polythiol composition, polymerizable composition for optical material and use thereof

专利摘要:
POLYTHIOL COMPOSITION, POLYMERIZABLE COMPOSITION FOR OPTICAL MATERIAL AND USE OF THE SAME. A polythiol composition according to the present invention includes a polythiol compound (A) having three or more mercapto groups and a nitrogen-containing compound (B) in which one of a mercapto group of the polythiol compound (A) is replaced with a group represented by the following formula (a) and another from a mercapto group of the polythiol compound (A) is replaced with a hydroxyl group, where the peak area of the nitrogen-containing compound (B) is equal to or less than 3, 0 with respect to the 100 peak area of the polythiol compound (A) in a high performance liquid chromatography measurement. 7.
公开号:BR112014025570B1
申请号:R112014025570-9
申请日:2013-08-13
公开日:2020-12-22
发明作者:Masaru Kawaguchi；Takeshi Nishimura
申请人:Mitsui Chemicals, Inc；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a polythiol composition, a polymerizable composition for an optical material and the use thereof. BACKGROUND OF THE TECHNIQUE
[002] Since a plastic lens is lighter, hardly broken and able to be tinted, compared to an inorganic lens, the plastic lens has recently become widely used quickly in an optical element such as a lens for glasses or a camera lens.
[003] Higher performance was required for a resin for the plastic lens and high refractive index, high Abbé coefficient, low density, high thermal resistance, or the like was required. So far, several types of resin materials for the lens have been developed and used.
[004] Among these, an optical material comprised of a polythurethane-based resin has a high refractive index and a high Abbé coefficient, and is excellent in impact resistance, color receptivity, processability, or the like. The polythiurethane-based resin can be obtained by reacting a polythiol with a polyisom (thio) cyanate compound, or the like.
[005] In a plastic lens use case, polythurethane based resin is required to cause less color, have excellent resin color and have transparency. In a case where the quality of the polythiol was deteriorated, there were cases where the quality of the resin obtained was also deteriorated.
[006] Patent Documents that refer to a process of producing polythiol include the following Patent documents.
[007] In Patent Document 1 or Patent Document 2, a method in which 2-mercaptoethanol reacts with epichlorohydrin, the compound obtained reacts with thiourea to obtain an isothiouronium salt, and then the isothiouronium salt is hydrolyzed to obtain the specific polythiol compound is described.
[008] In Patent Document 3, a process of producing a polythiol compound in which the amount of specific impurities included in 2-mercaptoethanol is adjusted to the predetermined range is described.
[009] In Patent Document 4, a process of producing a polythiol compound in which the calcium content included in the thiourea is adjusted to the predetermined range is described. RELATED DOCUMENT PATENT DOCUMENT
Patent Document 1 Japanese Unexamined Patent Publication No. 2-270859
Patent Document 2 Japanese Unexamined Patent Publication No. 7-252207
Patent Document 3 PCT International Publication No 2007/129449
Patent Document 4 PCT International Publication No 2007/129450 DESCRIPTION OF THE INVENTION
[0010] However, in a case where the plastic lens comprised of polythurethane-based resin is produced using the polythiol compound obtained in the methods described in the documents, there was scope for the improvement of optical properties such as color, transparency, streaking.
[0011] The present inventors confirmed that some of the specific component is included in the polythiol compound, as a result of extensive studies in order to improve the optical properties, and found that the specific component included in the predetermined amount affects the reaction activity ( polymerization) in a reaction (polymerization reaction) of the polythiol compound and a polyisocyanate compound.
[0012] The present invention can be provided as below. [1] A polythiol composition includes a polythiol compound (A) having three or more mercapto groups, and a nitrogen-containing compound (B) in which at least one of a mercapto group of the polythiol compound (A) is replaced with a group represented by the following formula (a)
where, in the formula, * represents an atomic bond, and at least one of a mercapto group of the polythiol compound (A) is replaced with a hydroxyl group, where the peak area of the nitrogen-containing compound (B) is equal to or less than 3.0, with respect to the 100 peak area of the polythiol compound (A) in a high performance liquid chromatography measurement. [2] The polythiol composition according to [1], wherein the polythiol compound (A) is represented by the following formula (5).
[3] The polythiol composition according to [1], wherein the polythiol compound (A) is mainly comprised of at least one type selected from the compounds represented by the following formulas (6) to (8).
[4] A polymerizable composition for an optical material includes the polythiol composition according to any one of [1] to [3] and a poly (thio) isocyanate compound. [5] A method of making a molded product, comprising mixing the polythiol composition according to any one of [1] to [3] and a poly (thio) isocyanate compound to obtain a polymerizable composition for an optical material; and placing the polymerizable composition in a mold and curing the composition. [6] A molded product that is obtained by curing the polymerizable composition according to [4]. [7] An optical element comprised of the product molded according to [6]. [8] A lens comprising the optical element according to [7].
[0013] It is possible to obtain a plastic lens comprised of polyethylene based resin which is excellent in quality such as color, transparency, streaking using the polythiol composition of the present invention.
[0014] That is, according to the present invention, by adjusting the nitrogen-containing compound (B) which is a trace component included in the polythiol composition to within the predetermined range, a plastic lens product in which the high quality as color, transparency, streaking, or the like is required can be industrially produced with a satisfactory yield. In addition, when the polymerizable composition is prepared, by adjusting the amount of the nitrogen-containing compound (B) included in the polythiol composition and still confirming the quantity, it is possible to suppress the occurrence of defects in quality such as streaking or coloring of the lens. plastic, and thus it is possible to improve the product's performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Fig. 1 shows an HPLC plot of a polythiol composition obtained in Example A-1.
[0016] Fig. 2 shows a high performance liquid chromatography (HPLC) graph of a polythiol composition obtained in Example C-1. DESCRIPTION OF THE MODALITIES
[0017] Next, the description will be given of a polyol composition of the present invention based on modalities.
[0018] The polythiol composition of the present embodiment includes a polythiol compound (A) and a nitrogen-containing compound (B). Then, description of the component will be given. (Polyol compound (A))
[0019] The polythiol compound (A) is a polythiol compound having three or more mercapto groups.
[0020] A polythiol compound (A) includes an aliphatic polythiol compound such as 1,2,3-propanotrityiol, tetracis (mercaptomethyl) methane, trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetracis (2-mercaptoacetate), pentaerythritol tetracis (3-mercaptopropionate), 1,2,3-tris (mercaptometiltio) propane 2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1, 11-dimercapto-3,6,9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9- tritiaundecane, tetracis (mercaptomethylthiomethyl) methane, tetracis (2-mercaptoethylthiomethyl) methane, tetracis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, ester of these polythiols and thioglycolic acids or mercaptopropionic acid, 1,1 , 3-tetracis (mercaptomethylthio) propane, 1,1,2,2-tetracis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, tris (mercaptomethylthio) methane, and tris (mercaptoethylthio) methane; an aromatic polythiol compound such as 1,3,5-trimercaptobenzene, 1,3,5-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyloxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene .
[0021] However, the polythiol compound (A) is not limited to exemplary compounds only.
[0022] In the present embodiment, as a polythiol compound (A), a polythiol compound that is mainly comprised of at least one type selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane represented the following formula (5), 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane represented by the following formula (6), 4,7-dimercaptomethyl-1,11-dimercapto-3,6, 9-tritiaundecane represented by the following formula (7), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane represented by the following formula (8) can preferably be used.
(Compound containing nitrogen (B))
[0023] The nitrogen-containing compound (B) has a structure in which at least one of a mercapto group of the polythiol compound (A) having three or more mercapto groups is replaced with a group represented by the following formula (a) and at least another mercapto group of the polythiol compound (A) is replaced with a hydroxyl group.

