However, depending on the purpose and application, resins are required to have excellent resistance to yellowing and transparency. However, when the dimethyl phthalate (DIP) diisocyanate composition contains certain compounds, the resistance to yellowing and transparency of the resin made from that DIP diisocyanate composition may decrease significantly.

[0010] Therefore, the present invention provides phthalic acid diisocyanate compositions, phthalic acid diisocyanate modified compositions, polymerizable compositions, resins, molded articles, optical elements and lenses that can stably manufacture resins with excellent resistance to yellowing and transparency.

[0011] Methods for solving problems

[0012] The present invention [1] comprises a phenylene diisocyanate composition comprising: phenylene diisocyanate; and a compound having a retention time of 14.0 min to 14.6 min when the above phenylene diisocyanate composition is measured by gas chromatography-mass spectrometry under the following determination conditions.

[0013] The content of the above-mentioned compounds is less than 2000 ppm.

[0014] (Gas Chromatography-Mass Spectrometry Determination Conditions)

[0015] Column: HP19091L-433HP-50+ (inner diameter 0.25mm × length 30m, membrane 0.25μm); Column oven temperature: hold at 50℃ for 1 minute, increase from 50℃ to 280℃ at 10.0℃ / min, and hold at 280℃ for 6 minutes.

[0016] Carrier gas: He 1.0 ml / min constant flow mode

[0017] Injection method: splitless pulse injection (150 kPa at 0.5 min),

[0018] Injection volume: 1.0 μL

[0019] Sample concentration: 1.0% by mass dichloromethane solution

[0020] Injection temperature: 200℃

[0021] Interface temperature: 280℃

[0022] Quadrupole temperature: 150℃

[0023] Ion source temperature: 230℃

[0024] Detection method: Scan method (m / z: 10~500).

[0025] The present invention [2] comprises the phenylene diisocyanate composition of [1] above, wherein the content of the above compound is more than 100 ppm.

[0026] The present invention [3] comprises the phenylene diisocyanate composition of [1] above, wherein the content of the above compound is 10 ppm or more.

[0027] The present invention [4] comprises any of the above-mentioned [1] to [3] phenylene diisocyanate compositions, wherein the molecular weight of the above-mentioned compounds is 161.

[0028] The present invention [5] comprises any of the above-described [1] to [4] diphenylene diisocyanate compositions, wherein the above-described compounds are represented by the following general formula (1).

[0029] [Chemical Formula 1]

[0030] Chemical Formula 1

[0031]

[0032] (In general formula (1), R) 1 Represents a hydrogen atom, methyl group, or ethyl group. R 2 This represents a hydrogen atom, methyl, ethyl, or formyl group. m represents an integer between 0 and 2.

[0033] The present invention [6] comprises the phenylene diisocyanate composition of [5] above, wherein the compound comprises an isocyanate containing a formyl group represented by the following chemical formula (2), and / or an isocyanate containing an ethyl group represented by the following chemical formula (3).

[0034] [Chemical Formula 2]

[0035] Chemical formula 2

[0036]

[0037] [Chemical Formula 3]

[0038] Chemical formula 3

[0039]

[0040] The present invention [7] comprises a phenylene diisocyanate composition comprising phenylene 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 less than 2000 ppm.

[0041] [Chemical Formula 1]

[0042] Chemical Formula 1

[0043]

[0044] (In general formula (1), R) 1 Represents a hydrogen atom, methyl group, or ethyl group. R 2 This represents a hydrogen atom, methyl, ethyl, or formyl group. m represents an integer between 0 and 2.

[0045] The present invention [8] comprises the phenylene diisocyanate composition of [7] above, wherein the content of the above compound is more than 100 ppm.

[0046] The present invention [9] comprises the phenylene diisocyanate composition of [7] above, wherein the content of the above compound is 10 ppm or more.

[0047] The present invention

[10] comprises any of the above-described [7] to [9] diphenylene diisocyanate compositions, wherein the compounds comprise isocyanates containing a formyl group represented by the following chemical formula (2), and / or isocyanates containing an ethyl group represented by the following chemical formula (3).

[0048] [Chemical Formula 2]

[0049] Chemical formula 2

[0050]

[0051] [Chemical Formula 3]

[0052] Chemical formula 3

[0053]

[0054] The present invention

[11] comprises any of the above-mentioned [1] to

[10] phenylene diisocyanate compositions, and further comprises chloromethylbenzyl isocyanate, wherein the content of the chloromethylbenzyl isocyanate is 0.2 ppm or more and 3000 ppm or less.

