Polythiol composition, polymerizable composition, resin, molded article, optical material and lens

Abstract

The polythiol composition comprises a polythiol compound A, a polythiol compound B, a polythiol compound C, a polythiol compound D, a polythiol compound E and a polythiol compound E, and the polythiol compound A is 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane; and a compound B1 which has a retention time of 65-75 minutes as determined by high performance liquid chromatography using measurement condition A, and in which the peak area of the compound B1 as determined by high performance liquid chromatography is 1.30 or less with respect to the peak area 100 of the polythiol compound A. Measurement conditions A: the column is ODS-A, the mobile phase is a mixed solution of acetonitrile / 0.01 mol / L-potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol), the measurement solution is a mixed solution of 160 mg of a polythiol composition and 10 mL of acetonitrile, the detector is an ultraviolet detector having a measurement wavelength of 230 nm, the column temperature is 40 DEG C, the flow rate is 1.0 mL / min, and the injection amount is 2 [mu] L.

Description

Technical Field

[0001] The present disclosure relates to a polythiol composition, a polymerizable composition, a resin, a molded body, an optical material, and a lens. Background Art

[0002] Plastic lenses are lighter and less prone to breakage than inorganic lenses, and can be dyed. Therefore, in recent years, they have rapidly become popular as optical elements such as eyeglass lenses and camera lenses.

[0003] Plastic lens resins are required to have higher performance, such as higher refractive index, higher Abbe number, lower specific gravity, higher heat resistance, etc. Various lens resin materials have been developed and used so far.

[0004] For example, Patent Document 1 describes a mercapto compound represented by a specific structural formula.

[0005] For example, Patent Document 2 describes a method for producing a polythiol compound, which includes the following steps: a step of reacting 2-mercaptoethanol with a specific epihalohydrin compound represented by formula (1) at a temperature of 10 to 50° C. to obtain a polyol compound represented by formula (2); a step of reacting the obtained polyol compound represented by formula (2) with thiourea in the presence of hydrogen chloride to obtain an isothiuronium salt; a step of adding aqueous ammonia to the reaction solution containing the obtained isothiuronium salt within 80 minutes while maintaining the temperature of the reaction solution containing the obtained isothiuronium salt at 15 to 60° C. to hydrolyze the isothiuronium salt to obtain a polythiol compound represented by formula (5); and a step of adding hydrochloric acid having a concentration of 25 to 36% to the solution containing the obtained polythiol compound, washing the solution at a temperature of 10 to 50° C. to purify the polythiol compound.

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2-270859

[0007] Patent Document 2: International Publication No. 2014-027427 Summary of the invention

[0008] Problems to be solved by the invention

[0009] Examples of the resin obtained using the polythiol composition include thiourethane resins.

[0010] Thiourethane resins are generally produced using a polythiol composition and a polyisocyanate compound as raw materials.

[0011] There is a case where further improvement in heat resistance is required for thiourethane resins.

[0012] An object of one embodiment of the present disclosure is to provide a polythiol composition capable of producing a resin having excellent heat resistance, and use thereof.

[0013] Means for solving problems

[0014] Means for solving the above-mentioned problems include the following embodiments.

[0015] <1> A polythiol composition, comprising: a polythiol compound (A), wherein the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; and a compound (B1), wherein the retention time of the compound (B1) in a high performance liquid chromatography measurement using the following measurement condition A is 65.0 minutes to 75.0 minutes, and the peak area of ​​the compound (B1) in the high performance liquid chromatography measurement is 1.30 or less relative to the peak area of ​​100 of the polythiol compound (A).

[0016] -Measurement Condition A-

[0017] As the column, YMC-Pack (registered trademark) OD SA (particle size S: 5 μm, pore diameter: 12 nm, column shape: Φ6 mm×150 mm) manufactured by YMC Corporation was used.

[0018] As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L-potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used, as the measuring solution, a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used, as the detector, an ultraviolet detector with a measuring wavelength of 230 nm was used, the column temperature was set to 40°C, the flow rate was set to 1.0 mL / min, and the injection volume was set to 2 μL.

[0019] <2> like <1> The polythiol composition, wherein the compound (B1) is a polythiol compound.

[0020] <3> like <1> or <2> The polythiol composition described above, wherein the compound (B1) is at least two selected from the group consisting of compounds represented by the following formula (1) to the following formula (6).

[0021] [Chemical formula 1]

[0022]

[0023] <4> like <1> ~ <3> The polythiol composition according to any one of the preceding claims, wherein the peak area of ​​the compound (B1) in the high performance liquid chromatography measurement is 1.20 or less relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition.

[0024] <5> like <1> ~ <4> The polythiol composition according to any one of the preceding claims, wherein the peak area of ​​the polythiol compound (A) in the high performance liquid chromatography measurement is 91.50 or more relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition.

[0025] <6> A polymerizable composition comprising <1> ~ <5> The polythiol composition and the polyiso(thio)cyanate compound described in any one of the above.

[0026] <7> like <6> The polymerizable composition, wherein the polyiso(thio)cyanate compound comprises at least one selected from pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and phenylene diisocyanate.

[0027] <8> like <6> The polymerizable composition comprises a polyiso(thio)cyanate composition, wherein the polyiso(thio)cyanate composition comprises the aforementioned polyiso(thio)cyanate compound,

[0028] The aforementioned polyiso(thio)cyanate composition comprises:

[0029] Xylylene diisocyanate, and

[0030] At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3),

[0031] When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography is 0.20 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate,

[0032] When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography is 0.05 ppm or more relative to 100 of the peak area of ​​xylylene diisocyanate,

[0033] When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in gas chromatography measurement is 0.10 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate.

[0034] [Chemical formula 2]

[0035]

[0036] <9> Resin comprising <6> ~ <8> A cured product of any one of the polymerizable compositions.