[0024] In the formula, * represents an atomic bond.
[0025] In addition, the nitrogen-containing compound (B) can include a salt of the compound having the structure described above. The salt is not particularly limited, however, for example, it includes carboxylic acid such as acetic acid, an organic acid such as methanesulfonic acid, a compound having a mercapto group (SH), an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric.
[0026] In the polyol composition of the present embodiment, the peak area of the nitrogen-containing compound (B) to the peak area of 100 of the polythiol compound (A) (hereinafter also referred to simply as “the ratio of the area of peak of nitrogen-containing compound (B) ”) is equal to or less than 3.0, preferably equal to or less than 1.5, and more preferably equal to or less than 0.50 in a liquid chromatography measurement high performance. The lower limit of the peak area ratio of the nitrogen-containing compound (B) does not exist particularly, however, it is preferably equal to or more than 0.01, considering the number of the step in purification on an industrial production scale.
[0027] In the usual case, the nitrogen-containing compound (B) is a mixture of a plurality of isomers, and appears as a peak in the predetermined retention time in high performance liquid chromatography. In addition, the peaks of the nitrogen-containing compound (B) which is a mixture of a plurality of isomers can be superimposed.
[0028] Adjusting the peak area ratio of the nitrogen-containing compound (B) to the range described above, it is possible to obtain the plastic lens comprised of the resin based on polythiourethane which is excellent in quality such as color, transparency, streaking .
[0029] The peak area ratio of the nitrogen-containing compound (B) can be calculated from the following expression based on the peak area of high performance liquid chromatography. Expression: {[eak area of the compound containing nitrogen (B)] / [eak area of the polythiol compound (A)]} * 100
[0030] In addition, high performance liquid chromatography conditions are appropriately selected according to structures, properties, or the like of the polythiol compound (A) and the nitrogen containing compound (B).
[0031] The peak area ratio of the nitrogen-containing compound (B) in the present embodiment, for example, can be described, in a case where the polythiol compound (A) is “4-mercaptomethyl-1,8-dimercapto- 3,6-dithiaoctane ”and the nitrogen-containing compound (B) is“ a compound in which one of a mercapto group of the polythiol compound (A) is replaced with a group represented by formula (a) described above and another from a group mercapto is replaced with a hydroxyl group.
[0032] In a case of measuring by high performance liquid chromatography under the conditions described below and calculating the peak area ratio of the nitrogen-containing compound (B) based on the expression described above, the peak area of the nitrogen-containing compound ( B) which appears at the retention time of 4.3 minutes to 5.6 minutes is equal to or less than 3.0, preferably equal to or less than 1.0, and more preferably equal to or less than 0 , 50, with respect to the peak area of 100 of the polythiol compound (A) appearing at the retention time of 12.0 minutes to 13.5 minutes. The lower limit of the peak area ratio of the nitrogen-containing compound (B) does not exist particularly, however, it is preferably equal to or more than 0.01, considering the number of the step in purification on an industrial production scale.
[0033] Furthermore, in a case of measuring under the conditions described below, any peak of the nitrogen-containing compound (B) which is a mixture of a plurality of isomers appears within the retention time described above and each peak can be overlaid. High performance liquid chromatography measurement conditions Column: YMC-Pack ODS-A A-312 (S5Φ6 mm x 150 mm) Mobile phase: acetonitrile / 0.01 mol aqueous solution of potassium phosphate dihydrogen = 60/40 (vol / vol) Column temperature: 40 ° C Flow rate: 1.0 ml / min Detector: UV detector, wavelength 230 nm Preparation of the measurement solution: 160 mg of a sample is dissolved and mixed in 10 ml of acetonitrile . Injection volume: 2 μL
[0034] In addition, the peak area ratio of the nitrogen-containing compound (B) in the present embodiment, for example, can also be described in a case where the polythiol compound (A) is “a polythiol compound that is mainly comprised of at least one type selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto3,6,9-tritiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane ”and the nitrogen-containing compound (B) is“ a compound in which one of a mercapto group of the polythiol compound (A) is replaced with a group represented by formula (a) described above and another group of mercapto group is replaced with a hydroxyl group ”.
[0035] In a case of measuring by high performance liquid chromatography under the conditions described below and calculating the peak area ratio of the nitrogen-containing compound (B) based on the expression described above, the peak area of the nitrogen-containing compound ( B) that appears at the retention time of 6.5 minutes to 8.0 minutes is equal to or less than 3.0, preferably equal to or less than 2.0, and more preferably equal to or less than 1 , 5, with respect to the peak area of 100 of the polythiol compound (A) appearing at the retention time of 22.0 minutes to 28.0 minutes. The lower limit of the peak area ratio of the nitrogen-containing compound (B) does not exist particularly, however, it is preferably equal to or more than 0.01, considering the number of the step in purification on an industrial production scale.
[0036] Furthermore, in a case of measuring under the conditions described below, any peak of the nitrogen-containing compound (B) which is a mixture of a plurality of isomers appears within the retention time described above and each peak can be overlaid. High performance liquid chromatography measurement conditions Column: YMC-Pack ODS-A A-312 (S5Φ6 mm x 150 mm) Mobile phase: acetonitrile / 0.01 mol aqueous solution of potassium phosphate dihydrogen = 60/40 (vol / vol) Column temperature: 40 ° C Flow rate: 1.0 ml / min Detector: UV detector, wavelength 230 nm Preparation of the measurement solution: 160 mg of a sample is dissolved and mixed in 10 ml of acetonitrile . Injection volume: 2 μL
[0037] By adjusting the peak area ratio of the nitrogen-containing compound (B) to the range described above, it is possible to obtain the plastic lens comprised of the resin based on polythiourethane which is excellent in quality such as color, transparency and striation .
[0038] As described above, in the present embodiment, providing two types of the polythiol compound described above as a polythiol compound (A), as an example, a case where the nitrogen-containing compound (B) is “a compound in that one of a mercapto group of two types of the polythiol compound described above is replaced with a group represented by the formula (a) described above and another of a mercapto group is substituted with a hydroxyl group ”, however, aspects including the compound containing nitrogen (B) such as (1) or (2) described below can also be included. (1) The nitrogen-containing compound (B) in which at least one of a mercapto group of two types of the polythiol compound described above is replaced with a group represented by formula (a) described above and at least two mercapto groups are replaced with a hydroxyl group. (2) The nitrogen-containing compound (B) in which at least two of a mercapto group of two types of the polythiol compound described above are replaced with a group represented by formula (a) described above and at least one of a mercapto group is replaced with a hydroxyl group.
[0039] Furthermore, in the present embodiment, a case where the polythiol compound (A) are two types of the polythiol compound described above is given as an example to be described, however, a polythiol compound except these two types selected from the exemplified polythiol compound described above can also be used. Process for producing polythiol composition
[0040] The polyol composition of the present modality can be produced by the following steps. Step A: The polyalcohol compound is obtained. Step B: The polyalcohol compound obtained in step A reacts with thiourea in the presence of hydrogen chloride to obtain an isothiouronium salt. Step C: although a reaction solution including the isothiouronium salt obtained in step B is maintained at a temperature of 20 ° C to 60 ° C, aqueous ammonia is added to the reaction solution within 80 minutes and the isothiouronium salt is hydrolyzed at a temperature of 20 ° C to 60 ° C to obtain the polythiol composition. Step D: The polythiol composition obtained in step C is purified.
[0041] In the present embodiment, cases where polythiol compositions including two types of the polythiol compound described below are obtained are described.
[0042] As a polythiol compound, a case of producing "a polythiol compound that is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane" is fitted with a modality I and a case of producing “A polythiol compound that is mainly comprised of at least one type selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto -3,6,9-tritiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane ”is adjusted to a mode II to be described. Mode I
[0043] Then, each step will be described in order. (Step A)
[0044] In step A, a 2-mercaptoethanol reacts with an epialohydrin compound represented by the following formula (1), in this way it is possible to obtain a triol compound represented by the following formula (2) as a polyalcohol compound.

[0045] In formula (1), X is a halogen atom that is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and preferably a chlorine atom.
[0046] In the present embodiment, the reaction can be carried out in a range of 10 ° C to 50 ° C, preferably from 15 ° C to 50 ° C, and more preferably from 25 ° C to 45 ° C. The reaction temperature is lower than 10 ° C, since the reaction does not progress in the first half of the reaction, unreacted materials are stagnant in the reaction system, and so there are cases where the reaction rapidly progresses. When higher than 50 ° C, there are cases where the color of the lens degenerates. That is, when in a temperature range described above, the reaction control capacity is excellent, in addition, the color of the obtained plastic lens is also excellent.
[0047] The reaction can be carried out for 2 hours to 12 hours, and preferably for 3 hours to 10 hours.
[0048] The reaction described above, for example, can be carried out as follows. First, then 2-mercaptoethanol and a base are added in water or lower alcoholic solvent such as methanol, or ethanol as needed, epialohydrin is added to the drops to carry out the reaction. It is preferable to adjust so that the reaction temperature and reaction time are in the ranges described above. In addition, the reaction time includes the time to add epialohydrin drops, and the temperature of the reaction solution needs to be adjusted to the reaction temperature described above when adding the drops. The amount of 2-mercaptoethanol used is more preferably equal to or more than 1.9 mol and equal to or less than 2.1 mol, with respect to 1 mol of epialohydrin.
[0049] As a base, a metal hydroxide such as sodium hydroxide, potassium hydroxide, a metal carbonate such as sodium carbonate, potassium carbonate, and a tertiary amine such as triethylamine, tributylamine are meanwhile included, sodium hydroxide it is most preferable, in the light of reactivity and economy. In a case of a monovalent base, the amount used of the base is equal to or more than 0.5 mol and equal to or less than 2 mol, and preferably equal to or more than 0.9 mol and equal to or less than 1.1 mol, with respect to 1 mol of epialohydrin. In the case of a bivalent base, half the amount of the used amount of a monovalent base is preferable. The base can be used as an aqueous solution, an alcoholic solution, or the like, and in a use case as a solution, the concentration of the base can be appropriately selected.
[0050] Furthermore, except for the method described above, by the double stage reaction in which once the diol is produced represented by the following formula (3), after 2-mercaptoethanol is added to the drops, it is also possible to obtain the compound of triol represented by formula (2).
[0051] In the method, 2-mercaptoethanol first reacts with an epialohydrin compound represented by the formula (1) described above to obtain a compound represented by the following formula (3).

[0052] The reaction temperature is 10 ° C to 20 ° C. The reaction time is approximately 2 hours to 10 hours.
[0053] Then, the compound described above represented by formula (3) is reacted with 2-mercaptoethanol to obtain the triol compound represented by formula (2). The reaction temperature is 10 ° C to 50 ° C, preferably 15 ° C to 50 ° C, and more preferably 20 ° C to 45 ° C. The reaction time is approximately 2 hours to 12 hours.
[0054] Performing the steps in a temperature range described above, the ability to control the reaction is excellent.
[0055] Specifically, the method can be performed as follows. [0056] First, epialohydrin is added to the drops in a solution comprised of 2-mercaptoethanol, and water or lower alcoholic solution such as methanol or ethanol as needed, and an aqueous solution of the base of the amount of catalyst or lower alcohol such as methanol or ethanol based on the amount of catalyst. It is preferable to adjust so that the reaction temperature and reaction time are in the ranges described above. In the solution to which epialohydrin is added to the drops, the amount of 2-mercaptoethanol used is equal to or more than 1 mol and equal to or less than 3 mol, and preferably equal to or more than 1 mol and equal to or less than 2 mol, with respect to 1 mol of epialohydrin. In addition, the base described above the amount of catalyst is used, and in a case of a monovalent base, the amount used of the base described above is equal to or more than 0.001 mol and equal to or less than 0.1 mol , with respect to epialohydrin. In the case of a bivalent base, half the amount of the used amount of a monovalent base is preferable. The base can be used as an aqueous solution, an alcoholic solution, or the like, and in a use case as a solution, the concentration of the base can be appropriately selected. By adding epialohydrin to the drops in the solution described above, the diol represented by formula (3) is obtained.
[0057] Subsequently, still adding 2-mercaptoethanol so that 2-mercaptoethanol is equal to or more than 1.5 mol and equal to or less than 3.0 mol, with respect to 1 mol of epialohydrin if there is any scarcity, and adding the scarcity of the base so that the base is equal to or more than 1.0 mol and equal to or less than 2.0 mol, with respect to epialohydrin, the represented polyalcohol compound by formula (2) can be obtained. It is preferable to adjust so that the reaction temperature and reaction time are in the ranges described above.
[0058] In a synthesis of diol represented by formula (3), in a case where a strong base such sodium hydroxide is used, it is appropriate that the reaction temperature is set to equal to or more than 10 ° C and equal at or less than 50 ° C. The reaction temperature is very high, since the base added with the amount of catalyst is consumed in a reaction to produce the polyalcohol compound from diol, there is some possibility of decreasing the yield of a diol. (Step B)
[0059] Then, the polyalcohol compound represented by formula (2) obtained in step A reacts with thiourea in the presence of hydrogen chloride to obtain the isothiouronium salt.
[0060] Specifically, thiourea which is equal to or more than 2.7 mol, preferably equal to or more than 2.7 mol and equal to or less than 6.0 mol, and more preferably equal to or more than that 2.9 mol and equal to or less than 3.2 mol, with respect to 1 mol of the polyalcohol compound, is added to the polyalcohol compound represented by formula (2) to react. The reaction is carried out in the presence of hydrogen chloride which is equal to or more than 3 mol, preferably equal to or more than 3 mol and equal to or less than 12 mol, and more preferably equal to or more than 3 mol is equal to or less than 5 mol, with respect to 1 mol of the polyalcohol compound, in a range of room temperature at reflux temperature, and preferably at a temperature of 90 ° C to 120 ° C, for approximately 1 hour at 10 hours. By the reaction of the polyalcohol and thiourea compound, the isothiouronium salt compound is formed. Using hydrogen chloride, it is possible to obtain sufficient reaction speed, in addition, to control the color of the thiol compound and the color of the obtained plastic lens. Like hydrogen chloride, an aqueous solution of hydrochloric acid and hydrogen chloride gas can be used. In an use case an aqueous hydrochloric acid solution, the concentration of this can be appropriately selected. (Step C)
[0061] Aqueous ammonia is added to the reaction solution including the isothiouronium salt obtained in step B, and the isothiouronium salt is hydrolyzed to obtain the polythiol compound. As a polythiol compound, it is possible to obtain the polythiol composition which is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane represented by the following formula (5).