[0055] The present invention

[12] comprises a phenylene diisocyanate modified composition, which is a modified composition obtained by modifying the phenylene diisocyanate composition described in any one of [1] to

[11] above, wherein the phenylene diisocyanate modified composition contains at least one of the functional groups (a) to (i) below.

[0056] (a) Isocyanurate group,

[0057] (b) Urea carbamate group,

[0058] (c) biuret group,

[0059] (d) Carbamate group,

[0060] (e) urea group,

[0061] (f) Iminooxadiazine dione group,

[0062] (g) ureidodione group,

[0063] (h) urea-ketone imine group,

[0064] (i) Carbodiimine group.

[0065] The present invention

[13] comprises a polymerizable composition comprising: an isocyanate component containing any one of the phenylene diisocyanate compositions described in [1] to

[11] above, and / or the phenylene diisocyanate modified composition described in

[12] above; and a component containing active hydrogen groups.

[0066] The present invention

[14] comprises a resin, which is a cured product of the polymeric composition described above

[13] .

[0067] The present invention

[15] includes a molded body comprising the resin described above

[14] .

[0068] The present invention

[16] includes an optical element comprising the molded body of

[15] described above.

[0069] The present invention

[17] includes a lens that includes the optical elements described above

[16] .

[0070] The effects of the invention

[0071] The phthalic acid diisocyanate composition of the present invention comprises phthalic acid diisocyanate and the above-mentioned compound, wherein the content of the above-mentioned compound is below the above-mentioned upper limit. Therefore, the resin made from the above-mentioned phthalic acid diisocyanate composition has excellent resistance to yellowing and transparency.

[0072] The phthalic acid diisocyanate modified composition of the present invention is obtained by modifying the above-mentioned phthalic acid diisocyanate composition. Therefore, the resin made from the above-mentioned phthalic acid diisocyanate modified composition has excellent resistance to yellowing and transparency.

[0073] The polymerizable composition of the present invention contains the above-described phthalic acid diisocyanate composition and / or the above-described phthalic acid diisocyanate modified composition as isocyanate components. Therefore, the resin manufactured from the above-described polymerizable composition exhibits excellent resistance to yellowing and transparency.

[0074] The resin, molded body, optical element, and lens of the present invention comprise cured products of the above-described polymeric composition. Therefore, the resin, molded body, optical element, and lens exhibit excellent resistance to yellowing and superior transparency. Detailed Implementation

[0075] 1. Phenylene diisocyanate composition

[0076] The phenylene diisocyanate composition of the present invention is a generally single compound (i.e., phenylene diisocyanate) containing more than 99% by mass of phenylene diisocyanate as the main component, but is defined as a phenylene diisocyanate composition because it contains specific compounds (more specifically, specific isocyanate compounds) as secondary components.

[0077] That is, the phenylene diisocyanate composition of the present invention contains phenylene diisocyanate and specific compounds described later as essential components.

[0078] In the following text, the diphenylene diisocyanate composition will be referred to as the XDI composition, and the diphenylene diisocyanate will be referred to as XDI.

[0079] Examples of XDIs include 1,2-XDI (adjacent XDI), 1,3-XDI (intermediate XDI), and 1,4-XDI (paired XDI).

[0080] These XDIs can be used individually or in combination with two or more.

[0081] Among XDIs, 1,3-XDI (inter-XDI) is a preferred example.

[0082] XDI can be manufactured, for example, using the known hydrochloride method. Specifically, XDI can be produced by reacting the hydrochloride of phenylenediamine with phosgene at atmospheric pressure (0.1 MPa). Furthermore, XDI can be purified as needed, for example, using known purification methods. Examples of purification methods include, for instance, distillation and extraction.

[0083] The XDI content (purity) relative to the total mass of the XDI composition is, for example, 99.00% by mass or more, preferably 99.50% by mass or more, more preferably 99.60% by mass or more, and even more preferably 99.80% by mass or more, and, for example, 99.95% by mass or less. The XDI content can be determined according to the method described in paragraph

[0377] of Japanese Patent No. 6373536.

[0084] Specific compounds may be included in the XDI composition, for example, by addition to XDI. It should be noted that specific compounds may also be included in the XDI composition as byproducts generated during the manufacture of XDI as described above.

[0085] When a specific compound is produced as a byproduct in the manufacture of XDI and is included in the XDI composition, there is no limitation on the method for adjusting the content of the specific compound in the XDI composition. The content of the specific compound in the XDI composition can be adjusted, for example, by known methods such as distillation or column purification.

[0086] Under the following determination conditions, when XDI compositions are determined by gas chromatography-mass spectrometry, the retention time of a specific compound is 14.0 min to 14.6 min.