[0037] <10> A molded body comprising <9> The resin.

[0038] <11> Optical material comprising <9> The resin.

[0039] <12> A lens comprising <9> The resin.

[0040] Effects of the Invention

[0041] According to one embodiment of the present disclosure, a polythiol composition capable of producing a resin having excellent heat resistance and use thereof may be provided. DETAILED DESCRIPTION

[0042] In the present disclosure, a numerical range expressed using "to" indicates a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0043] In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced by the upper limit value or the lower limit value of the numerical range described stepwise, or may be replaced by the value shown in the Examples.

[0044] In the present disclosure, when there are multiple substances belonging to each component in the material, the amount of each component in the material refers to the total amount of the multiple substances present in the material unless otherwise specified.

[0045] In the present disclosure, the term "iso(thio)cyanate" refers to isocyanate or isothiocyanate.

[0046] 《Polythiol Composition》

[0047] The polythiol composition of the present disclosure comprises: a polythiol compound (A), wherein the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; and a compound (B1), wherein the retention time of the compound (B1) in a high performance liquid chromatography measurement using the following measurement condition A is 65.0 minutes to 75.0 minutes,

[0048] The peak area of ​​the compound (B1) in the high performance liquid chromatography measurement is 1.30 or less relative to 100 of the peak area of ​​the polythiol compound (A).

[0049] -Measurement Condition A-

[0050] As the column, YMC-Pack (registered trademark) OD SA (particle size S: 5 μm, pore diameter: 12 nm, column shape: Φ6 mm×150 mm) manufactured by YMC Corporation was used.

[0051] As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used.

[0052] As the measurement solution, a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used.

[0053] As a detector, an ultraviolet detector with a measuring wavelength of 230 nm was used.

[0054] The column temperature was set to 40°C.

[0055] Make the flow rate 1.0mL / min,

[0056] The injection volume was set to 2 μL.

[0057] Since the polythiol composition of the present disclosure includes the above-mentioned constitution, a resin having excellent heat resistance can be produced.

[0058] <Polythiol Compound (A)>

[0059] The polythiol composition of the present disclosure comprises a polythiol compound (A), wherein the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0060] 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is a compound represented by the following formula (a-1).

[0061] [Chemical formula 3]

[0062]

[0063] The manufacturing method of polythiol compound (A) is not particularly limited and can be manufactured by a known method. For example, polythiol compound (A) can be manufactured by the method described in International Publication No. 2014 / 027427. In addition, polythiol compound (A) is preferably a compound obtained by using a catalyst comprising at least one selected from the group consisting of metal hydroxides such as sodium hydroxide and potassium hydroxide and metal carbonates such as sodium carbonate and potassium carbonate when, for example, 2-mercaptoethanol is reacted with an epihalohydrin compound.

[0064] The polythiol composition of the present disclosure may contain compounds other than the polythiol compound (A) and the compound (B1).

[0065] Specific examples of compounds other than the polythiol compound (A) and the compound (B1) will be described later.

[0066] For the polythiol composition of the present disclosure, it is preferred that the peak area of ​​the polythiol compound (A) in high performance liquid chromatography measurement (i.e., high performance liquid chromatography measurement using the following measurement condition A) is 91.50 or more relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0067] -Measurement Condition A-

[0068] As the column, YMC-Pack (registered trademark) OD SA (particle size S: 5 μm, pore diameter: 12 nm, column shape: Φ6 mm×150 mm) manufactured by YMC Corporation was used.

[0069] As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used.

[0070] As the measurement solution, a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used.

[0071] As a detector, an ultraviolet detector with a measuring wavelength of 230 nm was used.

[0072] The column temperature was set to 40°C.

[0073] Make the flow rate 1.0mL / min,

[0074] The injection volume was set to 2 μL.

[0075] When the peak area of ​​the polythiol compound (A) is 91.50 or more, excellent resin formability is achieved.

[0076] From the above viewpoints, the peak area of ​​the polythiol compound (A) is preferably 91.60 or more, more preferably 91.70 or more, and even more preferably 91.80 or more, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0077] In the high performance liquid chromatography measurement, from the viewpoint of producing a resin having excellent heat resistance, the peak area of ​​the polythiol compound (A) is preferably less than 100, more preferably 99.50 or less, further preferably 99.00 or less, and further preferably 95.00 or less, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0078] <Measurement of Peak Area of ​​Polythiol Compound (A)>

[0079] The peak area of ​​the polythiol compound (A) can be determined by high performance liquid chromatography (HPLC) measurement under the following conditions.

[0080] The peak area appearing at retention times of 11.5 to 13.5 minutes can be determined as the peak area of ​​the polythiol compound (A), and the ratio relative to the total peak area 100 of the compounds contained in the polythiol composition can be calculated.

[0081] (HPLC conditions)

[0082] Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm)

[0083] Mobile phase: acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol)

[0084] Column temperature: 40°C

[0085] Flow rate: 1.0ml / min

[0086] Detector: UV detector, wavelength 230nm

[0087] Preparation of the measurement solution: 160 mg of the polythiol composition was dissolved and mixed in 10 ml of acetonitrile.

[0088] Injection volume: 2μL

[0089] <Compound (B1)>

[0090] The polythiol composition of the present disclosure contains a compound (B1) having a retention time of 65.0 minutes to 75.0 minutes in high performance liquid chromatography measurement using the following measurement condition A.

[0091] -Measurement Condition A-

[0092] As the column, YMC-Pack (registered trademark) OD SA (particle size S: 5 μm, pore diameter: 12 nm, column shape: Φ6 mm×150 mm) manufactured by YMC Corporation was used.

[0093] As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used.

[0094] As the measurement solution, a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used.

[0095] As a detector, an ultraviolet detector with a measuring wavelength of 230 nm was used.

