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

Abstract

This polythiol composition comprises a compound (A) represented by formula (1) and a compound (B) represented by formula (2). In high-performance liquid chromatography measurement performed using a prescribed detector, the peak area of the compound (B) is 0.10 area% to 10.00 area% inclusive 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 independently 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 independently represent a divalent hydrocarbon group having 1 to 6 carbon atoms; and a1, b1, c1, d1, e1, and f1 are the same as or different from one another and each independently represent an integer of 0 to 3, wherein the sum of a1, b1, c1, d1, e1, and f1 is 6.)

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 made of the molded body, and a plastic lens made of the optical material.

[0002] Conventionally, from the viewpoint 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, suppression of yellowing is required for optical materials according to their uses and purposes.

[0007] The present invention provides a polythiol composition excellent in dyeability and suppressing yellowing, 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 made of the molded body, and a plastic lens made 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 an ultraviolet detector at a measurement wavelength of 200 nm, the peak area of ​​compound (B) is 0.10 area% or more and 10.00 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, d1, e1, and f1 are the same or different in phase and represent integers from 0 to 3, and the sum of a1, b1, c1, d1, e1, and f1 is 6.)

[0009] The present invention [2] further comprises the polythiol composition described in [1] above, which includes a compound (C) represented by the following formula (3). (In formula (3) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms. a2, b2, c2, d2, e2, and f2 are the same or different and represent integers from 0 to 3, and the sum of a2, b2, c2, d2, e2, and f2 is 7.)

[0010] The present invention [3] further comprises the polythiol composition described in [1] or [2] above, which includes a compound (D) represented by the following formula (4). (In formula (4) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms. a3, b3, c3, d3, e3, and f3 are the same or different and represent integers from 0 to 3, and the sum of a3, b3, c3, d3, e3, and f3 is 8.)

[0011] The present invention [4] further comprises the polythiol composition according to any one of the above claims [1] to [3], which comprises a compound (E) represented by the following formula (5). (In formula (5) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms. a4, b4, c4, d4, e4, and f4 are the same or different and represent integers from 0 to 3, and the sum of a4, b4, c4, d4, e4, and f4 is 5.)

[0012] The present invention [5] further comprises the polythiol composition according to any one of the above claims [1] to [4], which includes a compound (F) represented by the following formula (6). (In formula (6) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a5, b5, c5, d5, e5, and f5 are the same or different in phase and represent integers from 0 to 3, and the sum of a5, b5, c5, d5, e5, and f5 is 4.)

[0013] 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].

[0014] The present invention [7] includes a molded article comprising a cured product of the polymerizable composition for optical materials described in [6] above.

[0015] The present invention [8] includes an optical material comprising the molded article described in [7] above.

[0016] The present invention [9] includes a plastic lens made of the optical material described in [8] above.

[0017] 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 0.10 area% to 10.00 area% relative to 100 area% of the peak area of ​​compound (A). Therefore, it exhibits excellent staining properties and suppresses yellowing.

[0018] The polymerizable composition for optical materials of the present invention contains the polythiol composition of the present invention. Therefore, it exhibits excellent dyeability and can suppress yellowing.

[0019] The molded article of the present invention contains a cured product of the polymerizable composition for optical materials of the present invention. Therefore, it has excellent dyeability and can suppress yellowing.

[0020] The optical material of the present invention consists of a molded article of the present invention. Therefore, it has excellent dyeability and can suppress yellowing.

[0021] The plastic lens of the present invention is made of the optical material of the present invention. Therefore, it has excellent dyeability and can suppress yellowing.

[0022] 1. Polythiol composition The polythiol composition contains a predetermined compound (A) and a predetermined compound (B) as essential components.

[0023] <Compound (A)> Compound (A) is represented by the following formula (1). In formula (1) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] Furthermore, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R may have substituents. Examples of substituents include halogen groups, cyano groups, amino groups, carboxyl groups, sulfonyl groups, and alkoxy groups. These may be used individually or in combination of two or more. The number of substituents is set appropriately depending on the purpose and application. The substitution position is set appropriately depending on the purpose and application. Preferably, the divalent hydrocarbon group having 1 to 6 carbon atoms represented by R does not have substituents. That is, R preferably represents an unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms.

[0028] As will be explained in more detail later, compound (A) is obtained by reacting 1 mole of pentaerythritol with 4 moles of mercaptocarboxylic acid (described later).

[0029] Specific examples of 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). Furthermore, examples of compound (A) include compounds in which one of the four Rs is methylene and three are ethylene, compounds in which two of the four Rs are methylene and two are ethylene, and compounds in which three of the four Rs are methylene and one is ethylene. Preferably, compound (A) is pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate), and more preferably, pentaerythritol tetrakis(3-mercaptopropionate). In other words, in formula (1) above, preferably all R represents ethylene, or all R represents isopropylene, and more preferably all R represents ethylene.

[0030] Compound (A) can be used alone or in combination of two or more compounds.

[0031] <Compound (B)> Compound (B) is represented by the following formula (2).

[0032] In formula (2) above, the multiple Rs are the same or different and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0033] The R in formula (2) above is preferably the same as the R in formula (1) above.

[0034] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (2) 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.

[0035] In the above formula (2), 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, still more preferably methylene, ethylene, and iso-propylene, still more preferably methylene and ethylene, and particularly preferably ethylene.