[0087] (Gas Chromatography-Mass Spectrometry Determination Conditions)

[0088] Column: HP19091L-433HP-50+ (inner diameter 0.25mm × length 30m, membrane 0.25μm); Column oven temperature: hold at 50℃ for 1 minute, increase from 50℃ to 280℃ at 10.0℃ / min, and hold at 280℃ for 6 minutes.

[0089] Carrier gas: He 1.0 ml / min constant flow mode

[0090] Injection method: splitless pulse injection (150 kPa at 0.5 min),

[0091] Injection volume: 1.0 μL

[0092] Sample concentration: 1.0% by mass dichloromethane solution,

[0093] Injection temperature: 200℃

[0094] Interface temperature: 280℃

[0095] Quadrupole temperature: 150℃

[0096] Ion source temperature: 230℃

[0097] Detection method: Scan method (m / z: 10~500).

[0098] The molecular weight of the specific compound is 161. Specifically, examples of specific compounds include isocyanate compounds represented by the following general formula (1).

[0099] General formula (1)

[0100] [Chemical Formula 1]

[0101] Chemical Formula 1

[0102]

[0103] (In general formula (1), R) 1 Represents a hydrogen atom, methyl group, or ethyl group. R 2 This represents a hydrogen atom, methyl, ethyl, or formyl group. m represents an integer between 0 and 2.

[0104] In general formula (1), R 1 The preferred representation is a hydrogen atom.

[0105] In general formula (1), R 2 Preferably, it represents ethyl or formyl.

[0106] In general formula (1), m preferably represents 1.

[0107] The isocyanate compound represented by the above general formula (1) preferably includes an isocyanate containing a formyl group represented by the following chemical formula (2), and / or an isocyanate containing an ethyl group represented by the following chemical formula (3), more preferably an isocyanate containing a formyl group represented by the following chemical formula (2).

[0108] [Chemical Formula 2]

[0109] Chemical formula 2

[0110]

[0111] [Chemical Formula 3]

[0112] Chemical formula 3

[0113]

[0114] The content of a specific compound relative to the total mass of the XDI composition 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 also 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. The content of the specific compound can be calculated according to the method described in the examples below. It should be noted that the upper and lower limits can be appropriately combined.

[0115] When the content of the specific compound is at or above the aforementioned lower limit, the dyeability of the resin manufactured from the XDI composition can be improved. Furthermore, when the content of the specific compound is at or above the aforementioned lower limit, the decrease in the storage stability of the XDI composition can be suppressed. Additionally, when the content of the specific compound is at or above the aforementioned lower limit, the specific compound can be easily reduced, thus suppressing the decrease in the productivity of the XDI composition. When the content of the specific compound is below or above the aforementioned upper limit, the yellowing resistance and transparency of the resin manufactured from the XDI composition can be improved.

[0116] Additionally, the XDI composition may contain chloromethylbenzyl isocyanate (monochloromethylbenzyl isocyanate) as shown in the following chemical formula (4). Hereinafter, chloromethylbenzyl isocyanate will be referred to as CBI.

[0117] [Chemical Formula 4]

[0118] Chemical Formula 4

[0119]

[0120] CBI is a chlorinated compound produced as a byproduct in the manufacture of XDI. That is, CBI is sometimes produced as a byproduct in the manufacture of XDI. It should be noted that the structural isomers of CBI produced as a byproduct in the manufacture of XDI correspond to the structural isomers of the manufactured XDI.

[0121] As a CBI, examples include neighboring CBIs, intermediate CBIs, and relative CBIs.

[0122] The content of CBI relative to the total mass of the XDI composition is, for example, 0 ppm or more, preferably 0.2 ppm or more, more preferably 6 ppm or more, more preferably 100 ppm or more, and also, 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. The content of CBI can be determined according to the method described in paragraph

[0377] of Japanese Patent No. 6373536.

[0123] When the CBI content is within the above-mentioned range, the yellowing resistance of the resin manufactured from the XDI composition can be reliably improved. In particular, when the CBI content is below the above-mentioned upper limit, the yellowing resistance of the resin manufactured from the XDI composition can be reliably improved, and the mechanical properties of the resin can also be improved.

[0124] Additionally, the XDI composition may contain dichloromethylbenzyl isocyanate. Hereinafter, dichloromethylbenzyl isocyanate will be referred to as DCI.

[0125] The DCI content relative to the total mass of 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, for example, 60 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, and more preferably 20 ppm or less.

[0126] When the DCI content is within the above range, it can suppress yellowing and / or turbidity of resins made from XDI compositions.

