Title of the invention: Polythiol composition and its applications
Technical field
[0001]
The present disclosure relates to polythiol compositions and their applications.
Background technology
[0002]
Plastic lenses are lighter than inorganic lenses, are hard to break, and can be dyed, so they have rapidly become widespread in optical elements such as spectacle lenses and camera lenses in recent years.
[0003]
Resins for plastic lenses are required to have higher performance, higher refractive index, higher number of abbreviations, lower specific gravity, higher heat resistance, etc. Various resin materials for lenses have been developed and used so far.
[0004]
Among them, the optical material made of polythiourethane resin has a high refractive index and a high number of abbreviations, and is excellent in impact resistance, dyeability, processability, and the like. The polythiourethane-based resin is obtained by reacting a polythiol compound with a polyiso (thio) cyanate compound or the like.
[0005]
Examples of documents describing a method for producing a polythiol compound include the following Patent Documents 1 and 2.
In Patent Document 1, 2-mercaptoethanol and an epihalohydrin compound are reacted, and the obtained polyalcohol compound is reacted with thiourea to obtain an isotyuronium salt, and the obtained isotiuronium salt is hydrolyzed. A method for producing a polythiol compound is disclosed.
In Patent Document 2, 2-mercaptoethanol and an epihalohydrin compound are reacted, the obtained compound is reacted with sodium sulfide to obtain a polyalcohol compound, and the obtained polyalcohol compound is reacted with thiourea. A method for producing a polythiol compound by hydrolyzing the isothiuronium salt after making it into an isothiuronium salt is disclosed.
[Patent Document 1] International Publication No. 2014/027427
[Patent Document 2] International Publication No. 2014/027428
Outline of the invention
Problems to be solved by the invention
[0006]
As a resin obtained by curing a polymerizable composition containing a polythiol compound, it may be required to have good heat resistance and dyeability. Therefore, a composition containing a polythiol compound capable of producing a resin having an excellent balance between heat resistance and dyeability is desired.
[0007]
It is an object of the present disclosure to provide a polythiol composition capable of producing a resin having an excellent balance between heat resistance and dyeability and an application thereof.
Means to solve the problem
[0008]
The means for solving the above problems include the following aspects.
<1> 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecan, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecane , And a polythiol compound (A) containing at least one of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
A polythiol composition containing a polythiol compound (B) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
<2> The polythiol composition according to <1>, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 0.5 or more with respect to the total peak area 100 of the compounds contained in the polythiol composition. thing.
<3> The polythiol composition according to <1>, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 4 or more with respect to the total peak area 100 of the compounds contained in the polythiol composition.
<4> The polythiol composition according to <2>, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is less than 1.1 with respect to the total peak area 100 of the compounds contained in the polythiol composition. thing.
<5> In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is larger than 5.2 and less than 8.5 with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition <1>. The polythiol composition according to.
<6> The polythiol composition according to <1>, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is larger than 11.5 with respect to the total peak area 100 of the compounds contained in the polythiol composition. thing.
<7> In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (A) is 90 or less with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition, whichever is <1> to <6>. The polythiol composition according to one.
<8> In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 0.5 or more with respect to the total peak area 100 of the polythiol compound (A) and the polythiol compound (B) <1. > The polythiol composition according to any one of <7>.
<9> The polythiol compound (A) is selected from the group consisting of metal hydroxides and metal carbonates when reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following general formula (5). The polythiol composition according to any one of <1> to <8>, which is a compound obtained by using a catalyst containing at least one of the above.
[0009]
[Chemical 1]

[0010]
<10> The polythiol compound (B) is selected from the group consisting of metal hydroxides and metal carbonates when reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following general formula (5). The polythiol composition according to any one of <1> to <9>, which is a compound obtained by using a catalyst containing at least one of the above.
[0011]
[Chemical 2]