[0062] Specifically, although the reaction solution including the isothiouronium salt is maintained in a temperature range of 15 ° C to 60 ° C, preferably from 31 ° C to 55 ° C, more preferably from 31 ° C to 45 ° C, aqueous ammonia is added to the reaction solution equal to or shorter than 80 minutes, preferably equal to or shorter than 70 minutes, and more preferably 20 minutes to 60 minutes. The time to add aqueous ammonia is preferably shorter, however, the time is adjusted to within the time described above, considering the capacity of the equipment such as cooling capacity, or the like.
[0063] Before adding aqueous ammonia, an organic solvent is preferably added. By adding the organic solvent, the quality as well as color of the obtained plastic lens is improved. The amount of organic solvent additive is appropriately selected according to the classification of the solvent, or the like, however, it is possible to add with the amount which is 0.1 times to 3.0 times, and preferably 0.2 times to 1.0 times, with respect to the reaction solution of thiouronium salt. As an organic solvent, toluene, xylene, chlorobenzene, dichlorobenzene, and the like are included. Toluene is preferable from the point of view of the effect described above.
[0064] Aqueous ammonia can be added within the addition time described above so that ammonia (NH3) is equal to or more than 1 mol, preferably equal to or more than 1 mol and equal to or less than 3 mol , and more preferably equal to or more than 1.1 mol and equal to or less than 2 mol, with 1 mol of the used amount of hydrogen chloride described above. The aqueous ammonia concentration can be adjusted to 10% to 25%. In addition, ammoniacal gas can be used instead of aqueous ammonia. In a case where ammoniacal gas is added in place of all or part of aqueous ammonia, it is possible to perform under the same conditions (the amount used, the time of addition, the temperature of addition) as aqueous ammonia.
[0065] In the present embodiment, ammonia (NH3) is added so that the rate of addition is equal to or more than 1.25 mol% / minute, preferably equal to or more than 1.25 mol% / minute. minute is equal to or less than 3.75 mol% / min, and more preferably equal to or more than 1.38 mol% / min and equal to or less than 2.5 mol% / min, with 1 mole of hydrogen chloride. In the step, it is not necessary to continually add to the rate described above, and the average addition rate at the addition time described above just has to be included in the range.
[0066] And, after the aqueous ammonia is added, a hydrolysis reaction is continued to be carried out in an ambient temperature range at reflux temperature, and preferably from 30 ° C to 80 ° C, for approximately 1 hour to 8 hours . (Step D)
[0067] In the present embodiment, the polythiol composition obtained in step C is purified by washing.
[0068] Specifically, acid washing and then water washing multiple times can be performed. Aqueous wash before acid wash and alkaline wash after acid wash can be performed. It is possible to decrease the number of times of aqueous washing by alkaline washing. Through a washing step, it is possible to effectively remove impurities, or the like. Purifying by washing, it is possible to produce the high quality plastic lens in which the color of the plastic lens obtained from the polythiol composition is improved, in addition, the occurrence of turbidity and streaking is reduced, in a satisfactory yield , and the efficiency percentage is also improved. As an example of the preferred aspect, after hydrolysis, a method of carrying out aqueous washing, acid washing, aqueous washing, alkaline washing and aqueous washing in order, a method of carrying out acid washing, aqueous washing, alkaline washing and aqueous washing in order, a method of performing acid wash and aqueous wash in order, and the like can be included. Each wash can be repeated multiple times.
[0069] Acid washing can be performed by adding hydrochloric acid to the solution including the obtained polythiol composition. The hydrochloric acid concentration can be adjusted to 25% to 36%, and preferably 30% to 36%. When the hydrochloric acid concentration is lower than 25%, there are cases where turbidity occurs in the plastic lens due to impurities or the like. In addition, the acid wash temperature can be adjusted to 10 ° C to 50 ° C, preferably from 15 ° C to 50 ° C, more preferably and from 20 ° C to 50 ° C, and even more preferably 30 ° C at 45 ° C.
[0070] For aqueous washing, degassed water in which the oxygen concentration is equal to or less than 7 mg / L can be used.
[0071] As a process of producing degassed water, a method of blowing nitrogen to remove dissolved oxygen, a method of expelling dissolved oxygen by heat treatment, a method of expelling dissolved oxygen by vacuum degassing, and the like are included, however, method is not particularly limited, if the method can make the oxygen concentration equal to or less than 5 mg / L.
[0072] In this way, it is possible to effectively suppress the color or turbidity that becomes a problem in the optical material such as the plastic lens.
[0073] In addition, alkaline washing can be performed by adding an aqueous alkaline solution and stirring in a range of 20 ° C to 50 ° C for 10 minutes to 3 hours. As an aqueous alkaline solution, aqueous ammonia is preferable. In addition, the aqueous ammonia concentration can be adjusted to 0.1% to 10%, preferably 0.1% to 1%, more preferably 0.1% to 0.5%.
[0074] In addition, also in acid wash and alkaline wash, using water in which the oxygen concentration is equal to or less than 7 mg / L, it is possible to effectively suppress the color or turbidity that becomes a problem optical material such as the plastic lens.
[0075] After step D, by performing a step of removing a solvent, a step of removing a low boiling compound as needed, a filtration step, and a distillation step, it is possible to obtain the polythiol composition including 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a polythiol compound.
[0076] The step of removing a solvent is a step of removing an organic solvent under normal pressures or reduced pressure, and the degree of decompression and temperature are appropriately selected according to the solvent used or similar, however, it is preferable that the step is carried out at 100 ° C or less, and preferably 85 ° C or less, under reduced pressure.
[0077] The step of removing a low-boiling compound is a step of removing the low-boiling compound contained in the target compound under normal pressures or reduced pressure after the step of removing a solvent, and the degree of decompression and the temperature are appropriately selected according to the solvent used or the like, however, it is preferable that the step is carried out at or below 100 ° C, and preferably at or below 85 ° C, under reduced pressure. Therefore, the step can be performed while venting inert gas such as nitrogen gas.
[0078] The filtration step is a step of removing a solid material such as a salt by filtration, and a filtration method and the like are appropriately selected, however, filtration under reduced pressure or pressure filtration using a membrane filter or a cartridge filter and the like can be used. It is preferable that the step be carried out with a filter that the pore size of a filter is equal to or less than 5 μm, and preferably equal to or less than 2 μm.
[0079] The distillation step is a step of purifying the polyol compound by distillation, and the degree of decompression and temperature are appropriately selected according to the solvent used or the like, however, it is preferable that the step be carried out the same a or lower than 250 ° C, and preferably equal to or lower than 200 ° C, under reduced pressure.
[0080] In addition, in order to adjust the peak area ratio of the nitrogen-containing compound (B), a step of reducing the nitrogen-containing compound (B) by purifying by acid washing is sometimes used. In this case, it is necessary to confirm the amount of the nitrogen-containing compound (B) included in the polythiol composition and appropriately adjust the acid wash conditions so that the amount of the nitrogen-containing compound (B) is in the predetermined range.
[0081] It is considered that the peak area ratio of the nitrogen-containing compound (B) is multiplied by a combination of conditions in a plurality of stages during synthesis or purification. On the other hand, the production conditions disclosed in the present invention have extremely good repeatability and can provide the polythiol composition including the nitrogen-containing compound (B) in the predetermined range.
[0082] In addition, the production process of the present modality can also be conducted in the air, however, it is preferable that the integral production process is carried out under an atmosphere of nitrogen under colored light.
[0083] By such a production process, the polythiol composition including the polythiol compound (A) and the nitrogen-containing compound (B) with the predetermined range in the present modality can be adequately obtained. Mode II
[0084] In modality II, a case of producing “a polythiol compound that is mainly comprised of at least one type selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9tritiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane ”is described as follows. In addition, the description of the same steps as an I modality will not be repeated.
[0085] Then, each step is described in order. (Step A)
[0086] In the present modality, firstly by 2-mercaptoethanol reacting with an epialohydrin compound represented by the following formula (1)

[0087] It is possible to obtain a diol compound represented by the following formula (3).