[0096] The column temperature was set to 40°C.

[0097] Make the flow rate 1.0mL / min,

[0098] The injection volume was set to 2 μL.

[0099] In addition, when the compound (B1) having a retention time of 65.0 to 75.0 minutes in the high performance liquid chromatography measurement under the above measurement condition A was subjected to LC-MS analysis under the following measurement condition B, a molecular weight of 518 was confirmed.

[0100] -Measurement Condition B-

[0101] As an apparatus, a Waters LC-MS (ZQ) system was used.

[0102] As the column, YMC-Pack (registered trademark) C18Rs (particle size S: 3 μm, pore diameter: 8 nm, column shape: Φ4.6 mm×250 mm) manufactured by YMC Corporation was used.

[0103] As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L-ammonium acetate aqueous solution = 70 / 30 (vol / vol) was used.

[0104] As the measurement solution, a mixed solution of 10 μL of the polythiol composition and 1 mL of acetonitrile was used.

[0105] As a detector, an ultraviolet detector with a measuring wavelength of 230 nm was used.

[0106] The column temperature was set to 40°C.

[0107] The flow rate is 0.9 mL / min.

[0108] The injection volume was set to 10 μL.

[0109] (MS conditions)

[0110] Ionization Mode: ESI+

[0111] Capillary Voltage: 10V

[0112] Cone Voltage: 10V

[0113] Extractor Voltage: 4V

[0114] Source Temp.: 120℃

[0115] Desolvation Temp.: 400℃

[0116] Cone Gas Flow: 50L / Hr

[0117] Desolvation Gas Flow: 800L / Hr

[0118] Mass: 100-1000

[0119] The compound (B1) is preferably a polythiol compound.

[0120] More specifically, the compound (B1) is more preferably at least two selected from the group consisting of compounds represented by the following formula (1) to the following formula (6).

[0121] [Chemical formula 4]

[0122]

[0123] In the polythiol composition of the present disclosure, the peak area of ​​the compound (B1) in the HPLC measurement (i.e., HPLC measurement under measurement condition A) is 1.30 or less relative to the peak area 100 of the polythiol compound (A).

[0124] When the peak area of ​​the compound (B1) is 1.30 or less, a resin having excellent heat resistance can be produced.

[0125] From the above viewpoints, the peak area of ​​the compound (B1) is preferably 1.10 or less, more preferably 0.80 or less, and even more preferably 0.50 or less, relative to 100 of the peak area of ​​the polythiol compound (A).

[0126] The “peak area of ​​the compound (B1) relative to the peak area of ​​the polythiol compound (A) as 100” refers to the relative value of the peak area of ​​the compound (B1) when the peak area of ​​the polythiol compound (A) is taken as 100.

[0127] In the high performance liquid chromatography measurement, from the viewpoint of reducing the load of the operation of purifying and removing the compound (B1) from the polythiol composition, the peak area of ​​the compound (B1) is preferably greater than 0, more preferably 0.01 or more, further preferably 0.10 or more, and particularly preferably 0.20 or more, relative to the peak area of ​​100 of the polythiol compound (A).

[0128] Moreover, by making the total peak area of ​​the said compound (B1) satisfy|fill the said lower limit range, since the thickening rate can be increased, the polymerization can be accelerated|stimulated.

[0129] In the polythiol composition of the present disclosure, it is preferred that the peak area of ​​the compound (B1) measured by high performance liquid chromatography is 1.20 or less relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0130] When the peak area of ​​the compound (B1) is 1.20 or less, a resin having excellent heat resistance can be produced.

[0131] From the above viewpoints, the peak area of ​​the compound (B1) is preferably 1.00 or less, more preferably 0.80 or less, further preferably 0.60 or less, particularly preferably 0.40 or less, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0132] In the high performance liquid chromatography measurement, from the viewpoint of reducing the load of the operation of purifying and removing the compound (B1) from the polythiol composition, the peak area of ​​the compound (B1) is preferably greater than 0, more preferably 0.01 or more, further preferably 0.10 or more, and particularly preferably 0.20 or more, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0133] Moreover, by making the total peak area of ​​the said compound (B1) satisfy|fill the said lower limit range, since the thickening rate can be increased, the polymerization can be accelerated|stimulated.

[0134] The method for adjusting the peak area of ​​the compound (B1) relative to the peak area 100 of the polythiol compound (A) (and relative to the total peak area 100 of the compounds contained in the polythiol composition) is not particularly limited, and for example, it can be adjusted by operations such as column purification, washing, extraction, crystallization, etc.

[0135] <Measurement of Peak Area of ​​Compound (B1)>

[0136] The peak area of ​​compound (B1) can be determined by high performance liquid chromatography (HPLC) measurement under the following conditions.

[0137] The peak area appearing at a retention time of 65.0 minutes to 75.0 minutes can be judged as the peak area of ​​compound (B1), and the ratio relative to the peak area 100 of the polythiol compound (A) and the ratio relative to the total peak area 100 of the compounds contained in the polythiol composition can be calculated.

[0138] (HPLC conditions)

[0139] Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm)

[0140] Mobile phase: acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol)

[0141] Column temperature: 40°C

[0142] Flow rate: 1.0ml / min

[0143] Detector: UV detector, wavelength 230nm

[0144] Preparation of the measurement solution: 160 mg of the polythiol composition was dissolved and mixed in 10 ml of acetonitrile.

[0145] Injection volume: 2μL

[0146] <Compounds other than the polythiol compound (A) and the compound (B1)>

[0147] As described above, the polythiol composition of the present disclosure may contain compounds other than the polythiol compound (A) and the compound (B1).

[0148] Examples of the compound other than the polythiol compound (A) and the compound (B1) include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2-mercaptoethyl)sulfide, bis(2,3-dimercaptopropyl)sulfide, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 -dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiacyclohexane, 2,5-dimercapto-1,4-dithiacyclohexane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiacyclohexane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, and the like.