[0127] The DCI content can be determined according to the method described in paragraph

[0376] of Japanese Patent No. 6373536.

[0128] In addition, the XDI composition may contain other ingredients. Examples of other ingredients include dichloromethaneimino-methylbenzyl isocyanate, dichloromethylbenzene, and cyanobenzyl isocyanate.

[0129] XDI compositions may contain only one of the other ingredients, or they may contain two or more of them.

[0130] The proportion of other components relative to the total mass of the XDI composition is, for example, 0 ppm or more, or, for example, 0.2 ppm or less, preferably 300 ppm or less.

[0131] 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 also, for example, 1000 ppm or less, preferably 500 ppm or less, more preferably 200 ppm or less.

[0132] The concentration of hydrolyzable chlorine (HC) was determined in accordance with the method for determining hydrolyzable chlorine as described in JIS K-1603-3 (2007).

[0133] 2. Phenylene diisocyanate modified composition

[0134] The above-mentioned XDI composition can be modified and physicochemically modified as needed using known methods.

[0135] The phthalene diisocyanate modified composition (hereinafter referred to as XDI modified composition) is manufactured by modifying the above-mentioned XDI composition and contains at least one of the functional groups (a) to (i) below.

[0136] (a) Isocyanurate group,

[0137] (b) Urea carbamate group,

[0138] (c) biuret group,

[0139] (d) Carbamate group,

[0140] (e) urea group,

[0141] (f) Iminooxadiazine dione group,

[0142] (g) ureidodione group,

[0143] (h) urea-ketone imine group,

[0144] (i) Carbodiimine group.

[0145] More specifically, the XDI modified composition containing the functional group (isocyanurate group) of (a) above contains a trimer of XDI, which can be obtained, for example, by reacting the XDI composition in the presence of a known isocyanurate catalyst to esterify (e.g., trimerize) the XDI.

[0146] The XDI modified composition containing the functional group (urethane group) of (b) above contains an XDI urethane modified composition, which can be obtained, for example, by further reacting the XDI composition with a monohydric or dihydric alcohol in the presence of a known urethane esterification catalyst.

[0147] The XDI modified composition containing the functional group (biuret group) of (c) above contains a biuret modified XDI, which can be obtained, for example, by further reacting the XDI composition with water or a secondary amine in the presence of a known biuret catalyst.

[0148] The XDI modified composition containing the functional group (urethane group) described above (d) contains a polyol modified version of XDI, which can be obtained, for example, by reacting the XDI composition with a low molecular weight polyol (e.g., trimethylolpropane).

[0149] The XDI modified composition containing the functional group (urea group) mentioned above contains a polyamine modified XDI, which can be obtained, for example, by reacting an XDI composition with a polyamine.

[0150] The XDI modified composition containing the functional group (iminooxadiazine dione group) described above contains an iminooxadiazine dione modified XDI (asymmetric trimer), which can be obtained, for example, by reacting the XDI composition in the presence of a known iminooxadiazine dione catalyst to iminooxadiazine dione (e.g., trimerization).

[0151] The XDI modified composition containing the functional group (ureidone group) mentioned above contains an XDI ureidone modified composition, which can be obtained, for example, by reacting the XDI composition in the presence of a known ureidone catalyst to ureidate (e.g., dimerize) the XDI.

[0152] The XDI modified composition containing the functional group (urea ketimino group) described above contains an XDI urea ketimino modified form, which can be obtained, for example, by reacting an XDI composition to form a carbodiimino group in the presence of a known carbodiimino catalyst, and then adding XDI to the carbodiimino group.

[0153] The XDI modified composition containing the functional group (carbodiimide group) mentioned above contains a carbodiimide modified XDI, which can be obtained, for example, by reacting the XDI composition in the presence of a known carbodiimide catalyst.

[0154] It should be noted that the XDI modified composition may contain at least one of the functional groups described in (a) to (i) above, or may contain two or more. Such an XDI modified composition may be generated by appropriately combining it with the above-described reaction.

[0155] In addition, XDI modified compositions can be used alone or in combination of two or more.

[0156] <Effects>

[0157] The above-described XDI composition comprises XDI and the aforementioned specific compound, wherein the content of the aforementioned specific compound is below the aforementioned upper limit. Furthermore, the above-described XDI modified composition is obtained by modifying the above-described XDI composition.

[0158] Therefore, the resin made from the above-mentioned XDI composition and / or the above-mentioned XDI modified composition has excellent resistance to yellowing and transparency.

