Polythiol composition, polymerizable composition for optical material, molded body, optical material, and plastic lens

Abstract

This polythiol composition contains a compound (A) represented by formula (1) and a compound (B) represented by formula (2). In a high-performance liquid chromatography measurement performed using a specific detector, the peak area of the compound (B) is not more than 40.0 area% with respect to 100 area% of the peak area of the compound (A). (In formula (1), the plurality of R moieties are the same as or different from each other, and each represent a divalent hydrocarbon group having 1 to 6 carbon atoms.) (In formula (2), the plurality of R moieties are the same as or different from each other, and each represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a1, b1, c1, f1, g1, and h1 are the same as or different from one another, and each represent a number of 0 to 3. d1 and e1 are the same as or different from each other, and each represent a number of 1 to 2. The sum of a1, b1, c1, d1, e1, f1, g1, and h1 is 8.)

Description

Polythiol Composition, Polymerizable Composition for Optical Materials, Molded Body, Optical Material, and Plastic Lens

[0001] The present invention relates to a polythiol composition, a polymerizable composition for optical materials, a molded body, an optical material, and a plastic lens. More specifically, it relates to a polythiol composition, a polymerizable composition for optical materials containing the polythiol composition, a molded body containing a cured product of the polymerizable composition for optical materials, an optical material composed of the molded body, and a plastic lens composed of the optical material.

[0002] Conventionally, from the perspective of high refractive index, a polythiourethane resin obtained from a polymerizable composition containing an isocyanate compound and a thiol compound is known as an optical material.

[0003] As a thiol compound, for example, a thiol-containing composition for optical materials containing pentaerythritol tetrakis(3-mercaptopropionate), which is a reaction product of pentaerythritol and 3-mercaptopropionic acid, has been proposed (see, for example, Example 1 of Patent Document 1).

[0004] International Publication No. 2020 / 218508 Pamphlet

[0005] On the other hand, optical materials are dyed according to their uses and purposes. Therefore, optical materials are required to have a performance (dyeability) that is easily dyed by dyes.

[0006] In addition, optical materials are required to have excellent yellowing resistance.

[0007] The present invention provides a polythiol composition excellent in dyeability and yellowing resistance, a polymerizable composition for optical materials containing the polythiol composition, a molded body containing a cured product of the polymerizable composition for optical materials, an optical material composed of the molded body, and a plastic lens composed of the optical material.

[0008] The present invention [1] includes a polythiol composition comprising a compound (A) represented by the following formula (1) and a compound (B) represented by the following formula (2), wherein, in high-performance liquid chromatography measurements detected with a UV detector at a measurement wavelength of 200 nm, the peak area of ​​compound (B) is 40.0 area % or less relative to 100 area % of the peak area of ​​compound (A).

[0009]

[0010] (In formula (1) above, the multiple Rs are either the same or different in phase, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.)

[0011]

[0012] (In formula (2) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a1, b1, c1, f1, g1, and h1 are the same or different in phase and represent 0 to 3. d1 and e1 are the same or different in phase and represent 1 to 2. The sum of a1, b1, c1, d1, e1, f1, g1, and h1 is 8.)

[0013] The present invention [2] includes the polythiol composition described in [1] above, wherein in formula (2) above, d1 and e1 are 1.

[0014] The present invention [3] further comprises the polythiol composition described in [1] or [2] above, which comprises a compound (C) represented by the following formula (3).

[0015]

[0016] (In formula (3) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a2, b2, c2, f2, g2, and h2 are the same or different in phase and represent 0 to 3. d2 and e2 are the same or different in phase and represent 1 to 2. The sum of a2, b2, c2, d2, e2, f2, g2, and h2 is 7.)

[0017] The present invention [4] further comprises the polythiol composition according to any one of the above claims [1] to [3], which comprises a compound (D) represented by the following formula (4).

[0018]

[0019] (In formula (4) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a3, b3, c3, f3, g3, and h3 are the same or different in phase and represent 0 to 3. d3 and e3 are the same or different in phase and represent 1 to 2. The sum of a3, b3, c3, d3, e3, f3, g3, and h3 is 6.)

[0020] The present invention [5] further comprises the polythiol composition according to any one of the above claims [1] to [4], which comprises a compound (E) represented by the following formula (5).

[0021]

[0022] (In formula (5) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a4, b4, c4, f4, g4, and h4 are the same or different in phase and represent 0 to 3. d4 and e4 are the same or different in phase and represent 1 to 2. The sum of a4, b4, c4, d4, e4, f4, g4, and h4 is 9.)

[0023] The present invention [6] includes a polymerizable composition for optical materials comprising an isocyanate compound and a polythiol composition according to any one of the above [1] to [5].

[0024] The present invention [7] includes a molded article comprising a cured product of the polymerizable composition for optical materials described in [6] above.

[0025] The present invention [8] includes an optical material comprising the molded article described in [7] above.

[0026] The present invention [9] includes a plastic lens made of the optical material described in [8] above.

[0027] The polythiol composition of the present invention comprises compound (A) represented by formula (1) and compound (B) represented by formula (2). In high-performance liquid chromatography measurements using an ultraviolet detector with a measurement wavelength of 200 nm, the peak area of ​​compound (B) is 10.0 area% or less relative to the peak area of ​​compound (A) at 100 area%. Therefore, staining properties and resistance to yellowing can be improved.

[0028] The polymerizable composition for optical materials of the present invention contains the polythiol composition of the present invention. Therefore, stainability and resistance to yellowing can be improved.

[0029] The molded article of the present invention includes a cured product of the polymerizable composition for optical materials of the present invention. Therefore, dyeability and resistance to yellowing can be improved.

[0030] The optical material of the present invention consists of a molded article of the present invention. Therefore, dyeability and resistance to yellowing can be improved.

[0031] The plastic lens of the present invention is made of the optical material of the present invention. Therefore, its stainability and resistance to yellowing can be improved.

[0032] 1. Polythiol composition The polythiol composition contains a predetermined compound (A) and a predetermined compound (B) as essential components.

[0033] <Compound (A)> Compound (A) is represented by the following formula (1).

[0034]

[0035] In formula (1) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0036] Examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (1) above include divalent linear hydrocarbon groups having 1 to 6 carbon atoms and divalent branched hydrocarbon groups having 3 to 6 carbon atoms. Examples of divalent linear hydrocarbon groups having 1 to 6 carbon atoms include methylene, ethylene, n-propylene (also known as trimethylene), n-butylene (also known as tetramethylene), n-pentylene (also known as pentamethylene), and n-hexylene (also known as hexamethylene). Examples of divalent branched hydrocarbon groups having 3 to 6 carbon atoms include iso-propylene, iso-butylene, s-butylene, t-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 2,2-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, and 3,3-dimethyl-1,4-butylene.

[0037] In the above formula (1), the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably a divalent hydrocarbon group having 1 to 4 carbon atoms. That is, preferably a divalent linear hydrocarbon group having 1 to 4 carbon atoms and a divalent branched hydrocarbon group having 3 to 4 carbon atoms. Specifically, preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene are included, more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene are included, and even more preferably methylene, ethylene, and iso-propylene are included.

[0038] In formula (1) above, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is more preferably a divalent hydrocarbon group having 1 to 2 carbon atoms. That is, more preferably a divalent linear hydrocarbon group having 1 to 2 carbon atoms. Specifically, more preferably methylene and ethylene are mentioned, and particularly preferably ethylene.

[0039] Further, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R may have a substituent. Examples of the substituent include a halogeno group, a cyano group, an amino group, a carboxy group, a sulfonyl group, and an alkoxy group. These can be used alone or in combination of two or more. The number of substituents is appropriately set according to the purpose and application. The substitution position is appropriately set according to the purpose and application. The divalent hydrocarbon group having 1 to 6 carbon atoms represented by R preferably has no substituent. That is, R preferably represents a divalent unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

[0040] Although it will be described in detail later, the compound (A) can be obtained by reacting 4 moles of mercapto carboxylic acid with 1 mole of pentaerythritol.

[0041] Specific examples of the compound (A) include pentaerythritol tetrakis(mercaptoacetate) (all Rs are methylene), pentaerythritol tetrakis(3-mercaptopropionate) (all Rs are ethylene), and pentaerythritol tetrakis(3-mercaptobutyrate) (all Rs are iso-propylene). Further, as the compound (A), for example, a compound in which one of the four Rs represents methylene and three represent ethylene, a compound in which two of the four Rs represent methylene and two represent ethylene, and a compound in which three of the four Rs represent methylene and one represents ethylene can be mentioned. Preferably, the compound (A) includes pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate), and more preferably pentaerythritol tetrakis(3-mercaptopropionate). That is, in the above formula (1), preferably, all Rs represent ethylene or all Rs represent iso-propylene, and more preferably, all Rs represent ethylene.

