Title of Invention: Polythiol composition, polymerizable composition, resin, molded article, optical material and lens
Technical field
[0001]
The present disclosure relates to polythiol compositions, polymerizable compositions, resins, moldings, optical materials and lenses.
Background technology
[0002]
Compared to inorganic lenses, plastic lenses are lighter, less likely to break, and can be dyed.
[0003]
　Plastic lens resins are required to have even higher performance, and higher refractive index, higher Abbe number, lower specific gravity, and higher heat resistance have been required. Various resin materials for lenses have been developed and used so far.
[0004]
For example, Patent Document 1 describes a mercapto compound represented by a specific structural formula.
For example, in Patent Document 2, 2-mercaptoethanol and an epihalohydrin compound represented by a specific formula (1) are reacted at a temperature of 10 to 50° C. to obtain a compound represented by a specific formula (2). and obtaining an isothiuronium salt by reacting the obtained polyalcohol compound represented by formula (2) with thiourea in the presence of hydrogen chloride; Aqueous ammonia is added to the reaction solution within 80 minutes to hydrolyze the isothiuronium salt to obtain a polythiol compound represented by the specific formula (5) while maintaining the temperature of the reaction solution containing the and adding 25 to 36% hydrochloric acid to the resulting solution containing the polythiol compound and washing at a temperature of 10 to 50° C. to purify the polythiol compound. Have been described.
[0005]
　　Patent document 1: JP-A-2-270859
Patent Document 2: International Publication No. 2014-027427
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0006]
A resin obtained by curing a polymerizable composition containing a polythiol compound may be required to have reduced yellowness and devitrification.
In practice, polymerizable compositions containing polythiol compounds often contain compounds other than polythiol compounds.
The present inventors have found that when the polymerizable composition contains compounds other than the polythiol compound, the yellowness and devitrification of the resulting resin tend to be impaired.
As a result of various studies on the above tendency, we found that it may be difficult to obtain a resin with reduced yellowness and devitrification.
[0007]
A problem to be solved by one embodiment of the present disclosure is to provide a polythiol composition capable of producing a resin with reduced yellowness.
Means to solve problems
[0008]
The means for solving the above problems include the following embodiments.
<1> Contains a polythiol compound (A) and a compound represented by the following formula (1), and in high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is the polythiol composition The total peak area of ​​100 of the compounds contained in the polythiol composition is 9.0 or less.
[0009]
[Chemical 1]

[0010]
(In formula (1), X represents —CH 2— or a sulfur atom.)
<2> The polythiol composition according to <1>, wherein the polythiol compound (A) contains a polythiol compound obtained from 2-mercaptoethanol and thiourea as raw materials.
<3> The polythiol compound (A) contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6 ,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9 - The polythiol composition according to <1> or <2>, which contains a mixture of trithiundecane.
<4> Containing a polythiol compound (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a compound represented by the following formula (1),
In high performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition <1> to <3 The polythiol composition according to any one of >.
[0011]
[Chemical 2]

[0012]
(In formula (1), X represents —CH 2— or a sulfur atom.)
<5> In the high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is greater than 0 with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition <1>-< 4> The polythiol composition according to any one of 4>.
<6> A polymerizable composition containing the polythiol composition according to any one of <1> to <5> and a polyiso(thio)cyanate compound.
<7> The polyiso(thio)cyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanate Natomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate and phenylene The polymerizable composition according to <6>, containing at least one selected from diisocyanates.
<8> A resin containing a cured product of the polymerizable composition described in <6> or <7>.
<9> A molded article containing the resin described in <8>.
<10> An optical material containing the resin described in <8>.
<11> A lens containing the resin according to <8>.
Effect of the invention
[0013]
According to one embodiment of the present disclosure, it is possible to provide a polythiol composition capable of producing a resin with reduced yellowness.
MODE FOR CARRYING OUT THE INVENTION
[0014]
In the present disclosure, a numerical range indicated using "-" indicates a range that includes the numerical values ​​before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described in stages in the present disclosure, the upper or lower limit values ​​described in a certain numerical range may be replaced with the upper or lower limits of other numerical ranges described in stages, and , may be replaced by the values ​​shown in the examples.
In the present disclosure, when there are multiple substances corresponding to each component in the material, the amount of each component in the material means the total amount of multiple substances present in the material unless otherwise specified.
In the present disclosure, "iso(thio)cyanate" means isocyanate or isothiocyanate.
[0015]
<>
The polythiol composition of the present disclosure contains a polythiol compound (A) and a compound represented by the following formula (1), and in high performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition.
[0016]
[Chemical 3]

