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

Abstract

A polythiol composition containing a polythiol compound (A) and a compound represented by formula (1), the polythiol compound (A) being 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, and the peak area of the compound represented by formula (1) being 11.00 or less with respect to the total peak area 100 of the compounds contained in the polythiol composition in high performance liquid chromatography measurement. # imgabs0 #

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] A resin obtained by curing a polymerizable composition containing a polythiol compound may be required to have reduced yellowness and devitrification.

[0010] Actually, in many cases, the polymerizable composition containing a polythiol compound contains other compounds in addition to the polythiol compound.

[0011] The inventors of the present application have found that when the polymerizable composition contains other compounds in addition to the polythiol compound, the yellowness and devitrification degree of the obtained resin tend to be easily impaired.

[0012] Various studies have been conducted to address the above-mentioned tendency, and as a result, it has been found that it is sometimes difficult to obtain a resin having reduced yellowness and devitrification.

[0013] Examples of the resin obtained using the polythiol composition include thiourethane resins.

[0014] Thiourethane resins are generally produced using a polythiol composition and a polyisocyanate compound as raw materials.

[0015] There is a case where further improvement in heat resistance is required for thiourethane resins.

[0016] An object of one embodiment of the present disclosure is to provide a polythiol composition capable of producing a resin having reduced yellowness and devitrification and excellent heat resistance, and use thereof.

[0017] Means for solving problems

[0018] Means for solving the above-mentioned problems include the following embodiments.

[0019] <1> A polythiol composition comprising a polythiol compound (A) and a compound represented by the following formula (1), wherein the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and wherein the peak area of ​​the compound represented by the above formula (1) is 11.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition in high performance liquid chromatography measurement.

[0020] [Chemical formula 1]

[0021]

[0022] <2> like <1> The polythiol composition, wherein the peak area of ​​the compound represented by the formula (1) is 13.00 or less relative to the peak area of ​​100 of the polythiol compound (A) in high performance liquid chromatography.

[0023] <3> like <2> The polythiol composition described above, wherein the peak area of ​​the compound represented by the formula (1) is 8.00 or less relative to 100 of the peak area of ​​the polythiol compound (A).

[0024] <4> like <1> ~ <3> The polythiol composition described in any one of the above further comprises a polythiol compound (B), wherein the polythiol compound (B) comprises at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0025] <5> like <4> The polythiol composition, wherein the peak area of ​​the polythiol compound (B) is 3.10 or less relative to the total peak area 100 of the compounds contained in the polythiol composition in high performance liquid chromatography measurement.

[0026] <6> A polymerizable composition comprising <1> ~ <5> The polythiol composition and the polyiso(thio)cyanate compound described in any one of the above.

[0027] <7> A polymerizable composition as described in <5 6>, wherein the polyiso(thio)cyanate compound comprises 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.

[0028] <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,

[0029] The aforementioned polyiso(thio)cyanate composition comprises:

[0030] Xylylene diisocyanate, and

[0031] At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3),

[0032] 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,

[0033] 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,

[0034] 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.

[0035] [Chemical formula 2]

[0036]

[0037] <9> Resin comprising <6> ~ <8> A cured product of any one of the polymerizable compositions.

[0038] <10> A molded body comprising <9> The resin.

[0039] <11> Optical material comprising <9> The resin.

[0040] <12> A lens comprising <9> The resin.

[0041] Effects of the Invention

[0042] According to one embodiment of the present disclosure, a polythiol composition capable of producing a resin having reduced yellowness and devitrification and excellent heat resistance and its use can be provided. DETAILED DESCRIPTION

[0043] 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.

[0044] 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.

[0045] 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.

[0046] In the present disclosure, the term "iso(thio)cyanate" refers to isocyanate or isothiocyanate.

[0047] 《Polythiol Composition》

[0048] The polythiol composition of the present disclosure comprises a polythiol compound (A) and a compound represented by the following formula (1), wherein the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and in high performance liquid chromatography, the peak area of ​​the compound represented by the above formula (1) is 11.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0049] [Chemical formula 3]

[0050]

[0051] Since the polythiol composition of the present disclosure includes the above-mentioned structure, it is possible to produce a resin having reduced yellowness and devitrification and excellent heat resistance.

[0052] <Polythiol Compound (A)>

[0053] The polythiol composition of the present disclosure comprises a polythiol compound (A), and the polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0054] 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is a compound represented by the following formula (a-1).

[0055] [Chemical formula 4]

[0056]

[0057] 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 of 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.