[0012]
<11> A polymerizable composition containing the polythiol composition according to any one of <1> to <10> and a polyiso (thio) cyanate compound.
[0013]
<12> Polyiso (thio) cyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isosianatomethyl) cyclohexane, bis (isosianatocyclohexyl) methane, and 2,5-bis (isosyanato). Methyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and phenylenedi isocyanate The polymerizable composition according to <11>, which comprises at least one selected from.
[0014]
<13> A resin obtained by curing the polymerizable composition according to <11> or <12>.
<14> A molded body containing the resin according to <13>.
<15> An optical material containing the resin according to <13>.
<16> A lens containing the resin according to <13>.
Effect of the invention
[0015]
According to the present disclosure, it is possible to provide a polythiol composition capable of producing a resin having an excellent balance between heat resistance and dyeability and an application thereof.
A brief description of the drawing
[0016]
FIG. 1 shows the relationship between the peak area ratio of the polythiol compound (B) to the total peak area 100 of the compounds contained in the polythiol compositions in Examples 1 to 5 and ΔTg and light transmission in Production Examples 1 to 5. It is a graph which shows.
Embodiment for carrying out the invention
[0017]
In the present disclosure, the numerical range represented by using "-" means a range including the numerical values ​​before and after "-" as the lower limit value and the upper limit value.
In the present disclosure, the amount of each component in the composition is the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, "iso (thio) cyanate" means isocyanate or isothiocyanate.
[0018]
[Polythiol composition]
The polythiol compositions of the present disclosure are 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6. Polythiol compound (A) containing at least one of 9-trichiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4-mercaptomethyl-1, Includes polythiol compound (B), which is 8-dimercapto-3,6-dithiaoctane. The polythiol composition of the present disclosure can produce a resin having an excellent balance between heat resistance and dyeability by containing at least the above-mentioned two types of polythiol compounds.
[0019]
(Polythiol compound (A))
The polythiol composition of the present disclosure is represented by the following formula (1), 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecan, and the following formula (2). 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, and 5,7-Dimercaptomethyl-1,11-Dimercapto-3, represented by the following formula (3). Includes a polythiol compound (A) containing at least one of 6,9-trithiaundecane. The polythiol compound (A) may contain one of these three compounds, or may contain two or three mixtures of these three compounds.
[0020]
[Chemical 3]

[0021]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (A) is preferably 90 or less with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition from the viewpoint of dyeability of the resin, 87. The following is more preferable, 84 or less is further preferable, and 81 or less is particularly preferable.
[0022]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (A) is preferably 68 or more with respect to the total peak area 100 of the compounds contained in the polythiol composition from the viewpoint of heat resistance of the resin, 72. The above is more preferable, 76 or more is further preferable, and 80 or more is particularly preferable.
[0023]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (A) is 99 or less with respect to the total peak area 100 of the polythiol compound (A) and the polythiol compound (B) from the viewpoint of dyeability of the resin. Is preferable, 97 or less is more preferable, 94 or less is further preferable, and 93 or less is particularly preferable.
[0024]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (A) is 75 or more with respect to the total peak area 100 of the polythiol compound (A) and the polythiol compound (B) from the viewpoint of heat resistance of the resin. Is more preferable, 80 or more is more preferable, 85 or more is further preferable, and 91 or more is particularly preferable.
[0025]
High-speed liquid chromatography measurement may be performed by the method described in Examples described later.
[0026]
The method for producing the polythiol compound (A) is not particularly limited, and it can be produced by a known method. For example, the polythiol compound (A) can be produced by the method described in International Publication No. 2014/027428.
[0027]
The polythiol compound (A) is prepared by reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following general formula (5) to obtain a compound represented by the following general formula (6). , Obtained using a catalyst containing at least one selected from the group consisting of metal hydroxides such as potassium hydroxide and metal carbonates such as sodium carbonate and potassium carbonate. It is preferably a compound. It is more preferable to use sodium hydroxide as a catalyst from the viewpoint of reactivity and economy. For the detailed conditions for obtaining the compound represented by the general formula (6) and the subsequent reaction until the polythiolization reaction product (A) is obtained, the above-mentioned International Publication No. 2014/027428 may be referred to. Further, the total amount of the tertiary amine, the quaternary ammonium, the triphenylphosphine and the chromium compound in the above-mentioned catalyst is less than 0.001 mol with respect to 1 mol of the epihalohydrin compound represented by the following general formula (5). It is preferably 0.0005 mol or less, more preferably 0 mol or less. By using a catalyst containing at least one of a metal hydroxide and a metal carbonate, particularly a metal hydroxide such as sodium hydroxide, the hue of the produced polythiol compound (A) tends to be improved, and further. The thickening rate of the polythiol composition containing the polythiol compound (A) and the polymerizable composition obtained by mixing the polyiso (thio) cyanate compound is suppressed, and the pot life tends to be improved.
[0028]
[Changing 4]

[0029]
[Chemical 5]

[0030]
(Polythiol compound (B))
The polythiol composition of the present disclosure contains a polythiol compound (B) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane represented by the following formula (4).
[0031]
[Chemical 6]