[0017]
(In formula (1), X represents —CH 2— or a sulfur atom.)
[0018]
The polythiol composition of the present disclosure can produce a resin with reduced yellowness by including the above configuration.
[0019]
The polythiol compound (A) preferably contains a polythiol compound obtained from 2-mercaptoethanol and thiourea as raw materials.
Examples of polythiol compounds obtained from 2-mercaptoethanol and thiourea as raw materials include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 4,7-dimercapto. mixture of methyl-1,11-dimercapto-3,6,9-trithiundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4-mercaptomethyl-1 ,8-dimercapto-3,6-dithiaoctane and the like.
[0020]
The polythiol compound (A) contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9- Trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia It preferably contains mixtures of undecane.
[0021]
(other compounds)
The polythiol composition of the present disclosure is further a compound in which at least one of the three or more mercapto groups in the polythiol compound (XA) containing three or more mercapto groups is replaced with a group represented by the following formula (N1) (XB) may be included.
[0022]
[Compound (XB)]
The compound (XB) is a compound obtained by replacing at least one of the three or more mercapto groups in the polythiol compound (XA) containing three or more mercapto groups with a group represented by the following formula (N1).
The polythiol compound (XA) may be the same compound as or different from the polythiol compound (A) described above, but is preferably the same compound.
[0023]
[Chemical 4]

[0024]
In formula (N1), * represents a binding position.
[0025]
Examples of compound (XB) are shown below, but compound (XB) is not limited to the following examples.
[0026]
[Chemical 5]

[0027]
When the polythiol composition of the first embodiment described later further contains compound (XB), the ratio of the compound represented by formula (1) to compound (XB) (compound represented by formula (1)/compound ( XB)) is preferably 0.5 to 18, more preferably 1 to 15, and further preferably 2 to 12, from the viewpoint of reducing the yellowness and devitrification of the resulting resin. preferable.
When the polythiol composition of the second embodiment described later further contains compound (XB), the ratio of the compound represented by formula (1) to compound (XB) (compound represented by formula (1)/compound ( XB)) is preferably from 0.1 to 9 from the viewpoint of reducing the yellowness and degree of devitrification of the obtained resin and from the viewpoint of maintaining a good pot life of the polymerizable composition of the present disclosure. 0.5 to 7 is more preferred, and 0.9 to 5 is even more preferred.
The ratio of the compound represented by the formula (1) to the compound (XB) (compound represented by the formula (1)/compound (XB)) was obtained by measuring the polythiol composition by high performance liquid chromatography. It is the ratio of the peak area of ​​the compound represented by formula (1) to the peak area of ​​compound (XB) in the case. Measurement conditions for high-performance liquid chromatography are as described in below.
[0028]
The polythiol composition of the present disclosure includes the polythiol compositions of the following first and second embodiments.
[0029]

The polythiol composition of the first embodiment contains a polythiol compound (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a compound represented by the following formula (1), In high performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition.
[0030]
[Chemical 6]

[0031]
(In formula (1), X represents —CH 2— or a sulfur atom.)
[0032]
The polythiol composition of the first embodiment includes the above configuration, so that the combination of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a specific sulfur compound is included in the polymerizable composition. In some cases, resins with reduced yellowness and devitrification can be produced.
[0033]

of the first embodiment The polythiol composition contains a compound represented by the following formula (1).
[0034]
[Chemical 7]