[0149] (Compound represented by formula (X1))

[0150] As a compound other than the polythiol compound (A) and the compound (B1), there may be mentioned a compound represented by the following formula (X1).

[0151] [Chemical formula 5]

[0152]

[0153] In formula (X1), m and n each independently represent 0 or 1, and m+n=1.

[0154] The structure of the compound represented by formula (X1) is similar to that of the polythiol compound (A) in the present disclosure (ie, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; ie, the compound represented by formula (a-1)).

[0155] The structure of the compound represented by formula (X1) is different from the structure of the compound represented by formula (a-1) in which m and n are both 1 (ie, m+n=2) in that m and n each independently represent 0 or 1 and m+n=1.

[0156] Examples of the compound represented by formula (X1) include a compound represented by formula (X1a) and a compound represented by formula (X1b).

[0157] [Chemical formula 6]

[0158]

[0159] In addition, the polythiol composition of the present disclosure may contain a plurality of compounds represented by formula (X1). For example, the polythiol composition of the present disclosure may be a mixture of a compound represented by formula (X1a) and a compound represented by formula (X1b) as the compound represented by formula (X1).

[0160] The compound represented by formula (X1) may be a compound represented by formula (X1a), a compound represented by formula (X1b), or a mixture of a compound represented by formula (X1a) and a compound represented by formula (X1b).

[0161] When the compound represented by formula (X1) includes a compound represented by formula (X1a) and a compound represented by formula (X1b), the content of the compound represented by formula (X1a) is preferably 80 mass % or more, more preferably 90 mass % or more, and further preferably 95 mass % or more, relative to the total content of the compound represented by formula (X1a) and the compound represented by formula (X1b).

[0162] (Compound (XB))

[0163] Examples of the compound other than the polythiol compound (A) and the compound (B1) include the following compound (XB).

[0164] Compound (XB) may also include a compound obtained by replacing at least one of the three or more mercapto groups in a polythiol compound containing three or more mercapto groups (hereinafter also referred to as "polythiol compound (XA)") with a group represented by the following formula (XB-1).

[0165] Here, the polythiol compound (A) in the present disclosure (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; i.e., the compound represented by formula (a-1)) is also included in the scope of the polythiol compound containing three or more mercapto groups (i.e., the polythiol compound (XA)).

[0166] [Chemical formula 7]

[0167]

[0168] In formula (XB-1), * represents a bonding position.

[0169] Examples of the compound (XB) are shown below, but the compound (XB) is not limited to the following examples.

[0170] [Chemical formula 8]

[0171]

[0172] When the polythiol composition of the present disclosure contains a compound represented by formula (X1) and a compound (XB), the ratio thereof (compound represented by formula (X1) / compound (XB)) is preferably 1 to 30, more preferably 3 to 24, and even more preferably 5 to 18 from the viewpoint of reducing the yellowness and devitrification of the obtained resin and maintaining a good pot life of the polymerizable composition of the present disclosure.

[0173] 《Polymerizable composition》

[0174] The polymerizable composition of the present disclosure comprises the polythiol composition of the present disclosure and a polyiso(thio)cyanate compound.

[0175] (Polyiso(thio)cyanate compounds)

[0176] As the polyiso(thio)cyanate compound, there is no particular limitation as long as it can exert the effect of the present disclosure, and conventionally known compounds can be used. As long as it is a compound having at least two or more iso(thio)cyanate groups in one molecule, there is no particular limitation, and specifically, for example:

[0177] Aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine triisocyanate, and xylylene diisocyanate;

[0178] Alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, dicyclohexyldimethylmethane diisocyanate, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanate methyl)tricyclodecane, 3,9-bis(isocyanate methyl)tricyclodecane, 4,8-bis(isocyanate methyl)tricyclodecane, and 4,9-bis(isocyanate methyl)tricyclodecane;

[0179] Aromatic polyisocyanate compounds such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate, and phenylene diisocyanate;

[0180] Heterocyclic polyisocyanate compounds such as 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiolane, 2,5-bis(isocyanatomethyl)-1,4-dithiolane, 4,5-diisocyanato-1,3-dithiolane, and 4,5-bis(isocyanatomethyl)-1,3-dithiolane;

[0181] Aliphatic polyisothiocyanate compounds such as hexamethylene diisothiocyanate, lysine methyl ester diisothiocyanate, lysine triisothiocyanate, and xylylene diisothiocyanate;

[0182] Alicyclic polyisothiocyanate compounds such as isophorone diisothiocyanate, bis(isothiocyanate methyl) cyclohexane, bis(isothiocyanate cyclohexyl) methane, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5-bis(isothiocyanate methyl) bicyclo-[2.2.1]-heptane, 2,6-bis(isothiocyanate methyl) bicyclo-[2.2.1]-heptane, 3,8-bis(isothiocyanate methyl) tricyclodecane, 3,9-bis(isothiocyanate methyl) tricyclodecane, 4,8-bis(isothiocyanate methyl) tricyclodecane, and 4,9-bis(isothiocyanate methyl) tricyclodecane;

[0183] Aromatic polyisothiocyanate compounds such as toluene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyl sulfide-4,4-diisothiocyanate;

[0184] Sulfur-containing heterocyclic polyisothiocyanate compounds such as 2,5-diisothiocyanate thiophene, 2,5-bis(isothiocyanate methyl) thiophene, 2,5-isothiocyanate tetrahydrothiophene, 2,5-bis(isothiocyanate methyl) tetrahydrothiophene, 3,4-bis(isothiocyanate methyl) tetrahydrothiophene, 2,5-diisothiocyanate-1,4-dithiocyclohexane, 2,5-bis(isothiocyanate methyl)-1,4-dithiocyclohexane, 4,5-diisothiocyanate-1,3-dithiocyclopentane, and 4,5-bis(isothiocyanate methyl)-1,3-dithiocyclopentane; and the like.