[0058] In the polythiol composition of the present disclosure, it is preferred that the peak area of ​​the polythiol compound (A) measured by high performance liquid chromatography is 80.00 or more relative to 100 of the total peak area of ​​compounds contained in the polythiol composition.

[0059] When the peak area of ​​the polythiol compound (A) is 80.00 or more, excellent formation of a thiourethane resin is achieved.

[0060] From the above viewpoints, the peak area of ​​the polythiol compound (A) is preferably 81.00 or more, more preferably 82.00 or more, and even more preferably 86.50 or more, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0061] The “peak area of ​​the polythiol compound (A) relative to the total peak area of ​​the compounds contained in the polythiol composition as 100” refers to the relative value of the peak area of ​​the polythiol compound (A) when the total peak area of ​​the compounds contained in the polythiol composition is set to 100.

[0062] In the high performance liquid chromatography measurement, from the viewpoint of producing a thiourethane 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 95.00 or less, and particularly preferably 89.50 or less, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0063] <Measurement of Peak Area of ​​Polythiol Compound (A)>

[0064] The peak area of ​​the polythiol compound (A) can be determined by high performance liquid chromatography (HPLC) measurement under the following conditions.

[0065] The peak area appearing at retention times of 11.0 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.

[0066] (HPLC conditions)

[0067] Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm)

[0068] Mobile phase: acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol)

[0069] Column temperature: 40°C

[0070] Flow rate: 1.0ml / min

[0071] Detector: UV detector, wavelength 230nm

[0072] Preparation of the measurement solution: 160 mg of the polythiol composition was dissolved and mixed in 10 ml of acetonitrile.

[0073] Injection volume: 2μL

[0074] <Compound represented by formula (1)>

[0075] The polythiol composition of the present disclosure contains a compound represented by the following formula (1).

[0076] [Chemical formula 5]

[0077]

[0078] In the polythiol composition of the present disclosure, the peak area of ​​the compound represented by the above formula (1) is 11.00 or less relative to the total peak area 100 of the compounds contained in the polythiol composition in high performance liquid chromatography.

[0079] By setting the peak area of ​​the compound represented by the above formula (1) to 11.00 or less, it is possible to produce a resin having reduced yellowness and devitrification and excellent heat resistance.

[0080] From the above viewpoints, the peak area of ​​the compound represented by the formula (1) is preferably 8.50 or less, more preferably 6.00 or less, and even more preferably 4.00 or less, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0081] In the high performance liquid chromatography measurement, from the viewpoint of reducing the load of the operation of purifying and removing the compound represented by the formula (1) from the polythiol composition, the peak area of ​​the compound represented by the formula (1) is preferably greater than 0, more preferably 0.01 or more, further preferably 0.10 or more, and particularly preferably 0.27 or more, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0082] In the polythiol composition of the present disclosure, the peak area of ​​the compound represented by the above formula (1) is 13.00 or less relative to the peak area of ​​100 of the polythiol compound (A) in high performance liquid chromatography measurement.

[0083] By setting the peak area of ​​the compound represented by the above formula (1) to 13.00 or less, it is possible to produce a resin having reduced yellowness and devitrification and excellent heat resistance.

[0084] From the above viewpoints, the peak area of ​​the compound represented by the formula (1) is preferably 12.00 or less, more preferably 8.00 or less, and even more preferably 4.50 or less, relative to 100 of the peak area of ​​the polythiol compound (A).

[0085] In the high performance liquid chromatography measurement, from the viewpoint of reducing the load of the operation of purifying and removing the compound represented by the formula (1) from the polythiol composition, the peak area of ​​the compound represented by the above formula (1) is preferably greater than 0, more preferably 0.01 or more, further preferably 0.10 or more, and particularly preferably 0.30 or more, relative to the peak area of ​​100 of the polythiol compound (A).

[0086] <Measurement of Peak Area of ​​Compound Represented by Formula (1)>

[0087] The peak area of ​​the compound represented by formula (1) can be determined by high performance liquid chromatography (HPLC) measurement under the following conditions.

[0088] The peak area appearing at a retention time of 6.2 to 7.0 minutes can be determined as the peak area of ​​the compound represented by formula (1), and the ratio to the total peak area 100 of the compounds contained in the polythiol composition and the peak area 100 of the polythiol compound (A) can be calculated.