[0035]
(In formula (1), X represents —CH 2— or a sulfur atom.)
[0036]
The polythiol composition of the first embodiment contains a compound represented by the following formula (1), so that the combination of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a specific sulfur compound is When included in the polymerizable composition, the yellowness and devitrification of the resulting resin can be reduced. Moreover, the polythiol composition of the first embodiment can also produce a resin with a reduced degree of devitrification by including the above configuration.
[0037]
In the polythiol composition of the first embodiment, the peak area of ​​the compound represented by formula (1) is 9.0 with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition in high performance liquid chromatography measurement. It is below.
When the peak area of ​​the compound represented by the above formula (1) is 9.0 or less, the yellowness and devitrification of the resulting resin can be reduced.
From the same viewpoint as above, the total peak area of ​​100 of the compounds contained in the polythiol composition is preferably 7.0 or less, more preferably 5.0 or less, and 4.0 or less. is more preferable, and 3.0 or less is particularly preferable.
[0038]
"The peak area of ​​the compound represented by the formula (1) with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition" is the total peak area of ​​the compounds contained in the polythiol composition, when the total peak area is 100, the formula ( It means the relative value of the peak area of ​​the compound represented by 1).
[0039]
In the high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is the polythiol composition from the viewpoint of reducing the work load of refining and removing the compound represented by the formula (1) from the polythiol composition It is preferably greater than 0, more preferably 0.02 or more, even more preferably 0.05 or more, and 0.1 or more with respect to 100 of the total peak area of ​​the compounds contained in the substance. is particularly preferred, 0.2 or more is particularly preferred, 0.3 or more is particularly preferred, 0.5 or more is even more preferred, and 0.8 or more is even more preferred. .
In addition, when the peak area of ​​the compound represented by formula (1) satisfies the above lower limit range, the thickening rate can be increased, and thus the polymerization can be promoted.
[0040]
The method for adjusting the peak area of ​​the compound represented by formula (1) with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition is not particularly limited, but for example, column purification, washing, extraction, crystallization, etc. can be adjusted by the operation of
[0041]

The peak area of ​​the compound represented by formula (1) with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition is obtained by high performance liquid chromatography (HPLC) measurement based on the following conditions.
The peak area appearing at a retention time of 3.6 minutes to 4.8 minutes is determined to be the peak area of ​​the compound represented by formula (1), and the ratio of the compounds contained in the polythiol composition to the total peak area of ​​100 is calculated. Just do it.
(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: 1.0ml/min
Detector: UV detector, wavelength 230 nm
Preparation of measurement solution: Dissolve and mix 160 mg of sample with 10 ml of acetonitrile.
Injection volume: 2 μL
[0042]
(Polythiol compound (A))
The polythiol composition of the first embodiment contains a polythiol compound (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is a compound represented by the following formula (2).
[0043]
[Chemical 8]

[0044]
The method for producing the polythiol compound (A) is not particularly limited, and it can be produced by a known method. For example, polythiol compound (A) can be produced by the method described in International Publication No. 2014/027427. In addition, the polythiol compound (A) can be produced from metal hydroxides such as sodium hydroxide and potassium hydroxide and metal carbonates such as sodium carbonate and potassium carbonate when, for example, 2-mercaptoethanol and an epihalohydrin compound are reacted. It is preferably a compound obtained using a catalyst containing at least one selected from the group consisting of:
[0045]
The polythiol composition of the first embodiment may contain compounds other than the polythiol compound (A) and the compound represented by formula (1).
For example, a polythiol compound having a mercapto group other than the polythiol compound (A) and the compound represented by formula (1) (hereinafter also referred to as "another polythiol compound") may be included.
[0046]
Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate). , tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2-mercaptoethyl)sulfide, bis(2,3-dimercaptopropyl) sulfide, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane and the like.
[0047]

The polythiol composition of the second embodiment contains 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3, A polythiol compound (A) containing a mixture of 6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, represented by the following formula (1) and a compound represented by the above formula (1) in high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition. be.
[0048]
[Chemical 9]