[0032]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) may be larger than 0 with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition from the viewpoint of dyeability of the resin, for example, 0. It is preferably 5 or more, more preferably 1 or more, further preferably 3 or more, particularly preferably 4 or more, extremely preferably larger than 6, and 9 or more. Is even more preferred, and even more preferably greater than 11.5.
[0033]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is preferably 20 or less with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition from the viewpoint of heat resistance of the resin. It is more preferably less than or equal to, more preferably 10 or less, particularly preferably less than 8.5, and extremely preferably less than 1.1. Since the peak area of ​​the polythiol compound (B) is 10 or less with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition, the dyeability tends to be adjusted while maintaining high heat resistance. For example, when the above-mentioned value is 10 or less, increasing the above-mentioned value tends to improve the dyeability.
[0034]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is from 5.2 with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition from the viewpoint of achieving both dyeability and heat resistance of the resin. It is preferably less than 8.5.
[0035]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 0.5 or more with respect to the total peak area of ​​100 of the polythiol compound (A) and the polythiol compound (B) from the viewpoint of dyeability of the resin. It is preferably 1 or more, more preferably 3 or more, particularly preferably 4 or more, extremely preferably 6 or more, and even more preferably 7 or more. ..
[0036]
In the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 23 or less with respect to the total peak area 100 of the polythiol compound (A) and the polythiol compound (B) from the viewpoint of heat resistance of the resin. Is preferable, 17 or less is more preferable, 12 or less is further preferable, and 9.5 or less is particularly preferable. Since the peak area of ​​the polythiol compound (B) is 12 or less with respect to the total peak area of ​​100 of the polythiol compound (A) and the polythiol compound (B), the dyeability tends to be adjusted while maintaining the heat resistance. be. For example, when the above-mentioned value is 12 or less, increasing the above-mentioned value tends to improve the dyeability.
[0037]
The method for producing the polythiol compound (B) is not particularly limited, and it can be produced by a known method. For example, the polythiol compound (B) can be produced by the method described in International Publication No. 2014/027427. Further, the polythiol compound (B) is a metal hydroxide such as sodium hydroxide and potassium hydroxide when reacting 2-mercaptoethanol with the epihalohydrin compound represented by the above-mentioned general formula (5). It is preferable that the compound is obtained by using a catalyst containing at least one selected from the group consisting of metal carbonates such as sodium carbonate and potassium carbonate.
[0038]