[0088] In the formula (1) described above, X is a halogen atom that is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and preferably a chlorine atom.
[0089] In the present embodiment, the reaction can be carried out in a range of 2 ° C to 30 ° C, preferably from 5 ° C to 20 ° C, and more preferably from 5 ° C to 15 ° C. The reaction can be carried out for 2 hours to 10 hours.
[0090] Specifically, the reaction can be carried out as follows.
[0091] First, epialohydrin is added to the drops in a solution comprised of 2-mercaptoethanol, and water or lower alcoholic solution such as methanol or ethanol as needed, and an aqueous solution of the base or lower alcohol above such as methanol or ethanol solution from the base above. It is preferable to adjust so that the reaction temperature and reaction time are in the ranges described above. In the solution to which epialohydrin is added to the drops, the amount of 2-mercaptoethanol used is equal to or more than 0.5 mol and equal to or less than 3 mol, preferably equal to or more than 0.7 mol and equal to or less than 2 mol, and more preferably equal to or more than 0.9 mol and equal to or less than 1.1 mol, with respect to 1 mol of epialohydrin. In addition, the base described above the amount of catalyst is used, and in a case of a monovalent base, the amount used of the base described above is preferably equal to or more than 0.001 mol and equal to or less than 0.1 mole, with respect to 1 mole of epialohydrin. In the case of a bivalent base, half the amount of the used amount of a monovalent base is preferable. The base can be used as an aqueous solution, an alcoholic solution, or the like, and in a use case as a solution, the concentration of the base can be appropriately selected. By adding epialohydrin to the drops in the solution described above, diol represented by formula (3) is obtained. (Step B)
[0092] Then, by the diol compound represented by the formula (3) described above reacting with sodium sulfide, a tetraol compound represented by the following formula (4) can be obtained.

[0093] In the present modality, the reaction can be carried out in a range of 10 ° C to 50 ° C, and preferably from 20 ° C to 40 ° C. The reaction can be carried out for 1 hour to 10 hours.
[0094] Specifically, the reaction can be carried out as follows.
[0095] Aqueous sodium sulfide solution is added to the drops or the solid sodium sulfide is loaded into the reaction solution including the diol compound after the reaction described above. It is preferable to adjust so that the reaction temperature and reaction time are in the ranges described above. Sodium sulfide can be used with the amount of 0.4 mol to 0.6 mol, preferably 0.45 mol to 0.57 mol, more preferably 0.48 mol to 0.55 mol, with respect to 1 mol of the compound of diol. (Step C)
[0096] Then, by the tetraol compound obtained in step B and represented by formula (4) reacting with thiourea in the presence of hydrogen chloride to obtain the isothiouronium salt.
[0097] Specifically, thiourea which is equal to or more than 3 mol, preferably equal to or more than 3 mol and equal to or less than 6 mol, and more preferably equal to or more than 4.6 mol and equal to or less than 5.0 mol, with respect to 1 mol of the tetraol compound is added to the tetraol compound to react. The reaction is carried out in the presence of hydrogen chloride which is equal to or more than 3.0 mol, and preferably equal to or more than 3 mol and equal to or less than 12 mol, with respect to 1 mol of the compound of tetraol in a room temperature range at reflux temperature, and preferably at a temperature of 90 ° C to 120 ° C, for approximately 1 hour to 10 hours. By the reaction of the tetraol and thiourea compound, the isothiouronium salt compound is formed. Using hydrogen chloride, it is possible to obtain sufficient reaction speed, in addition, to control the color of a product. Like hydrogen chloride, an aqueous solution of hydrochloric acid and hydrogen chloride gas can be used. (Step D)
[0098] Aqueous ammonia is added to the reaction solution including the isothiouronium salt obtained in step C to hydrolyze the isothiouronium salt and the polythiol composition is obtained.
[0099] In the present embodiment, as a polythiol compound, it is possible to obtain the polythiol composition including the polythiol compound which is mainly comprised of at least one type selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto -3,6,9-tritiaundecane represented by the following formula (6), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane represented by the following formula (7), and 5,7-dimercaptomethyl- 1,11-dimercapto -3,6,9-tritiaundecane represented by the following formula (8).