[0049]
(In formula (1), X represents —CH 2— or a sulfur atom.)
[0050]
The polythiol composition of the second embodiment can produce a resin with reduced yellowness by including the above configuration.
[0051]
In the polythiol composition of the second embodiment, the peak area of ​​the compound represented by formula (1) is 9.0 with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition in high performance liquid chromatography measurement. It is below.
When the peak area of ​​the compound represented by the above formula (1) is 9.0 or less, the yellowness of the resulting resin can be reduced.
From the same viewpoint as above, the total peak area of ​​100 of the compounds contained in the polythiol composition is preferably 7.0 or less, more preferably 5.0 or less, and 4.0 or less. is more preferable, and 3.0 or less is particularly preferable.
[0052]
In the high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is the polythiol composition from the viewpoint of reducing the work load of refining and removing the compound represented by the formula (1) from the polythiol composition It is preferably greater than 0, more preferably 0.02 or more, even more preferably 0.05 or more, and 0.1 or more with respect to 100 of the total peak area of ​​the compounds contained in the substance. is particularly preferred, 0.2 or more is particularly preferred, 0.3 or more is particularly preferred, 0.5 or more is even more preferred, and 0.8 or more is even more preferred. .
In addition, when the peak area of ​​the compound represented by formula (1) satisfies the above lower limit range, the thickening rate can be increased, and thus the polymerization can be promoted.
[0053]
Specific aspects of the compound represented by formula (1) in the second embodiment, a preferred aspect, the definition of the peak area of ​​the compound represented by formula (1) with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition and Details of the measurement method and the like include the specific embodiment and preferred embodiment of the compound represented by the formula (1) described above, and the peak of the compound represented by the formula (1) with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition. It is the same as the definition of the area and the details such as the measurement method.
[0054]
The polythiol composition of the second embodiment may contain compounds other than the polythiol compound (A) and the compound represented by formula (1).
Details such as specific examples and preferred specific examples of other polythiol compounds in the second embodiment are the same as details of specific examples and preferred specific examples of other polythiol compounds in the first embodiment.
[0055]
<>
The polymerizable composition of the present disclosure includes the polythiol composition of the present disclosure and a polyiso(thio)cyanate compound.
[0056]
(Polyiso (thio) cyanate compound)
The polyiso(thio)cyanate compound is not particularly limited as long as it can exhibit the effects of the present disclosure, and conventionally known compounds can be used. Any compound having at least two or more iso(thio)cyanate groups in one molecule is not particularly limited, and specific examples include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, Aliphatic polyisocyanate compounds such as octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, and xylylene diisocyanate;
isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, dicyclohexyldimethylmethane diisocyanate, 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- Alicyclic polyisocyanate compounds such as bis(isocyanatomethyl)tricyclodecane and 4,9-bis(isocyanatomethyl)tricyclodecane;
aromatic polyisocyanate compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate, and phenylene diisocyanate;
2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis( isocyanatomethyl)tetrahydrothiophene , 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis(isocyanato heterocyclic polyisocyanate compounds such as methyl)-1,3-dithiolane;
Aliphatic polyisothiocyanate compounds such as hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, and xylylene diisothiocyanate;
isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, bis(isothiocyanatocyclohexyl)methane, cyclohexanediisothiocyanate, methylcyclohexanediisothiocyanate, 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 polyisothiocyanate compounds such as (isothiocyanatomethyl)tricyclodecane, 4,8-bis(isothiocyanatomethyl)tricyclodecane, 4,9-bis(isothiocyanatomethyl)tricyclodecane;
aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, diphenyl disulfide-4,4-diisothiocyanate;
2,5-diisothiocyanatothiophene, 2,5-bis(isothiocyanatomethyl)thiophene, 2,5-isothiocyanatotetrahydrothiophene, 2,5-bis(isothiocyanatomethyl)tetrahydrothiophene, 3,4 -bis(isothiocyanatomethyl)tetrahydrothiophene, 2,5-diisothiocyanato-1,4-dithiane, 2,5-bis(isothiocyanatomethyl)-1,4-dithiane, 4,5-diisothiophene sulfur-containing heterocyclic polyisothiocyanate compounds such as ocyanato-1,3-dithiolane and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane; The polyiso(thio)cyanate compound can contain at least one selected from these.
[0057]
Polyiso(thio)cyanate compounds include halogen-substituted products such as chlorine-substituted products and bromine-substituted products thereof, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols, and carbodiimides. Modified products, urea modified products, buret modified products, dimerization or trimerization reaction products, etc. can also be used.
[0058]
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 phenylene diisocyanate. .
[0059]
The mixing ratio of the polythiol composition and the polyiso(thio)cyanate compound is not particularly limited. 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 more preferred. 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 a plastic lens or the like in a well-balanced manner.
[0060]
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 of the resin, operability, polymerization reactivity of the polymerizable composition, and the like. good too.
Other ingredients include polymerization catalysts, internal release agents, resin modifiers, chain extenders, cross-linking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion Blue ink agents such as property improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments are included.
[0061]
Examples of polymerization catalysts include tertiary amine compounds, inorganic or organic acid salts thereof, metal compounds, quaternary ammonium salts, organic sulfonic acids, and the like.
[0062]
An acidic phosphate ester can be used as the internal release agent. Examples of acidic phosphates include phosphate monoesters and phosphate diesters, each of which can be used alone or in combination of two or more.
[0063]
Examples of resin modifiers 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.
[0064]
In the polymerizable composition of the present disclosure, the glass transition temperature Tg when cured to form a molded article is preferably 80°C or higher, more preferably 85°C or higher, from the viewpoint of heat resistance. The glass transition temperature Tg may be 130° C. or lower, or 125° C. or lower.
In the present disclosure, the glass transition temperature Tg when formed into a molded product is a value measured by the method described in Examples using a plastic flat plate molded according to in Examples described later.
[0065]
≪Molded body≫
The molded article of the present disclosure contains the resin of the present disclosure.
The resin of the present disclosure includes a cured product of the polymerizable composition of the present disclosure.
The method for producing the molded article of the present disclosure is not particularly limited, and casting polymerization is a preferred production method. First, the polymerizable composition is injected between molding molds held by gaskets, tape, or the like. At this time, depending on the physical properties required for the plastic lens to be obtained, it is often preferable to perform defoaming treatment under reduced pressure, filtration treatment such as pressurization or reduced pressure, or the like, if necessary.
[0066]
The polymerization conditions are not limited because the conditions vary greatly depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc. For example, the temperature is -50° C. to 150° C. for 1 hour or more. It takes 50 hours. Depending on the case, it is preferable to hold or gradually raise the temperature in the temperature range of 10° C. to 150° C. and cure in 1 hour to 48 hours.
[0067]
The molded body may be subjected to processing such as annealing as necessary. A treatment such as annealing is usually performed at a temperature of 50°C to 150°C, preferably 90°C to 140°C, more preferably 100°C to 130°C.
[0068]
[Use]
The resin obtained from the polymerizable composition of the present disclosure can be used as a material for producing molded articles of various shapes by changing the type of mold during casting polymerization.
[0069]
≪Optical Materials≫
The optical material of the present disclosure includes the resin of the present disclosure.
A molded article obtained from the polymerizable composition of the present disclosure can be a material with reduced yellowness without impairing transparency. In addition, the molded article obtained from the polymerizable composition containing the polythiol composition of the first embodiment can also obtain a material having an excellent degree of devitrification.
Therefore, it can be used for various optical materials such as plastic lenses.
[0070]
≪Lens≫
The lens of the present disclosure contains the resin of the present disclosure.
Lenses are particularly suitable as optical materials.
Examples of lenses include plastic spectacle lenses and plastic polarized lenses.
[0071]
[Plastic spectacle lenses]
A plastic spectacle lens using a lens substrate made of the molded article of the present disclosure may be provided with a coating layer on one side or both sides, if necessary.
The plastic spectacle lens of the present disclosure includes a lens substrate containing the cured polymerizable composition described above and a coating layer.
[0072]
Specific examples of coating layers 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 as a multilayer. When the coating layer is applied to both surfaces, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.
[0073]
These coating layers are composed of infrared absorbers to protect the eyes from infrared rays, light stabilizers and antioxidants to improve the weather resistance of the lenses, and photochromic compounds, dyes, and dyes to enhance the fashionability of the lenses. In addition to pigments, other known additives such as antistatic agents may be used in combination for the purpose of enhancing lens performance.
Various leveling agents may be used for the purpose of improving coatability for layers that are coated by application.
In addition, an antifog layer, an antifouling layer, and a water repellent layer may be formed on the antireflection layer as necessary.
[0074]
Although the embodiments of the present disclosure have been described above, these are examples of the present disclosure, and various configurations other than the above can be adopted within a range that does not impair the effects of the present disclosure.
Example
[0075]
The polythiol composition of the present disclosure will be described in detail below with reference to Examples. In addition, the polythiol composition of the present disclosure is not limited to the description of these examples. "Parts" are based on mass unless otherwise specified.
[0076]