[0159] It should be noted that, in the above embodiments, the specific compounds can be those represented by the general formula (1) above, specifically, isocyanates containing a formyl group represented by the chemical formula (2) above and isocyanates containing an ethyl group represented by the chemical formula (3) above. However, the specific compounds are not limited to these.

[0160] Any compound whose retention time is 14.0 to 14.6 minutes when measured by gas chromatography-mass spectrometry under the above-mentioned determination conditions is acceptable. Specific compounds may not be included in the above general formula (1).

[0161] In addition, any compound that is included in the above general formula (1) and has a molecular weight of 161 is acceptable. Regarding the retention time of a specific compound, when the XDI composition is measured by gas chromatography-mass spectrometry under the above-mentioned determination conditions, the retention time can be outside the range of 14.0 minutes to 14.6 minutes.

[0162] 3. Polymerizable compositions

[0163] The above-described XDI compositions and / or XDI modified compositions can be suitably used as raw materials for resins. More specifically, the XDI compositions and / or XDI modified compositions are included as isocyanate components in the raw materials for resins, i.e., polymerizable compositions.

[0164] The polymerizable composition contains an isocyanate component and a component containing active hydrogen groups.

[0165] The isocyanate component contains an XDI composition and / or an XDI modified composition, preferably composed of an XDI composition and / or an XDI modified composition.

[0166] Examples of components containing active hydrogen groups include polyols, polythiols, and polyamines.

[0167] Components containing active hydrogen groups can be used alone or in combination of two or more.

[0168] Among the components containing active hydrogen groups, polyols and polythiols are preferred.

[0169] Examples of polyol components include, for example, low molecular weight polyols and high molecular weight polyols.

[0170] Low molecular weight polyols are compounds 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 low molecular weight polyols include diols, triols, tetraols, pentols, hexaols, heptols, and octols. Among low molecular weight polyols, diols and triols are preferred.

[0171] Examples of diols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, alkane (7–22)diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol (C(carbon number, as in hereinafter, 17–20), isosorbide, 1,3- or 1,4-cyclohexanediol 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.

[0172] Examples of trihydric alcohols include glycerol and trimethylolpropane.

[0173] In addition, examples of low molecular weight polyols include polyalkylene oxides with a number average molecular weight of 60 or more and less than 400. Polyalkylene oxides comprise random and / or block copolymers of two or more alkylene oxides. In the case of polyalkylene oxides, they are obtained by adding alkylene oxides (e.g., ethylene oxide, propylene oxide) using the aforementioned alcohol as an initiator.

[0174] High molecular weight polyols are compounds 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.

[0175] Examples of high molecular weight polyols include, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, polysiloxane polyols, fluorinated polyols, and vinyl monomer-modified polyols.

[0176] Such polyol components can be used alone or in combination of two or more.

[0177] The hydroxyl value of the polyol component is, for example, 5 mg KOH / g or more, preferably 10 mg KOH / g or more, and also, for example, 300 mg KOH / g or less, preferably 250 mg KOH / g or less. It should be noted that the hydroxyl value can be determined by acetylation or phthaloylation methods according to JIS K1557-1, Method A or Method B.

[0178] In addition, regarding the number-average molecular weight of the polyol component, it is, for example, 2000 or more, preferably 5000 or more, based on the standard polystyrene conversion determined by gel permeation chromatography (GPC), and is also, for example, 100000 or less, preferably 50000 or less.

[0179] Examples of polythiols include: methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, tetra(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tri(2-mercaptoacetate), trimethylolpropane tri(3-mercaptopropionate), trimethylolethane tri(2-mercaptoacetate), trimethylolethane tri(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide. bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1 11-Dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiacyclohexane, 2,5-dimercapto-1,4-dithiacyclohexane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiacyclohexane, and their thioacetic acid and thiopropionic acid esters, hydroxymethyl sulfide bis(2-mercaptoacetic acid ester), hydroxymethyl sulfide bis(3-mercaptopropionate ester), hydroxyethyl sulfide bis(2-mercaptoacetic acid ester) ), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiacetic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), dithiodiacetic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,Aliphatic polythiols such as 3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, and 2,5-bis(mercaptomethyl)-1,4-dithiacyclohexane;

[0180] Aromatic polythiols 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(mercaptomethyloxy)benzene, 1,3,5-tris(mercaptoethyloxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol;

[0181] Heterocyclic polythiool compounds such as 2-methylamino-4,6-dithiol-triazine, 3,4-thiophene dithiol, and 2,5-dimercapto-1,3,4-thiadiazole (bismuthiol).

[0182] Such polythiol components can be used alone or in combination of two or more.