[0089] (HPLC conditions)

[0090] Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm)

[0091] Mobile phase: acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol)

[0092] Column temperature: 40°C

[0093] Flow rate: 1.0ml / min

[0094] Detector: UV detector, wavelength 230nm

[0095] Preparation of the measurement solution: 160 mg of the polythiol composition was dissolved and mixed in 10 ml of acetonitrile.

[0096] Injection volume: 2μL

[0097] <Compounds other than the polythiol compound (A) and the compound represented by the formula (1)>

[0098] The polythiol composition of the present disclosure may contain compounds other than the polythiol compound (A) and the compound represented by formula (1).

[0099] For example, the polythiol composition of the present disclosure may contain polythiol compounds other than the polythiol compound (A) and the compound represented by formula (1) (hereinafter also referred to as “other polythiol compounds”) and the like.

[0100] Examples of other polythiol compounds 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, 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, etc.

[0101] (Polythiol compound (B))

[0102] The polythiol composition of the present disclosure preferably comprises a polythiol compound (B), wherein the polythiol compound (B) comprises at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0103] In high performance liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is preferably 3.10 or less relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition.

[0104] Furthermore, the peak area of ​​the polythiol compound (B) is more preferably 3.05 or less relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition.

[0105] In high performance liquid chromatography measurement, the peak area of ​​the polythiol compound (B) may be greater than 0, 0.10 or more, or 0.20 or more relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0106] <Measurement of Peak Area of ​​Polythiol Compound (B)>

[0107] The peak area of ​​the polythiol compound (B) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition can be determined by high performance liquid chromatography (HPLC) measurement under the following conditions.

[0108] The peak area appearing at retention times of 21.0 to 24.0 minutes can be determined as the peak area of ​​the polythiol compound (B), and the ratio relative to the total peak area 100 of the compounds contained in the polythiol composition can be calculated.

[0109] (HPLC conditions)

[0110] Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm)

[0111] Mobile phase: acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol)

[0112] Column temperature: 40°C

[0113] Flow rate: 1.0ml / min

[0114] Detector: UV detector, wavelength 230nm

[0115] Preparation of the measurement solution: 160 mg of the polythiol composition was dissolved and mixed in 10 ml of acetonitrile.

[0116] Injection volume: 2μL

[0117] (Compound represented by formula (X1))

[0118] As a compound other than the polythiol compound (A) and the compound represented by the formula (1) which may be contained in the polythiol composition of the present disclosure, there may be mentioned a compound represented by the following formula (X1).

[0119] [Chemical formula 6]

[0120]

[0121] In formula (X1), m and n each independently represent 0 or 1, and m+n=1.

[0122] 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)).

[0123] 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.

[0124] Examples of the compound represented by formula (X1) include a compound represented by formula (X1a) and a compound represented by formula (X1b).

[0125] [Chemical formula 7]

[0126]

[0127] 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).

[0128] 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).

[0129] 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).

[0130] (Compound (XB))

[0131] Examples of the compound other than the polythiol compound (A) and the compound (B1) include the following compound (XB).

[0132] 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).

[0133] 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)).

[0134] [Chemical formula 8]

[0135]

[0136] In formula (XB-1), * represents a bonding position.

[0137] Examples of the compound (XB) are shown below, but the compound (XB) is not limited to the following examples.

[0138] [Chemical formula 9]

[0139]

[0140] 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.

[0141] 《Polymerizable composition》

[0142] The polymerizable composition of the present disclosure comprises the polythiol composition of the present disclosure and a polyiso(thio)cyanate compound.

[0143] (Polyiso(thio)cyanate compounds)

[0144] 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:

[0145] 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 diisocyanate, lysine triisocyanate, and xylylene diisocyanate;

[0146] 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;

[0147] Aromatic polyisocyanate compounds such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl sulfide-4,4'-diisocyanate, and phenylene diisocyanate;

[0148] 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;

[0149] Aliphatic polyisothiocyanate compounds such as hexamethylene diisothiocyanate, lysine methyl ester diisothiocyanate, lysine triisothiocyanate, and xylylene diisothiocyanate;

[0150] 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;

[0151] Aromatic polyisothiocyanate compounds such as toluene diisothiocyanate, 4,4'-diphenylmethane diisothiocyanate, and diphenyl sulfide-4,4'-diisothiocyanate;

[0152] 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.

[0153] The polyiso(thio)cyanate compound may contain at least one selected from these.

[0154] 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.

[0155] The polyiso(thio)cyanate compound is preferably a polyisocyanate compound, preferably comprising at least one selected from the group consisting of 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.

[0156] 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.