In this example, the evaluation method for each physical property of the plastic flat plate is as follows. The results are shown in Table 1.
・Refractive index (ne), Abbe number (νe)
Using a Shimadzu Pulfrich refractometer KPR-30, the refractive index (ne, nF′, nC′) were measured, and the refractive index (ne) and Abbe number (νe) were obtained.
·Heat-resistant
Using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, the glass transition temperature Tg is measured by the TMA penation method (50 g load, pin tip 0.5 mmφ, temperature increase rate 10 ° C./min), and is an index of heat resistance. and
・Yellow index (also called YI)
The resin was prepared as a circular plastic plate with a thickness of 9 mm and a diameter of 75 mm, and the YI value was obtained using a spectrophotometer CM-5 manufactured by Konica Minolta.
Note that there is a correlation that the smaller the YI value, the smaller the yellowness of the plastic flat plate, and the larger the YI value, the greater the yellowness.
・Degree of devitrification
The resin was produced as a circular plastic flat plate with a thickness of 9 mm and a diameter of 75 mm, and light from a light source (Luminar Ace LA-150A manufactured by Hayashi Repic) was transmitted through the flat plate from the side of the flat plate. An image of light from the front of the flat plate was captured in an image processing device (manufactured by Ube Information Systems Co., Ltd.), and the captured image was subjected to gradation processing. The degree of gradation of the processed image was quantified for each pixel, and the average value of the numerical values ​​of the degree of gradation of each pixel was obtained to obtain the degree of devitrification of the flat plate.
The smaller the degree of devitrification, the less the transparency of the resin (here, flat plate) is impaired (that is, the transparency of the resin is excellent).
[0077]
The polythiol composition of the first embodiment will be described in detail below with reference to examples. In addition, the polythiol composition of the first embodiment is not limited to the description of these examples.
[0078]