[0036] In the above formula (2), a1, b1, c1, d1, e1 and f1 are the same or different and represent integers from 0 to 3. a1, b1, c1, d1, e1 and f1 preferably represent 0 or 1. The sum of a1, b1, c1, d1, e1 and f1 is 6. In other words, the compound (B) contains six structural units derived from mercaptocarboxylic acid (described later). Although it will be described in detail later, the compound (B) is obtained by reacting 6 moles of mercaptocarboxylic acid with 1 mole of dipentaerythritol.

[0037] Examples of the compound (B) include a compound (B) having no hydroxyl group and a compound (B) having a hydroxyl group.

[0038] Although it will be described in detail later, the compound (B) is obtained by the reaction of dipentaerythritol and mercaptocarboxylic acid, and in the reaction, the hydroxyl group derived from dipentaerythritol may remain.

[0039] The compound (B) having no hydroxyl group is a compound having no hydroxyl group derived from dipentaerythritol, and the compound (B) having a hydroxyl group is a compound having a hydroxyl group derived from dipentaerythritol.

[0040] Examples of the compound (B) having no hydroxyl group include, for example, the compound represented by the following formula (3) (in the above formula (2), the compound in which a1, b1, c1, d1, e1 and f1 are 1). In the following formula (3), a plurality of Rs have the same meaning as R in the above formula (2). That is, the plurality of Rs are the same or different and represent the above-mentioned divalent hydrocarbon group having 1 to 6 carbon atoms).

[0041] Examples of the compound (B) having a hydroxyl group include, for example, a compound in which at least one of a1, b1, c1, d1, e1 and f1 represents 2 and at least one represents 0 in the above formula (2).

[0042] Specifically, examples of the compound (B) having a hydroxyl group include, for example, the compound represented by the following formula (4-1) (in the above formula (2), the compound in which e1 represents 2, f1 represents 0, and a1, b1, c1 and d1 represent 1), the compound represented by the following formula (4-2) (in the above formula (2), the compound in which e1 represents 3, d1 and f1 represent 0, and a1, b1 and c1 represent 1), and the compound represented by the following formula (4-3) (in the above formula (2), the compound in which e1 and f1 represent 2, c1 and d1 represent 0, and a1 and b1 represent 1). In the following formulas (4-1) to (4-3), a plurality of Rs have the same meaning as R in the above formula (2). That is, the plurality of Rs are the same or different and represent the above-mentioned divalent hydrocarbon group having 1 to 6 carbon atoms).

[0043] From the viewpoint of reactivity, the compound (B) preferably includes a compound (B) having no hydroxyl group.

[0044] The compound (B) can be used alone or in combination of two or more.

[0045] <Compound (C)> The polythiol composition may contain, if necessary, a compound (C) represented by the following formula (5).

[0046] In the above formula (5), a plurality of Rs are the same or different and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. The R in the above formula (5) preferably has the same meaning as R in the above formula (1).

[0047] 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.

[0048] 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.

[0049] Furthermore, in formula (5) above, a2, b2, c2, d2, e2, and f2 are the same or different integers from 0 to 3. Preferably, a2, b2, c2, d2, e2, and f2 are 0 or 1. The sum of a2, b2, c2, d2, e2, and f2 is 7. In other words, compound (C) contains seven constituent units derived from mercaptocarboxylic acid (described later). As will be described in detail later, compound (C) is obtained by reacting 7 moles of mercaptocarboxylic acid with 1 mole of dipentaerythritol.

[0050] Examples of compound (C) include compound (C) without a hydroxyl group and compound (C) having a hydroxyl group.

[0051] Compound (C) that does not have a hydroxyl group is a compound that does not have a hydroxyl group derived from the dipentaerythritol described above.

[0052] Examples of compounds (C) that do not have a hydroxyl group include compounds in formula (5) above in which one of a2, b2, c2, d2, e2, and f2 is 2 and the remainder is 1.

[0053] Specifically, as a compound (C) that does not have a hydroxyl group, for example, the compound shown in formula (6) below (a compound in which e2 is 2 and a2, b2, c2, d2, and f2 are 1 in formula (5) above). In formula (6) below, the multiple Rs are the same as the Rs in formula (5) above. That is, the multiple Rs are the same or different and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0054] Compound (C) having a hydroxyl group is a compound having a hydroxyl group derived from the dipentaerythritol described above.

[0055] Examples of compounds having a hydroxyl group (C) include compounds in which at least one of a2, b2, c2, d2, e2, and f2 is 0.

[0056] Specifically, examples of compounds (C) having a hydroxyl group include the compound shown in formula (7-1) below (a compound in formula (5) above where e2 is 3, f2 is 0, and a2, b2, c2, and d2 are 1), the compound shown in formula (7-2) below (a compound in formula (5) above where d2 and e2 are 2, f2 is 0, and a2, b2, and c2 are 1), and the compound shown in formula (7-3) below (a compound in formula (5) above where e2 is 3, d2 is 2, c2 and f2 are 0, and a2 and b2 are 1). In formulas (7-1) to (7-3) below, the multiple Rs are synonymous with the Rs in formula (5) above. That is, the multiple Rs are the same or different in phase, and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0057] From the viewpoint of reactivity, a compound (C) that does not have a hydroxyl group is preferred as compound (C).

[0058] Compound (C) can be used alone or in combination of two or more compounds.

[0059] <Compound (D)> The polythiol composition may optionally contain compound (D) represented by the following formula (8).

[0060] In formula (8) above, the multiple Rs are the same or different in phase and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0061] In formula (8) above, R is preferably the same as R in formula (1) above.

[0062] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (8) 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.

[0063] In formula (8) 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.