The peak areas of the polythiol compound (A) and the polythiol compound (B) with respect to the total peak area 100 of the compounds contained in the polythiol composition can be determined by performing high-speed liquid chromatography (HPLC) measurement based on the following conditions. The peak area appearing in the retention time of 12.0 to 13.5 minutes is determined to be the peak area of ​​the polythiol compound (B), and the peak area appearing in the retention time of 22.0 to 28.0 minutes is the peak area of ​​the polythiol compound (A). It may be judged as the peak area.
(HPLC conditions)
Column: YMC-Pack ODS-A A-312 (S5Φ6mm x 150mm)
Mobile phase: acetonitrile / 0.01 mol / L-potassium dihydrogen phosphate aqueous solution = 60/40 (vol / vol)
Column temperature: 40 ° C
Flow rate: 1.0 ml / min
Detector: UV detector, wavelength 230 nm
Preparation of measurement solution: 160 mg of sample is dissolved and mixed with 10 ml of acetonitrile.
Injection amount: 2 μL
[0039]
The polythiol composition of the present disclosure may contain a compound other than the polythiol compound (A) and the polythiol compound (B), and the polythiol compound having a mercapto group other than the polythiol compound (A) and the polythiol compound (B) (hereinafter, , "Other polythiol compounds") and the like.
[0040]
Examples of other polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis (2-mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate). , Bis (mercaptoethyl) sulfide, 2,5-dimercaptomethyl-1,4-ditian, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) Methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercaptomethyl-1,4-ditian, 2,5-dimercapto-1,4-ditian, 2,5-dimercaptomethyl-2, 5-Dimethyl-1,4-ditian, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio)- 1,3-Ditian and the like can be mentioned.
[0041]
[Polymerizable composition]
The polymerizable composition of the present disclosure includes the above-mentioned polythiol composition of the present disclosure and a polyiso (thio) cyanate compound.
[0042]
(Polyiso (thio) cyanate compound)
The polyiso (thio) cyanate compound is not particularly limited as long as the effects of the present invention can be exhibited, and conventionally known compounds can be used. The compound is not particularly limited as long as it is a compound having at least two iso (thio) cyanate groups in one molecule, and specifically, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, and the like. An aliphatic polyisocyanate compound such as octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, and xylylene diisocyanate;
Isophoron diisocyanate, bis (isosianatomethyl) cyclohexane, bis (isosianatocyclohexyl) methane, dicyclohexyldimethylmethanediisocyanate, 2,5-bis (isosyanatomethyl) 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- Alicyclic polyisocyanate compounds such as bis (isocyanatomethyl) tricyclodecane and 4,9-bis (isosianatomethyl) tricyclodecane;
Aromatic polyisocyanate compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenylsulfide-4,4-diisocyanate, and phenylenedi isocyanate;
2,5-Diisosyanatothiophene, 2,5-bis (isosyanatomethyl) thiophene, 2,5-diisosyanatotetrahydrothiophene, 2,5-bis (isosyanatomethyl) tetrahydrothiophene, 3,4-bis (3,4-bis) Isocyanatomethyl) tetrahydrothiophene, 2,5-diisosyanato-1,4-dithian, 2,5-bis (isosyanatomethyl) -1,4-ditian, 4,5-diisosyanato-1,3-dithiolan, 4, Heterocyclic polyisocyanate compounds such as 5-bis (isocyanatomethyl) -1,3-dithiolane;
An aliphatic polyisothiocianate compound such as hexamethylene diisothiocianate, lysine diisothiocianate methyl ester, lysine triisothiocianate, xylylene diisothiocianate;
Isophoron diisothiocianate, bis (isothiocyanatomethyl) cyclohexane, bis (isothiocyanatocyclohexyl) methane, cyclohexanediisothiocianate, methylcyclohexanediisothiocianate, 2,5-bis (isothiocyanatomethyl) bicyclo- [2. 2.1] -Heptane, 2,6-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 3,8-bis (isothiocyanatomethyl) tricyclodecane, 3,9-bis Alicyclic polyisothiocianates such as (isothiocyanatomethyl) tricyclodecane, 4,8-bis (isothiocyanatomethyl) tricyclodecane, 4,9-bis (isothiocyanatomethyl) tricyclodecane;
Aromatic polyisothiocyanate compounds such as tolylene diisothiocianate, 4,4-diphenylmethane diisothiocianate, diphenyldisulfide-4,4-diisothiocianate;
2,5-Diisothiocyanatothiophene, 2,5-bis (isothiocianatomethyl) thiophene, 2,5-isothiocianatotetrahydrothiophene, 2,5-bis (isothiocianatomethyl) tetrahydrothiophene, 3,4 -Bis (isothiocyanatomethyl) tetrahydrothiophene, 2,5-diisothiocianato-1,4-ditian, 2,5-bis (isothiocianatomethyl) -1,4-ditian, 4,5-diisoti Examples thereof include sulfur-containing heterocyclic polyisothiocianate compounds such as ossianato-1,3-dithiolane and 4,5-bis (isothiocyanatomethyl) -1,3-dithiolane. The polyiso (thio) cyanate compound can include at least one selected from these.
[0043]
Further, as the polyiso (thio) cyanate compound, these chlorine-substituted products, halogen-substituted products such as bromine-substituted products, alkyl-substituted products, and arcoki are used.Si-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, bullet-modified products, dimerization or trimmerization reaction products, and the like can also be used.
[0044]
As the polyiso (thio) cyanate compound, a polyisocyanate compound is preferable.
Pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -Heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and phenylenedi isocyanate are preferably contained at least one selected from each other. ..
[0045]
The mixing ratio of the polythiol composition and the polyiso (thio) cyanate compound is not particularly limited, and for example, the molars of the mercapto group of the polythiol compound and the iso (thio) cyanate group of the polyiso (thio) cyanate compound contained in the polythiol composition. The ratio (mercapto group / iso (thio) cyanate group) is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and 0.8 to 1.3. Is even more preferable. When the mixing ratio is within the above range, it tends to be possible to satisfy various performances such as refractive index and heat resistance required for plastic lenses and the like in a well-balanced manner.
[0046]
The polymerizable composition of the present disclosure contains other components other than the polythiol compound and the polyiso (thio) cyanate compound for the purpose of improving various physical properties, operability, polymerization reactivity of the polymerizable composition and the like of the resin. May be good.
Other components include polymerization catalyst, internal mold release agent, resin modifier, chain extender, cross-linking agent, radical trapping agent, light stabilizer, ultraviolet absorber, antioxidant, oil-soluble dye, filler, adhesion. Examples thereof include property improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, blue ink agents such as inorganic pigments, and the like.
[0047]
Examples of the polymerization catalyst include tertiary amine compounds, inorganic acid salts or organic acid salts thereof, metal compounds, quaternary ammonium salts, organic sulfonic acid and the like.
[0048]
As the internal mold release agent, an acidic phosphoric acid ester can be used. Examples of the acidic phosphoric acid ester include a phosphoric acid monoester and a phosphoric acid diester, which can be used alone or in combination of two or more.
[0049]
Examples of the resin modifier include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, olefin compounds including (meth) acrylate compounds, and the like.
The polymerizable composition of the present disclosure can be obtained by mixing the above components.
[0050]
In the polymerizable composition of the present disclosure, the glass transition temperature Tg when cured into a molded product is preferably 100 ° C. or higher, more preferably 101 ° C. or higher, and more preferably 102 ° C. or higher. It is more preferably 102.5 ° C. or higher, and particularly preferably 102.5 ° C. or higher. Further, in the polymerizable composition of the present disclosure, the above-mentioned glass transition temperature Tg may be 104 ° C. or lower, or 103 ° C. or lower.
In particular, when the peak area of ​​the above-mentioned polythiol compound (B) is larger than 6 or 9 or more with respect to the total peak area 100 of the compounds contained in the polythiol composition, both heat resistance and dyeability are compatible. From the viewpoint, in the polymerizable composition of the present disclosure, it is preferable that the above-mentioned glass transition temperature Tg satisfies the above-mentioned numerical range.
In the present disclosure, the glass transition temperature Tg when formed into a molded body is a value measured by the method described in Examples using a plastic lens molded according to in Examples described later.
[0051]
[Molded body]
The molded body of the present disclosure contains a resin obtained by curing the polymerizable composition of the present disclosure. The method for producing the molded product of the present disclosure is not particularly limited, and a preferred production method includes cast polymerization. First, the polymerizable composition is injected between the molding molds held by a gasket, tape or the like. At this time, depending on the physical properties required for the obtained plastic lens, it is often preferable to perform defoaming treatment under reduced pressure, filtering treatment such as pressurization and reduced pressure, and the like, if necessary.
[0052]
The polymerization conditions are not limited because they differ greatly depending on the composition of the polymerizable composition, the type and amount of the catalyst used, the shape of the mold, etc., and are not limited, for example, for 1 hour at a temperature of -50 ° C to 150 ° C. It takes 50 hours. In some cases, it is preferable to keep the temperature in the temperature range of 10 ° C. to 150 ° C. or gradually raise the temperature to cure in 1 hour to 48 hours.
[0053]
The molded body may be subjected to a treatment such as annealing, if necessary. The treatment such as annealing is usually performed between 50 ° C. and 150 ° C., preferably 90 ° C. to 140 ° C., and more preferably 100 ° C. to 130 ° C.
[0054]
[Use]
The resin obtained from the polymerizable composition of the present disclosure can be obtained as molded bodies having various shapes by changing the type of mold at the time of casting polymerization.
[0055]
The molded product obtained from the polymerizable composition of the present disclosure can be used as a material having excellent dimming performance and surface strength without impairing transparency, and thus can be used for various optical materials such as plastic lenses. It is possible to use. In particular, it can be suitably used as a plastic spectacle lens or a plastic polarized lens.
[0056]
[Plastic spectacle lens]
The plastic spectacle lens using the lens base material made of the molded body of the present disclosure may be coated on one side or both sides, if necessary.
The plastic spectacle lens of the present disclosure includes a lens base material obtained by curing the above-mentioned polymerizable composition and a coating layer.
[0057]
Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water repellent layer. Each of these coating layers can be used alone, or a plurality of coating layers can be used in layers. When the coating layers are applied to both surfaces, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.
[0058]
Each of these coating layers is an infrared absorber to protect the eyes from infrared rays, a light stabilizer to improve the weather resistance of the lens, an antioxidant, etc., and a photochromic compound, a dye, etc. to enhance the fashionability of the lens. In addition to pigments and the like, known additives such as antistatic agents may be used in combination for the purpose of enhancing the performance of the lens.
Various leveling agents for the purpose of improving coatability may be used for the layer to be coated by coating.
Further, an antifogging layer, an antifouling layer, and a water repellent layer may be formed on the antireflection layer, if necessary.
[0059]
Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted as long as the effects of the present invention are not impaired.
Example
[0060]
Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to the following examples as long as the gist of the present disclosure is not exceeded. Unless otherwise specified, "parts" are based on mass.
[0061]