[0157] The polymerizable composition of the present disclosure may include a polyiso(thio)cyanate composition including the above-mentioned polyiso(thio)cyanate compound.

[0158] Here, the polyiso(thio)cyanate composition refers to a composition containing at least one polyiso(thio)cyanate compound.

[0159] The polyiso(thio)cyanate composition may contain components other than the polyiso(thio)cyanate compound as impurities.

[0160] The polyiso(thio)cyanate composition preferably contains at least one polyiso(thio)cyanate compound as a main component.

[0161] The polyiso(thio)cyanate composition preferably comprises xylylene diisocyanate.

[0162] Hereinafter, the polyiso(thio)cyanate composition containing xylylenediisocyanate is also referred to as an XDI composition.

[0163] The XDI composition preferably contains xylylene diisocyanate as a main component.

[0164] 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).

[0165] [Chemical formula 10]

[0166]

[0167] 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.

[0168] 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.

[0169] -GC Condition 1-

[0170] Filler: DB-1 (film thickness) 1.5 μm

[0171] Column: inner diameter 0.53 mm × length 60 m (manufactured by Agilent)

[0172] 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.

[0173] Split ratio: Pulse splitless method

[0174] Inlet temperature: 280℃

[0175] Detector temperature: 300°C

[0176] Carrier gas: N2 158kPa, H2 55kPa, air 45kPa (constant pressure control)

[0177] Solvent: Chloroform

[0178] Sample concentration: 2.0 mass% chloroform solution

[0179] Injection volume: 2μL

[0180] Detection method: FID

[0181] 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.

[0182] 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.

[0183] The peak area of ​​the compound (N1) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0184] 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.

[0185] -GC Condition 2-

[0186] Column: HP-50+, inner diameter 0.25 mm×length 30 m×film thickness 0.25 μm (manufactured by Hewlett-Packard Company)

[0187] Column box temperature: increase from 50°C to 280°C at 10°C / min, and maintain at 280°C for 6 minutes.

[0188] Split ratio: Pulse splitless method

[0189] Inlet temperature: 200℃

[0190] Detector temperature: 280°C

[0191] Carrier gas: He

[0192] Carrier gas flow rate: 1.0ml / min (constant flow control)

[0193] Sample concentration: 1.0 mass% dichloromethane solution

[0194] Injection volume: 1.0 μL

[0195] Detection method: SIM (monitoring ions: m / z 180, 215) (content ratio of xylylenediisocyanate (XDI))

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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, relative to the peak area 1 of xylylenediisocyanate.

[0202] The peak area of ​​the compound (N3) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0203] 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.

[0204] The lower limit of the acid content of the XDI composition is not particularly limited, and the lower limit is, for example, 1 ppm.

[0205] The acid content of the XDI composition can be measured according to the method described in paragraph 0091 of International Publication No. 2021 / 256417.

[0206] Additionally, the XDI composition may contain a stabilizer.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] The polymerizable composition of the present disclosure can be obtained by mixing the above components.

[0213] Forming

[0214] The molded article of the present disclosure contains the resin of the present disclosure.

[0215] The resin of the present disclosure includes a cured product of the polymerizable composition of the present disclosure.

[0216] 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.

[0217] 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.

[0218] 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.

[0219] [use]

[0220] 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.

[0221] Optical Materials

[0222] The optical material of the present disclosure includes the resin of the present disclosure.

[0223] 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.

[0224] Therefore, it can be used in various optical materials such as plastic lenses.

[0225] "lens"

[0226] The lens of the present disclosure includes the resin of the present disclosure.

[0227] As the optical material, a lens is particularly preferred.

[0228] Examples of the lens include plastic eyeglass lenses and plastic polarizing lenses.

[0229] [Plastic eyeglass lenses]

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] For the layer applied by coating, various leveling agents may be used for the purpose of improving coating properties.

[0235] Furthermore, an anti-fog layer, an anti-fouling layer, and a water-repellent layer may be formed on the anti-reflection layer as required.

[0236] 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.

[0237] Example

[0238] 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.

[0239] <Evaluation method>

[0240] In this example, the evaluation method of various physical properties of the plastic lens is as follows. The results are shown in Table 1.

[0241] Yellow Index (also called YI)

[0242] The resin was made into a circular plastic plate having a thickness of 9 mm and a diameter of 75 mm, and the YI value was determined using a spectrophotometer CR-400 manufactured by Ko nica Minolta, Inc.