[0064] Furthermore, in formula (8) above, a3, b3, c3, d3, e3, and f3 are the same or different integers from 0 to 3. Preferably, a3, b3, c3, d3, e3, and f3 are 0 or 1. The sum of a3, b3, c3, d3, e3, and f3 is 8. In other words, compound (D) contains eight constituent units derived from mercaptocarboxylic acid (described later). As will be described in detail later, compound (D) is obtained by reacting 8 moles of mercaptocarboxylic acid with 1 mole of dipentaerythritol.

[0065] Examples of compound (D) include compound (D) without a hydroxyl group and compound (D) having a hydroxyl group.

[0066] Compound (D) that does not have a hydroxyl group is a compound that does not have a hydroxyl group derived from the dipentaerythritol described above.

[0067] Examples of compounds (D) that do not have a hydroxyl group include, in formula (8) above, compound D1 in which one of a3, b3, c3, d3, e3, and f3 is 3 and the remainder is 1, and compound D2 in which two are 2 and the remainder is 1.

[0068] Examples of compounds without hydroxyl groups (D1) include the compounds shown in the following formula (9) (compounds in which e3 represents 3 and a3, b3, c3, d3, and f3 represent 1 in formula (8) above). In formula (9) below, the multiple Rs are equivalent to the Rs in formula (8) above. That is, the multiple Rs are the same or different and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0069] Examples of compounds without hydroxyl groups (D2) include the compounds shown in the following formula (10) (compounds in which e3 and f3 represent 2 and a3, b3, c3 and d3 represent 1 in formula (8) above). In formula (10) below, the multiple Rs are equivalent to the Rs in formula (8) above. That is, the multiple Rs are the same or different in phase and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0070] Compound (D) having a hydroxyl group is a compound having a hydroxyl group derived from the dipentaerythritol described above.

[0071] Examples of compounds (D) having a hydroxyl group include the compound shown in formula (11) below (a compound in which f3 represents 3, e3 represents 2, d3 represents 0, and a3, b3, and c3 represent 1 in formula (8) above). In formula (11) below, the multiple Rs are equivalent to the Rs in formula (8) above. That is, the multiple Rs are the same or different in phase and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0072] Compound (D) can be used alone or in combination of two or more compounds.

[0073] <Compound (E)> The polythiol composition may optionally contain compound (E) represented by the following formula (12).

[0074] In formula (12) above, the multiple Rs are the same or different in phase, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0075] The R in formula (12) above is preferably the same as the R in formula (1) above.

[0076] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (12) 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.

[0077] In the above formula (12), 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.

[0078] Furthermore, in formula (12) above, a4, b4, c4, d4, e4, and f4 are the same or different, and represent integers from 0 to 3. Preferably, a4, b4, c4, d4, e4, and f4 represent 0 or 1. The sum of a4, b4, c4, d4, e4, and f4 is 5. In other words, compound (E) contains five constituent units derived from mercaptocarboxylic acid (described later). As will be described in detail later, compound (E) is obtained by reacting 5 moles of mercaptocarboxylic acid with 1 mole of dipentaerythritol.

[0079] Compound (E) has a hydroxyl group derived from the dipentaerythritol described above.

[0080] Examples of compound (E) include the compound shown in formula (13-1) below (a compound in which a4, b4, c4, d4, and e4 are 1 and f4 is 0 in formula (12) above), and the compound shown in formula (13-2) below (a compound in which e4 is 2, d4 and f4 are 0 and a4, b4, and c4 are 1 in formula (12) above). In formulas (13-1) to (13-2) below, the multiple Rs are synonymous with the Rs in formula (12) above. That is, the multiple Rs are the same or different in phase and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0081] Compound (E) can be used alone or in combination of two or more compounds.

[0082] <Compound (F)> The polythiol composition may optionally contain compound (F) represented by the following formula (14).

[0083] In formula (14) above, the multiple Rs are either the same or different in phase, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0084] The R in formula (14) above is preferably the same as the R in formula (1) above.

[0085] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formula (14) 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.

[0086] In the above formula (14), 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.

[0087] Furthermore, in formula (14) above, a5, b5, c5, d5, e5, and f5 are the same or different, and represent integers from 0 to 3. Preferably, a5, b5, c5, d5, e5, and f5 represent 0 or 1. The sum of a5, b5, c5, d5, e5, and f5 is 4. In other words, compound (F) contains four constituent units derived from mercaptocarboxylic acid (described later). As will be described in detail later, compound (F) is obtained by reacting 4 moles of mercaptocarboxylic acid with 1 mole of dipentaerythritol.

[0088] Compound (F) has a hydroxyl group derived from the dipentaerythritol described above.

[0089] Examples of compound (F) include the compound shown in formula (15-1) below (a compound in formula (14) above where e5 and f5 are 0 and a5, b5, c5 and d5 are 1), and the compound shown in formula (15-2) below (a compound in formula (14) above where e5 is 2, c5, d5 and f5 are 0 and a5 and b5 are 1). In formulas (15-1) to (15-2) below, the multiple Rs are synonymous with the Rs in formula (14) above. That is, the multiple Rs are the same or different in phase and represent the divalent hydrocarbon groups having 1 to 6 carbon atoms as described above.

[0090] Compound (F) can be used alone or in combination of two or more compounds.

[0091] <Other Compounds> The polythiol composition may also contain other compounds as needed.

[0092] Other compounds include, for example, compounds (G1) to (G3) shown in the following formulas (16-1) to (16-3).

[0093] In the above formulas (16-1) to (16-3), the multiple Rs are either the same or different in nature, and represent divalent hydrocarbon groups having 1 to 6 carbon atoms.