A reactor was charged with 124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water. At 12° C. to 35° C., 101.5 parts by mass of a 32% by mass sodium hydroxide aqueous solution was added dropwise over 40 minutes, followed by 73.6 parts of epichlorohydrin.The mass part was added dropwise at 29° C. to 36° C. over 4.5 hours, followed by stirring for 40 minutes. NMR data confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol.
331.5 parts by mass of 35.5% by mass hydrochloric acid was charged, then 183.8 parts by mass of thiourea with a purity of 99.90% was charged, and the mixture was stirred at 110°C under reflux for 3 hours, A thiuronium chloride reaction was carried out. After cooling to 45°C, 320.5 parts by mass of toluene was added, cooled to 31°C, and 243.1 parts by mass of a 25% by mass ammonia aqueous solution was charged at 31°C to 41°C over 44 minutes, and heated to 54°C. A 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% by mass hydrochloric acid was added to this toluene solution, and acid washing was carried out 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% by mass aqueous ammonia was added and washed for 30 minutes. 174.2 parts by mass of degassed water was added and washing was performed twice at 35° C. to 45° C. for 30 minutes. After removing toluene and trace amounts of water under heating and reduced pressure, filtration under reduced pressure with a 1.2 μm PTFE type membrane filter was performed to remove 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is the polythiol compound (A). 205.0 parts by mass of polythiol composition (A) as a main component was obtained.
[0079]
[Example 1, Example 2 and Comparative Example 1]
The polythiol composition (A) obtained as described above and γ-thiobutyrolactone (manufactured by Sigma-Aldrich; compound represented by formula (1)) were mixed to obtain a polythiol composition.
At that time, the mixing ratio was changed so that the peak area of ​​the compound represented by formula (1) with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition was the value shown in Table 1.
[0080]

The ratio (area%) of γ-thiobutyrolactone by HPLC was measured by the method described in the above section .
The results are shown in Table 1.
[0081]