[0185] The polyiso(thio)cyanate compound may contain at least one selected from these.

[0186] In addition, as polyiso(thio)cyanate compounds, their chlorine-substituted products, bromine-substituted products and other halogen-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization reaction products, etc. can also be used.

[0187] As the polyiso(thio)cyanate compound, a polyisocyanate compound is preferably used.

[0188] Preferably, it contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and phenylene diisocyanate.

[0189] The mixing ratio of the polythiol composition and the polyiso(thio)cyanate compound is not particularly limited. For example, the molar ratio of the mercapto group of the polythiol compound and the iso(thio)cyanate group of the polyiso(thio)cyanate compound contained in the polythiol composition (mercapto group / iso(thio)cyanate group) is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and further preferably 0.8 to 1.3. If the mixing ratio is within the above range, there is a tendency that various properties such as the refractive index and heat resistance required as a plastic lens, etc. can be satisfied with good balance.

[0190] The polymerizable composition of the present disclosure may include a polyiso(thio)cyanate composition including the above-mentioned polyiso(thio)cyanate compound.

[0191] Here, the polyiso(thio)cyanate composition refers to a composition containing at least one polyiso(thio)cyanate compound.

[0192] The polyiso(thio)cyanate composition may contain components other than the polyiso(thio)cyanate compound as impurities.

[0193] The polyiso(thio)cyanate composition preferably contains at least one polyiso(thio)cyanate compound as a main component.

[0194] The polyiso(thio)cyanate composition preferably comprises xylylene diisocyanate.

[0195] Hereinafter, the polyiso(thio)cyanate composition containing xylylenediisocyanate is also referred to as an XDI composition.

[0196] The XDI composition preferably contains xylylene diisocyanate as a main component.

[0197] The XDI composition preferably contains at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).

[0198] [Chemical formula 9]

[0199]

[0200] Hereinafter, preferred embodiments of the XDI composition will be described from the viewpoint of achieving more excellent stability of the polyiso(thio)cyanate composition and transparency of a resin formed using the polyiso(thio)cyanate composition.

[0201] When the XDI composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement under the following GC condition 1 is preferably 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate.

[0202] -GC Condition 1-

[0203] Filler: DB-1 (film thickness) 1.5 μm

[0204] Column: inner diameter 0.53 mm × length 60 m (manufactured by Agilent)

[0205] Column box temperature: increase from 130°C to 220°C at 3°C / min. After reaching 220°C, increase to 300°C at 10°C / min.

[0206] Split ratio: Pulse splitless method

[0207] Inlet temperature: 280℃

[0208] Detector temperature: 300°C

[0209] Carrier gas: N 2158kPa,H 2 55kPa, air 45kPa (constant pressure control)

[0210] Solvent: Chloroform

[0211] Sample concentration: 2.0 mass% chloroform solution

[0212] Injection volume: 2μL

[0213] Detection method: FID

[0214] The peak area of ​​the compound (N1) is more preferably 5.0 ppm or more, further preferably 50 ppm or more, and further preferably 100 ppm or more, relative to the peak area 1 of xylylenediisocyanate.

[0215] The peak area of ​​the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, further preferably 2000 ppm or less, further preferably 1500 ppm or less, further preferably 1000 ppm or less, relative to the peak area 1 of xylylenediisocyanate.

[0216] The peak area of ​​the compound (N1) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0217] When the XDI composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area 1 of xylylene diisocyanate.

[0218] -GC Condition 2-

[0219] Column: HP-50+, inner diameter 0.25 mm×length 30 m×film thickness 0.25 μm (manufactured by Hewlett-Packard Company)

[0220] Column box temperature: increase from 50°C to 280°C at 10°C / min, and maintain at 280°C for 6 minutes.

[0221] Split ratio: Pulse splitless method

[0222] Inlet temperature: 200℃

[0223] Detector temperature: 280°C

[0224] Carrier gas: He

[0225] Carrier gas flow rate: 1.0ml / min (constant flow control)

[0226] Sample concentration: 1.0 mass% dichloromethane solution

[0227] Injection volume: 1.0 μL

[0228] Detection method: SIM (monitoring ions: m / z 180, 215) (content ratio of xylylenediisocyanate (XDI))

[0229] The peak area of ​​the compound (N2) is more preferably 0.1 ppm or more, further preferably 0.3 ppm or more, and further preferably 0.6 ppm or more, relative to the peak area 1 of xylylenediisocyanate.

[0230] The peak area of ​​the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, further preferably 100 ppm or less, further preferably 80 ppm or less, further preferably 70 ppm or less, further preferably 60 ppm or less, relative to the peak area 1 of xylylenediisocyanate.

[0231] The peak area of ​​the compound (N2) can be measured according to the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.

[0232] When the XDI composition contains the compound (N3), the peak area of ​​the compound (N3) in the gas chromatography measurement under the above-mentioned GC condition 1 is preferably 0.10 ppm or more relative to the peak area 1 of xylylenediisocyanate.

[0233] The peak area of ​​the compound (N3) is more preferably 0.1 ppm or more, further preferably 3.0 ppm or more, and further preferably 5.0 ppm or more, relative to the peak area 1 of xylylenediisocyanate.

[0234] The peak area of ​​the compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 300 ppm or less, further preferably 100 ppm or less, further preferably 75 ppm or less, based on the peak area 1 of xylylenediisocyanate.

[0235] The peak area of ​​the compound (N3) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0236] The acid content of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, further preferably 1000 ppm or less, further preferably 100 ppm or less, further preferably 50 ppm or less, further preferably 30 ppm or less, further preferably less than 15 ppm.