[00100] Specifically, although the reaction solution including the isothiouronium salt is maintained in a temperature range of 20 ° C to 60 ° C, preferably from 25 ° C to 55 ° C, and more preferably from 25 ° C to 50 ° C, aqueous ammonia is added to the reaction solution equal to or shorter than 80 minutes, preferably equal to or shorter than 70 minutes, more preferably 20 minutes to 60 minutes, and even more preferably 20 minutes 30 minutes. The time to add aqueous ammonia is preferably shorter, however, the time is adjusted to within the time described above, considering the capacity of the equipment such as cooling capacity, or the like.
[00101] Before adding aqueous ammonia, an organic solvent is preferably added. By adding the organic solvent, it is possible to suppress producing a by-product. The amount of additive of the organic solvent is appropriately selected according to the classification of the solvent, or similar, however, it is possible to add with the amount that is 0.1 times to 3.0 times, and preferably 0.2 times to 2.0 times, with respect to the thiouronium salt reaction solution. As an organic solvent, toluene, xylene, chlorobenzene, dichlorobenzene, and the like are included. Toluene is preferable, from the point of view of the effect described above.
[00102] Aqueous ammonia can be added within the addition time described above so that ammonia (NH3) is equal to or more than 1 mol, preferably equal to or more than 1 mol and equal to or less than 3 moles , and more preferably equal to or more than 1.1 mol and equal to or less than 2 mol, with 1 mol of the used amount of hydrogen chloride described above. The aqueous ammonia concentration can be adjusted to 10% to 25%. In addition, ammoniacal gas can also be used instead of aqueous ammonia. In a case where ammoniacal gas is added in place of all or part of the aqueous ammonia, it is possible to perform under the same conditions (the amount used, the addition time, the addition temperature) as aqueous ammonia.
[00103] In the present embodiment, ammonia (NH3) is added so that the rate of addition is equal to or more than 1.25 mol% / minute, preferably equal to or more than 1.25 mol% / minute. minute is equal to or less than 3.75 mol% / min, and more preferably equal to or more than 1.38 mol% / min and equal to or less than 2.5 mol% / min, with respect to 1 mole of hydrogen chloride. In the step, it is not necessary to continuously add to the rate described above, and the average addition rate at the addition time described above has to be included only in the range.
[00104] And, after the aqueous ammonia is added, a hydrolysis reaction is continued to be carried out in an ambient temperature range At reflux temperature, and preferably at a temperature of 30 ° C to 80 ° C, for approximately 1 hour at 8 hours. (Step E)
[00105] In the present embodiment, the polyol composition obtained in step D is purified. Step E in the present mode can be performed in the same way as mode I.
[00106] In addition, the stage after stage E can also be performed in the same way as Mode I.
[00107] By such a production process, the polythiol composition including the polythiol compound (A) and the nitrogen containing compound (B) in the predetermined range in the present modality can be adequately obtained.
[00108] As described above, in the present embodiment, specifically, the description of the process of producing the polythiol composition including two types of polythiol compound like the polythiol compound (A) has been given as an example, however, another method can be used if the peak area ratio of the nitrogen-containing compound (B) can be adjusted to the predetermined range.
[00109] In addition, for still the polythiol compound except the two selected types of the exemplified polythiol compounds described above, by changing the production conditions appropriately, the peak area ratio of the nitrogen-containing compound (B) can be adjusted to the predetermined range. Polymerizable composition for optical material
[00110] The polymerizable composition for the optical material in the present embodiment includes the polyol composition for the optical material that is obtained by the method described above and composed of poly (iso) thio cyanate.
[00111] The poly iso (thio) cyanate compound is not particularly limited as long as the poly iso (thio) cyanate compound is a compound having at least two or more iso (thio) cyanate groups in a molecule. However, specifically, the poly (iso) cyanoate includes an aliphatic polyisocyanate compound such as hexamethylene diisocyanate, 1,5-pentane diisocyanate, 2,2-dimethylpentane diisocyanate, di-isocyanate 2,2,4-trimethylhexane isocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-hexamethylene trimethyldiisocyanate, 1,6,11- triisocyanate undecane, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, diisocyanatomethyl lysine ester, or lysine triisocyanate; an alicyclic polyisocyanate compound such as isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclo isocyanate -hexyldimethylmethane, 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 3,8-bis (isocyanatomethyl) tricyclodecane , 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cycle -hexane, or 1,4-bis (isocyanatomethyl) cyclohexane; a polyisocyanate compound having an aromatic ring compound such as 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, tolylene diisocyanate, 2,4-diisocyanate isocyanatotoluene, 2,6-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylene benzene diisocyanate, triisisis triisbenzene triisis, triis biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis (phenyl isocyanate), 4,4'-methylenebis (2-methylphenyl isocyanate), bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatomethyl) benzene, m-xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylylene, bis (isocyanatobutyl) ) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ether, bis (isocyanatoethyl) phthalate, or 2,5-di (isocyanatomethyl) furan; a sulfur-containing aliphatic polyisocyanate compound such as bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (issocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanate ) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1 , 2,3-tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptanotetra isocyanate, 2,6-diisocyanate isocyanatomethyl -3,5-dithia-1,7-heptane, 2,5-diisocyanate methyl thiophene, or 4-isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate; a polyisocyanate compound based on aromatic sulfide such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, or bis (4-isocyanatomethylphenyl) sulfide; a polyisocyanate compound based on aromatic disulfide such as bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl -6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, or bis (4-methoxy-3-isocyanatophenyl) disulfide; a sulfur-containing alicyclic polyisocyanate compound such as 2,5-diisocyanate tetrahydrothiophene, 2,5-diisocyanatomethyl tetrahydrothiophene, 3,4-diisocyanatomethyl tetrahydrothiophene, 2,5-diisocyanate -1,4- dithian, 2,5-diisocyanatomethyl-1,4-dithian, 4,5-diisocyanate-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, or 4,5- diisocyanatomethyl-2-methyl-1,3-dithiolane; an aliphatic polyisothiocyanate compound such as 1,2-diisothiocyanatoethane or 1,6-diisothiocyanatoexane; an alicyclic polyisothiocyanate compound such as cyclohexane diisothiocyanate; an aromatic polyisothiocyanate compound such as benzene 1,2-diisothiocyanate, benzene 1,3-diisothiocyanate, benzene 1,4-diisothiocyanate, toluene 2,4-diisothiocyanate, 2,5-di -m-xylene isothiocyanate, 4,4'-methylenebis (phenyl isothiocyanate), 4,4'-methylenebis (2-methylphenyl isothiocyanate), 4,4-methylenebis (3-methylphenyl isothiocyanate), 4.4 ' benzophenone di-isothiocyanate, 4,4'-diisothiocyanate-3,3 '-dimethyl benzophenone, or bis (4-isothiocyanatophenyl) ether;
[00112] In addition, a carbonyl polyisothiocyanate compound such as 1,3-benzene dicarbonyl diisothiocyanate, 1,4-benzene dicarbonyl diisothiocyanate, or (2,2-pyridine) diisothiocyanate -4,4-dicarbonyl; a sulfur-containing aliphatic polyisothiocyanate compound such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), or dithiobis (2-isothiocyanatoethane); a sulfur-containing aromatic polyisothiocyanate compound such as 1-isothiocyanate-4 - [(2-isothiocyanate) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), or dithiobis (4-isothiocyanatobenzene); a sulfur-containing alicyclic polyisothiocyanate compound such as 2,5-diisothiocyanatothiophene, or 2,5-diisothiocyanate -1,4-dithian; a compound having an isocyanate group and an isothiocyanate group such as 1-isocyanato-6-isothiocyanatoexane, 1-isocyanato-4isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2 isocyanate-4,6-diisothiocyanate1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanatophenyl sulfide, or 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide, and the like.
[00113] A polyisoc (thio) cyanate compound preferably includes an aliphatic based polyisocyanate compound such as hexamethylene diisocyanate, 1,5-pentanediisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2,2,1] heptane, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, or 1,4-bis (isocyanatomethyl) cyclohexane; a polyisocyanate compound having an aromatic ring compound such as bis (isocyanatomethyl) benzene, m-xylylene diisocyanate, 1,3-diisocyanatobenzene, tolylene diisocyanate, 2,4-diisocyanatotoluene, 2, 6-diisocyanatotoluene, 4,4'-methylenebis (phenylisocyanate).
[00114] Furthermore, it is possible to use a halogen substitution of this one such as a chlorine substitution or a bromine substitution, an alkyl substitution of this, an alkoxy substitution of this, a substitution of nitro of this, a modified product of the pre type -polymer polymer, a carbodiimide-modified product, a urea-modified product, a burette-modified product, a dimerization or trimerization reaction product, and the like. The compounds can be used alone or in a combination of two or more types.
[00115] As a polythiol compound used in the polymerizable composition for the optical material, in addition to the polythiol compound for the optical material that is obtained by the method described above, another polythiol compound for the optical material can be used.
[00116] Another polythiol compound for the optical material preferably includes an aliphatic polythiol compound such as methane dithiol, 1,2-ethanedithiol, 1,2,3-propanotrithiol, pentaerythritol tetracis (2-mercaptoacetate), tetracis (3- mercaptopropionate) of pentaerythritol, bis (mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-dithian, tetracis (mercaptomethyl methyl) methane, tetracis (2-mercaptoethylthio methyl) methane, tetracis (3-mercaptopropyl methyl) methane, bis ( 2,3-dimercaptopropyl) sulfide, 2,5-dimercaptomethyl-1,4-dithian, 2,5-dimercapto-1,4-dithian, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithian, 1,1,3,3-tetracis (mercaptomethylthio) propane, 1,1,2,2-tetracis (mercaptomethylthio) ethane, or 4,6-bis (mercaptomethylthio) -1,3-dithian.