[0042] The compound (A) can be used alone or in combination of two or more.

[0043] <Compound (B)> The compound (B) is represented by the following formula (2).

[0044]

[0045] In the above formula (2), the plurality of Rs are the same or different and each represents a divalent hydrocarbon group having 1 to 6 carbon atoms.

[0046] R in the above formula (2) is preferably synonymous with R in the above formula (1).

[0047] That is, examples of the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R in the above formula (2) include, for example, the divalent hydrocarbon groups having 1 to 6 carbon atoms exemplified as R in the above formula (1), and specifically include the above-described divalent linear hydrocarbon groups having 1 to 6 carbon atoms and the above-described divalent branched hydrocarbon groups having 3 to 6 carbon atoms.

[0048] Examples of the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R in the above formula (2) preferably include methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene, more preferably include methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene, still more preferably include methylene, ethylene, and iso-propylene, still more preferably include methylene and ethylene, and particularly preferably include ethylene.

[0049] In the above formula (2), a1, b1, c1, f1, g1, and h1 are the same or different and each represents 0 to 3. a1, b1, c1, f1, g1, and h1 preferably represent 0 or 1.

[0050] In the above formula (2), d1 and e1 are the same or different and each represents 1 to 2. d1 and e1 preferably represent 1.

[0051] In the above formula (2), the sum of a1, b1, c1, d1, e1, f1, g1, and h1 is 8. In other words, the compound (B) contains 6 structural units derived from mercaptocarboxylic acid and 1 structural unit derived from a dithioacetal compound (described later).

[0052] Examples of compound (B) include compound (B) without a hydroxyl group and compound (B) having a hydroxyl group.

[0053] As will be explained in more detail later, compound (B) is obtained by the reaction of pentaerythritol with a dithioacetal compound (described later) and a mercaptocarboxylic acid. In this reaction, the reaction product may or may not contain residual hydroxyl groups derived from pentaerythritol.

[0054] Compound (B) without a hydroxyl group is a reaction product derived from pentaerythritol that does not have a hydroxyl group, while compound (B) with a hydroxyl group is a reaction product derived from pentaerythritol that has a hydroxyl group.

[0055] Examples of compounds (B) that do not have a hydroxyl group include the compounds shown in the following formula (2-1) (compounds in which a1, b1, c1, d1, e1, f1, g1 and h1 are 1 in formula (2) above).

[0056]

[0057] Examples of compounds having a hydroxyl group (B) include the compound shown in the following formula (2-2) (a compound in which a1, b1, c1, d1, e1, and f1 represent 1, g1 represents 2, and h1 represents 0).

[0058] Furthermore, as compounds (B) having a hydroxyl group, for example, there are compounds shown in the following formula (2-3) (compounds in which a1, b1, d1 and e1 represent 1, c1 and g1 represent 2, and f1 and h1 represent 0).

[0059]

[0060] In formulas (2-1) to (2-3) above, the multiple Rs are synonymous with the R in formula (2). That is, the multiple Rs are either the same or different and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0061] Compound (B) is not limited to the compounds shown in formulas (2-1) to (2-3) above. Compound (B) can be used alone or in combination of two or more types.

[0062] From the viewpoint of reactivity, compound (B) is preferably a compound (B) that does not have a hydroxyl group.

[0063] <Compound (C)> The polythiol composition may optionally contain compound (C) represented by the following formula (3). Preferably, the polythiol composition contains compound (C) represented by the following formula (3).

[0064]

[0065] In formula (3) above, the multiple Rs are the same or different in phase and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0066] The R in formula (3) above is preferably the same as the R in formula (1) above.

[0067] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (3) above include the divalent hydrocarbon groups having 1 to 6 carbon atoms exemplified as R in formula (1) above, and specifically include the divalent linear hydrocarbon groups having 1 to 6 carbon atoms and the divalent branched hydrocarbon groups having 3 to 6 carbon atoms mentioned above.

[0068] In formula (3) above, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene; more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene; even more preferably methylene, ethylene, and iso-propylene; even more preferably methylene and ethylene; and particularly preferably ethylene.

[0069] In the above formula (3), a2, b2, c2, f2, g2, and h2 are the same or different, and represent values ​​from 0 to 3. Preferably, a2, b2, c2, f2, g2, and h2 represent 0 or 1.

[0070] In formula (3) above, d2 and e2 are the same or different, and represent 1 to 2. Preferably, d2 and e2 represent 1.

[0071] In formula (3) above, the sum of a2, b2, c2, d2, e2, f2, g2, and h2 is 7. In other words, compound (C) contains five structural units derived from mercaptocarboxylic acid and one structural unit derived from a dithioacetal compound (described later). Compound (C) also contains at least one hydroxyl group.

[0072] As will be explained in more detail later, compound (C) is obtained by the reaction of pentaerythritol with a dithioacetal compound (described later) and a mercaptocarboxylic acid. The reaction product from this reaction retains a hydroxyl group derived from pentaerythritol. In other words, compound (C) has the hydroxyl group derived from the aforementioned pentaerythritol.

[0073] Specifically, as compound (C), for example, there is the compound shown in the following formula (3-1) (a compound in which a2, b2, c2, d2, e2, f2, and g2 are 1 and h2 is 0 in formula (3) above).

[0074] Furthermore, as compound (C), for example, there is the compound shown in the following formula (3-2) (a compound in which a2, b2, c2, d2, and e2 are 1, g2 is 2, and f2 and h2 are 0 in formula (3) above).

[0075]

[0076] In formulas (3-1) to (3-2) above, the multiple Rs are equivalent to the Rs in formula (3) above. That is, the multiple Rs are either the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0077] Compound (C) is not limited to the compounds shown in formulas (3-1) to (3-2) above. Compound (C) can be used alone or in combination of two or more types.

[0078] <Compound (D)> The polythiol composition may optionally contain compound (D) represented by the following formula (4). Preferably, the polythiol composition contains compound (D) represented by the following formula (4).

[0079]

[0080] In formula (4) above, the multiple Rs are the same or different in phase and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0081] The R in formula (4) above is preferably the same as the R in formula (1) above.

[0082] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (4) include the divalent hydrocarbon groups having 1 to 6 carbon atoms exemplified as R in formula (1), and specifically include the divalent linear hydrocarbon groups having 1 to 6 carbon atoms and the divalent branched hydrocarbon groups having 3 to 6 carbon atoms.

[0083] In formula (4) above, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene; more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene; even more preferably methylene, ethylene, and iso-propylene; even more preferably methylene and ethylene; and particularly preferably ethylene.

[0084] In the above formula (4), a3, b3, c3, f3, g3, and h3 are the same or different, and represent values ​​from 0 to 3. Preferably, a3, b3, c3, f3, g3, and h3 represent 0 or 1.

[0085] In the above formula (4), d3 and e3 are the same or different, and represent 1 to 2. Preferably, d3 and e3 represent 1.

[0086] In formula (4) above, the sum of a3, b3, c3, d3, e3, f3, g3, and h3 is 6. In other words, compound (D) contains four constituent units derived from mercaptocarboxylic acid and one constituent unit derived from a dithioacetal compound (described later). Compound (D) also contains at least two hydroxyl groups.

[0087] Specifically, as compound (D), for example, there is the compound shown in the following formula (4-1) (a compound in which b3, c3, d3, e3, f3, and g3 are 1 and a3 and h3 are 0 in the above formula (4)).

[0088] Furthermore, as compound (D), for example, there is the compound shown in the following formula (4-2) (a compound in which b3, c3, d3, and e3 are 1, g3 is 2, and a3, f3, and h3 are 0 in formula (4) above).

[0089]

[0090] In formulas (4-1) to (4-2) above, the multiple Rs are equivalent to the Rs in formula (4) above. That is, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0091] Compound (D) is not limited to the compounds shown in formulas (4-1) to (4-2) above. Compound (D) can be used alone or in combination of two or more types.

[0092] <Compound (E)> The polythiol composition may optionally contain compound (E) represented by the following formula (5). Preferably, the polythiol composition contains compound (E) represented by the following formula (5).

[0093]

[0094] In formula (5) above, the multiple Rs are the same or different in phase, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0095] The R in formula (5) above is preferably the same as the R in formula (1) above.

[0096] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (5) above include the divalent hydrocarbon groups having 1 to 6 carbon atoms exemplified as R in formula (1) above, and specifically include the divalent linear hydrocarbon groups having 1 to 6 carbon atoms and the divalent branched hydrocarbon groups having 3 to 6 carbon atoms mentioned above.