[Production Example 1]
52 parts by mass of m-xylylene diisocyanate, 0.01 part by mass of dibutyltin dichloride as a curing catalyst, Zelec UN (trade name Stepan product; acidic phosphate) 0.10 parts by mass, and Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.; Ultraviolet absorber) 1.5 parts by mass were mixed and dissolved at 20°C. 48 parts by mass of the polythiol composition of Example 1 was charged and mixed to obtain a mixed uniform liquid. This homogeneous liquid was defoamed at 600 Pa for 1 hour, filtered through a 1 μm Teflon (registered trademark) filter, and then poured into a mold consisting of a glass mold and a tape. This mold was put into an oven, and the temperature was gradually raised from 10° C. to 120° C., and polymerization was carried out in 38 hours. After the polymerization was completed, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120° C. for 1 hour to produce a plastic flat plate. Each physical property was obtained based on the evaluation method for each physical property of the plastic flat plate described above.
[0082]
[Production Example 2]
A plastic flat plate was produced in the same manner as in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Example 2. Each physical property was obtained based on the evaluation method for each physical property of the plastic flat plate described above.
[0083]
[Production Example 3]
A plastic flat plate was produced in the same manner as in Production Example 1, except that in Production Example 1, 48 parts by mass of the polythiol composition of Example 1 was changed to 48 parts by mass of the polythiol composition of Comparative Example 1. Each physical property was obtained based on the evaluation method for each physical property of the plastic flat plate described above.
Table 1 shows the physical properties of the plastic flat plates of Production Examples 1 to 3.
[0084]
[table 1]

[0085]
As shown in Table 1, a polythiol compound (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a compound represented by formula (1) are included, and high performance liquid chromatography is performed. In the measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition. It was possible to produce a resin with reduced hardness and devitrification. Moreover, the polythiol compositions according to the examples were excellent in heat resistance.
On the other hand, the polythiol composition according to Comparative Example 1, in which the peak area of ​​the compound represented by formula (1) exceeds 9.0 with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition, has a yellowness index of And a resin with a reduced degree of devitrification could not be produced.
[0086]
The polythiol composition of the second embodiment will be described in detail below with reference to examples. In addition, the polythiol composition of the second embodiment is not limited to the description of these examples.
[0087]

A reactor was charged with 51.2 parts by mass of 2-mercaptoethanol, 26.5 parts by mass of degassed water (dissolved oxygen concentration of 2 ppm), and 0.16 parts by mass of a 49% by mass sodium hydroxide aqueous solution. 61.99 parts by mass of epichlorohydrin was added dropwise at 9 to 11° C. over 6.5 hours, followed by stirring for 60 minutes. NMR data confirmed the formation of 1-chloro-3-(2-hydroxyethylthio)-2-propanol.
Then, 150.0 parts by mass of a 17.3% by mass sodium sulfide aqueous solution was added dropwise at 7 to 37° C. over 5.5 hours, and the mixture was stirred for 120 minutes. NMR data confirmed the formation of 1,5,9,13-tetrahydroxy-3,7,11-trithiatridecane. Then, 279.0 parts by mass of 35.5% by mass hydrochloric acid was charged, then 125.8 parts by mass of thiourea with a purity of 99.90% was charged, and the mixture was stirred under reflux at 110°C for 3 hours. thiuronium chloride reaction was carried out. After cooling to 45°C, add 214.0 parts by mass of toluene and cool to 26°C. A hydrolysis reaction was carried out by stirring at ~65°C for 1 hour to give 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 4,7-dimercaptomethyl-1,11- A toluene solution of polythiol containing dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as main components was obtained. 59.4 parts by mass of 36% by mass hydrochloric acid was added to the toluene solution, and acid washing was performed twice at 34° C. to 39° C. for 30 minutes. Further, 118.7 parts by mass of degassed water (dissolved oxygen concentration 2 ppm) was added, and washing was carried out five times at 35° C. to 45° C. for 30 minutes. After removing toluene and trace amounts of water under heating and reduced pressure, filtration under reduced pressure with a 1.2 μm PTFE type membrane filter gave 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane are mainly used. 115.9 parts by mass of polythiol composition (A) as a component was obtained.
[0088]
[Example 3, Example 4 and Comparative Example 2]
The polythiol composition (A) obtained as described above and γ-thiobutyrolactone (manufactured by Sigma-Aldrich; compound represented by formula (1)) were mixed to obtain a polythiol composition.
At that time, the mixing ratio was changed so that the peak area of ​​the compound represented by formula (1) with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition was the value shown in Table 2.
[0089]

The ratio (area%) of γ-thiobutyrolactone by HPLC was measured by the method described in the above section .
The results are shown in Table 2.
[0090]