[00117] The ratio of use of the polythiol compound and the poly-iso (thio) cyanate compound is not particularly limited, however, the molar ratio is usually within the range of an SH group / an NCO group = 0.5 to 3.0, within a range of preferably 0.6 to 2.0, and more preferably 0.8 to 1.3. If the reason for use is within the range described above, it becomes possible to satisfy a refined balance of various types of performance such as the refractive index or the thermal resistance required as the optical material such as the plastic lens and the transparent material.
[00118] For the purpose of improving various properties, operability, polymerization reactivity, or the like of the polyurethane-based resin of the present invention, other substances may be added, in addition to the polythiol compound and the iso compound (uncle) cyanate that form a urethane resin. For example, at least one type of an active hydrogen compound that is typified by amine or the like, a carbonate compound, an ester compound, a metal, a metal oxide, an organic metal compound, an inorganic substance, or the like can be added, in addition to a urethane-forming material.
[00119] Furthermore, according to the purpose, various types of substances such as a chain extender, a crosslinker, a light stabilizer, an ultraviolet absorber, an antioxidant agent, an oil paint, a filler, or a mold release agent can be added in the same way as a well known forming process. In order to adjust the desired reaction rate, a well-known reaction catalyst used in the production of a thiocarbamic acid s-alkyl ester or a polythiurethane based resin can be appropriately added.
[00120] As a reaction catalyst, a well-known reaction catalyst used to produce a thiocarbamic acid s-alkyl ester or a polythiurethane-based resin can be appropriately added.
[00121] A reaction catalyst includes dialkltin halides such as dibutyltin dichloride, or dimethyl tin dichloride, dialkltin dicarboxylates such as dimethyl tin diacetate, dibutyltin dioctanoate, or dibutyltin dioxide dichloride such as dibutyltidoxide, dialoxide dioctyltin, or dialktyltin dithioaloxides such as dibutyltin di (thiobutoxide), dialkyl tin oxides such as di (2-ethylhexyl) tin oxide, dioctyltin oxide, or bis (butoxy dibutyltin oxide such as dialkyl sulfides) dibutyltin are included. Dialkyl tin halides such as dibutyltin dichloride, dimethyl tin dichloride, as a preferred example.
[00122] In addition, as a purpose of modifying a resin, a resin modifying agent such as a hydroxyl compound, an epoxy compound, an episulfide compound, an organic acid and an anhydride thereof, an olefin compound including a composed of (meta) acrylate or the like can be added. Here, a resin modifying agent is a compound that adjusts or improves the properties of a material comprised of a resin based on thiourethane such as the refractive index, the Abbé number, the thermal resistance and specific gravity, and the mechanical strength of this such as impact resistance, or the like.
[00123] In addition, the polymerizable composition for the optical material of the present embodiment can include a bleaching agent as needed. The bleaching agent has an absorption band in a wavelength range from orange to yellow in a visible light region and has a function of adjusting the color of an optical material comprised of a resin. More specifically, the bleaching agent includes a substance that shows from blue to purple.
[00124] The bleaching agent used in the polymerizable composition for the optical material of the present embodiment is not particularly limited, specifically, a dye, a fluorescent polishing agent, a fluorescent pigment, an inorganic pigment and the like are included, however, among the substances that can be used as a bleaching agent, the bleaching agent is appropriately selected, according to physical properties that are required for optical components, resin color, or the like. The bleaching agents can be used respectively alone or in a combination of two or more types.
[00125] Among the bleaching agents, a dye is preferable, from the point of view of solubility for the polymerizable composition and from the point of view of the transparency of the optical material that is obtained. [00126] From the point of view of the absorption wavelength, it is preferred that a dye in which the maximum absorption wavelength is equal to or more than 520 nm and equal to or less than 600 nm is used . It is more preferred that a dye in which the maximum absorption wavelength is equal to or more than 540 nm and equal to or less than 580 nm is used.
[00127] Furthermore, a dye based on anthraquinone is preferable, from the point of view of the structure of the compound.
[00128] A method of adding the bleaching agent is not particularly limited, and it is desired to add it to a monomeric system in advance. Like the method, various types of methods such as a method of being dissolved in a monomer or a method in which a main solution containing the high concentration of the bluing agent is prepared and the main solution is diluted by a monomer or other additive which is used to be added can be used.
[00129] The polymerizable composition for the optical material of the present modality is obtained as a mixed liquid, specifically, by mixing the polythiol composition obtained by the production process described above and the polyiso (thio) cyanate compound, in addition , other components as needed. The mixed liquid is placed in a mold and is usually gradually heated from a low temperature to a high temperature to be polymerized after degassing by an appropriate method as needed.
[00130] In this way, a molded product comprised of the polyurethane-based resin obtained by curing the polymerizable composition of the present modality has characteristics that are the high refractive index, low dispersion, excellent thermal resistance and durability, light weight, and resistance to the excellent impact, in addition, the color is favorable and it is suitable as the optical material such as a lens for glasses, a lens for camera and the element of transparent material.
[00131] In addition, the plastic lens obtained using the polyurethane based resin of the present modality can be subjected to a physical or chemical treatment such as surface polishing, antistatic treatment, hard coating treatment, anti-reflective coating treatment, dyeing treatment, gloss reduction treatment as needed, in order to achieve an improvement in anti-reflection, communicating high hardness, enhancing abrasive resistance, enhancing chemical resistance, communicating anti-fog properties, communicating conformability, or similar. Examples
[00132] Next, more detailed description will be given of the present invention according to the Examples, however, the present invention is not limited to these.
[00133] In addition, in the following examples, properties were measured by the following measurement methods. Specific gravity: measured in accordance with JIS K 0061. ■ APHA: APHA is a color display method and determined using a standard solution that was prepared by dissolving a platinum and cobalt reagent and comparing the diluted solution of standard solution having the concentration equal to the color of the samples, the “frequency” was adjusted to the measured value. ■ The amount of water: A monomer was dissolved in toluene, and the aqueous measurement was conducted by Karl Fischer Moisture Titrate. ■ Viscosity: It was measured according to JIS K 7117. ■ Refractive index: It was measured at 20 ° C by a digital refractometer RA-600 manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. ■ Ammonium content: A monomer was dissolved in chloroform, extracted with water and measured by ion chromatography. ■ Acid content: A monomer was dissolved in a solvent, calculated as the HCl content by titration with a methanol solution of KOH. ■ Degree of loss of transparency of the resin: A 9 mm flat plate was produced with the production conditions of the plastic lenses of the Examples to measure by a degree of loss of transparency measuring device (manufactured by HAYASHI WATCH-WORKS: LUMINAR ACE LA-150SE). ■ YI of the resin: it is a yellow index in the color evaluation. YI is measured by a color difference meter. A 9 mm flat plate was produced with the production conditions of the plastic lenses of the Examples to measure a YI value using a color difference meter (CR-400) manufactured by KONICA MINOLTA, INC. ■ Streaking: The lens was produced with the production conditions of the plastic lenses of the Examples and visually observed under a high pressure mercury lamp, and the lens in which a stripe-like pattern was not observed was O and the lens in which a stripe-like pattern was observed was X.
[00134] In addition, dissolved oxygen was extracted from the water by blowing hydrogen into the water to obtain degassed water which is 2 ppm of the dissolved oxygen concentration. Example A-1 (Synthesis of the polythiol composition which is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane)
[00135] 124.6 parts by weight of 2-mercaptoethanol and 18.3 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were loaded into a reaction vessel. After 101.5 parts by weight of 32% by weight of aqueous sodium hydroxide solution were added in drops and charged from 12 ° C to 35 ° C for 40 minutes, 73.6 parts by weight of epichlorohydrin were added in drops and charged from 29 ° C to 36 ° C for 4.5 hours, and continuously, stirring was performed for 40 minutes. From NMR data, the production of 1,3-bis (2-hydroxyethylthio) -2-propanol was confirmed.
[00136] 331.5 parts by weight of 35.5% hydrochloric acid were loaded, and subsequently, 183.8 parts by weight of the purity of 99.90% thiourea were loaded and stirred at 110 ° C for 3 hours under reflux to convert to a thiouronium salt. After cooling to 45 ° C, 320.5 parts by weight of toluene were added and cooled to 31 ° C, 243.1 parts by weight of 25% by weight of aqueous ammonia solution were loaded from 31 ° C to 41 ° C for 44 minutes and stirred from 54 ° C to 62 ° C for 3 hours, and a solution of toluene of the polythiol composition which is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was gotten. 162.8 parts by weight of 35.5% hydrochloric acid were added to the toluene solution and the acid wash was performed at 35 ° C to 43 ° C for 1 hour. 174.1 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were added and the wash that was carried out from 35 ° C to 45 ° C for 30 minutes was carried out twice. 162.1 parts by weight of 0.1% aqueous ammonia were added to the wash for 30 minutes. 174.2 parts by weight of degassed water were added and the wash that was carried out from 35 ° C to 45 ° C for 30 minutes was conducted twice. After toluene and trace water were removed under heating and reduced pressure, filtration under reduced pressure was performed by a 1.2 μm PTFE membrane filter to obtain 205.0 parts by weight of a polythiol composition that is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. The physical properties of the obtained polythiol composition are shown in Table 1.
[00137] The results of an elementary analysis and an NMR analysis of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane are shown. Elementary analysis (such as C7H16S5) CHS analysis value 32.12 6.19 61.69 Calculated value