[0097] In formula (5) above, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene; more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene; even more preferably methylene, ethylene, and iso-propylene; even more preferably methylene and ethylene; and particularly preferably ethylene.

[0098] In the above formula (5), a4, b4, c4, f4, g4, and h4 are the same or different, and represent values ​​from 0 to 3. Preferably, a4, b4, c4, f4, g4, and h4 represent 0 or 1.

[0099] In formula (5) above, d4 and e4 are the same or different, and represent 1 to 2. Preferably, d4 and e4 represent 1.

[0100] In the above formula (5), the sum of a4, b4, c4, d4, e4, f4, g4, and h4 is 9. In other words, compound (E) contains seven constituent units derived from mercaptocarboxylic acid and one constituent unit derived from a dithioacetal compound (described later).

[0101] Examples of compound (E) include compound (E) without a hydroxyl group and compound (E) having a hydroxyl group.

[0102] Compound (E) without a hydroxyl group is a reaction product derived from pentaerythritol that does not have a hydroxyl group, while compound (E) with a hydroxyl group is a reaction product derived from pentaerythritol that has a hydroxyl group.

[0103] Examples of compounds (E) that do not have a hydroxyl group include the compound shown in the following formula (5-1) (a compound in which a4, b4, c4, d4, e4, f4, and h4 represent 1 and g4 represents 2).

[0104] Examples of compounds having a hydroxyl group (E) include the compound shown in the following formula (5-2) (a compound in which a4, b4, d4, e4, and f4 represent 1, c4 and g4 represent 2, and h4 represents 0).

[0105]

[0106] In formulas (5-1) to (5-2) above, the multiple Rs are equivalent to the Rs in formula (5). That is, the multiple Rs are either the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0107] Compound (E) is not limited to the compounds shown in formulas (5-1) to (5-2) above. Compound (E) can be used alone or in combination of two or more types.

[0108] From the viewpoint of reactivity, a compound (E) that does not have a hydroxyl group is preferred.

[0109] <Compound (F)> The polythiol composition may optionally contain compound (F) represented by the following formula (6). Preferably, the polythiol composition contains compound (F) represented by the following formula (6).

[0110]

[0111] In formula (6) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0112] The R in formula (6) above is preferably the same as the R in formula (1) above.

[0113] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (6) include the divalent hydrocarbon groups having 1 to 6 carbon atoms exemplified as R in formula (1), and specifically include the divalent linear hydrocarbon groups having 1 to 6 carbon atoms and the divalent branched hydrocarbon groups having 3 to 6 carbon atoms.

[0114] In the above formula (6), the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene; more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene; even more preferably methylene, ethylene, and iso-propylene; even more preferably methylene and ethylene; and particularly preferably ethylene.

[0115] In the above formula (6), a5, b5, c5, f5, g5, and h5 are the same or different, and represent values ​​from 0 to 3. Preferably, a5, b5, c5, f5, g5, and h5 represent 0 or 1.

[0116] In the above formula (6), d5 and e5 are the same or different, and represent 1 to 2. Preferably, d5 and e5 represent 1.

[0117] In formula (6) above, the sum of a5, b5, c5, d5, e5, f5, g5, and h5 is 10. In other words, compound (F) contains eight structural units derived from mercaptocarboxylic acid and one structural unit derived from a dithioacetal compound (described later).

[0118] Examples of compound (F) include compounds (F) that do not have a hydroxyl group and compounds (F) that do have a hydroxyl group.

[0119] Compound (F) without a hydroxyl group is a reaction product derived from pentaerythritol that does not have a hydroxyl group, while compound (F) with a hydroxyl group is a reaction product derived from pentaerythritol that has a hydroxyl group.

[0120] Examples of compounds (F) that do not have a hydroxyl group include the compound shown in the following formula (6-1) (a compound in which a5, b5, d5, e5, f5, and h5 represent 1, and c5 and g5 represent 2).

[0121] Examples of compounds (F) having a hydroxyl group include the compound shown in the following formula (6-2) (a compound in which a5, b5, d5, and e5 represent 1, c5, f5, and g5 represent 2, and h5 represents 0).

[0122]

[0123] In formulas (6-1) to (6-2) above, the multiple Rs are synonymous with the R in formula (6). That is, the multiple Rs are either the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0124] Compound (F) is not limited to the compounds shown in formulas (6-1) to (6-2) above. Compound (F) can be used alone or in combination of two or more types.

[0125] From the viewpoint of reactivity, a compound (F) that does not have a hydroxyl group is preferred as compound (F).

[0126] <Other Compounds> The polythiol composition may also contain other compounds as needed.

[0127] Other compounds include, for example, compounds (G1) to (G3) shown in formulas (7-1) to (7-3) below.

[0128]

[0129] In the above formulas (7-1) to (7-3), the multiple Rs are either the same or different in phase, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0130] In formulas (7-1) to (7-3) above, R is preferably the same as R in formula (1) above.

[0131] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formulas (7-1) to (7-3) above include the divalent hydrocarbon groups having 1 to 6 carbon atoms exemplified as R in formula (1) above, and specifically include the divalent linear hydrocarbon groups having 1 to 6 carbon atoms and the divalent branched hydrocarbon groups having 3 to 6 carbon atoms mentioned above.

[0132] In formulas (7-1) to (7-3) above, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene; more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene; even more preferably methylene, ethylene, and iso-propylene; even more preferably methylene and ethylene; and particularly preferably ethylene.

[0133] As will be explained in more detail later, compound (G1) represented by formula (7-1) above is obtained by reacting 1 mole of mercaptocarboxylic acid with 1 mole of pentaerythritol. Compound (G2) represented by formula (7-2) above is obtained by reacting 2 moles of mercaptocarboxylic acid with 1 mole of pentaerythritol. Compound (G3) represented by formula (7-3) above is obtained by reacting 3 moles of mercaptocarboxylic acid with 1 mole of pentaerythritol.

[0134] <Method for producing polythiol compositions> Polythiol compositions are obtained by reacting a dithioacetal compound with a mercaptocarboxylic acid and pentaerythritol. More specifically, polythiol compositions are obtained by reacting a monoaldehyde with a mercaptocarboxylic acid and pentaerythritol.

[0135] More specifically, the method for producing the polythiol composition comprises: a first step of bonding two molecules of mercaptocarboxylic acid with one carbon atom to obtain a dithioacetal compound; a second step of reacting the dithioacetal compound, mercaptocarboxylic acid, and pentaerythritol to obtain a reaction solution containing the above compound (A) and the above compound (B); and a third step of neutralizing the reaction solution by adding a neutralizing agent, and then purifying the reaction solution by liquid-liquid separation.

[0136] [Step 1] In Step 1, two molecules of mercaptocarboxylic acid are bonded together by one carbon atom to obtain a dithioacetal compound.

[0137] In the first step, the method for obtaining the dithioacetal compound is not particularly limited, but for example, a monoaldehyde represented by formula (8) below and a mercaptocarboxylic acid represented by formula (9) below are mixed and heated.

[0138]

[0139] In formula (8) above, R' represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, and propyl. R' preferably represents a hydrogen atom.

[0140] More specifically, examples of monoaldehydes represented by formula (8) above include formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. Formaldehyde is a preferred example of the monoaldehyde. Monoaldehydes can be used alone or in combination of two or more types.

[0141] In formula (9) above, R represents a divalent hydrocarbon group having 1 to 6 carbon atoms.

[0142] In formula (9) above, R is preferably the same as R in formula (1) above.

[0143] In other words, examples of the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R in formula (9) above include the divalent hydrocarbon group having 1 to 6 carbon atoms exemplified as R in formula (1) above, and specifically include the divalent linear hydrocarbon group having 1 to 6 carbon atoms and the divalent branched hydrocarbon group having 3 to 6 carbon atoms mentioned above.

[0144] In the above formula (9), the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R is preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, iso-butylene, s-butylene, and t-butylene; more preferably methylene, ethylene, n-propylene, n-butylene, iso-propylene, and iso-butylene; even more preferably methylene, ethylene, and iso-propylene; even more preferably methylene and ethylene; and particularly preferably ethylene.

[0145] More specifically, examples of mercaptocarboxylic acids represented by formula (9) above include mercaptoacetic acid (thioglycolic acid), mercaptopropionic acid (3-mercaptopropionic acid), and mercaptobutyric acid (3-mercaptobutyric acid), preferably mercaptoacetic acid and mercaptopropionic acid, and more preferably mercaptopropionic acid. Mercaptocarboxylic acids can be used alone or in combination of two or more types.