[0237] The lower limit of the acid content of the XDI composition is not particularly limited, and the lower limit is, for example, 1 ppm.

[0238] The acid content of the XDI composition can be measured according to the method described in paragraph 0091 of International Publication No. 2021 / 256417.

[0239] Additionally, the XDI composition may contain a stabilizer.

[0240] The polymerizable composition of the present disclosure may contain other components in addition to the polythiol compound and the polyiso(thio)cyanate compound for the purpose of improving various physical properties of the resin, handling properties, polymerization reactivity of the polymerizable composition, and the like.

[0241] Other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, free radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, blueing agents such as inorganic pigments, and the like.

[0242] Examples of the polymerization catalyst include tertiary amine compounds, inorganic acid salts or organic acid salts thereof, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0243] As the internal mold release agent, an acidic phosphate ester can be used. Examples of the acidic phosphate ester include phosphoric acid monoesters and phosphoric acid diesters, and each of these can be used alone or in combination of two or more.

[0244] Examples of the resin modifier include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and anhydrides thereof, and olefin compounds including (meth)acrylate compounds.

[0245] The polymerizable composition of the present disclosure can be obtained by mixing the above components.

[0246] <<Molding>>

[0247] The molded article of the present disclosure contains the resin of the present disclosure.

[0248] The resin of the present disclosure includes a cured product of the polymerizable composition of the present disclosure.

[0249] The method for producing the molded body of the present disclosure is not particularly limited, and cast polymerization can be cited as a preferred production method. First, a polymerizable composition is injected into a molding die held by a gasket or tape. At this time, depending on the physical properties required for the obtained plastic lens, it is often preferred to perform a degassing treatment under reduced pressure, a filtration treatment such as pressurization or reduced pressure, etc. as needed.

[0250] The polymerization conditions vary greatly depending on the composition of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, etc., and are not limited thereto, but can be carried out at a temperature of -50°C to 150°C for 1 to 50 hours. Depending on the circumstances, it is preferred to maintain or gradually increase the temperature within a range of 10°C to 150°C and cure within 1 to 48 hours.

[0251] The molded product may be subjected to annealing or the like as necessary. The annealing or the like is usually performed at 50°C to 150°C, preferably 90°C to 140°C, and more preferably 100°C to 130°C.

[0252] [use]

[0253] The resin obtained from the polymerizable composition of the present disclosure can be used as a material for producing molded products of various shapes by changing the type of mold used in cast polymerization.

[0254] <<Optical Materials>

[0255] The optical material of the present disclosure includes the resin of the present disclosure.

[0256] The molded article obtained from the polymerizable composition of the present disclosure can obtain a material with reduced yellowness without impairing transparency. In addition, the molded article obtained from the polymerizable composition including the polythiol composition of the first embodiment can also obtain a material having excellent devitrification.

[0257] Therefore, it can be used in various optical materials such as plastic lenses.

[0258] "lens"

[0259] The lens of the present disclosure includes the resin of the present disclosure.

[0260] As the optical material, a lens is particularly preferred.

[0261] Examples of the lens include plastic eyeglass lenses and plastic polarizing lenses.

[0262] [Plastic eyeglass lenses]

[0263] The plastic eyeglass lens using the lens substrate formed of the molded article of the present disclosure may be provided with a coating layer on one or both surfaces as necessary.

[0264] The plastic eyeglass lens of the present disclosure comprises a lens substrate including a cured product of the above-mentioned polymerizable composition, and a coating layer.

[0265] As the coating layer, specifically, a primer layer, a hard coating layer, an antireflection layer, an antifogging coating layer, an anti-pollution layer, a waterproof layer, etc. can be cited. These coating layers can be used alone, or multiple coating layers can be multilayered and used. When the coating layers are applied to both sides, the same coating layer can be applied to each side, or different coating layers can be applied.

[0266] Each of these coating layers can be used in combination with known additives such as infrared absorbers for the purpose of protecting eyes from infrared damage, light stabilizers, antioxidants, etc. for the purpose of improving the weather resistance of the lens, photochromic compounds, dyes, pigments, etc. for the purpose of improving the fashionability of the lens, and antistatic agents for the purpose of improving lens performance.

[0267] For the layer applied by coating, various leveling agents may be used for the purpose of improving coating properties.

[0268] Furthermore, an anti-fog layer, an anti-fouling layer, and a water-repellent layer may be formed on the anti-reflection layer as required.

[0269] As mentioned above, although the embodiment of this disclosure was demonstrated, these are examples of this disclosure, and various structures other than the above-mentioned can be adopted within the range which does not impair the effect of this disclosure.

[0270] Example

[0271] Hereinafter, the present disclosure will be described in detail with reference to the examples. It should be noted that the present disclosure is not limited by the description of these examples. It should be noted that, unless otherwise specified, "parts" are based on mass.

[0272] <Evaluation method>

[0273] In this example, the evaluation method of various physical properties of the plastic lens is as follows. The results are shown in Table 1.

[0274] Heat resistance

[0275] A resin test piece with a length of 10 mm, a width of 10 mm, and a thickness of 2.5 mm was prepared. A thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation was used to measure the glass transition temperature (Tg) as an indicator of heat resistance by using the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min).

[0276] It should be noted that the higher the glass transition temperature (Tg), the better the heat resistance.

[0277] <Preparation of Polythiol Composition (A)>

[0278] 124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of deaerated water were placed in the reactor. 101.5 parts by mass of a 32% by mass sodium hydroxide aqueous solution was added dropwise at 12°C to 35°C over 40 minutes, and then 73.6 parts by mass of epichlorohydrin was added dropwise at 29°C to 36°C over 4.5 hours, and stirring was continued for 40 minutes. The formation of 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed from the NMR data of the obtained reaction solution.