[0183] In addition, the preferred polythiol component is 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-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-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, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0184] <Effects>

[0185] The polymerizable composition described above contains the aforementioned XDI composition and / or the aforementioned XDI modified composition as isocyanate components. Therefore, the resin manufactured from the aforementioned polymerizable composition exhibits excellent resistance to yellowing and transparency.

[0186] 4. Resin

[0187] A resin is manufactured by reacting the aforementioned isocyanate component with the aforementioned component containing active hydrogen groups. In other words, the resin is a cured product of a polymeric composition. The resin is preferably molded using a known molding method. That is, the molded body comprises the resin.

[0188] As a molded body of resin, an optical element can be cited as an example.

[0189] As optical elements, examples include lenses, sheets, and films, with lenses being the most preferred.

[0190] Lenses can be manufactured, for example, by reacting the aforementioned XDI composition with the aforementioned polythiol component. In the manufacture of lenses, for example, casting can be employed.

[0191] Examples of lenses include transparent lenses, sunglasses lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lens lenses.

[0192] In addition, polymerizable compositions can also be used as raw materials for two-component curing resins.

[0193] Two-component curing resin raw materials include Agent A as a curing agent and Agent B as a main agent.

[0194] Agent A may contain, for example, the XDI-modified composition described above. Agent B may contain, for example, the polyol component described above.

[0195] Examples of two-liquid curable resin raw materials include, for example, two-liquid curable coating raw materials. Examples of coatings include, for example, paints and adhesives.

[0196] <Effects>

[0197] The aforementioned resin, molded body, optical element, lens, and coating comprise cured products of the aforementioned polymeric composition. Therefore, the resin, molded body, optical element, lens, and coating exhibit excellent resistance to yellowing and transparency.

[0198] Example

[0199] The following examples illustrate the invention in more detail, but the invention is not limited thereto. The specific numerical values ​​of proportions (including ratios), physical property values, parameters, etc., used in the following description can be replaced with the corresponding upper limit values ​​(defined as "below" or "less than") or lower limit values ​​(defined as "above" or "exceeding") of the proportions (including ratios), physical property values, parameters, etc., described in the "Detailed Embodiments" above. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

[0200] <Evaluation Methods>

[0201] In the embodiments, the evaluation methods for various properties of the plastic lens are described below.

[0202] <Refractive index (ne), Abbe number (νe)>

[0203] Using a Pulfrich KPR-30 refractometer 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.

[0204] <Heat resistance>

[0205] Using the Shimadzu Corporation's TMA-60 thermomechanical analysis apparatus, the TMA permeation method (50g load, needle tip) was employed. The glass transition temperature Tg was determined using a heating rate of 10℃ / min and used as an indicator of heat resistance.

[0206] <Calculation of the Yellow Index (YI value) of Plastic Lenses (Resin)>

[0207] A circular flat plastic lens with a thickness of 9 mm and a diameter of 75 mm was made from resin. The YI value was determined using a CM-5 spectrophotometer manufactured by KONICA MINOLTA.

[0208] It should be noted that the following correlation exists: the smaller the YI value, the better the hue of the plastic lens; the larger the YI value, the worse the hue.

[0209] <Devitrification of Plastic Lenses (Resin)>

[0210] A circular, flat plastic lens with a thickness of 9 mm and a diameter of 75 mm was made of resin. Light from a light source (H-repic Luminar Ace LA-150A) was allowed to pass through the flat lens. The image of the light passing through the flat lens was captured in an image processing device (Ube Information Systems Co., Ltd.), where the image underwent density processing. The density of the processed image was quantified for each pixel, and the average density value of each pixel was obtained to calculate the deflection of the flat lens.

[0211] The lower the devitrification, the less the transparency of the resin (in this case, a flat lens) is impaired (i.e., the resin has excellent transparency).

[0212] 2. Preparation Example 1: Preparation of XDI

[0213] A high-pressure autoclave (internal volume 2m³) equipped with a pressure regulator, including a reflux condenser, stirring blades, thermometer, hydrogen chloride gas inlet pipe, phosgene inlet pipe, raw material tank, and raw material loading pump. 3 It was used as a reactor. 846 kg of o-dichlorobenzene was charged into the reactor as an inactive solvent, and 136.2 kg (1.0 kmol) of m-phenylenediamine and 621 kg of o-dichlorobenzene (total amine concentration of 8.5% by mass) were charged into the feed tank.