[0146] The blending ratio of monoaldehyde to mercaptocarboxylic acid is adjusted based on the equivalent ratio of the mercapto group of mercaptocarboxylic acid to the aldehyde group of monoaldehyde (mercapto group / aldehyde group). More specifically, the equivalent ratio of the mercapto group of mercaptocarboxylic acid to the aldehyde group of monoaldehyde (mercapto group / aldehyde group) is, for example, greater than 2 and 100 or less, preferably 3 to 50 or less, and more preferably 10 to 25 or less.

[0147] Furthermore, the reaction between the monoaldehyde and the mercaptocarboxylic acid preferably occurs in the presence of a catalyst. Examples of catalysts include known dehydration catalysts, specifically p-toluenesulfonic acid. The catalyst can be used alone or in combination of two or more. The amount and timing of catalyst addition are determined as appropriate.

[0148] Furthermore, the monoaldehyde and mercaptocarboxylic acid preferably react in a solvent. Examples of solvents include aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated aliphatic hydrocarbons. Examples of aliphatic hydrocarbons include n-hexane, n-heptane, and octane. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of halogenated aliphatic hydrocarbons include chloroform and dichloroethane. Aromatic hydrocarbons are preferably used as solvents. Toluene is more preferably used as a solvent. The solvent can be used alone or in combination of two or more types. The amount and timing of solvent addition can be set as appropriate.

[0149] In the reaction between monoaldehyde and mercaptocarboxylic acid, the reaction temperature is, for example, 80°C to 150°C, preferably 100°C to 130°C. The reaction time is, for example, 0.5 hours to 6 hours, preferably 1 hour to 3 hours.

[0150] As a result of the above reaction, one molecule of monoaldehyde and two molecules of mercaptocarboxylic acid undergo a dehydration reaction, as shown in formula (10) below, to obtain a dithioacetal compound represented by formula (11) below.

[0151]

[0152] In formulas (10) and (11) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. R' represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0153] Dithioacetal compounds are reaction products of one molecule of monoaldehyde and two molecules of mercaptocarboxylic acid. Dithioacetal compounds are contained in the reaction solution obtained by the reaction of monoaldehyde and mercaptocarboxylic acid.

[0154] Furthermore, as described above, the equivalent ratio of the mercapto group of the mercaptocarboxylic acid to the aldehyde group of the monoaldehyde (mercapto group / aldehyde group) is, for example, greater than 2. In such cases, the reaction solution obtained by the reaction of the monoaldehyde and the mercaptocarboxylic acid contains unreacted mercaptocarboxylic acid. In other words, in the first step, preferably, a reaction solution containing the dithioacetal compound and unreacted mercaptocarboxylic acid is obtained.

[0155] In the above reaction, the condensation water produced as a by-product is removed by known methods as necessary.

[0156] [Step 2] In Step 2, a dithioacetal compound and a mercaptocarboxylic acid are reacted with pentaerythritol to obtain a reaction solution containing compound (A) and compound (B).

[0157] More specifically, for example, if a reaction solution containing a dithioacetal compound and unreacted mercaptocarboxylic acid is obtained in the first step described above, then in the second step, pentaerythritol is added to the reaction solution obtained in the first step, and the dithioacetal compound and mercaptocarboxylic acid are reacted with the pentaerythritol.

[0158] The proportion of pentaerythritol is adjusted, for example, based on the equivalent ratio (hydroxyl group / carboxyl group) of the hydroxyl groups of pentaerythritol to the carboxyl groups of the mercaptocarboxylic acid used in the first step. More specifically, the equivalent ratio (hydroxyl group / carboxyl group) of the hydroxyl groups of pentaerythritol to the carboxyl groups of the mercaptocarboxylic acid used in the first step is, for example, 0.75 to 3.0, preferably 0.85 to 2.0, and more preferably 0.95 to 1.2.

[0159] Furthermore, for example, the amount of pentaerythritol blended with 1 mole of mercaptocarboxylic acid used in the first step is, for example, 0.18 moles or more and 0.75 moles or less, preferably 0.21 moles or more and 0.50 moles or less, and more preferably 0.23 moles or more and 0.30 moles or less.

[0160] Furthermore, for example, if the reaction solution obtained in the first step does not contain unreacted mercaptocarboxylic acid, or if the amount of unreacted mercaptocarboxylic acid in the reaction solution is relatively small, then in the second step, for example, pentaerythritol and mercaptocarboxylic acid may be added to the reaction solution obtained in the first step according to the equivalent ratio described above.

[0161] Furthermore, the dithioacetal compound and mercaptocarboxylic acid react with pentaerythritol, preferably in the presence of a catalyst. Examples of catalysts include known esterification catalysts, specifically p-toluenesulfonic acid. The catalyst can be used alone or in combination of two or more. The amount and timing of catalyst addition are determined as appropriate.

[0162] Furthermore, the dithioacetal compound and the mercaptocarboxylic acid react with pentaerythritol in the solvent described above. The amount and timing of the solvent addition are set as appropriate.

[0163] In the reaction between a dithioacetal compound and a mercaptocarboxylic acid and pentaerythritol, the reaction temperature is, for example, 80°C to 150°C, preferably 100°C to 130°C. The reaction time is, for example, 0.5 hours to 24 hours, preferably 3 hours to 12 hours.

[0164] As a result of the above reaction, the dithioacetal compound and the mercaptocarboxylic acid are esterified with pentaerythritol, as shown in formula (12) below, to obtain compounds (A) and (B).

[0165]

[0166] The reaction product shown in the above reaction formula (12) is the same as compound (A) shown in formula (1) and compound (B) shown in formula (2). In formula (12), R, a1, b1, c1, f1, g1, and h1 are equivalent to those in formula (1) and formula (2), respectively.

[0167] More specifically, in the reaction shown in formula (12) above, for example, as shown in formula (13) below, two pentaerythritols undergo an esterification reaction with one dithioacetal compound to obtain the reaction product (14).

[0168]

[0169] In equation (13) above, R is the same as R in equation (3) above.

[0170] Furthermore, in the reaction shown in formula (12) above, as shown in formula (15) below, 6 moles of mercaptocarboxylic acid are esterified to the reaction product (14) of the pentaerythritol and the dithioacetal compound, yielding compound (B) containing six constituent units derived from mercaptocarboxylic acid.

[0171]

[0172] The reaction product shown in reaction formula (15) above is compound (B) shown in formula (2) above (where d1 and e1 represent 1). In reaction formula (15) above, R, a1, b1, c1, f1, g1 and h1 are equivalent to those in formula (2) above.

[0173] In addition, as shown in the reaction formula (16) below, the reaction product (14) of pentaerythritol and a dithioacetal compound may react with mercaptocarboxylic acid to obtain compound (C).

[0174] In this reaction, five moles of mercaptocarboxylic acid react with the reaction product (14) of pentaerythritol and a dithioacetal compound to obtain compound (C) containing five structural units derived from mercaptocarboxylic acid. In such cases, the polythiol composition contains compound (C).

[0175]

[0176] The reaction product shown in reaction formula (10) above is compound (C) shown in formula (3) above (where d2 and e2 represent 1). In reaction formula (10) above, R, a2, b2, c2, f2, g2 and h2 are equivalent to those in formula (3) above.

[0177] In addition, as shown in the reaction formula (17) below, the reaction product (14) of pentaerythritol and a dithioacetal compound may react with mercaptocarboxylic acid to obtain compound (D).

[0178] In this reaction, four moles of mercaptocarboxylic acid react with the reaction product (14) of pentaerythritol and a dithioacetal compound to obtain compound (D) containing four structural units derived from mercaptocarboxylic acid. In such cases, the polythiol composition contains compound (D).

[0179]

[0180] The reaction product shown in reaction formula (17) above is compound (D) shown in formula (4) above (where d3 and e3 represent 1). In reaction formula (11) above, R, a3, b3, c3, f3, g3 and h3 are equivalent to those in formula (4) above.

[0181] In addition, as shown in the reaction formula (18) below, the reaction product (14) of pentaerythritol and a dithioacetal compound may react with mercaptocarboxylic acid to obtain compound (E).

[0182] In this reaction, 7 moles of mercaptocarboxylic acid react with the reaction product (14) of pentaerythritol and a dithioacetal compound to obtain compound (E) containing 7 structural units derived from mercaptocarboxylic acid. In such cases, the polythiol composition contains compound (E).

[0183]

[0184] The reaction product shown in reaction formula (18) above is compound (E) shown in formula (5) above (where d4 and e4 represent 1). In reaction formula (12) above, the multiple R, a4, b4, c4, f4, g4 and h4 are equivalent to those in formula (5) above.