[0094] In formulas (16-1) to (16-3) above, R is preferably the same as R in formula (1) above.

[0095] In other words, examples of divalent hydrocarbon groups having 1 to 6 carbon atoms represented by R in formulas (16-1) to (16-3) 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.

[0096] In formulas (16-1) to (16-3) 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.

[0097] As will be explained in more detail later, compound (G1) is obtained by reacting 1 mole of pentaerythritol with 1 mole of mercaptocarboxylic acid. Compound (G2) is obtained by reacting 1 mole of pentaerythritol with 2 moles of mercaptocarboxylic acid. Compound (G3) is obtained by reacting 1 mole of pentaerythritol with 3 moles of mercaptocarboxylic acid.

[0098] <Method for producing a polythiol composition> The method for producing a polythiol composition comprises a first step of reacting pentaerythritol and mercaptocarboxylic acid to obtain a first reaction product containing compound (A), a second step of reacting dipentaerythritol and mercaptocarboxylic acid to obtain a second reaction product containing compound (B), and a third step of mixing the first reaction product and the second reaction product.

[0099] [Step 1] In Step 1, pentaerythritol and mercaptocarboxylic acid are reacted to obtain a first reaction product containing compound (A).

[0100] Examples of mercaptocarboxylic acids 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.

[0101] The blending ratio of mercaptocarboxylic acid to 1 mole of pentaerythritol is, for example, 3.8 to 4.2, preferably 3.9 to 4.1.

[0102] Furthermore, the above reaction is preferably carried out in a solvent.

[0103] 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. Preferably, aromatic hydrocarbons are used as solvents. More preferably, toluene is used as a solvent. Solvents can be used alone or in combination of two or more types.

[0104] Furthermore, in the above reaction, an esterification catalyst (for example, p-toluenesulfonic acid) is preferably included.

[0105] The reaction is carried out at atmospheric pressure. The reaction conditions include a reaction temperature of, for example, 80°C to 150°C, preferably 105°C to 135°C. The reaction time is, for example, 0.5 hours to 24 hours, preferably 1 hour to 18 hours.

[0106] As a result, as shown in the reaction formula (17) below, 1 mole of pentaerythritol and 4 moles of mercaptocarboxylic acid are reacted to obtain compound (A). In the above reaction formula (17), the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. Preferably, the R in formula (17) is the same as the R in formula (1).

[0107] Furthermore, in the above reaction, one mole of pentaerythritol may react with one mole of mercaptocarboxylic acid, two moles of mercaptocarboxylic acid, or three moles of mercaptocarboxylic acid.

[0108] More specifically, as shown in reaction equation (18) below, when 1 mole of pentaerythritol reacts with 1 mole of mercaptocarboxylic acid, compound (G1) is obtained. Also, as shown in reaction equation (19) below, when 1 mole of pentaerythritol reacts with 2 moles of mercaptocarboxylic acid, compound (G2) is obtained. As shown in reaction equation (20) below, when 1 mole of unreacted pentaerythritol reacts with 3 moles of mercaptocarboxylic acid, compound (G3) is obtained.

[0109] In the above reaction formulas (18) to (20), the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. Preferably, the R in formulas (18) to (20) is the same as the R in formula (1).

[0110] As a result, a reaction solution is obtained that contains a first reaction product comprising compound (A), compound (G1) if necessary, compound (G2) if necessary, and compound (G3) if necessary.

[0111] Subsequently, if necessary, a neutralizing agent is added to the reaction solution of the first reaction product to neutralize the reaction solution of the first reaction product (specifically, the esterification catalyst (e.g., p-toluenesulfonic acid)), and then the first reaction product is purified by liquid-liquid separation. Liquid-liquid separation is an operation in which the reaction solution containing the first reaction product is separated into an organic phase and an aqueous phase (the aqueous phase containing the esterification catalyst), and then the organic phase is removed to extract the first reaction product.

[0112] Specifically, first, a neutralizing agent (for example, aqueous ammonia) is added to the reaction solution containing the first reaction product to neutralize the first reaction product.

[0113] Next, the first reaction product is purified by liquid-liquid separation. Specifically, water is added to the reaction solution containing the first reaction product, and the reaction solution containing the first reaction product is separated into an aqueous phase and an organic phase. At this time, the aqueous phase contains the esterification catalyst, and the organic phase contains compound (A), compound (G1) obtained as needed, compound (G2) obtained as needed, and compound (G3) obtained as needed. After that, the organic layer is removed and distilled as needed. This yields the first reaction product.

[0114] [Step 2] In step 2, dipentaerythritol and mercaptocarboxylic acid are reacted to obtain a second reaction product containing compound (B).

[0115] The ratio of mercaptocarboxylic acid to 1 mole of dipentaerythritol is, for example, 3.5 to 4.1, preferably 3.6 to 3.8.

[0116] Furthermore, the above reaction is preferably carried out in a solvent.

[0117] Examples of solvents include those listed in the first step above. More preferably, toluene is used as the solvent.

[0118] Furthermore, in the above reaction, an esterification catalyst (for example, p-toluenesulfonic acid) is preferably included.

[0119] The reaction is carried out at atmospheric pressure. The reaction conditions include a reaction temperature of, for example, 80°C to 150°C, preferably 105°C to 135°C. The reaction time is, for example, 0.5 hours to 24 hours, preferably 1 hour to 18 hours.