In the examples, the evaluation method of each physical property of the plastic lens is as follows. The results are shown in Table 1.
Refraction rate (ne), Abbe number (νe): Using a refraction meter KPR-20 (manufactured by Carnew Optical Industry Co., Ltd.), a wavelength of 546.1 nm (mercury e-ray) and a wavelength of 480.0 nm (Cd F) at 20 ° C. The refractive index (ne, nF', nC') at the'line) and the wavelength 643.9 nm (Cd C'line) was measured, respectively, and the Abbe number (νe) was determined.
Heat resistance: The glass transition temperature Tg by the TMA penation method (50 g load, pin tip 0.5 mmφ, heating rate 10 ° C./min) was measured and used as an index of heat resistance.
-Resin specific gravity: Measured by the Archimedes method.
YI (YI value): The resin was prepared as a circular flat plate plastic lens with a thickness of 9 mm and a diameter of 75 mm, and the chromaticity coordinates x and y were measured using a color difference meter CT-210 manufactured by Konica Minolta Co., Ltd. did. Based on the values ​​of x and y, which are the measurement results, Y. I. The value was calculated.
Y. I. Value = (234 x x + 106 x y + 106) / y (5)
In addition, Y. I. The smaller the value, the better the hue of the plastic lens. I. There is a correlation that the larger the value, the worse the hue.
-Dyeability (light transmission rate): 3000 g of pure water, 2.3 g of "FSP Red EA" (manufactured by Futaba Sangyo Co., Ltd., dye), "FSP Yellow PE" (manufactured by Futaba Sangyo Co., Ltd., dye) 1.5g, "FSP Blue AUL-S" (manufactured by Futaba Sangyo Co., Ltd., dye) 6.0g, "Nikka Sun Salt # 7000" (manufactured by Nikka Kagaku Co., Ltd., dye dispersant) 6.0g, "DK-" "CN" (manufactured by Daiwa Chemical Industry Co., Ltd., dyeing aid) 6.0 g was added to prepare a dye dispersion. A 9 mm thick resin was immersed in a dye dispersion for 30 minutes at 80 ° C. for dyeing. The light transmittance (%) of the dyed resin at 350 nm to 800 nm was measured. Table 1 shows the light transmission rates (%) at 638 nm, 567 nm and 452 nm, respectively.
The more dyed, the more light is absorbed by the dye, so the lower the light transmission rate at each wavelength, the better the dyeability.
Further, in Examples 1 to 5 described later, a graph showing the relationship between the peak area ratio of the polythiol compound (B) to the total peak area 100 of the compounds contained in the polythiol composition and ΔTg and light transmission described later is shown. It is shown in FIG.
[0062]