[0185] In addition, as shown in the reaction formula (19) below, the reaction product (14) of pentaerythritol and a dithioacetal compound may react with mercaptocarboxylic acid to obtain compound (F).

[0186] In this reaction, eight moles of mercaptocarboxylic acid react with the reaction product (14) of pentaerythritol and a dithioacetal compound to obtain compound (F) containing eight structural units derived from mercaptocarboxylic acid. In such cases, the polythiol composition contains compound (F).

[0187]

[0188] The reaction product shown in reaction formula (19) above is compound (F) shown in formula (6) above (where d5 and e5 represent 1). In reaction formula (12) above, the multiple R, a5, b5, c5, f5, g5 and h5 are equivalent to each of the values ​​in formula (6) above.

[0189] In addition, as shown in the reaction equation (20) below, 1 mole of unreacted pentaerythritol reacts with 4 moles of mercaptocarboxylic acid to obtain compound (A).

[0190]

[0191] In the above reaction equation (20), the multiple Rs are equivalent to the Rs in equation (1) above.

[0192] In addition, one mole of unreacted pentaerythritol may react with one mole of mercaptocarboxylic acid, two moles of mercaptocarboxylic acid, or three moles of mercaptocarboxylic acid.

[0193] More specifically, as shown in reaction equation (21) below, when 1 mole of mercaptocarboxylic acid reacts with 1 mole of unreacted pentaerythritol, compound (G1) is obtained. Also, as shown in reaction equation (22) below, when 2 moles of mercaptocarboxylic acid react with 1 mole of unreacted pentaerythritol, compound (G2) is obtained. As shown in reaction equation (23) below, when 3 moles of mercaptocarboxylic acid react with 1 mole of unreacted pentaerythritol, compound (G3) is obtained.

[0194]

[0195] Furthermore, the above reaction can be carried out in the same solvent, in the presence of the same esterification catalyst, and under the same reaction conditions as the reaction between pentaerythritol and a dithioacetal compound.

[0196] [Third Step] In the third step, a neutralizing agent is added to the reaction solution to neutralize it, and then the reaction solution is purified by liquid-liquid separation. Liquid-liquid separation is an operation in which the reaction solution is separated into an organic phase and an aqueous phase, and then the organic phase is removed to extract the polythiol composition.

[0197] Specifically, first, a neutralizing agent (for example, aqueous ammonia) is added to the reaction solution to neutralize it.

[0198] Next, the reaction mixture is purified by liquid-liquid separation. Specifically, water is added to the reaction mixture to separate it into an aqueous phase and an organic phase. At this time, the aqueous phase contains an esterification catalyst, and the organic phase contains a polythiol composition comprising compound (A), compound (B), compound (C) obtained as needed, compound (D) obtained as needed, compound (E) obtained as needed, compound (F) obtained as needed, compound (G1) obtained as needed, compound (G2) obtained as needed, and compound (G3) obtained as needed. After that, the organic layer is removed and, if necessary, distilled.

[0199] As a result, a polythiol composition is obtained comprising compound (A), compound (B), compound (C) obtained as needed, compound (D) obtained as needed, compound (E) obtained as needed, compound (F) obtained as needed, compound (G1) obtained as needed, compound (G2) obtained as needed, and compound (G3) obtained as needed.

[0200] The polythiol composition may be diluted with a solvent as needed. Examples of solvents include those listed above.

[0201] The solid content concentration of the diluted polythiol composition (the polythiol composition does not contain a solvent) is, for example, 10% to 70% by mass.

[0202] Alternatively, for example, compound (A) represented by formula (1) above can be produced and purified by known methods, and then the reaction product solution from the above reaction and compound (A) represented by formula (1) above can be mixed so that the content ratio of each component described later is within a predetermined range, thereby obtaining a polythiol composition.

[0203] Furthermore, for example, in multiple formulations, reaction product solutions are prepared in the above reaction, and multiple reaction product solutions are mixed so that the content ratio of each component described later falls within a predetermined range to obtain a polythiol composition.

[0204] <Content ratio of each component> As described above, the polythiol composition contains compound (A), compound (B), compound (C) obtained as needed, compound (D) obtained as needed, compound (E) obtained as needed, compound (F) obtained as needed, compound (G1) obtained as needed, compound (G2) obtained as needed, and compound (G3) obtained as needed.

[0205] The content of each component can be estimated based on the peak area assigned to each component by high-performance liquid chromatography (HCM) measurement using a UV detector with a measurement wavelength of 200 nm. More specifically, the HCM measurement is not particularly limited as long as it uses a UV detector with a measurement wavelength of 200 nm and allows each component to be separated as a single peak, but for example, reverse-phase chromatography is used. Specifically, first, the molecular weight of the detected peak is determined using a liquid chromatograph-mass spectrometer (reverse-phase chromatography), and each component is identified based on that molecular weight. Next, the HCM measurement described above is performed, and the peaks of each component are assigned by correlating the detected peaks in the liquid chromatograph-mass spectrometer with the detected peaks in the HCM. More specifically, the measurement conditions other than the detector for HCM measurement will be described in detail in the examples below.

[0206] The peak area of ​​compound (B) is 40.0 area% or less, preferably 25.0 area% or less, more preferably 10.0 area% or less, even more preferably 5.0 area% or less, particularly preferably 1.0 area% or less, and also, for example, 0.1 area% or more, relative to 100 area% of the peak area of ​​compound (A).

[0207] If the peak area of ​​compound (B) relative to 100 area% of the peak area of ​​compound (A) is less than or equal to the above upper limit, then resistance to yellowing can be improved.

[0208] On the other hand, if the peak area of ​​compound (B) relative to 100 area% of the peak area of ​​compound (A) exceeds the above upper limit, resistance to yellowing decreases.

[0209] Furthermore, if the peak area of ​​compound (B) relative to 100 area% of the peak area of ​​compound (A) is above the above lower limit, the ease of dyeing by the dye (hereinafter referred to as dyeability) is improved.

[0210] The peak area of ​​compound (B) is, from the viewpoint of resistance to yellowing, for example, 15.0 area% or less, preferably 10.0 area% or less, more preferably 5.0 area% or less, even more preferably 1.0 area% or less, and particularly preferably 0.5 area% or less, relative to 100 area% of the peak area of ​​the polythiol composition (100 area% of all peaks measured in the examples described later, the same applies hereinafter). From the viewpoint of stainability, it is, for example, 0.1 area% or more.

[0211] Furthermore, the retention time of compound (B) in the examples described later is 25.0 minutes to 32.0 minutes.

[0212] The peak area of ​​compound (C) is, from the viewpoint of resistance to yellowing, for example, 12.0 area% or less, preferably 10.0 area% or less, more preferably 5.0 area% or less, even more preferably 3.0 area% or less, and particularly preferably 1.0 area% or less, relative to 100 area% of the peak area of ​​compound (A). From the viewpoint of stainability, it is, for example, 0.1 area% or more.

[0213] The peak area of ​​compound (C) is, from the viewpoint of resistance to yellowing, for example, 5.0 area% or less, preferably 3.0 area% or less, more preferably 1.0 area% or less, even more preferably 0.5 area% or less, and particularly preferably 0.1 area% or less, relative to 100 area% of the peak area of ​​the polythiol composition. From the viewpoint of stainability, it is, for example, 0.01 area% or more.

[0214] Furthermore, the polythiol composition does not need to contain compound (C).

[0215] Furthermore, the retention time of compound (C) in the examples described later is 14.0 minutes to 18.0 minutes.

[0216] The peak area of ​​compound (D) is, from the viewpoint of resistance to yellowing, for example, 2.0 area% or less, preferably 1.5 area% or less, more preferably 1.0 area% or less, even more preferably 0.5 area% or less, and particularly preferably 0.1 area% or less, relative to 100 area% of the peak area of ​​compound (A). From the viewpoint of stainability, it is, for example, 0.01 area% or more.

[0217] The peak area of ​​compound (D) is, from the viewpoint of resistance to yellowing, for example, 1.0 area% or less, preferably 0.7 area% or less, more preferably 0.5 area% or less, even more preferably 0.3 area% or less, and particularly preferably 0.1 area% or less, relative to 100 area% of the peak area of ​​the polythiol composition. From the viewpoint of stainability, it is, for example, 0.01 area% or more.

[0218] Furthermore, the polythiol composition does not necessarily have to contain compound (D).

[0219] Furthermore, the retention time of compound (D) in the examples described later is 6.0 minutes to 9.0 minutes.

[0220] The peak area of ​​compound (E) is, from the viewpoint of resistance to yellowing, for example, 10.0 area% or less, preferably 7.0 area% or less, more preferably 5.0 area% or less, even more preferably 3.0 area% or less, and particularly preferably 1.0 area% or less, relative to 100 area% of the peak area of ​​compound (A). From the viewpoint of stainability, it is, for example, 0.01 area% or more.