[0120] As a result, compound (B) is obtained by reacting 1 mole of dipentaerythritol with 6 moles of mercaptocarboxylic acid, as shown in the reaction formula (21) below.

[0121] In the above reaction equation (21), the multiple R, a1, b1, c1, d1, e1, and f1 are equivalent to each of the values ​​in equation (2) above.

[0122] Furthermore, as shown in the reaction equation (22) below, compound (C) may be obtained when 7 moles of mercaptocarboxylic acid react with 1 mole of dipentaerythritol.

[0123] In the above reaction equation (22), the multiple R, a2, b2, c2, d2, e2, and f2 are equivalent to each of the values ​​in equation (3) above.

[0124] Furthermore, as shown in the reaction equation (23) below, compound (D) may be obtained when 8 moles of mercaptocarboxylic acid react with 1 mole of dipentaerythritol.

[0125] In the above reaction equation (23), the multiple R, a3, b3, c3, d3, e3, and f3 are equivalent to each of the values ​​in equation (4) above.

[0126] Furthermore, as shown in the reaction equation (24) below, compound (E) may be obtained when 5 moles of mercaptocarboxylic acid react with 1 mole of dipentaerythritol.

[0127] In the above reaction equation (24), the multiple R, a4, b4, c4, d4, e4, and f4 are equivalent to each of the values ​​in equation (5) above.

[0128] Furthermore, as shown in the reaction equation (25) below, compound (F) may be obtained when 4 moles of mercaptocarboxylic acid react with 1 mole of dipentaerythritol.

[0129] In the above reaction equation (25), the multiple R, a5, b5, c5, d5, e5, and f5 are equivalent to each of the values ​​in equation (6) above.

[0130] As a result, a second reaction product is obtained containing compound (B), compound (C) if necessary, compound (D) if necessary, compound (E) if necessary, and compound (F) if necessary.

[0131] Subsequently, if necessary, the second reaction product is purified by liquid-liquid separation in the same manner as in the first step described above.

[0132] [Third step] In the third step, the first reaction product and the second reaction product are mixed.

[0133] Specifically, the first and second reaction products are mixed so that the peak area of ​​compound (B) (described later) relative to 100 area percent of the peak area of ​​compound (A) falls within a predetermined range.

[0134] This yields a polythiol composition.

[0135] Furthermore, the polythiol composition may be diluted with a solvent as needed. Examples of solvents include those listed above.

[0136] The solid content concentration of the solution of the polythiol composition is, for example, 10% to 70% by mass (the polythiol composition does not contain solvents).

[0137] <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.

[0138] 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.

[0139] The peak area of ​​compound (B) is 0.10 area% to 10.00 area%, preferably 0.20 area% to 8.00 area%, more preferably 0.30 area% to 5.00 area%, even more preferably 0.40 area% to 3.00 area%, and most preferably 0.50 area% to 1.00 area%, relative to 100 area% of the peak area of ​​compound (A).

[0140] More specifically, the peak area of ​​compound (B) is 0.10 area% or more, preferably 0.20 area% or more, more preferably 0.30 area% or more, even more preferably 0.40 area% or more, particularly preferably 0.50 area% or more, and 10.00 area% or less, preferably 8.00 area% or less, more preferably 5.00 area% or less, even more preferably 3.00 area% or less, and particularly preferably 1.00 area% or less, relative to 100 area% of the peak area of ​​compound (A).

[0141] 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.

[0142] On the other hand, if the peak area of ​​compound (B) relative to 100 area% of the peak area of ​​compound (A) is less than the lower limit mentioned above, the staining performance will decrease.

[0143] Furthermore, if the peak area of ​​compound (B) relative to 100 area% of the peak area of ​​compound (A) is below the above upper limit, yellowing can be suppressed.

[0144] 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, yellowing cannot be suppressed.

[0145] Furthermore, the peak area of ​​compound (B) is, for example, 0.01 to 5.00 area%, preferably 0.10 to 3.00 area%, more preferably 0.20 to 2.00 area%, and even more preferably 0.30 to 1.00 area%, 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).

[0146] More specifically, the peak area of ​​compound (B) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.10 area% or more, more preferably 0.20 area% or more, and even more preferably 0.30 area% or more, relative to 100 area% of the peak area of ​​the polythiol composition. Furthermore, from the viewpoint of suppressing yellowing, for example, 5.00 area% or less, preferably 3.00 area% or less, more preferably 2.00 area% or less, and even more preferably 1.00 area% or less.

[0147] Furthermore, the retention time of compound (B) in the examples described later is 16.0 minutes to 21.0 minutes.

[0148] The peak area of ​​compound (C) is, for example, 0.01 area% to 5.00 area%, preferably 0.10 area% to 3.00 area%, more preferably 0.20 area% to 2.00 area%, and even more preferably 0.30 area% to 1.00 area%, relative to 100 area% of the peak area of ​​compound (A).

[0149] More specifically, the peak area of ​​compound (C) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.10 area% or more, more preferably 0.20 area% or more, and even more preferably 0.30 area% or more, relative to 100 area% of the peak area of ​​compound (A). Furthermore, from the viewpoint of suppressing yellowing, it is, for example, 5.00 area% or less, preferably 3.00 area% or less, more preferably 2.00 area% or less, and even more preferably 1.00 area% or less.

[0150] Furthermore, the peak area of ​​compound (C) is, for example, 0.01 area% to 3.00 area% of the peak area of ​​the polythiol composition, preferably 0.10 area% to 2.00 area% and more preferably 0.20 area% to 0.50 area%.