[0214] Next, the reactor temperature was raised to 120°C, and the internal pressure was adjusted to 0.01 MPa higher than atmospheric pressure. Then, hydrogen chloride gas was introduced into the reactor from the hydrogen chloride gas inlet pipe at a rate of 43.8 kg / hr. Simultaneously, m-phenylenediamine diluted with an inactive solvent was introduced from the feed tank using a feed pump at a rate of 379 kg / hr, with the entire amount being introduced over 2 hours. Then, the reactor was further matured for 1 hour while hydrogen chloride gas was introduced at a rate of 20 kg / hr.

[0215] Next, the reaction solution (hydrochloride slurry) was heated to 160°C in the reactor, and phosgene was introduced through the phosgene inlet pipe at a rate of 100 kg / hr (1.0 kmol / hr). The reaction was maintained at the temperature for 8 hours. After the reaction was completed, nitrogen was purged into the reactor to remove unreacted phosgene and hydrogen chloride gas. Then, the reaction solution was filtered to remove 0.8 kg (dry weight) of unreacted hydrochloride. The obtained filtrate was desolventized to obtain 188.6 kg of reactant with a purity of 98.10% XDI.

[0216] Next, the obtained reactants were distilled to obtain meta-XDI with a purity of 99.99% by mass.

[0217] 3. Preparation Example 2: Preparation of isocyanates containing formyl groups

[0218] To a 500ml pressure vessel, add 10g (0.078 mol) of 1,3-dicyanobenzene (manufactured by Fujifilm and Kohden Chemical Co., Ltd.), 16.6g (0.0078 mol) of 5% palladium-supported carbon catalyst (manufactured by NECHEMCAT CORPORATION, NX type, 49% water content) and 100g of methanol (manufactured by Fujifilm and Kohden Chemical Co., Ltd.) as the reaction solvent.

[0219] Next, nitrogen was supplied to the autoclave, raising the pressure inside to 3.1 MPa (absolute pressure). Then, the nitrogen was discharged from the autoclave, reducing the pressure inside to 0.2 MPa (absolute pressure). This operation was repeated four times to perform nitrogen replacement inside the autoclave.

[0220] Next, hydrogen was supplied to the autoclave, raising the pressure inside to 2.1 MPa (absolute pressure), after which the hydrogen was discharged from the autoclave, reducing the pressure inside to 0.2 MPa (absolute pressure). This operation was repeated four times to perform hydrogen replacement in the autoclave.

[0221] Next, hydrogen is supplied to the autoclave using an accumulator, raising the pressure inside the autoclave to 1.0 MPa (absolute pressure). Then, while maintaining the pressure inside the autoclave, the contents are stirred to allow the 1,3-dicyanobenzene to undergo a hydrogenation reaction.

[0222] At the point when approximately 75% of the theoretical amount of hydrogen has been absorbed, nitrogen is replaced inside the autoclave to remove the hydrogen.

[0223] Next, the reaction solution was filtered using filter paper to remove the palladium-supported carbon catalyst. Then, the filtrate was concentrated using a rotary evaporator. Finally, a vacuum pump was used to remove low-boiling-point components from the concentrated filtrate.

[0224] Thus, a composition with 1-iminomethyl-3-(aminomethyl)benzene as the main component was obtained. Hydrolysis of this composition yielded a composition with 3-(aminomethyl)benzaldehyde as the main component.

[0225] Next, the composition with 3-(aminomethyl)benzaldehyde as the main component was reacted with triphosgene in toluene to prepare the isocyanate containing a formyl group (3-(methyl isocyanate)benzaldehyde) represented by the above chemical formula (2). After removing toluene from the reaction solution by distillation, the isocyanate containing a formyl group was obtained by vacuum distillation.

[0226] The obtained isocyanates containing formyl groups were analyzed under the above-mentioned gas chromatography-mass spectrometry conditions, and the peaks were confirmed at retention times of 14.0 min to 14.6 min.

[0227] 4. Examples 1-4 and Comparative Example 1

[0228] The XDI obtained in Preparation Example 1 and the formyl isocyanate obtained in Preparation Example 2 were mixed in such a way that the proportion of the formyl isocyanate in the XDI composition was as shown in Table 1. Thus, the XDI composition was obtained.

[0229] It should be noted that the proportion of formyl isocyanates in the XDI composition was calculated as follows: The internal standard substance described below was added to the obtained XDI composition, and analysis was performed under the above-described gas chromatography-mass spectrometry conditions. The proportion was calculated based on the area ratio of the internal standard substance appearing at retention time 12.1 minutes to the formyl isocyanates appearing at retention times of 14.0 to 14.6 minutes. The results are shown in Table 1.

[0230] Internal standard: Add 0.5 mg of methylnaphthalene relative to 100 mg of the analytical sample, and bring the volume to 10 mL.