51.2 parts by mass of 2-mercaptoethanol, 26.5 parts by mass of degassed water, and 0.16 parts by mass of 49% by mass of sodium hydroxide aqueous solution were charged into the reactor. 61.99 parts by mass of epichlorohydrin was added dropwise at 9 ° C to 11 ° C over 6.5 hours, and stirring was continued for 60 minutes. From the NMR data, the formation of 1-chloro-3- (2-hydroxyethylthio) -2-propanol was confirmed.
Next, 150.0 parts by mass of a 17.3% sodium sulfide aqueous solution was added dropwise at 7 ° C to 37 ° C over 5.5 hours, and the mixture was stirred for 120 minutes. From the NMR data, the formation of the tetraol compound was confirmed. Then, 279.0 parts by mass of 35.5% hydrochloric acid was charged, then 125.8 parts by mass of thiourea having a purity of 99.90% was charged, and the mixture was stirred at 110 ° C. for 3 hours. , Thiuronium chloride reaction was carried out. After cooling to 45 ° C, 214.0 parts by mass of toluene is added, cooled to 26 ° C, and 206.2 parts by mass of a 25% by mass ammonia aqueous solution is charged at 26 ° C to 50 ° C over 30 minutes, and charged at 50 ° C. The hydrolysis reaction was carried out by stirring at ~ 65 ° C. for 1 hour, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11- A toluene solution of polythiol containing dimercapto-3,6,9-trichiaundecan and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as main components was obtained. 59.4 parts by mass of 36% hydrochloric acid was added to the toluene solution, and acid washing was carried out twice at 34 ° C. to 39 ° C. for 30 minutes. 118.7 parts by mass of degassed water was added, and washing was carried out 5 times at 35 ° C to 45 ° C for 30 minutes. After removing toluene and a trace amount of water under heating and reduced pressure, the mixture was filtered under reduced pressure with a 1.2 μm PTFE type membrane filter. As a result, the polythiol compound (A) 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3, Polythiol composition (A) 115.9 quality containing 6,9-trichiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecan as main components. Obtained a quantity part.
[0063]