(Purification and confirmation of the structure)
[00138] By silica gel column chromatography (toluene-methanol, stepped method) was repeatedly performed, a nitrogen-containing compound (referred to as B-1) was fractionated and purified from the polythiol composition which is mainly comprised of 4- mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
[00139] From the results of instrumental analysis, it was identified that the nitrogen-containing compound (B-1) had a structure in which one of a 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane mercapto group was substituted with a group represented by the following formula (a), in addition, another one of a mercapto group has been replaced with a hydroxyl group. In the following formula (a), * represents an atomic bond.
(1) FAB-MS mass spectrum: m / z370 (M +) (m-NBA Matrix) (2) IR (Universal ATR Method): 3300 cm-1: NH stretch, 2541 cm-1: SH stretch , 1606 cm-1: C = H stretch, 1520 cm-1: NH sale. (3) 1H-NMR (DMSO-d6): δ ppm 2.3 2.9 (11H (-CH2-, SH)), 3.1 3.45 (3H (-CH-, CH2OH)), 6, 6 6.8 (6H (NH2)). (4) 13C-NMR (DMSO-d6): δ ppm 24 40 (CH2), 46 48 (CH), 70.3 (C-OH (C adjacent to O)), 166.5, 178.1 (- CN- (melamine skeleton)).
[00140] The peak area ratio of the nitrogen-containing compound (B-1) to 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (referred to as a polythiol compound (A-1)) was determined in next way. 1. Conditions for measuring high performance liquid chromatography Column: YMC-Pack ODS-A A-312 (S5Φ6 mm x 150 mm) Mobile phase: acetonitrile / 0.01 mol aqueous solution of potassium dihydrogen phosphate = 60/40 ( vol / vol) Column temperature: 40 ° C Flow rate: 1.0 ml / min Detector: UV detector, 230 nm wavelength Preparation of the measurement solution: 160 mg of a sample is dissolved and mixed in 10 ml acetonitrile. Injection volume: 2 μL 2. Peak area ratio of the nitrogen-containing compound (B-1)
[00141] In the polythiol composition that was produced in Example A-1, the peak area ratio of the nitrogen-containing compound (B-1) to the polythiol compound (A-1) was calculated using the following expression. Expression: {[eak area of nitrogen-containing compound (B-1)] / [eak area of polythiol compound (A-1)]} x100
[00142] The result calculated using the computation expression described above was 0.21.
[00143] In addition, the retention times of the polythiol compound (A-1) and the nitrogen-containing compound (B-1) were as follows. A high performance liquid chromatography graph is shown in Fig. 1. Polythiol compound (A-1): from 12.0 minutes to 13.5 minutes. Compound containing nitrogen (B-1): from 4.3 minutes to 5.6 minutes. (Plastic lens manufacturing)
[00144] 52 parts by weight of m-xylylene diisocyanate, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 parts by weight of Viosorb 583 (trade name, manufactured by CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 48 parts by weight of the obtained polyol composition which is mainly comprised of the polythiol compound (A-1) were loaded and mixed to adjust to a homogeneous mixed liquid. After the homogeneous liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid was placed in a mold matrix consisting of a glass mold and a tape after filtration using a 1 μm Teflon filter (trademark). The mold matrix was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized for 20 hours. After the polymerization was completed, the mold matrix was removed from the oven to obtain a resin freeing itself from the mold matrix. The obtained resin was annealed at 120 ° C for 3 hours. The physical properties of the obtained plastic lens are shown in Table 1. Examples A-2 to A-10
[00145] The polythiol composition that is mainly comprised of the polythiol compound (A-1) in the same way as Example A-1 except adjusted to the production conditions described in Table 1 was produced and the plastic lens was manufactured. The results are shown in Table 1. Example B-1 (Synthesis of the polythiol composition which is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane)
[00146] 124.6 parts by weight of 2-mercaptoethanol and 18.3 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were loaded into a reaction vessel. After 101.5 parts by weight of 32% by weight of aqueous sodium hydroxide solution were added to the drops and charged from 12 ° C to 35 ° C for 40 minutes, 73.6 parts by weight of epichlorohydrin were added in drops and charged at 28 ° C to 36 ° C for 4.5 hours, and continuously, stirring was performed for 40 minutes. From NMR data, the production of 1,3-bis (2-hydroxyethylthio) -2-propanol was confirmed.
[00147] Then, 183.7 parts by weight of the purity of 99.90% thiourea were loaded, 108.6 parts by weight of the purity of 90.7% hydrochloric acid gas were blown and stirred at 110 ° C for 3 hours under reflux to convert to a thiouronium salt. After cooling to 45 ° C, 320.5 parts by weight of toluene were added and cooled to 31 ° C, 216.7 parts by weight of 25% by weight of aqueous ammonia solution were charged from 31 ° C to 40 ° For 29 minutes and matured from 54 ° C to 63 ° C for 3 hours, and a toluene solution of the polythiol composition that is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was obtained . 162.9 parts by weight of 35.5% hydrochloric acid were added to the toluene solution and the acid wash was carried out from 34 ° C to 43 ° C for 1 hour. 174.2 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were added and the washing which was carried out from 35 ° C to 45 ° C for 30 minutes was carried out twice. 162.8 parts by weight of 0.1% aqueous ammonia were added to the wash for 30 minutes. 174.2 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were added and the wash which was carried out from 34 ° C to 43 ° C for 30 min was carried out twice. After toluene and trace water were removed under heating and reduced pressure, filtration under reduced pressure was performed by a 1.2 μm PTFE membrane filter to obtain 205.0 parts by weight of polythiol composition which is mainly comprised of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (a polythiol compound (A-1)). The physical properties of the obtained polythiol composition are shown in Table 1.
[00148] The identification of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was performed in the same way as Example A-1 and the same results were obtained. (Purification and confirmation of the structure)
[00149] By silica gel column chromatography (toluene-methanol, stepped method) was repeatedly performed, the nitrogen-containing compound (B-1) was fractionated and purified from the polythiol composition which is mainly comprised of polythiol compound ( TO 1).
[00150] From the results of instrumental analysis, it was identified that the nitrogen-containing compound (B-1) had a structure in which one of a mercapto group of 4-mercaptomethyl-1,8-dimercapto -3,6-dithiaoctane was substituted with a group represented by the following formula (a), in addition, another one of a mercapto group has been replaced with a hydroxyl group. In the following formula (a), * represents an atomic bond.
(1) FAB-MS mass spectrum: m / z370 (M +) (m-NBA Matrix) (2) IR (Universal ATR Method): 3300 cm-1: NH stretch, 2541 cm-1: SH stretch , 1606 cm-1: C = H stretch, 1520 cm-1: NH sale. (3) 1H-NMR (DMSO-d6): δ ppm 2.3 2.9 (11H (-CH2-, SH)), 3.1 3.45 (3H (-CH-, CH2OH)), 6, 6 6.8 (6H (NH2)). (4) 13C-NMR (DMSO-d6): δ ppm 24 40 (CH2), 46 48 (CH), 70.3 (C-OH (C adjacent to O)), 166.5, 178.1 (- CN- (melamine skeleton)).
[00151] The peak area ratio of the nitrogen-containing compound (B-1) to 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (referred to as a polythiol compound (A-1)) was determined by performing in the same way as Example A-1. (Plastic lens manufacturing)
[00152] 52 parts by weight of m-xylylene diisocyanate, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 parts by weight of Viosorb 583 (trade name, manufactured by KYODO CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 48 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-1) were loaded and mixed to adjust to a homogeneous mixed liquid. After the homogeneous liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid was placed in a mold matrix consisting of a glass mold and a tape after filtration using a 1 μm Teflon filter (trademark). The mold matrix was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized for 20 hours. After the polymerization was completed, the mold matrix was removed from the oven to obtain a resin freeing itself from the mold matrix. The obtained resin was annealed at 120 ° C for 3 hours. The physical properties of the obtained lens are shown in Table 1. Examples B-2 to B-10
[00153] The polythiol composition that is mainly comprised of the polythiol compound (A-1) in the same way as Example B-1 except adjusting to the production conditions described in Table 1 was produced and the plastic lens was manufactured. The results are shown in Table 1. Table 1
Table 1 continued-
Condition I: Conditions for reacting 2-mercaptoethanol with epichlorohydrin. Condition II: Conditions for loading an aqueous ammonia solution in a hydrolysis reaction. Condition III: Washing conditions with hydrochloric acid. Peak area ratio of nitrogen-containing compound: Expression {[eak area of nitrogen-containing compound (B-1)] / [eak area of polythiol compound (A-1)]} x100 Examples I-1 to I-4, Comparative Example I-1 (Preparation of the thiol composition added to the predetermined amount of nitrogen-containing compound (B-1))
[00154] The predetermined amount of the nitrogen-containing compound (B-1) that has been fractionated in advance has been added to the polythiol composition which is mainly comprised of the polythiol compound (A-1), the peak area ratio of the nitrogen-containing compound ( B-1) for the polythiol compound (A-1) was analyzed by high performance liquid chromatography according to the conditions described above. The results are shown in Table 2. (Measurement of the viscosity of the polymerizable composition)
[00155] The production time of the polymerizable composition was adjusted to 0 hours and the viscosity after 7 hours was evaluated as an index.
[00156] 52 parts by weight of m-xylylene diisocyanate, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 parts by weight of Viosorb 583 (trade name, manufactured by KYODO CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 48 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-1) were loaded and mixed to adjust to a homogeneous mixed liquid. The production time of the mixed homogeneous solution was adjusted to 0 hours and the viscosity after 7 hours was evaluated by a Brookfield type viscometer. The results are shown in Table 2. (Plastic lens manufacturing)
[00157] 52 parts by weight of m-xylylene diisocyanate, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 parts by weight of Viosorb 583 (trade name, manufactured by KYODO CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 48 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-1) were loaded and mixed to adjust to a homogeneous mixed liquid. Then, the homogeneous liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid was placed in a mold matrix consisting of a glass mold and a tape after filtration using a 1 μm Teflon (trademark) filter. The mold matrix was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized for 20 hours. After the polymerization was completed, the mold matrix was removed from the oven to obtain a resin freeing itself from the mold matrix. The obtained resin was annealed at 120 ° C for 3 hours. The physical properties of the obtained plastic lens are shown in Table 2.Table 2
Peak area ratio of nitrogen-containing compound Expression: {[eak area of nitrogen-containing compound (B-1)] / [eak area of polythiol compound (A-1)]} x100
[00158] From the results described above, in a case where the peak area ratio of the nitrogen-containing compound (B-1) to the polythiol compound (A-1) was equal to or less than 3.0 as Examples I-1 to I-4, the color and the degree of loss of transparency were excellent and the streaking did not occur either. In addition, the viscosity of the polymerizable composition after 7 hours was low and handling characteristics were excellent.
[00159] On the other hand, in a case where the peak area ratio of the nitrogen-containing compound (B-1) was above 3.0 as Comparative Example I-1, since the viscosity of the polymerizable composition after 7 hours was above 1,000 mPa ^ s, it is clear that the manufacturing stability of the plastic lens was also affected. Example C-1 (Synthesis of the polythiol composition which is mainly comprised of bis (mercaptomethyl) -3,6,9-tritia-1,11-undecanedithiol)
[00160] 51.2 parts by weight of 2-mercaptoethanol, 26.5 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm), and 0.16 parts by weight of 49% aqueous sodium hydroxide solution % by weight was loaded into a reaction vessel. 61.99 parts by weight of epichlorohydrin were added to the drops and charged from 9 ° C to 11 ° C for 6.5 hours, and the stirring was continued for 60 minutes. From NMR data, the production of 1-chloro-3- (2-hydroxyethylthio) -2-propanol was confirmed.
[00161] Next, 150.0 parts by weight of 17.3% aqueous sodium sulfide solution were added to the drops and charged at 7 ° C to 37 ° C for 5.5 hours and stirred for 120 min. From NMR data, the production of a tetraol compound of formula (4) was confirmed. Then, 279.0 parts by weight of 35.5% hydrochloric acid were charged, and then 125.8 parts by weight of the purity of 99.90% thiourea were charged and stirred at 110 ° C for 3 hours under reflux to convert to a thiouronium salt. After cooling to 45 ° C, 214.0 parts by weight of toluene were added and cooled to 26 ° C, 206.2 parts by weight of 25% by weight aqueous ammonia solution were loaded from 26 ° C to 50 ° C. ° C for 30 minutes and stirred at 50 ° C to 65 ° C for 1 hour, and a solution of toluene of the polythiol composition which is mainly comprised of 4,8-dimercaptomethyl-1,11-dimercapto-3,6, 9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane was obtained. The toluene solution was added in 59.4 parts by weight of 36% hydrochloric acid and the acid wash that was carried out from 34 ° C to 39 ° C for 30 minutes was conducted twice. 118.7 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were added and the wash that was carried out from 35 ° C to 45 ° C for 30 minutes was conducted five times. After toluene and trace water were removed under heating and reduced pressure, filtration under reduced pressure was performed by a 1.2 μm PTFE membrane filter to obtain 115.9 parts by weight of the polythiol composition which is mainly comprised of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane (hereinafter compound A), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane (hereinafter compound B), and 5,7-dimercaptomethyl-1,11-dimercapto -3,6,9-tritiaundecane (hereinafter compound C) (an isomeric mixture of compound A / B / C = 85/5/10 (ratio molar)). The physical properties of the obtained polythiol composition are shown in Table 3.
[00162] The polyol comprised of the isomers was isolated and identified respectively by reverse phase chromatography. First, the results of elemental analysis, IR, MS and NMR of compound A are shown.