[0221] The peak area of ​​compound (E) is, from the viewpoint of resistance to yellowing, for example, 5.0 area% or less, preferably 3.0 area% or less, more preferably 1.0 area% or less, even more preferably 0.5 area% or less, and particularly preferably 0.10 area% or less, relative to 100 area% of the peak area of ​​the polythiol composition. From the viewpoint of stainability, for example, 0 area% or more, preferably 0.01 area% or more.

[0222] Furthermore, the polythiol composition does not need to contain compound (E).

[0223] Furthermore, the retention time of compound (E) in the examples described later is 40.0 minutes to 47.0 minutes.

[0224] The peak area of ​​compound (F) is, from the viewpoint of resistance to yellowing, for example, 1.5 area% or less, preferably 1.0 area% or less, more preferably 0.5 area% or less, even more preferably 0.1 area% or less, and particularly preferably 0.05 area% or less, relative to 100 area% of the peak area of ​​compound (A). From the viewpoint of stainability, it is, for example, 0.01 area% or more.

[0225] The peak area of ​​compound (F) is, from the viewpoint of resistance to yellowing, for example, 0.5 area% or less, preferably 0.3 area% or less, more preferably 0.2 area% or less, even more preferably 0.1 area% or less, and particularly preferably 0.05 area% or less, relative to 100 area% of the peak area of ​​the polythiol composition. From the viewpoint of stainability, for example, 0.01 area% or more.

[0226] Furthermore, the polythiol composition does not necessarily have to contain compound (F).

[0227] Furthermore, the retention time of compound (F) in the examples described later is 48.0 minutes to 56.0 minutes.

[0228] The peak area of ​​compound (G1) is, from the viewpoint of liquid-liquid properties, for example, 1.0 area% or less, preferably 0.1 area% or less, and more preferably 0 area%, relative to 100 area% of the peak area of ​​compound (A). In other words, more preferably, the polythiol composition does not contain compound (G1).

[0229] Furthermore, the retention time of compound (G1) in the examples described later is 1.0 to 3.0 minutes.

[0230] The peak area of ​​compound (G2) is, from the viewpoint of liquid-liquid properties, for example, 1.0 area% or less, preferably 0.1 area% or less, and more preferably 0 area%, relative to 100 area% of the peak area of ​​compound (A). In other words, more preferably, the polythiol composition does not contain compound (G2).

[0231] Furthermore, the retention time of compound (G2) in the examples described later is 2.0 to 4.0 minutes.

[0232] The peak area of ​​compound (G3) is, from the viewpoint of liquid-liquid properties, for example, 1.0 area% or less, preferably 0.1 area% or less, and more preferably 0 area%, relative to 100 area% of the peak area of ​​compound (A). In other words, more preferably, the polythiol composition does not contain compound (G3).

[0233] Furthermore, the retention time of compound (G3) in the examples described later is 4.0 to 6.0 minutes.

[0234] The peak area of ​​compound (A) is, for example, 50.0 area% to 70.0 area% of the peak area of ​​the polythiol composition, preferably 55.0 area% to 68.0 area% and more preferably 60.0 area% to 65.0 area%.

[0235] More specifically, the peak area of ​​compound (A) is, from the viewpoint of resistance to yellowing, for example, 50.0 area% or more, preferably 55.0 area% or more, and more preferably 60.0 area% or more, relative to 100 area% of the peak area of ​​the polythiol composition. From the viewpoint of stainability, for example, 70.0 area% or less, preferably 68.0 area% or less, and more preferably 65.0 area% or less.

[0236] Furthermore, the retention time of compound (A) in the examples described later is 7.5 to 9.0 minutes.

[0237] Furthermore, if the molar extinction coefficients at 200 nm for each component can be considered identical, the peak area can be directly estimated as the mass ratio.

[0238] The proportions of each component mentioned above can be adjusted, for example, by changing the proportion of monoaldehyde, mercaptocarboxylic acid, pentaerythritol, and the reaction conditions.

[0239] Furthermore, as described above, the reaction product of monoaldehyde, mercaptocarboxylic acid, and pentaerythritol can be mixed with compound (A) represented by formula (1) above, and the proportion of each component can be adjusted.

[0240] Furthermore, for example, in multiple formulations, it is possible to prepare reaction product solutions in the above reaction, mix multiple reaction product solutions, and adjust the content ratio of each of the above-mentioned components.

[0241] Furthermore, the polythiol composition contains compound (A) and compound (B), and in high-performance liquid chromatography measurements detected with a 200 nm ultraviolet detector, the peak area of ​​compound (B) is 40.0 area% or less compared to the peak area of ​​compound (A) at 100 area%. Therefore, staining properties and resistance to yellowing can be improved.

[0242] Therefore, polythiol compositions can be suitably used in the production of polymerizable compositions for optical materials.

[0243] 2. Polymerizable compositions for optical materials Polymerizable compositions for optical materials are compositions used in the manufacture of optical materials.

[0244] The polymerizable composition for optical materials comprises an isocyanate compound and the above-mentioned polythiol composition.

[0245] <Isocyanate Compounds> Examples of isocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

[0246] Examples of aliphatic polyisocyanates include aliphatic diisocyanates. Examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate (1,6-HDI), 1,5-pentamethylene diisocyanate (1,5-PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate.

[0247] Examples of alicyclic polyisocyanates include alicyclic diisocyanates. Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-,2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or mixtures thereof (H １２ MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H６ Examples include XDI, bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0248] Examples of aromatic polyisocyanates include aromatic diisocyanates. Examples of aromatic diisocyanates include 4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4-, or 2,6-tolylene diisocyanate or a mixture thereof (TDI), o-tolidine diisocyanate, 1,5-naphthalene diisocyanate (NDI), m-, or p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate.

[0249] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates. Examples of aromatic aliphatic diisocyanates include xylylene diisocyanate (1,2-, 1,3-, or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), 1,3-, or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), and ω,ω'-diisocyanate-1,4-diethylbenzene.

[0250] Isocyanate compounds include the polyisocyanate derivatives described above.

[0251] Examples of polyisocyanate derivatives include polymers of the polyisocyanates mentioned above, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretodione derivatives, and uretonimine derivatives.

[0252] Examples of polyisocyanate derivatives include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI, polynuclear-containing diphenylmethane diisocyanate) and carbodiimide-modified polymethylene polyphenyl polyisocyanate.

[0253] Preferably, the isocyanate compound is an alicyclic polyisocyanate. More preferably, the isocyanate compound is 1,3-H ６ Examples include XDI and NBDI.

[0254] Isocyanate compounds can be used alone or in combination of two or more types.

[0255] The proportion of the isocyanate compound is, for example, 40 to 60 parts by mass, preferably 48 to 55 parts by mass, based on 100 parts by mass of the total amount of the isocyanate compound, the polythiol composition (solid content), and other components (described later).

[0256] <Polythiol Composition> The polythiol composition content is, for example, 10 to 30 parts by mass, preferably 20 to 26 parts by mass, based on 100 parts by mass of the total amount of the isocyanate compound, the polythiol composition (solid content), and other components (described later).

[0257] <Other Components> Polymerizable compositions for optical materials may also contain other components as needed.

[0258] Other components include other polythiol compounds and polyol compounds.

[0259] Other polythiol compounds are compounds other than those in the polythiol composition described above.

[0260] Other examples of polythiol compounds include those described in International Publication No. 2008 / 105138.

[0261] Other polythiol compounds include, for example, bis(mercaptoethyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-di Examples include mercapto-3,6,9-trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, and ethylene glycol bis(3-mercaptopropionate). Other polythiol compounds that are preferred include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0262] Other polythiol compounds can be used alone or in combination of two or more.

[0263] Examples of polyol compounds include those described in International Publication No. 2017 / 047684.

[0264] The other components preferably consist of other polythiol compounds and do not contain polyol compounds.

[0265] The proportion of other components is, for example, 10 to 30 parts by mass, preferably 20 to 26 parts by mass, based on 100 parts by mass of the total amount of the isocyanate compound, the polythiol composition (solids), and the other components.

[0266] Furthermore, the equivalent ratio of active hydrogen groups (the total amount of thiol groups in the polythiol composition, thiol groups in other polythiol compounds, and hydroxyl groups in the polyol compound) to the isocyanate groups of the isocyanate compound is, for example, 0.5 to 3.0, preferably 0.6 to 2.0, and more preferably 0.8 to 1.3.