[0231] 5. Manufacturing of Plastic Lenses

[0232] At 20°C, 52 parts by weight of the XDI compositions of each example and comparative example, 0.01 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name: Stepan Corporation; acidic phosphate ester), and 1.5 parts by weight of BioSorb 583 (manufactured by Sakai Chemical Co., Ltd.; ultraviolet absorber) were mixed and dissolved. 48 parts by weight of a polythiol component with 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as the main component were added and mixed to prepare a homogeneous liquid. After degassing the homogeneous liquid at 600 Pa for 1 hour, it was filtered through a 1 μm Teflon (registered trademark) filter and then injected into a mold consisting of a glass mold and adhesive tape. The mold was placed in an oven, and the temperature was gradually increased from 10°C to 120°C for polymerization for 38 hours. After polymerization, the mold was removed from the oven and demolded to obtain the resin. The obtained resin was further annealed at 120°C for 1 hour to manufacture a plastic lens. Based on the aforementioned evaluation method for the properties of the plastic lens, each property was determined. The results are shown in Table 1.

[0233] [Table 1]

[0234] Table 1

[0235]

[0236] It should be noted that the above-described invention is provided as an example embodiment of the present invention, but these are merely examples and should not be interpreted as limiting. Variations of the present invention known to those skilled in the art are included in the following claims.

[0237] Industrial availability

[0238] The phthalic acid diisocyanate composition, phthalic acid diisocyanate modified composition, polymerizable composition, resin and molded body of the present invention can be used in optical components such as lenses, sheets and films.

Claims

1. A phenylene diisocyanate composition comprising: 99% or more of phenylene diisocyanate; The following chemical formulas represent isocyanates containing a formyl group; and Dichloromethylbenzyl isocyanate, The proportion of the isocyanate containing a formyl group is less than 2000 ppm. The content of the dichloromethyl benzyl isocyanate is below 60 ppm. Chemical formula: [Chemical Formula 1] 2. The phenylene diisocyanate composition according to claim 1, wherein, The isocyanate containing formyl groups is present in a proportion exceeding 100 ppm.

3. The phenylene diisocyanate composition according to claim 1, wherein, The isocyanate containing formyl groups is present in a concentration of 10 ppm or higher.

4. The phenylene diisocyanate composition according to any one of claims 1 to 3, further comprising chloromethylbenzyl isocyanate, wherein the chloromethylbenzyl isocyanate content is 0.2 ppm to 3000 ppm.

5. A phenylene diisocyanate modified composition, which is a modified composition obtained by modifying the phenylene diisocyanate composition according to any one of claims 1 to 4. The phenylene diisocyanate modified composition contains at least one of the functional groups of (a) to (i) below. (a) Isocyanurate group, (b) Urea carbamate group, (c) biuret group, (d) Carbamate group, (e) urea group, (f) Iminooxadiazine dione group, (g) ureidodione group, (h) urea-ketone imine group, (i) Carbodiimine group.

6. A polymerizable composition comprising: The isocyanate component comprises the phenylene diisocyanate composition according to any one of claims 1 to 4, and / or the phenylene diisocyanate modified composition according to claim 5; and, Components containing active hydrogen groups.

7. A resin, which is a cured product of the polymeric composition of claim 6.

8. A molded article comprising the resin of claim 7.

9. An optical element comprising the molded body of claim 8.

10. A lens comprising the optical element of claim 9.

11. Use of the phenylene diisocyanate composition according to any one of claims 1 to 4 in the manufacture of lenses.

12. Use of a phenylene diisocyanate composition in the manufacture of lenses, said phenylene diisocyanate composition comprising: 99% or more of phenylene diisocyanate; Isocyanates containing a formyl group, represented by the following chemical formulas; and Chloromethylbenzyl isocyanate, The proportion of the isocyanate containing a formyl group is less than 2000 ppm. The content of the chloromethyl benzyl isocyanate is below 3000 ppm. Chemical formula: [Chemical Formula 1] 13. Use of the phenylene diisocyanate composition of claim 12 in the manufacture of lenses, wherein, The isocyanate containing formyl groups is present in a proportion exceeding 100 ppm.

14. Use of the phenylene diisocyanate composition of claim 12 in the manufacture of lenses, wherein, The isocyanate containing formyl groups is present in a concentration of 10 ppm or higher.

15. Use of the phenylene diisocyanate composition according to any one of claims 12 to 14 in the manufacture of lenses, wherein, The content of the chloromethyl benzyl isocyanate is 0.2 ppm or more.

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