124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water were charged into the reactor. 101.5 parts by mass of a 32 mass% sodium hydroxide aqueous solution was added dropwise over 40 minutes at 12 ° C to 35 ° C, and then 73.6 parts by mass of epichlorohydrin was added dropwise at 29 ° C to 36 ° C for 4.5 hours. It was dropped and charged, and the mixture was continuously stirred for 40 minutes. From the NMR data, the formation of 1,3-bis (2-hydroxyethylthio) -2-propanol was confirmed.
Charged with 331.5 parts by mass of 35.5% hydrochloric acid, then charged with 183.8 parts by mass of thiourea with a purity of 99.90%, stirred at 110 ° C. for 3 hours, and thiuronium. A chloride reaction was carried out. After cooling to 45 ° C, 320.5 parts by mass of toluene is added, the mixture is cooled to 31 ° C, and 243.1 parts by mass of a 25% by mass ammonia aqueous solution is charged at 31 ° C to 41 ° C over 44 minutes to charge 54 ° C. The hydrolysis reaction was carried out by stirring at ~ 62 ° C. for 3 hours to obtain a toluene solution of polythiol containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a main component. 162.8 parts by mass of 35.5% hydrochloric acid was added to the toluene solution, and the mixture was acid-washed at 35 ° C. to 43 ° C. for 1 hour. 174.1 parts by mass of degassed water was added, and washing was carried out twice at 35 ° C. to 45 ° C. for 30 minutes. 162.1 parts by mass of 0.1% ammonia water was added, and the mixture was washed for 30 minutes. 174.2 parts by mass of degassed water was added, and washing was carried out twice at 35 ° C. to 45 ° C. for 30 minutes. After removing toluene and a small amount of water under heating and reduced pressure, filter under reduced pressure with a 1.2 μm PTFE type membrane filter to obtain 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is a polythiol compound (B). 205.0 parts by mass of the polythiol composition (B) as a main component was obtained.
[0064]
[Examples 1 to 5]
The polythiol composition (A) and the polythiol composition (B) obtained as described above were mixed at different mixing ratios to obtain the polythiol compositions of Examples 1 to 5.
[0065]
[Comparative Example 1]
The polythiol composition (B) obtained as described above was used as the polythiol composition of Comparative Example 1.
[0066]

High-speed liquid chromatography measurements were performed on the polythiol compositions of Examples 1 to 5 based on the following conditions, and the polythiol compound (A) and the polythiol compound (B) were subjected to a total peak area of ​​100 of the compounds contained in the polythiol composition. The peak area was calculated. The peak area appearing in the retention time of 12.0 to 13.5 minutes is determined to be the peak area of ​​the polythiol compound (B), and the peak area appearing in the retention time of 22.0 to 28.0 minutes is determined to be the polythiol compound (A). ) Was judged to be the peak area.
(HPLC conditions)
Column: YMC-Pack ODS-A A-312 (S5Φ6mm x 150mm)
Mobile phase: acetonitrile / 0.01 mol / L-potassium dihydrogen phosphate aqueous solution = 60/40 (vol / vol)
Column temperature: 40 ° C
Flow rate: 1.0 ml / min
Detector: UV detector, wavelength 230 nm
Preparation of measurement solution: 160 mg of sample is dissolved and mixed with 10 ml of acetonitrile.
Injection amount: 2 μL
The results are shown in Table 1.
[0067]

[Production Example 1]
50.6 parts by mass of m-xylylene diisocyanate, 0.01 part by mass of dibutyltin dichloride as a curing catalyst, 0.10 part by mass of Zelek UN (trade name Stepan product; acidic phosphate ester), Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) ; UV absorber) 0.05 parts by mass was mixed and dissolved at 20 ° C. 49.4 parts by mass of the obtained polythiol composition of Example 1 was charged and mixed to prepare a mixed uniform liquid. This uniform liquid was defoamed at 600 Pa for 1 hour, filtered through a 1 μm Teflon (registered trademark) filter, and then poured into a mold made of a glass mold and a tape. This mold was placed in an oven, gradually heated to 10 ° C to 120 ° C, and polymerized in 20 hours. After completion of the polymerization, the mold was taken out from the oven and separated to obtain a resin. The obtained resin was further annealed at 120 ° C. for 3 hours to produce a plastic lens. Based on the above-mentioned evaluation method of each physical property of the plastic lens, each physical property was obtained.
[0068]
[Production Example 2]
Production Example 1 except that m-xylylene diisocyanate was changed to 50.7 parts by mass and 49.4 parts by mass of the polythiol composition of Example 1 was changed to 49.4 parts by mass of the polythiol composition of Example 2 in Production Example 1. A plastic lens was manufactured by the method described in 1. Based on the above-mentioned evaluation method of each physical property of the plastic lens, each physical property was obtained.
[0069]
[Production Example 3]
Production Example 1 except that m-xylylene diisocyanate was changed to 50.7 parts by mass and 49.4 parts by mass of the polythiol composition of Example 1 was changed to 49.3 parts by mass of the polythiol composition of Example 3 in Production Example 1. A plastic lens was manufactured by the method described in 1. Based on the above-mentioned evaluation method of each physical property of the plastic lens, each physical property was obtained.
[0070]
[Production Example 4]
Production Example 1 except that m-xylylene diisocyanate was changed to 50.8 parts by mass and 49.4 parts by mass of the polythiol composition of Example 1 was changed to 49.2 parts by mass of the polythiol composition of Example 4 in Production Example 1. A plastic lens was manufactured by the method described in 1. Based on the above-mentioned evaluation method of each physical property of the plastic lens, each physical property was obtained.
[0071]
[Production Example 5]
Production Example 1 except that m-xylylene diisocyanate was changed to 50.8 parts by mass and 49.4 parts by mass of the polythiol composition of Example 1 was changed to 49.2 parts by mass of the polythiol composition of Example 5 in Production Example 1. A plastic lens was manufactured by the method described in 1. Based on the above-mentioned evaluation method of each physical property of the plastic lens, each physical property was obtained.
[0072]
[Production Example 6]
In Production Example 1, 52.0 parts by mass of m-xylylene diisocyanate, 49.4 parts by mass of the polythiol composition of Example 1, 48.0 parts by mass of the polythiol composition of Comparative Example 1, and 0.015 parts of dibutyltin dichloride. A plastic lens was manufactured by the method described in Production Example 1 except that the mass part was changed. Based on the above-mentioned evaluation method of each physical property of the plastic lens, each physical property was obtained.
[0073]
Table 1 shows the physical properties of the plastic lenses of Production Examples 1 to 5 obtained by using the polythiol compositions of Examples 1 to 5. The heat resistance of the plastic lens of Production Example 6 obtained by using the polythiol composition of Comparative Example 1 was 87.0 ° C.
ΔTg [%] described in Table 1 means the rate of increase of Tg in the plastic lens of each production example from Tg in the plastic lens of production example 6.
[0074]
[table 1]