[00163] Next, the NMR results of compound C are shown. The results of elementary analysis, IR and MS were the same as compound A.

[00164] Finally, the NMR results of compound B are shown. The results of elementary analysis, IR and MS were the same as compound A.
(Fractionation and confirmation of the structure)
[00165] The nitrogen-containing compound (referred to as B-2) included in the polythiol composition was fractionated from the polythiol composition which is mainly comprised of the polythiol compound (referred to as A-2) comprised of 5,7-dimercaptomethyl-1, 11-dimercapto -3,6,9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -tritiaundecane performing preparative high performance liquid chromatography.
[00166] From the results of instrumental analysis, it was proved that the nitrogen-containing compound (B-2) had a structure in which one of a mercapto group of the polythiol compound (A-2) consisting of 5,7-dimercaptomethyl -1,11-dimercapto-3,6,9-tritiaundecane 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane, and 4,8-dimercaptomethyl -1,11-dimercapto-3,6 , 9-tritiaundecane has been replaced with a group represented by the following formula (a), in addition, another from a mercapto group has been replaced with a hydroxyl group. In the following formula (a), * represents an atomic bond.
[00167] The results of an analysis of the nitrogen-containing compound (B-2) included in the polythiol composition are shown.
(1) FAB-MS mass spectrum: m / z476 (M +) (m-NBA matrix) (2) IR (Universal ATR Method): 3329, 3198 cm-1: NH stretch, 2539 cm-1: stretch of SH, 1606 cm-1: stretch of C = H, 1525 cm-1: sale of NH. (3) 1H-NMR (CDCl3): δ ppm 1.6 1.8 (4H (SH)), 2.5 3.5 (33H (-CH2-, -CH-)), 3.8 3.9 (3H (-CHOH, CH2OH)). (4) 13C-NMR (CDCl3): δ ppm 25 39 (CH2), 48 50 (CH), 61 (CH2-OH (C adjacent to O), 69 70 (CH-OH (C adjacent to O)), 166, 180 (-CN- (C of a triazine backbone)).
[00168] The peak area ratio of the nitrogen-containing compound (B-2) to the polythiol compound (A-2) was determined in the following manner. 1. Conditions for measuring high performance liquid chromatography Column: YMC-Pack ODS-A A-312 (S5Φ6 mm x 150 mm) Mobile phase: acetonitrile / 0.01 mol aqueous solution of potassium dihydrogen phosphate = 60/40 ( vol / vol) Column temperature: 40 ° C Flow rate: 1.0 ml / min Detector: UV detector, 230 nm wavelength Preparation of the measurement solution: 160 mg of a sample is dissolved and mixed in 10 ml acetonitrile. Injection volume: 2 μL 2. Peak area ratio of nitrogen-containing compound (B-2)
[00169] The composition ratio of the polythiol composition that was produced in Example C-1 was calculated using the following expression. Expression: {[eak area of nitrogen-containing compound (B-2)] / [eak area of polythiol compound (A-2)]} x100
[00170] The result calculated using the computation expression described above was 1.16.
[00171] In addition, the retention times of the polythiol compound (A-2) and the nitrogen-containing compound (B-2) were as follows. A high performance liquid chromatography graph is shown in Fig. 2. Polythiol compound (A-2): from 22.0 minutes to 28.0 minutes Nitrogen-containing compound (B-2): from 6.5 minutes to 8 , 0 minutes (Plastic lens manufacturing)
[00172] 50.7 parts by weight of m-xylylene diisocyanate, 0.01 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 parts by weight of Viosorb 583 (trade name, manufactured by KYODO CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 49.3 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-2) were loaded and mixed to adjust to a homogeneous mixed liquid. After the homogeneous liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid was placed in a mold matrix consisting of a glass mold and a tape after filtration using a 1 μm Teflon (trademark) filter. The mold matrix was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized for 20 hours. After the polymerization was completed, the mold matrix was removed from the oven to obtain a resin freeing itself from the mold matrix. The obtained resin was annealed at 130 ° C for 4 hours. The physical properties of the obtained lens are shown in Table 3. Examples C-2 to C-10
[00173] The polythiol composition that is mainly comprised of the polythiol compound (A-2) in the same way as Example C-1 except adjusting to the production conditions described in Table 3 was produced and the plastic lens was manufactured. The results are shown in Table 3. Example D-1 (Synthesis of the polythiol composition which is mainly comprised of bis (mercaptomethyl) -3,6,9-tritia-1,11-undecanedithiol)
[00174] 51.2 parts by weight of 2-mercaptoethanol, 26.5 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm), and 0.16 parts by weight of 49% aqueous sodium hydroxide solution % by weight was loaded into a reaction vessel. 61.99 parts by weight of epichlorohydrin were added to the drops and charged from 9 ° C to 13 ° C for 6.5 hours, and continuously, stirring was performed for 40 minutes. From NMR data, the production of 1-chloro-3- (2-hydroxyethylthio) -2-propanol was confirmed.
[00175] Then, 150.0 parts by weight of 17.3% aqueous sodium sulfide solution were added to the drops and charged at 5 ° C to 42 ° C for 4.5 hours, and continuously, agitating was performed for 40 minutes. From NMR data, the production of a tetraol compound of formula (4) was confirmed. Then, 117.4 parts by weight of the purity of 99.90% thiourea were loaded, 84.3 parts by weight of the purity of 90.7% hydrochloric acid gas were blown and stirred at 110 ° C for 3 hours under reflux to convert to a thiouronium salt. After cooling to 45 ° C, 214.0 parts by weight of toluene were added and cooled to 26 ° C, 15 8.4 parts by weight of 25% by weight aqueous ammonia solution was loaded from 26 ° C to 46 ° C for 25 minutes and matured from 54 ° C to 62 ° C for 1 hour, and a toluene solution of the polythiol composition that is mainly comprised of the polythiol compound (A-2) consisting of 5,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-tritiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-tritiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 -tritiaundecane was obtained. 59.4 parts by weight of 36% hydrochloric acid were added to the toluene solution and the acid wash that was carried out from 33 ° C to 40 ° C for 30 minutes was conducted twice. 118.7 parts by weight of degassed water (the dissolved oxygen concentration is 2 ppm) were added and the washing which was carried out from 35 ° C to 45 ° C for 30 min was carried out five times. After toluene and trace water were removed under heating and reduced pressure, filtration under reduced pressure was performed by a 1.2 μm PTFE membrane filter to obtain 115.0 parts by weight of the polyol composition which is mainly comprised of polythiol compound (A-2). The physical properties of the obtained polythiol composition are shown in Table 3. The identification of the polythiol compounds was carried out by NMR, and the same results as Example C-1 were obtained. (Fractionation and confirmation of the structure)
[00176] The nitrogen-containing compound (referred to as B-2) included in the polythiol composition was fractionated from the polythiol composition which is mainly comprised of the polythiol compound (A-2) by performing preparative high performance liquid chromatography.
[00177] From the results of instrumental analysis, it was proved that the nitrogen-containing compound (B-2) had a structure in which one of a mercapto group of the polythiol compound (A-2) was replaced with a group represented by formula (a) below, in addition, another one from a mercapto group has been replaced with a hydroxyl group. In the following formula (a), * represents an atomic bond.
[00178] The results of an analysis of the nitrogen-containing compound (B-2) included in the polythiol composition are shown.
(1) FAB-MS mass spectrum: m / z476 (M +) (m-NBA matrix) (2) IR (Universal ATR Method): 3329, 3198 cm-1: NH stretch, 2539 cm-1: stretch of SH, 1606 cm-1: stretch of C = H, 1525 cm-1: sale of NH. (3) 1H-NMR (CDCl3): δ ppm 1.6 1.8 (4H (SH)), 2.5 3.5 (33H (-CH2-, -CH-)), 3.8 3.9 (3H (-CHOH, CH2OH)). (4) 13C-NMR (CDCl3): δ ppm 25 39 (CH2), 48 50 (CH), 61 (CH2-OH (C adjacent to O)), 69 70 (CH-OH (C adjacent to O)) , 166, 180 (-CN- (C of a triazine skeleton)).
[00179] The peak area ratio of the nitrogen-containing compound (B-2) to the polythiol compound (A-2) was determined by carrying out in the same manner as Example C-1. (Plastic lens manufacturing)
[00180] 50.7 parts by weight of m-xylylene diisocyanate, 0.01 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 parts by weight of Viosorb 583 (trade name, manufactured by KYODO CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 49.3 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-2) were loaded and mixed to adjust to a homogeneous mixed liquid. After the homogeneous liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid was placed in a mold matrix consisting of a glass mold and a tape after filtration using a 1 μm Teflon (trademark) filter. The mold matrix was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized for 20 hours. After the polymerization was completed, the mold matrix was removed from the oven to obtain a resin freeing itself from the mold matrix. The obtained resin was annealed at 130 ° C for 4 hours. The physical properties of the obtained lens are shown in Table 3. Examples D-2 to D-10
[00181] The polythiol composition that is mainly comprised of the polythiol compound (A-2) in the same way as Example D-1 except adjusting to the production conditions described in Table 3 was produced and the plastic lens was manufactured. The results are shown in Table 3. Table 3
Table 3 -continuation-
Condition I: Conditions for reacting 2-mercaptoethanol with epichlorohydrin. Condition II: Conditions for loading an aqueous ammonia solution in a hydrolysis reaction. Condition III: Washing conditions with hydrochloric acid. Peak area ratio of nitrogen-containing compound: Expression {[eak area of nitrogen-containing compound (B-2)] / [eak area of polythiol compound (A-2)]} x100 Examples II-1 to II-3, Comparative Example II-1 (Preparation of the thiol composition added to the predetermined amount of nitrogen-containing compound (B-2))
[00182] The predetermined amount of the nitrogen-containing compound (B-2) that has been fractionated in advance has been added to the polythiol composition which is mainly comprised of the polythiol compound (A-2), the peak area ratio of the nitrogen-containing compound ( B-2) was analyzed by high performance liquid chromatography according to the conditions described above. The results are shown in Table 4. (Measurement of the viscosity of the polymerizable composition)
[00183] The production time of the polymerizable composition was adjusted to 0 hours and the viscosity after 7 hours was evaluated as an index.
[00184] 50.7 parts by weight of m-xylylene diisocyanate, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 part by weight of Viosorb 583 (trade name, manufactured by KYODO CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 49.3 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-2) were loaded and mixed to adjust to a homogeneous mixed liquid. The production time of the mixed homogeneous solution was adjusted to 0 hours and the viscosity after 7 hours was evaluated by a Brookfield type viscometer. The results are shown in Table 4. (Plastic lens manufacturing)
[00185] 50.7 parts by weight of m-xylylene diisocyanate, 0.01 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, a product manufactured by Stepan Company; phosphoric acid ester), 0.05 part by weight of Viosorb 583 (trade name, manufactured by CHEMICAL CO., LTD .; ultraviolet absorbing agent) were mixed and dissolved at 20 ° C. 49.3 parts by weight of the polythiol composition which is mainly comprised of the obtained polythiol compound (A-2) were loaded and mixed to adjust to a homogeneous mixed liquid. After the homogeneous liquid was degassed at 600 Pa for 1 hour, the homogeneous liquid was placed in a mold matrix consisting of a glass mold and a tape after filtration using a 1 μm Teflon (trademark) filter. The mold matrix was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized for 20 hours. After the polymerization was completed, the mold matrix was removed from the oven to obtain a resin freeing itself from the mold matrix. The obtained resin was annealed at 130 ° C for 4 hours. The physical properties of the obtained plastic lens are shown in Table 4.
Peak area ratio of nitrogen-containing compoundExpression: {[eak area of nitrogen-containing compound (B-2)] / [eak area of polythiol compound (A-2)]} × 100
[00186] From the results described above, in a case where the peak area ratio of the nitrogen-containing compound (B-2) to the polythiol compound (A-2) was 3.0 or less like Examples II- 1 to II-3, color and the degree of loss of transparency were excellent and stripping did not occur either. In addition, the viscosity of the polymerizable composition after 7 hours was low and handling characteristics were excellent.
[00187] On the other hand, in a case where the peak area ratio of the nitrogen-containing compound (B-2) was above 3.0 as Comparative Example 10 II-1, since the viscosity of the polymerizable composition after 7 hours was above 1,000 mPa ^ s, it is clear that the manufacturing stability of the plastic lens was also affected.
[00188] This application claims a priority based on Japanese Patent Application No. 2012-179899, filed on August 14, 15 2012 and a priority based on PCT / JP2013 / 001201, filed on February 28, 2013, and all description of these references is incorporated in the present application.

权利要求:
Claims (8)
[0001]
1. Polythiol composition characterized by the fact that it comprises: a polythiol compound (A) having three or more mercapto groups; and a nitrogen-containing compound (B) in which one of a mercapto group of the polythiol compound (A) is replaced with a group represented by the following formula (a)
[0002]
2. Polyol composition according to claim 1, characterized by the fact that the polyol compound (A) is represented by the following formula (5)
[0003]
3. Polyol composition according to claim 1, characterized in that the polyol compound (A) is mainly comprised of at least one selected type of the compounds represented by the following formulas (6) to (8)
[0004]
4. Polymerizable composition for an optical material characterized by the fact that it comprises: the polyol composition as defined in any one of claims 1 to 3; and a poly (thio) isocyanate compound.
[0005]
5. Method of making a molded product, characterized in that it comprises: mixing the polythiol composition as defined in any one of claims 1 to 3, and a poly (thio) isocyanate compound to obtain a polymerizable composition for an optical material ; and placing the polymerizable composition in a mold and curing the composition.
[0006]
6. Molded product characterized by the fact that it is obtained by curing the polymerizable composition as defined in claim 4.
[0007]
7. Optical element characterized by the fact that it is comprised of the molded product as defined in claim 6.
[0008]
8. Lens characterized by the fact that it is comprised of the optical element as defined in the claim

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法律状态:
2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012179899|2012-08-14|

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JP2012-179899|2012-08-14|

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JP2013001201|2013-02-28|

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JPPCT/JP2013/001201|2013-02-28|

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PCT/JP2013/071891|WO2014027665A1|2012-08-14|2013-08-13|Polythiol composition, polymerizable composition for optical materials, and use of polymerizable composition for optical materials|

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