[0151] More specifically, the peak area of ​​compound (C) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.10 area% or more, and more preferably 0.20 area% or more, relative to 100 area% of the peak area of ​​the polythiol composition. Furthermore, from the viewpoint of suppressing yellowing, for example, 3.00 area% or less, preferably 2.00 area% or less, and more preferably 0.50 area% or less.

[0152] Furthermore, the retention time of compound (C) in the examples described later is 23.0 minutes to 28.0 minutes.

[0153] The peak area of ​​compound (D) is, for example, 0.01 area% to 3.00 area%, preferably 0.05 area% to 2.00 area%, more preferably 0.08 area% to 1.00 area%, and even more preferably 0.10 area% to 0.50 area%, relative to 100 area% of the peak area of ​​compound (A).

[0154] More specifically, the peak area of ​​compound (D) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.05 area% or more, more preferably 0.08 area% or more, and even more preferably 0.10 area% or more, relative to 100 area% of the peak area of ​​compound (A). Furthermore, from the viewpoint of suppressing yellowing, it is, for example, 3.00 area% or less, preferably 2.00 area% or less, more preferably 1.00 area% or less, and even more preferably 0.50 area% or less.

[0155] Furthermore, the peak area of ​​compound (D) is, for example, 0.01 area% to 2.00 area% of the peak area of ​​the polythiol composition, preferably 0.05 area% to 1.00 area%, and more preferably 0.10 area% to 0.50 area%.

[0156] More specifically, the peak area of ​​compound (D) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.05 area% or more, and more preferably 0.10 area% or more, relative to 100 area% of the peak area of ​​the polythiol composition. Furthermore, from the viewpoint of suppressing yellowing, for example, 2.00 area% or less, preferably 1.00 area% or less, and more preferably 0.50 area% or less.

[0157] Furthermore, the retention time of compound (D) in the examples described later is 34.0 minutes to 46.0 minutes.

[0158] The peak area of ​​compound (E) is, for example, 0.01 area% to 2.00 area% of the peak area of ​​compound (A), preferably 0.05 area% to 1.00 area%, and more preferably 0.10 area% to 0.50 area%.

[0159] More specifically, the peak area of ​​compound (E) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.05 area% or more, and more preferably 0.10 area% or more, relative to 100 area% of the peak area of ​​compound (A). Furthermore, from the viewpoint of suppressing yellowing, for example, 2.00 area% or less, preferably 1.00 area% or less, and more preferably 0.50 area% or less.

[0160] Furthermore, the peak area of ​​compound (E) is, for example, 0.01 area% to 1.00 area% of the peak area of ​​the polythiol composition, preferably 0.03 area% to 0.50 area% and more preferably 0.05 area% to 0.20 area%.

[0161] More specifically, the peak area of ​​compound (E) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.03 area% or more, and more preferably 0.05 area% or more, relative to 100 area% of the peak area of ​​the polythiol composition. Furthermore, from the viewpoint of suppressing yellowing, it is, for example, 1.00 area% or less, preferably 0.50 area% or less, and more preferably 0.20 area% or less.

[0162] Furthermore, the retention time of compound (E) in the examples described later is 9.5 minutes to 14.0 minutes.

[0163] The peak area of ​​compound (F) is, for example, 0.01 to 0.05 area%, preferably 0.02 to 0.04 area%, relative to 100 area% of the peak area of ​​compound (A).

[0164] More specifically, the peak area of ​​compound (F) is, from the viewpoint of staining properties, for example, 0.01 area% or more, preferably 0.02 area% or more, relative to 100 area% of the peak area of ​​compound (A), and from the viewpoint of suppressing yellowing, for example, 0.05 area% or less, preferably 0.04 area% or less.

[0165] Furthermore, the peak area of ​​compound (F) is, for example, 0.01% to 0.04% of the peak area of ​​the polythiol composition, relative to 100% of the total peak area.

[0166] Furthermore, the retention time of compound (F) in the examples described later is 4.0 minutes to 9.0 minutes.

[0167] The peak area of ​​compound (G1) is, from the viewpoint of suppressing staining and yellowing, 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).

[0168] Furthermore, the retention time of compound (G1) in the examples described later is 1.0 to 3.0 minutes.

[0169] The peak area of ​​compound (G2) is, from the viewpoint of suppressing staining and yellowing, 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).

[0170] Furthermore, the retention time of compound (G2) in the examples described later is 3.0 to 5.0 minutes.

[0171] The peak area of ​​compound (G3) is, from the viewpoint of suppressing staining and yellowing, 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).

[0172] Furthermore, the retention time of compound (G3) in the examples described later is 6.0 to 8.0 minutes.

[0173] The peak area of ​​compound (A) is, for example, 60.0 area% to 65.6 area% of the peak area of ​​the polythiol composition, preferably 63.0 area% to 65.3 area%, and more preferably 64.0 area% to 65.2 area%.

[0174] More specifically, the peak area of ​​compound (A) is, from the viewpoint of suppressing yellowing, for example, 60.0 area% or more, preferably 63.0 area% or more, and more preferably 64.0 area% or more, relative to 100 area% of the peak area of ​​the polythiol composition. From the viewpoint of stainability, it is 65.6 area% or less, preferably 65.3 area% or less, and more preferably 65.2 area% or less.

[0175] Furthermore, the retention time of compound (A) in the examples described later is 7.5 to 9.0 minutes.

[0176] 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.

[0177] The proportions of each component mentioned above can be adjusted by changing the proportion of pentaerythritol, dipentaerythritol, mercaptocarboxylic acid, and the reaction conditions.