[0243] It should be noted that there is the following correlation: the smaller the YI value, the smaller the yellowness of the plastic plate, and the larger the YI value, the larger the yellowness.

[0244] Devitrification

[0245] The resin was made into a circular plastic flat plate with a thickness of 9 mm and a diameter of 75 mm. Light from a light source (Luminar Ace LA-150A manufactured by HAYASHI-REPIC CO., LTD.) was transmitted from the side of the flat plate. An image of light from the front of the flat plate was captured in an image processing device (manufactured by Ube Information Systems, Inc.), and the captured image was gray-scale processed. The gray-scale degree of the processed image was digitized for each pixel, and the average value of the gray-scale degree of each pixel was obtained to obtain the devitrification of the flat plate.

[0246] The smaller the devitrification degree is, the less the transparency of the resin (here, the flat plate) is impaired (that is, the transparency of the resin is excellent).

[0247] Heat resistance

[0248] 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).

[0249] It should be noted that the higher the glass transition temperature (Tg), the better the heat resistance.

[0250] <Preparation of Polythiol Composition (A)>

[0251] 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 NMR data of the obtained reaction solution confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol.

[0252] Next, 331.5 parts by mass of hydrochloric acid having a concentration of 35.5% by mass was charged into the 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 perform a thiourea salt reaction.

[0253] 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 at 31°C to 41°C over 44 minutes, and the mixture was stirred at 54°C to 62°C for 3 hours to carry out a hydrolysis reaction, thereby obtaining a toluene solution of a polythiol containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a main component.

[0254] 162.8 parts by mass of hydrochloric acid having a concentration of 35.5% by mass was added to the toluene solution, and acid cleaning was performed at 35°C to 43°C for 1 hour. The toluene solution after the acid cleaning was subjected to an operation of adding 174.1 parts by mass of degassed water and performing cleaning at 35°C to 45°C for 30 minutes twice. 162.1 parts by mass of ammonia water having a concentration of 0.1% by mass was added to the toluene solution after the degassed water cleaning, and cleaning was performed for 30 minutes. The toluene solution after the ammonia cleaning was subjected to an operation of adding 174.2 parts by mass of degassed water and performing cleaning at 35°C to 45°C for 30 minutes twice.

[0255] 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 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.

[0256] <Preparation of Polythiol Composition (B)>

[0257] 51.2 parts by mass of 2-mercaptoethanol, 26.5 parts by mass of deaerated water, and 0.16 parts by mass of a 49% by mass sodium hydroxide aqueous solution were placed in the reactor. 61.99 parts by mass of epichlorohydrin were added dropwise at 9 to 11° C. over 6.5 hours, and stirring was continued for 60 minutes. The NMR data of the obtained reaction solution confirmed the formation of 1-chloro-3-(2-hydroxyethylthio)-2-propanol.

[0258] Next, 150.0 parts by mass of a 17.3% by mass sodium sulfide aqueous solution was added dropwise to the reactor containing 1-chloro-3-(2-hydroxyethylthio)-2-propanol at 7 to 37° C. over 5.5 hours, and the mixture was stirred for 120 minutes. As a result, the generation of 1,5,9,13-tetrahydroxy-3,7,11-trithiatridecane was confirmed based on NMR data.

[0259] Next, 279.0 parts by mass of hydrochloric acid having a concentration of 35.5% by mass was charged into the reactor containing 1,5,9,13-tetrahydroxy-3,7,11-trithiatridecane, followed by 125.8 parts by mass of thiourea having a purity of 99.90%, and the mixture was stirred at 110° C. under reflux for 3 hours to perform thiourea salt reaction.

[0260] The reaction solution after the thiourea salting reaction was cooled to 45°C, 214.0 parts by mass of toluene was added, and the mixture was cooled to 26°C. 206.2 parts by mass of an aqueous ammonia solution having a concentration of 25% by mass was added thereto at 26 to 50°C over 30 minutes, and the mixture was stirred at 50 to 65°C for 1 hour to carry out a hydrolysis reaction, thereby obtaining a toluene solution of a polythiol having at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a main component.

[0261] The obtained toluene solution was subjected to an acid washing operation twice by adding 59.4 parts by mass of hydrochloric acid having a concentration of 36% by mass and performing acid washing at 34°C to 39°C for 30 minutes. The toluene solution after the acid washing was subjected to an acid washing operation five times by adding 118.7 parts by mass of degassed water and performing washing at 35°C to 45°C for 30 minutes. 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 1.2 μm PTFE membrane filter to obtain 115.9 parts by mass of a polythiol composition (B) containing at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a main component.