[0075]
As shown in Table 1 above, the polythiol composition of the present disclosure could produce a resin having an excellent balance between heat resistance and dyeability by containing two kinds of polythiol compounds.
Further, as shown in Table 1, when the peak area ratio of the polythiol compound (B) to the total peak area 100 of the compounds contained in the polythiol composition is 10 or less, the dyeability is adjusted while maintaining high heat resistance. I found that I could do it.
[0076]
The disclosure of Japanese Patent Application No. 2019-131886 filed on July 17, 2019 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as specifically and individually stated that the individual documents, patent applications, and technical standards are incorporated by reference. Incorporated by reference herein.
The scope of the claims
[Claim 1]
4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, and 5 , 7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane-containing polythiol compound (A), and
A polythiol composition containing a polythiol compound (B) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
[Claim 2]
The polythiol composition according to claim 1, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 0.5 or more with respect to the total peak area 100 of the compounds contained in the polythiol composition.
[Claim 3]
The polythiol composition according to claim 1, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is 4 or more with respect to the total peak area 100 of the compounds contained in the polythiol composition.
[Claim 4]
The polythiol composition according to claim 2, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is less than 1.1 with respect to the total peak area 100 of the compounds contained in the polythiol composition.
[Claim 5]
The first aspect of claim 1, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is larger than 5.2 and less than 8.5 with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition. Polythiol composition.
[Claim 6]
The polythiol composition according to claim 1, wherein in the high-speed liquid chromatography measurement, the peak area of ​​the polythiol compound (B) is larger than 11.5 with respect to the total peak area 100 of the compounds contained in the polythiol composition.
[Claim 7]
According to any one of claims 1 to 6, the peak area of ​​the polythiol compound (A) is 90 or less with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition in the high-speed liquid chromatography measurement. The polythiol composition described.
[Claim 8]
Claims 1 to claim that the peak area of ​​the polythiol compound (B) is 0.5 or more with respect to the total peak area 100 of the polythiol compound (A) and the polythiol compound (B) in the high-speed liquid chromatography measurement. Item 2. The polythiol composition according to any one of Item 7.
[Claim 9]
The polythiol compound (A) is at least one selected from the group consisting of metal hydroxides and metal carbonates when reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following general formula (5). The polythiol composition according to any one of claims 1 to 8, which is a compound obtained by using a catalyst containing.
[Chemical 1]

[Claim 10]
The polythiol compound (B) is at least one selected from the group consisting of metal hydroxides and metal carbonates when reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following general formula (5). The polythiol composition according to any one of claims 1 to 9, which is a compound obtained by using a catalyst containing.
[Chemical 2]

[Claim 11]
A polymerizable composition containing the polythiol composition according to any one of claims 1 to 10 and a polyiso (thio) cyanate compound.
[Claim 12]
Polyiso (thio) cyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis (isosianatomethyl) cyclohexane, bis (isosianatocyclohexyl) methane, and 2,5-bis (isosyanatomethyl) bicyclo. -[2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and phenylenedi isocyanate selected from The polymerizable composition according to claim 11, which comprises at least one of these.
[Claim 13]
A resin obtained by curing the polymerizable composition according to claim 11 or 12.
[Claim 14]
A molded body containing the resin according to claim 13.
[Claim 15]
Claim 1 An optical material containing the resin according to 3.
[Claim 16]
A lens containing the resin according to claim 13.