[0279] Next, 331.5 parts by mass of hydrochloric acid having a concentration of 35.5% by mass was charged into the above-mentioned reactor containing 1,3-bis(2-hydroxyethylthio)-2-propanol, and then 183.8 parts by mass of thiourea having a purity of 99.90% by mass was charged, and the mixture was stirred at 110° C. under reflux for 3 hours to carry out a thiourea salt reaction.

[0280] After the reaction liquid after the thiourea salt reaction was cooled to 45°C, 320.5 parts by mass of toluene was added thereto, and the mixture was cooled to 31°C. 243.1 parts by mass of a 25% by mass ammonia solution was added thereto at 31°C to 41°C over 44 minutes, and a hydrolysis reaction was carried out by stirring at 54°C to 62°C for 3 hours to obtain a toluene solution of a polythiol containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as the main component.

[0281] To the toluene solution, 162.8 parts by mass of hydrochloric acid having a concentration of 35.5% by mass was added, and acid cleaning was performed at 35°C to 43°C for 1 hour. For the toluene solution after the acid cleaning, 174.1 parts by mass of degassed water was added and the cleaning was performed at 35°C to 45°C for 30 minutes twice. To the toluene solution after the cleaning with degassed water, 162.1 parts by mass of ammonia water having a concentration of 0.1% by mass was added and the cleaning was performed for 30 minutes. For the toluene solution after the cleaning with ammonia water, 174.2 parts by mass of degassed water was added and the cleaning was performed at 35°C to 45°C for 30 minutes twice.

[0282] Next, toluene and a trace amount of water were removed from the toluene solution after washing with degassed water under heating and reduced pressure, and then reduced pressure filtration was performed using a 1.2 μm PTFE membrane filter to obtain 205.0 parts by mass of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as the polythiol compound (A) as the main component.

[0283] <Preparation of Polythiol Composition (B1) Containing Compound (B1)>

[0284] 80.0 parts by mass of the polythiol composition (A) and 80.0 parts by mass of an aqueous ammonia solution having a concentration of 25% by mass were placed in the reactor. Air was blown into the obtained solution at a flow rate of 20 mL / min while stirring at 60°C for 4 days. The obtained reactant was dissolved in 125.4 parts by mass of toluene, and after toluene extraction, 30.0 parts by mass of hydrochloric acid having a concentration of 35.5% by mass was added to the obtained toluene solution, and acid washing was performed at 35°C to 43°C for 15 minutes. For the toluene solution after acid washing, 30.0 parts by mass of degassed water was added and washed at 35°C to 45°C for 30 minutes twice. 30.0 parts by mass of ammonia water having a concentration of 0.1% by mass was added to the toluene solution after washing with degassed water, and washing was performed for 30 minutes. For the toluene solution after washing with ammonia water, 30.0 parts by mass of degassed water was added and washed at 35°C to 45°C for 30 minutes twice.

[0285] Next, toluene and a trace amount of water were removed from the toluene solution after washing with degassed water under heating and reduced pressure, and then the solution was filtered under reduced pressure using a 3 μm PTFE membrane filter to obtain 75.4 parts by mass of a polythiol composition (B1) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as the polythiol compound (A) as the main component and further containing the compound (B1).

[0286] The total content of the compound (B1) was 13.0 with respect to the total peak area 100 of the compounds contained in the obtained polythiol composition (B1).

[0287] In the HPLC analysis using the above measurement condition A, the area values ​​of the two peaks (ie, isomers) at 65 min and 74 min were totaled to calculate the area ratio (13.0) of compound (B1).

[0288] The two peaks were analyzed by LC-MS using the measurement condition B. It was confirmed that the two peaks at 65 min and 74 min (i.e., isomers) both having a molecular weight of 518 were at least two selected from the group consisting of compounds represented by formula (1) to formula (6).

[0289] [Example 1 to Example 4, Comparative Example 1 to Comparative Example 2]

[0290] The polythiol composition (A) obtained as described above is mixed with the polythiol composition (B1) to obtain a polythiol composition.

[0291] At this time, the mixture was mixed at a different mixing ratio so that the total peak area of ​​the compound (B1) relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition became the value described in Table 1.

[0292] <Measurement of the Ratio (Area %) of Polythiol Compound (A) and Compound (B1)>

[0293] The ratio (area %) of the polythiol compound (A) and the compound (B1) by HPLC was measured by the method described in the above-mentioned <Measurement of the peak area of ​​the polythiol compound (A)> and <Measurement of the peak area of ​​the compound (B1)>.

[0294] The results are shown in Table 1.

[0295] <Manufacturing of plastic lenses>

[0296] [Production Example 1]

[0297] 52 parts by mass of m-xylylene diisocyanate, 0.01 parts by mass of dibutyltin dichloride as a curing catalyst, 0.10 parts by mass of ZELEC UN (product of Stepan; acidic phosphate), and 1.5 parts by mass of VIOSORB 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.; ultraviolet absorber) were mixed and dissolved at 20°C. 48 parts by mass of the polythiol composition of Example 1 were added thereto and mixed to prepare a mixed uniform liquid. After degassing the uniform liquid at 600 Pa for 1 hour, it was filtered using a 1μm Teflon (registered trademark) filter and then injected into a mold formed by a glass mold and tape. The mold was put into an oven, slowly heated from 10°C to 120°C, and polymerized for 38 hours. After the polymerization was completed, the mold was taken out of the oven and demolded to obtain a resin. The obtained resin was further annealed at 120°C for 1 hour to manufacture a plastic lens. Based on the evaluation method of the various physical properties of the plastic lens described above, the various physical properties were obtained.

[0298] [Production Example 2]

[0299] In Production Example 1, a plastic lens was produced by the same method as that described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Example 2. The various properties were determined according to the evaluation methods of various properties of plastic lenses described above.