[0178] 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 0.10 area% to 10.00 area% relative to the peak area of ​​compound (A) (100 area%). Therefore, it exhibits excellent staining properties and suppresses yellowing. Such a polythiol composition can be suitably used in the production of polymerizable compositions for optical materials.

[0179] 2. Polymerizable compositions for optical materials Polymerizable compositions for optical materials are compositions used in the manufacture of optical materials.

[0180] The polymerizable composition for optical materials comprises an isocyanate compound and the above-mentioned polythiol composition.

[0181] <Isocyanate Compounds> Examples of isocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

[0182] 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.

[0183] 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 (H ６ 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.

[0184] 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.

[0185] 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.

[0186] Isocyanate compounds include the polyisocyanate derivatives described above.

[0187] 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.

[0188] Examples of polyisocyanate derivatives include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI, polynuclear-containing diphenylmethane diisocyanate) and carbodiimide-modified polymethylene polyphenyl polyisocyanate.

[0189] Preferably, the isocyanate compound is an alicyclic polyisocyanate. More preferably, the isocyanate compound is 1,3-H ６ Examples include XDI and NBDI.

[0190] Isocyanate compounds can be used alone or in combination of two or more types.

[0191] 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).

[0192] <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).

[0193] <Other Components> Polymerizable compositions for optical materials may also contain other components as needed.

[0194] Other components include other polythiol compounds and polyol compounds.

[0195] Other polythiol compounds are compounds other than those in the polythiol composition described above.

[0196] Other examples of polythiol compounds include those described in International Publication No. 2008 / 105138.

[0197] 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.

[0198] Other polythiol compounds can be used alone or in combination of two or more.

[0199] Examples of polyol compounds include those described in International Publication No. 2017 / 047684.

[0200] The other components preferably consist of other polythiol compounds and do not contain polyol compounds.

[0201] 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.

[0202] 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.

[0203] <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.

[0204] Additives can be used individually or in combination of two or more types.

[0205] The polymerizable composition for optical materials contains the above-mentioned polythiol composition. Therefore, the polymerizable composition for optical materials has excellent dyeability and can suppress yellowing. Such a polymerizable composition for optical materials can be suitably used in the manufacture of molded articles for manufacturing optical materials.

[0206] 3. The molded article contains a cured product of a polymerizable composition for optical materials.

[0207] The molded article is obtained by curing and molding a polymerizable composition for optical materials.

[0208] The molding method is not particularly limited and includes, for example, casting and heat compression molding. Casting is preferred as the molding method.

[0209] In casting, for example, a polymerizable composition for optical materials is degassed, then injected into a molding mold and heated.

[0210] 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.

[0211] As a result, the polymerizable composition for optical materials hardens and is molded, yielding a molded article.

[0212] 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.

[0213] If the glass transition temperature of the molded product is above the lower limit mentioned above, the heat resistance can be improved.

[0214] The method for measuring the glass transition temperature will be described in detail in the examples below.

[0215] 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.

[0216] 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.

[0217] The molded article contains a cured product of a polymerizable composition for optical materials. Therefore, the molded article has excellent dyeability and can suppress yellowing. Such a molded article can be suitably used in the manufacture of optical materials.

[0218] 4. Optical materials: Optical materials consist of molded bodies.

[0219] Optical materials are materials used to manufacture optical components. Examples of optical components include plastic lenses, headlamp covers, reflectors, spot lamps, and polarizing lenses.

[0220] Furthermore, optical materials are dyed according to their application and purpose.

[0221] To stain optical materials, first prepare a dye dispersion.

[0222] To prepare a dye dispersion, the dye is dispersed in water.

[0223] The dyes are not particularly limited and include well-known dyes. Specifically, the Dianix series (manufactured by Dystar) can be mentioned.

[0224] Next, the optical material is immersed in a dye dispersion.

[0225] 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.

[0226] This process stains the optical material.

[0227] On the other hand, the optical material is made of the molded body described above. Therefore, it has excellent dyeability and can suppress yellowing.

[0228] <Effects> The polythiol composition contains compound (A) and compound (B). In high-performance liquid chromatography measurements using a UV detector with a measurement wavelength of 200 nm, the peak area of ​​compound (B) is 0.10 area% to 10.00 area% relative to the peak area of ​​compound (A) (100 area%). Therefore, it exhibits excellent staining properties and suppresses yellowing.

[0229] <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.

[0230] In the above description, in the first step, pentaerythritol and mercaptocarboxylic acid are reacted to obtain a first reaction product containing compound (A); in the second step, dipentaerythritol and mercaptocarboxylic acid are reacted to obtain a second reaction product containing compound (B); and in the third step, the first reaction product and the second reaction product are mixed.

[0231] Alternatively, a polythiol composition containing compound (A) and compound (B) can be produced by compounding pentaerythritol, dipentaerythritol, and mercaptocarboxylic acid together.

[0232] 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.

[0233] <Details of ingredients> NBDI: Bis(isocyanatomethyl)norbornane 1,3-H ６ XDI: 1,3-bis(isocyanatomethyl)cyclohexane

[0234] <Production of Polythiol Composition, Polymerizable Composition for Optical Materials, and Molded Articles> Example 1 (Production of Polythiol Composition) [Step 1] 8.5 g of pentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), 26.3 g of 3-mercaptopropionic acid (purified product), 0.3 g of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 12.2 g of toluene were added to a reactor fitted with a Dean Stark tube. The reaction temperature was then gradually increased from room temperature (25°C) 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 95.2% of the theoretically produced water. After reacting for 8 hours, it was allowed to cool to room temperature (25°C). This yielded a reaction solution containing the first reaction product.