[0262] <Preparation of Polythiol Composition (C)>

[0263] The polythiol composition (A) and the polythiol composition (B) are mixed at an arbitrary ratio to prepare a polythiol composition (C).

[0264] [Example 1 to Example 6]

[0265] The polythiol composition (C) obtained as described above is mixed with the compound represented by the formula (1) to obtain a polythiol composition.

[0266] At this time, the mixing ratio was changed so that the total peak area of ​​the compounds represented by formula (1) relative to the total peak area of ​​the compounds contained in the polythiol composition as 100 would be the value described in Table 1, and the compounds were mixed.

[0267] <Measurement of the ratio (area %) of the polythiol compound (A), the polythiol compound (B) and the compound represented by the formula (1)>

[0268] The ratio (area %) of the polythiol compound (A), the polythiol compound (B) and the compound represented by formula (1) based on HPLC is determined by the method described in the above-mentioned <Determination of the peak area of ​​the polythiol compound (A)>, <Determination of the peak area of ​​the polythiol compound (B)> and <Determination of the peak area of ​​the compound represented by formula (1)>.

[0269] The results are shown in Table 1.

[0270] <Manufacturing of plastic lenses>

[0271] [Production Example 1]

[0272] 52 parts by mass of m-xylylene diisocyanate, 0.015 parts by mass of dibutyltin dichloride as a curing catalyst, 0.10 parts by mass of ZELEC UN (product of Stepan; acidic phosphate), and 0.05 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.

[0273] [Production Example 2]

[0274] 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.

[0275] [Production Example 3]

[0276] 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.

[0277] [Production Example 4]

[0278] 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.

[0279] [Production Example 5]

[0280] 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 5. The various properties were determined according to the evaluation methods of various properties of plastic lenses described above.

[0281] [Production Example 6]

[0282] 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 6. The various properties were determined according to the evaluation methods of the various properties of the plastic lens described above.

[0283] Table 1 shows the physical properties of the plastic lenses of Production Examples 1 to 6 (ie, Examples 1 to 6).

[0284] [Table 1]

[0285]

[0286] As shown in Table 1, each Example using a polythiol composition containing a polythiol compound (A) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a compound represented by formula (1), wherein the peak area of ​​the compound represented by the above formula (1) in high performance liquid chromatography measurement is 11.0 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition, was excellent in the evaluation of yellowness and devitrification, and was excellent in heat resistance.

[0287] Therefore, a resin having reduced yellowness and devitrification and excellent heat resistance can be produced.

[0288] Among them, Examples 1 to 5 using polythiol compositions in which the peak area of ​​the compound represented by formula (1) was 10.0 or less relative to the total peak area 100 of the compounds contained in the polythiol composition, had more excellent heat resistance.

[0289] [Manufacturing Example 1X to Manufacturing Example 6X]

[0290] 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.

[0291] - Changes from each of Production Examples 1 to 6 -

[0292] 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.

[0293] 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.

[0294] In XDI composition X1, gas chromatography was performed using the above-mentioned GC conditions 1 and GC conditions 2, respectively. The results showed that:

[0295] The peak area of ​​the compound (N1) is 0.20 ppm or more (specifically, 600 ppm) relative to the peak area 1 of XDI,

[0296] The peak area of ​​the compound (N2) is 0.05 ppm or more (specifically, 18 ppm) relative to the peak area 1 of XDI,

[0297] The peak area of ​​the compound (N3) is 0.10 ppm or more (specifically, 100 ppm) relative to the peak area 1 of XDI.

[0298] The entire disclosure of Japanese Patent Application No. 2022-165813 filed on October 14, 2022 is incorporated into this specification by reference.

[0299] 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 represented by the following formula (1): In high performance liquid chromatography, the peak area of ​​the compound represented by the formula (1) is 11.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition, [Chemical formula 1] 2. The polythiol composition according to claim 1, wherein In high performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 13.00 or less relative to 100 of the peak area of ​​the polythiol compound (A).

3. The polythiol composition according to claim 2, wherein The peak area of ​​the compound represented by the formula (1) is 8.00 or less relative to 100 of the peak area of ​​the polythiol compound (A).

4. The polythiol composition according to claim 1, further comprising a polythiol compound (B), wherein the polythiol compound (B) comprises at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

5. The polythiol composition according to claim 4, wherein In high performance liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 3.10 or less 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 includes at least one selected from the group consisting of 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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