[0267] <Additives> Polymerizable compositions for optical materials may contain additives in appropriate proportions as needed. Examples of additives include polymerization catalysts (e.g., dibutyltin dichloride), ultraviolet absorbers (e.g., 2-(2H-benzotriazole-2-yl)-4-tert-octylphenol), mold release agents (e.g., acidic phosphate esters), modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, antioxidants, fillers, adhesion enhancers, antibacterial agents, and antistatic agents.

[0268] Additives can be used individually or in combination of two or more types.

[0269] The polymerizable composition for optical materials contains the above-mentioned polythiol composition. Therefore, the polymerizable composition for optical materials has excellent dyeability and resistance to yellowing. Because the polymerizable composition for optical materials has excellent dyeability and resistance to yellowing, it can be suitably used in the manufacture of molded articles for producing optical materials.

[0270] 3. The molded article contains a cured product of a polymerizable composition for optical materials.

[0271] The molded article is obtained by curing and molding a polymerizable composition for optical materials.

[0272] The molding method is not particularly limited and includes, for example, casting and heat compression molding. Casting is preferred as the molding method.

[0273] In casting, for example, a polymerizable composition for optical materials is degassed, then injected into a molding mold and heated.

[0274] The heating conditions include a heating temperature of, for example, 40°C to 150°C, and a heating time of, for example, 1 hour to 50 hours. Preferably, the temperature is gradually raised from 10°C to 120°C over 1 hour to 50 hours.

[0275] As a result, the polymerizable composition for optical materials hardens and is molded, yielding a molded article.

[0276] The glass transition temperature of the molded article is, for example, 90°C or higher, preferably 95°C or higher, more preferably 100°C or higher, even more preferably 105°C or higher, particularly preferably 110°C or higher, most preferably 115°C or higher, and also, for example, 150°C or lower.

[0277] If the glass transition temperature of the molded product is above the lower limit mentioned above, the heat resistance can be improved.

[0278] The method for measuring the glass transition temperature of the molded body will be described in detail in the examples below.

[0279] The refractive index of the molded article is, for example, 1.57 or higher, preferably 1.60 or higher, and for example, 1.80 or lower.

[0280] The total light transmittance of the molded article (JIS K 7375-2008) is, for example, 80% or more, preferably 90% or more, and more preferably 95% or more.

[0281] The molded article contains a cured product of a polymerizable composition for optical materials. Therefore, the molded article has excellent dyeability and resistance to yellowing. Because the molded article has excellent dyeability and resistance to yellowing, it can be suitably used in the manufacture of optical materials.

[0282] 4. Optical materials: Optical materials consist of molded bodies.

[0283] Optical materials are materials used to manufacture optical components. Examples of optical components include plastic lenses, headlamp covers, reflectors, spot lamps, and polarizing lenses.

[0284] Furthermore, optical materials are dyed according to their application and purpose.

[0285] To stain optical materials, first prepare a dye dispersion.

[0286] To prepare a dye dispersion, the dye is dispersed in water.

[0287] The dyes are not particularly limited and include well-known dyes. Specifically, the Dianix series (manufactured by Dystar) can be mentioned.

[0288] Next, the optical material is immersed in a dye dispersion.

[0289] The immersion conditions include an immersion temperature of, for example, 40°C to 120°C, preferably 70°C to 100°C. The immersion time is, for example, 10 minutes to 60 minutes.

[0290] This process stains the optical material.

[0291] On the other hand, the optical material is made of the molded body described above. Therefore, it has excellent dyeability and resistance to yellowing.

[0292] <Effects> The polythiol composition contains compound (A) and compound (B). In high-performance liquid chromatography measurements using a 200 nm ultraviolet detector, the peak area of ​​compound (B) is 40.0 area% or less compared to the peak area of ​​compound (A) (100 area%). Therefore, staining properties and resistance to yellowing can be improved.

[0293] <Modified Examples> In the modified examples, the same reference numerals are used for components and processes as in the first embodiment, and their detailed descriptions are omitted. Furthermore, the modified examples can achieve the same effects and advantages as the first embodiment, unless otherwise specified. Moreover, the first embodiment and its modified examples can be combined as appropriate.

[0294] In the above explanation, first, in the first step, a monoaldehyde and a mercaptocarboxylic acid are reacted to obtain a reaction solution containing a dithioacetal compound and unreacted mercaptocarboxylic acid. Then, in the second step, pentaerythritol is added to the reaction solution to react the dithioacetal compound and the unreacted mercaptocarboxylic acid with the pentaerythritol. By this method, a compound in which d1 and e1 are 1 in chemical formula (B) shown in formula (2) above is obtained.

[0295] On the other hand, first, in the first step, a monoaldehyde and a mercaptocarboxylic acid are reacted to obtain a reaction solution containing a dithioacetal compound and unreacted mercaptocarboxylic acid. Then, the dithioacetal compound and the mercaptocarboxylic acid are reacted further to add the mercaptocarboxylic acid to the molecular terminus of the dithioacetal compound by thioester condensation. In other words, a thioester condensate of the dithioacetal compound and mercaptocarboxylic acid can be obtained. Subsequently, in this method, the thioester condensate of the dithioacetal compound and mercaptocarboxylic acid, and the unreacted mercaptocarboxylic acid can be reacted with pentaerythritol. By this method, a compound in which d1 and / or e1 is 2 in compound (B) shown in formula (2) above can be produced.

[0296] Furthermore, for example, the monoaldehyde used in the first step and the pentaerythritol used in the second step can be obtained by, for example, decomposing bispentaerythritol.

[0297] The specific numerical values ​​such as blending ratios (content percentages), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numbers defined as "less than or equal to" or "less than") or lower limits (numbers defined as "greater than or equal to" or "greater than") of the blending ratios (content percentages), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above. Furthermore, unless otherwise specified in the following description, "parts" and "%" refer to mass.

[0298] <Production of Polythiol Composition> Comparative Example 1 In a reactor equipped with a Dean Stark tube, 8.5 g of pentaerythritol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.3 g of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 12.2 g of toluene were mixed. The reaction temperature was then gradually increased from room temperature to a reflux state. The mixture was mixed for 2 hours and then allowed to cool to room temperature.

[0299] 26.3 g of 3-mercaptopropionic acid (purified product) was added to the mixture, and the reaction temperature was gradually increased from room temperature to reflux. At this time, the internal temperature rose to 115°C, and the by-product water was continuously removed under reflux. The amount of water removed totaled 95.2% of the theoretically produced water. After reacting for 8 hours, it was allowed to cool to room temperature.

[0300] 5.9 g of 1% ammonia aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution and neutralized to neutral conditions. After stirring and washing for 15 minutes, the upper aqueous solution was separated, 12.5 g of pure water (first time) was added, and stirring and washing was performed for 15 minutes, after which the upper aqueous solution was separated. Again, 12.5 g of pure water (second time) was added, and stirring and washing was performed for 15 minutes, and the upper aqueous solution was separated. As a result, a toluene solution of the polythiol composition was obtained from the lower layer.

[0301] Next, toluene was removed using an evaporator, followed by holding under vacuum at 120°C for 3 hours, and then reduced-pressure filtration (PTFE (polytetrafluoroethylene), 3.0 μm) was performed to obtain 29.4 g of the polythiol composition. The formulation and reaction conditions are shown in Table 1.

[0302] Comparative Example 2 [Step 1] In a reactor fitted with a Dean Stark tube, 106.0 g of 3-mercaptopropionic acid (refined product), 4.1 g of 37% formaldehyde solution, 0.3 g of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 48.0 g of toluene were mixed. The reaction temperature was then gradually increased from room temperature to a reflux state. During this time, the water produced as a by-product under reflux was continuously drained. After reacting for 2 hours, the mixture was allowed to cool to room temperature. In the above reaction, the amount of 3-mercaptopropionic acid was approximately 1 mole, and the amount of formaldehyde (solid content 1.5 g) was approximately 0.05 moles. Based on these formulations, it was determined that the above reaction solution is a composition containing a dithioacetal compound and unreacted 3-mercaptopropionic acid.

[0303] [Step 2] 34.0 g of pentaerythritol was added to the reaction solution, and the reaction temperature was gradually increased from room temperature to a reflux state. At this time, the internal temperature rose to 115°C, and the by-product water was continuously removed under reflux. The amount of water removed totaled 93.2% of the theoretically produced water. After reacting for 8 hours, it was allowed to cool to room temperature.

[0304] [Step 3] 23.6 g of 1% ammonia aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution and neutralized to neutral conditions. After stirring and washing for 15 minutes, the upper aqueous solution was separated, 50.0 g of pure water (first time) was added, and stirring and washing was performed for 15 minutes, after which the upper aqueous solution was separated. Again, 50.0 g of pure water (second time) was added, and stirring and washing was performed for 15 minutes, and the upper aqueous solution was separated. As a result, a toluene solution of the polythiol composition was obtained from the lower layer.