[0300] [Production Example 3]

[0301] In Production Example 1, a plastic lens was produced by the same method as that described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Example 3. The various properties were determined according to the evaluation methods of the various properties of the plastic lens described above.

[0302] [Production Example 4]

[0303] In Production Example 1, a plastic lens was produced by the same method as that described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Example 4. The various properties were determined according to the evaluation methods of the various properties of the plastic lens described above.

[0304] [Production Example 5]

[0305] In Production Example 1, a plastic lens was produced by the same method as that described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Comparative Example 1. The various properties were determined according to the evaluation methods of the various properties of the plastic lens described above.

[0306] [Production Example 6]

[0307] In Production Example 1, a plastic lens was produced by the same method as that described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Comparative Example 2. The various properties were determined according to the evaluation methods of the various properties of the plastic lens described above.

[0308] Table 1 shows the physical properties of the plastic lenses of Production Examples 1 to 6 (ie, Examples 1 to 4 and Comparative Examples 1 and 2).

[0309] [Table 1]

[0310]

[0311] As shown in Table 1, the Tg temperature of each example using a polythiol composition comprising a polythiol compound (A) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a compound (B1) having a retention time of 65.0 minutes to 75.0 minutes in a high performance liquid chromatography measurement under measurement condition A, and a peak area of ​​the compound (B1) in the above-mentioned high performance liquid chromatography measurement being 1.30 or less relative to the peak area of ​​the polythiol compound (A) as 100, is high, and a resin having excellent heat resistance can be produced.

[0312] On the other hand, in Comparative Examples 1 and 2 where the peak area of ​​the compound (B1) was not 1.30 or less relative to 100 of the peak area of ​​the polythiol compound (A), the Tg temperature was low and a resin excellent in heat resistance could not be produced.

[0313] [Manufacturing Example 1X to Manufacturing Example 6X]

[0314] As Manufacturing Examples 1X to 6X, the manufacture of the plastic lens was changed as described below, and the same operations as those of Manufacturing Examples 1 to 6 were performed. As a result, the same results as those of Manufacturing Examples 1 to 6 (i.e., Examples 1 to 4, Comparison Examples 1 to 2) (Table 1) were obtained.

[0315] - Changes from each of Production Examples 1 to 6 -

[0316] In each of Manufacturing Examples 1 to 6, meta-xylylene diisocyanate (XDI) (52 parts by mass) was used in the manufacture of the plastic lens, but in each of Manufacturing Examples 1X to 6X, XDI (52 parts by mass) was changed to XDI composition X1 (the amount of XDI contained was 52 parts by mass) which is the aforementioned XDI composition.

[0317] The XDI composition X1 is produced by adding a trace amount of the compound (N1), a trace amount of the compound (N2), and a trace amount of the compound (N3) to XDI as a main component and mixing them.

[0318] In XDI composition X1, gas chromatography was performed using the above-mentioned GC conditions 1 and GC conditions 2, respectively. The results showed that:

[0319] The peak area of ​​the compound (N1) is 0.20 ppm or more (specifically, 600 ppm) relative to the peak area 1 of XDI,

[0320] The peak area of ​​the compound (N2) is 0.05 ppm or more (specifically, 18 ppm) relative to the peak area 1 of XDI,

[0321] The peak area of ​​the compound (N3) is 0.10 ppm or more (specifically, 100 ppm) relative to the peak area 1 of XDI.

[0322] The entire disclosure of Japanese Patent Application No. 2022-165812 filed on October 14, 2022 is incorporated into this specification by reference.

[0323] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

Claims

1. A polythiol composition comprising: A polythiol compound (A), wherein the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; and A compound (B1), wherein the retention time of the compound (B1) in a high performance liquid chromatography measurement using the following measurement condition A is 65.0 minutes to 75.0 minutes, The peak area of ​​the compound (B1) in the high performance liquid chromatography measurement is 1.30 or less relative to the peak area of ​​the polythiol compound (A) as 100, -Measurement Condition A- As the column, YMC-Pack (registered trademark) OD SA (particle size S: 5 μm, pore diameter: 12 nm, column shape: Φ6 mm×150 mm) manufactured by YMC Corporation was used. As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used. As the measurement solution, a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used. As a detector, an ultraviolet detector with a measuring wavelength of 230 nm was used. The column temperature was set to 40°C. Make the flow rate 1.0mL / min, The injection volume was set to 2 μL.

2. The polythiol composition according to claim 1, wherein The compound (B1) is a polythiol compound.

3. The polythiol composition according to claim 1, wherein The compound (B1) is at least two selected from the group consisting of compounds represented by the following formula (1) to the following formula (6), [Chemical formula 1] 4. The polythiol composition according to claim 1, wherein The peak area of ​​the compound (B1) in the high performance liquid chromatography measurement is 1.20 or less relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition.

5. The polythiol composition according to claim 1, wherein The peak area of ​​the polythiol compound (A) in the high performance liquid chromatography measurement is 91.50 or more relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition.

6. A polymerizable composition comprising: The polythiol composition according to any one of claims 1 to 5, and Polyisothiocyanate compounds.

7. The polymerizable composition according to claim 6, wherein The polyiso(thio)cyanate compound comprises at least one selected from pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and phenylene diisocyanate.

8. The polymerizable composition according to claim 6, comprising a polyiso(thio)cyanate composition, wherein the polyiso(thio)cyanate composition comprises the polyiso(thio)cyanate compound, The polyiso(thio)cyanate composition comprises: Xylylene diisocyanate, and At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3), When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement is 0.20 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement is 0.05 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in gas chromatography measurement is 0.10 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, [Chemical formula 2] 9. A resin comprising a cured product of the polymerizable composition according to claim 6.

10. A molded article comprising the resin according to claim 9.

11. An optical material comprising the resin according to claim 9.

12. A lens comprising the resin according to claim 9.

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