[0235] Next, 5.9 g of 1% aqueous ammonia solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution containing the first reaction product 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 carried out for 15 minutes, after which the upper aqueous solution was separated. Then, 12.5 g of pure water (second time) was added again, and stirring and washing was carried out for 15 minutes, and the upper aqueous solution was separated. As a result, a toluene solution containing the first reaction product was obtained from the lower layer.

[0236] Next, toluene was removed using an evaporator, and the mixture was held under vacuum at 120°C for 3 hours. After that, 29.4 g of the first reaction product was obtained by vacuum filtration (PTFE (polytetrafluoroethylene), 3.0 μm).

[0237] [Step 2] In a reactor fitted with a Dean Stark tube, 36.2 g of dipentaerythritol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 106.0 g of 3-mercaptopropionic acid (purified product), 0.5 g of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 12.2 g of toluene were added. The reaction temperature was then gradually increased from room temperature (25°C) to a reflux state. During this time, the internal temperature rose to 130°C, and the by-product water was continuously removed under reflux. The amount of water removed totaled 98.2% of the theoretically produced water. After reacting for 8 hours, the mixture was allowed to cool to room temperature (25°C). This yielded a reaction solution containing the second reaction product.

[0238] Next, 23.6 g of 1% aqueous ammonia solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution containing the second reaction product 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. Then, 50.0 g of pure water (second time) was added again, and stirring and washing was performed for 15 minutes, and the upper aqueous solution was separated again. As a result, a toluene solution containing the second reaction product was obtained from the lower layer.

[0239] Next, toluene was removed using an evaporator, and the mixture was held under vacuum at 120°C for 3 hours. After that, 137.3 g of the second reaction product was obtained by vacuum filtration (PTFE (polytetrafluoroethylene), 3.0 μm).

[0240] [Step 3] The first and second reaction products were mixed to obtain a polythiol composition, such that the peak areas attributed to each component, as measured by high-performance liquid chromatography using a UV detector with a measurement wavelength of 200 nm, were as shown in Table 1.

[0241] (Preparation 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) is used 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) is used as an ultraviolet absorber, Zelec-UN (Stephan, acidic phosphate ester) (1000 ppm by mass relative to the resulting polymerizable composition for optical materials) is used as a release agent, and NBDI is used as an isocyanate compound. A polymerizable composition for optical materials was prepared by mixing 51 parts by mass of the polythiol compound with 25 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (T-1) as another polythiol compound and 24 parts by mass of the polythiol composition (solid content), and stirring and mixing at room temperature (25°C) for 1 hour.

[0242] (Manufacturing of molded articles) The polymerizable composition for optical materials was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then degassed thoroughly 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. Next, the oven was cooled. This resulted in obtaining a molded article (thickness 9 mm).

[0243] Examples 2 to 8 and Comparative Examples 1 to 4: Polythiol compositions, polymerizable compositions for optical materials, and molded articles were produced based on the same procedure as in Example 1. However, in the third step of the production of the polythiol composition, the first reaction product and the second reaction product were mixed so that the peak areas attributed to each component, as measured by high-performance liquid chromatography using a UV detector with a measurement wavelength of 200 nm, were the values ​​shown in Tables 1 and 2.

[0244] <Evaluation> [High-Performance Liquid Chromatography Measurement] For each example and comparative example of the 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), compound (E), compound (F)) 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 (F) relative to 100 area % of the peak area of ​​compound (A) were calculated. The results are shown in Tables 1 and 2.

[0245] {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

[0246] {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

[0247] [Color] (Appearance) The color of the polythiol compositions of each example and comparative example was visually confirmed. The results are shown in Tables 1 and 2.

[0248] 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.

[0249] [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 Tables 1 and 2.

[0250] [Dyeability] The dyeability of the molded articles of each example and each comparative example was evaluated.

[0251] 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 Tables 1 and 2.

[0252] 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.

[0253] 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 Tables 1 and 2.

[0254] 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 Tables 1 and 2.

[0255]

[0256]

[0257] 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.

[0258] 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 0.10 area% or more and 10.00 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 nature, 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, d1, e1, and f1 are the same or different in phase and represent integers from 0 to 3, and the sum of a1, b1, c1, d1, e1, and f1 is 6.) 2. 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 and represent divalent hydrocarbon groups having 1 to 6 carbon atoms. a2, b2, c2, d2, e2, and f2 are the same or different and represent integers from 0 to 3, and the sum of a2, b2, c2, d2, e2, and f2 is 7.) 3. 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 and represent divalent hydrocarbon groups having 1 to 6 carbon atoms. a3, b3, c3, d3, e3, and f3 are the same or different and represent integers from 0 to 3, and the sum of a3, b3, c3, d3, e3, and f3 is 8.) 4. 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 and represent divalent hydrocarbon groups having 1 to 6 carbon atoms. a4, b4, c4, d4, e4, and f4 are the same or different and represent integers from 0 to 3, and the sum of a4, b4, c4, d4, e4, and f4 is 5.) 5. The polythiol composition according to claim 1, further comprising compound (F) represented by the following formula (6). (In formula (6) above, the multiple Rs are the same or different in phase and represent a divalent hydrocarbon group having 1 to 6 carbon atoms. a5, b5, c5, d5, e5, and f5 are the same or different in phase and represent integers from 0 to 3, and the sum of a5, b5, c5, d5, e5, and f5 is 4.) 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 article described in claim 7.

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

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