[Production Example 4]
50.8 parts by mass of m-xylylene diisocyanate, 0.01 part by mass of dimethyltin dichloride as a curing catalyst, Zelec UN (manufactured by Stepan; acidic phosphate ester) 0.10 parts by mass, and Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.; Ultraviolet absorber) 0.6 parts by mass and Seesorb 706 (manufactured by Shipro Kasei; ultraviolet absorber) 0.6 parts by mass were mixed and dissolved at 20°C. 49.2 parts by mass of the polythiol composition of Example 3 was charged and mixed to obtain a mixed uniform liquid. This homogeneous liquid was defoamed at 600 Pa for 1 hour, filtered through a 1 μm Teflon (registered trademark) filter, and then poured into a mold consisting of a glass mold and a tape. This mold was put into an oven, and the temperature was gradually raised from 20° C. to 120° C., and polymerization was carried out for 30 hours. After the polymerization was completed, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120° C. for 1 hour to produce a plastic flat plate. Each physical property was obtained based on the evaluation method for each physical property of the plastic flat plate described above.
[0091]
[Production Example 5]
A plastic plate was produced in the same manner as in Production Example 4, except that 49.2 parts by mass of the polythiol composition of Example 3 was changed to 49.2 parts by mass of the polythiol composition of Example 4. Each physical property was obtained based on the evaluation method for each physical property of the plastic flat plate described above.
[0092]
[Production Example 6]
A plastic flat plate was produced in the same manner as in Production Example 4, except that 49.2 parts by mass of the polythiol composition of Example 3 was changed to 49.2 parts by mass of the polythiol composition of Comparative Example 2. Each physical property was obtained based on the evaluation method for each physical property of the plastic flat plate described above.
Table 2 shows the physical properties of the plastic flat plates of Production Examples 4 to 6.
[0093]
[Table 2]

[0094]
As shown in Table 2, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9 - a polythiol compound (A) comprising a mixture of trithiundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and a compound represented by formula (1); In the high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition. Such polythiol compositions were able to produce resins with reduced yellowness. Moreover, the polythiol compositions according to the examples were excellent in heat resistance.
On the other hand, the polythiol composition according to Comparative Example 2, in which the peak area of ​​the compound represented by formula (1) exceeds 9.0 with respect to the total peak area of ​​100 of the compounds contained in the polythiol composition, has a yellowness index of could not produce a resin with reduced
[0095]
The disclosure of Japanese Patent Application No. 2020-189834 filed on November 13, 2020 is incorporated herein by reference in its entirety.
All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.
The scope of the claims
[Claim 1]
a polythiol compound (A),
a compound represented by the following formula (1),
including
A polythiol composition in which the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition in high-performance liquid chromatography measurement.
[Chemical 1]

(In formula (1), X represents —CH 2— or a sulfur atom.)
[Claim 2]
The polythiol compound (A) uses 2-mercaptoethanol as a raw material and a polythiol compound obtained from thiourea.
[Claim 3]
The polythiol compound (A) contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9- Trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia 3. A polythiol composition according to claim 1 or claim 2, comprising a mixture of undecanes.
[Claim 4]
a polythiol compound (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
a compound represented by the following formula (1),
including
In high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is 9.0 or less with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition. 4. The polythiol composition according to any one of 3.
[Chemical 2]

(In formula (1), X represents —CH 2— or a sulfur atom.)
[Claim 5]
In high-performance liquid chromatography measurement, the peak area of ​​the compound represented by the formula (1) is greater than 0 with respect to 100 of the total peak area of ​​the compounds contained in the polythiol composition. A polythiol composition according to any one of claims 1 to 3.
[Claim 6]
the polythiol composition according to any one of claims 1 to 5;
A polyiso (thio) cyanate compound and
A polymerizable composition comprising:
[Claim 7]
The polyiso(thio)cyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, and 2,5-bis(isocyanatomethyl). selected from bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate and phenylene diisocyanate 7. The polymerizable composition according to claim 6, comprising at least one of
[Claim 8]
A resin containing a cured product of the polymerizable composition according to claim 6 or claim 7.
[Claim 9]
A molded body containing the resin according to claim 8.
[Claim 10]
An optical material containing the resin according to claim 8.
[Claim 11]
A lens containing the resin according to claim 8.