[0305] Next, toluene was removed using an evaporator, followed by holding under vacuum at 120°C for 3 hours, and then reduced-pressure filtration (PTFE (polytetrafluoroethylene), 3.0 μm) was performed to obtain 29.4 g of the polythiol composition. The formulation and reaction conditions are shown in Table 1.

[0306] Manufacturing Examples 1-3 The polythiol composition of Manufacturing Comparative Example 1 and the polythiol composition of Manufacturing Comparative Example 2 were mixed. The mixing ratio was adjusted so that the proportions of each component shown in Table 1 were obtained in the HPLC analysis of the polythiol composition.

[0307] <Production of polymerizable composition and molded article for optical materials> Example 1 [Production of polymerizable composition for optical materials] In a flask equipped with a stirring device, dibutyltin dichloride (600 ppm by mass relative to the resulting polymerizable composition for optical materials) was added as a polymerization catalyst, Tinuvin 329 (BASF Japan, 2-(2H-benzotriazole-2-yl)-4-tert-octylphenol) (1000 ppm by mass relative to the resulting polymerizable composition for optical materials) was added as an ultraviolet absorber, Zelec-UN (Stephan, acidic phosphate ester) (1000 ppm by mass relative to the resulting polymerizable composition for optical materials) was added as a release agent, and NBDI was added as an isocyanate compound. 51 parts by mass of the compound, 25 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (T-1) as another polythiol compound, and 24 parts by mass (solid content) of the polythiol composition from Production Example 1 were mixed and stirred at room temperature (25°C) for 1 hour to produce a polymerizable composition for optical materials (a transparent homogeneous solution).

[0308] [Manufacturing of Molded Articles] The polymerizable composition for optical materials was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then thoroughly degassed under reduced pressure of 600 Pa until no foaming was observed. Next, this polymerizable composition for optical materials was injected between a pair of glass molds fixed with tape. Then, the glass molds were placed in an oven, and the oven temperature was raised from 10°C to 120°C over 17 hours. This cured the polymerizable composition for optical materials, yielding a molded article (2.5 mm thick).

[0309] Examples 2 to 6 and Comparative Examples 1 to 4: Polymerizable compositions and molded articles for optical materials were produced based on the same procedure as in Example 1. However, the formulations of each component were changed based on Table 2.

[0310] <Evaluation> [High-Performance Liquid Chromatography Measurement] For each polythiol composition, first, the molecular weight of the detected peak was identified using a liquid chromatograph-mass spectrometer, and each component was identified based on that molecular weight. Next, high-performance liquid chromatography measurements were performed based on the following conditions. The detected peaks in the liquid chromatograph-mass spectrometer and the detected peaks in high-performance liquid chromatography were correlated, and the peaks of each component were assigned. From the above, the peak areas of each component (compound (A), compound (B), compound (C), compound (D), and compound (E)) contained in the polythiol composition, and the peak area of ​​the polythiol composition were determined. Then, the peak area of ​​each component relative to 100 area % of the peak area of ​​the polythiol composition, and the peak areas of compounds (B) to (E) relative to 100 area % of the peak area of ​​compound (A) were calculated. The results are shown in Table 2.

[0311] {Liquid Chromatography Mass Spectrometer Measurement Conditions} Column: YMC-Pack ODS-A (150 mm × 6.0 mm ID, 5 μl) Mobile Phase: 10 mM ammonium acetate aqueous solution / acetonitrile = 40 / 60 Sample: Mixed solution of 50 mg of polythiol composition and 5 mL of acetonitrile Detector: Ultraviolet detector with measurement wavelength of 200 nm, mass detector Flow Rate: 1.0 mL / min Column Temperature: 45°C

[0312] {High-Performance Liquid Chromatography Measurement Conditions} Column: Mightysil RP-18 GP (registered trademark) manufactured by Kanto Chemical Co., Ltd. (particle size S: 5 μm, column shape: Φ6 mm × 150 mm, product number: 25477-96) Mobile phase: Mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Sample: Mixed solution of 500 mg of polythiol composition and 5 mL of acetonitrile Detector: Ultraviolet detector with measurement wavelength of 200 nm Column temperature: 40°C Flow rate: 1.0 mL / min Injection volume: 1 μL

[0313] [Color] The color of the polythiol compositions in each example and comparative example was visually confirmed. The results are shown in Table 2.

[0314] Furthermore, the yellowness (Yellow Index, Y.I. value) of the molded articles of each example and comparative example was determined using a Konica Minolta CM-5 spectrophotometer. A lower yellowness value indicates superior hue.

[0315] [Heat Resistance] The glass transition temperature (Tg) was measured for the molded articles of each example and comparative example. Specifically, the glass transition temperature (Tg) was measured using the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10°C / min) with a Shimadzu TMA-60 thermomechanical analyzer. Specifically, the surface of the molded article was pressed with the above load, and the article was heated at the above heating rate while observing the surface hardness. The temperature at which the surface hardness changed was measured as the glass transition temperature. A higher glass transition temperature indicates better heat resistance. The results are shown in Table 2.

[0316] [Dyeability] The dyeability of the molded articles of each example and each comparative example was evaluated.

[0317] Specifically, the light transmittance (%) of the molded body was first measured from 350 nm to 800 nm, and from the measurement results, the light transmittance (%) at the maximum absorption wavelength of 460 nm was determined (sometimes referred to as the light transmittance before staining). The results are shown in Table 2.

[0318] Next, the molded body was dyed. Specifically, a dye dispersion was prepared by adding 0.05 g of Dianix Brown S-3R (dye manufactured by DyStar) to 1999.9 g of pure water and mixing. Then, the molded body was immersed in this dye dispersion at 90°C for 45 minutes. This dyed the molded body.

[0319] The light transmittance (%) of the molded body after staining was measured from 350 nm to 800 nm, and from the measurement results, the light transmittance (%) at the maximum absorption wavelength of 460 nm was determined (sometimes referred to as the light transmittance after staining). The results are shown in Table 2.

[0320] Next, the difference between the light transmittance before staining and the light transmittance after staining (light transmittance before staining - light transmittance after staining) was calculated and defined as the degree of staining. A higher degree of staining indicates superior staining performance. The results are shown in Table 2.

[0321]

[0322]

[0323] The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims described below.

[0324] The polythiol composition, polymerizable composition for optical materials, molded articles, and optical materials of the present invention are suitably used in plastic lenses.

Claims

1. A polythiol composition comprising compound (A) represented by the following formula (1) and compound (B) represented by the following formula (2), wherein, in high-performance liquid chromatography measurements detected with a UV detector at a measurement wavelength of 200 nm, the peak area of ​​compound (B) is 40.0 area % or less relative to 100 area % of the peak area of ​​compound (A). (In formula (1) above, the multiple Rs are either the same or different in phase, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.) (In formula (2) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a1, b1, c1, f1, g1, and h1 are the same or different in phase and represent 0 to 3. d1 and e1 are the same or different in phase and represent 1 to 2. The sum of a1, b1, c1, d1, e1, f1, g1, and h1 is 8.) 2. The polythiol composition according to claim 1, wherein in formula (2) above, d1 and e1 are 1.

3. The polythiol composition according to claim 1, further comprising compound (C) represented by the following formula (3). (In formula (3) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a2, b2, c2, f2, g2, and h2 are the same or different in phase and represent 0 to 3. d2 and e2 are the same or different in phase and represent 1 to 2. The sum of a2, b2, c2, d2, e2, f2, g2, and h2 is 7.) 4. The polythiol composition according to claim 1, further comprising compound (D) represented by the following formula (4). (In formula (4) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a3, b3, c3, f3, g3, and h3 are the same or different in phase and represent 0 to 3. d3 and e3 are the same or different in phase and represent 1 to 2. The sum of a3, b3, c3, d3, e3, f3, g3, and h3 is 6.) 5. The polythiol composition according to claim 1, further comprising compound (E) represented by the following formula (5). (In formula (5) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a4, b4, c4, f4, g4, and h4 are the same or different in phase and represent 0 to 3. d4 and e4 are the same or different in phase and represent 1 to 2. The sum of a4, b4, c4, d4, e4, f4, g4, and h4 is 9.) 6. A polymerizable composition for optical materials comprising an isocyanate compound and the polythiol composition according to any one of claims 1 to 5.

7. A molded article comprising a cured product of the polymerizable composition for optical materials described in claim 6.

8. An optical material comprising the molded body described in claim 7.

9. A plastic lens made of the optical material described in claim 8.

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