KR102564990B1 - Polythiol composition and polymerizable composition including the same - Google Patents

Abstract

A polythiol composition according to exemplary embodiments includes a tetrafunctional polythiol compound and a subpolythiol compound including a compound represented by C ₁₃ H ₂₈ S ₉ and a compound represented by C ₁₅ H ₃₂ S ₁₀ . The ratio of the sub-polythiol compound measured through a high-performance liquid chromatography (HPLC) analysis graph is 1 to 5%. An optical product having excellent transmittance and optical properties can be manufactured through the control of the sub-polythiol compound.

Description

Polythiol composition and polymerizable composition containing the same {POLYTHIOL COMPOSITION AND POLYMERIZABLE COMPOSITION INCLUDING THE SAME}

The present invention relates to a polythiol composition and a polymerizable composition comprising the same. More specifically, it relates to a polythiol composition comprising different polythiol-based compounds and an optical composition comprising the same.

Polythiol compounds are widely used, for example, as raw materials for producing polyurethane-based resins. For example, a polythiol compound is used to manufacture an optical lens in which a polyurethane-based resin is used, and quality such as purity of the polythiol compound as a manufacturing raw material may directly affect the quality of the optical lens.

For example, a polythiourethane-based compound prepared by reacting a polythiol compound and an isocyanate compound may be used as a base material of the optical lens.

For example, Korean Patent Publication No. 10-1338568 discloses a method for synthesizing a polythiol compound by reacting a polyol compound with thiourea to produce an isothiouronium salt and hydrolyzing it using ammonia water.

Depending on the functional number, chain length, molecular weight, purity, etc. of the synthesized polythiol compound, optical properties such as transparency and refractive index of the lens may be slightly changed. Therefore, it may be necessary to fine-tune the composition of the polythiol compound in order to reliably implement an optical lens having desired optical properties.

Korea Patent Registration No. 10-1338568

One object according to exemplary embodiments is to provide a polythiol composition having improved transparency and optical properties and a manufacturing method thereof.

One problem according to exemplary embodiments is to provide a polymerizable composition comprising a polythiol composition having improved transparency and optical properties.

An object according to exemplary embodiments is to provide an optical product manufactured using the polythiol composition or polymerizable composition.

A polythiol composition according to exemplary embodiments includes a tetrafunctional polythiol compound and a subpolythiol compound including a compound represented by C ₁₃ H ₂₈ S ₉ and a compound represented by C ₁₅ H ₃₂ S ₁₀ . The ratio of the subpolythiol compound represented by Formula 1 below is 1 to 5%.

[Equation 1]

Subpolythiol compound ratio = 100% × [(C ₁₃ H ₂₈ S ₉ peak area (%)) + (C ₁₅ H ₃₂ S ₁₀ peak area (%))]/(peak area of tetrafunctional polythiol compound) (%))

(In Formula 1, the peak area (%) is the peak area (%) of the compound measured through a high-performance liquid chromatography (HPLC) analysis graph obtained at a wavelength of 230 nm).

In some embodiments, the tetrafunctional polythiol compound may include at least one of tetrafunctional polythiol compounds represented by Chemical Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In some embodiments, the compound represented by C ₁₃ H ₂₈ S ₉ may have a structure represented by Chemical Formula 2-1 below.

[Formula 2-1]

In some embodiments, the compound represented by C ₁₅ H ₃₂ S ₁₀ may have a structure represented by Chemical Formula 2-2 below.

[Formula 2-2]

In the method for preparing a polythiol composition according to exemplary embodiments, a polyol intermediate is produced by adding a metal sulfide to a preliminary polyol compound. The polyol intermediate is converted into a polythiol-based compound through thiolation. The polythiol compound includes a tetrafunctional polythiol compound and a subpolythiol compound having a higher molecular weight or higher functional number than the tetrafunctional polythiol compound. The metal sulfide was dissolved in distilled water in an amount of 17.3 parts by weight based on 100 parts by weight of distilled water, and then the absorbance measured for light with a wavelength of 350 nm in a quartz cell having an optical path length of 50 mm was 0.7 to 2.0.

In some embodiments, the subpolythiol compound includes a compound represented by C ₁₃ H ₂₈ S ₉ and a compound represented by C ₁₅ H ₃₂ S ₁₀ , and the ratio of the subpolythiol compound represented by Formula 1 is 1 to 5%.

In some embodiments, when the absorbance of the metal sulfide is less than 0.7, the metal sulfide may be treated to have an absorbance in the range of 0.7 to 2.0 by washing and drying with alcohol, water, or an aqueous alcohol solution.

In some embodiments, the metal sulfide may include Na ₂ S,

According to exemplary embodiments, a polymerizable composition including the above-described polythiol composition and an isocyanate-based compound is provided.

According to exemplary embodiments, an optical product including a polythiourethane resin prepared from the above-described polythiol composition or polymerizable composition is provided.

In some embodiments, the polymerizable composition or the optical product may further include at least one additive selected from the group consisting of a release agent, a reaction catalyst, a heat stabilizer, a UV absorber, and a bluing agent.

According to the above-described embodiments, the polythiol composition according to exemplary embodiments may include a tetrafunctional polythiol-based compound, and a sub-polythiol compound having a predetermined structure in a predetermined content range measured by HPLC. can include

The sub-polythiol compound may have a relatively large chain length or large functional number. By adjusting the content of the sub-polythiol compound, it is possible to improve lens yield and purity while reducing optical defects such as cloudiness, yellowing, and striae of the polythiol composition.

In some embodiments, a metal sulfide having an absorbance of 350 nm wavelength light in a predetermined range may be used during synthesis of the polythiol-based compound. The content of the subpolythiol compound may be finely controlled by adjusting the absorbance of the metal sulfide.

Hereinafter, embodiments of the present application will be described in detail. However, since the present invention can have various changes and various forms, specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in this application, they are not interpreted in an ideal or excessively formal meaning. .

According to one aspect of the present application, a polythiol composition including polythiol-based compounds is provided.

According to exemplary embodiments, the polythiol composition may include a tetrafunctional polythiol compound and a subpolythiol compound.

The tetrafunctional polythiol compound may be included as a target polythiol compound or a main polythiol compound of the polythiol composition.

Non-limiting examples of the tetrafunctional polythiol compound include compounds represented by Formulas 1-1 to 1-3 below. For example, the main polythiol compound may include at least one of compounds represented by Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In a preferred embodiment, a compound represented by Chemical Formula 1-1 may be used as the tetrafunctional polythiol compound.

The sub-polythiol compound may have a larger chain length, a larger molecular weight, or a larger functional number (eg, the number of thiol functional groups) than the tetrafunctional polythiol compound.

In some embodiments, the sub-polythiol compound may be a 5-functional polythiol compound. In one embodiment, the sub-polythiol compound may include at least two different 5-functional polythiol compounds.

In some embodiments, the sub-polythiol compound may include a compound represented by C ₁₃ H ₂₈ S ₉ . For example, the sub-polythiol compound may include a compound represented by Formula 2-1 below.

[Formula 2-1]

In some embodiments, the sub-polythiol compound may include a compound represented by C ₁₅ H ₃₂ S ₁₀ . For example, the sub-polythiol compound may include a compound represented by Formula 2-2 below.

[Formula 2-2]

According to exemplary embodiments, the ratio of the sub-polythiol compound defined by Equation 1 below may be in the range of 1 to 5%.

[Equation 1]

Subpolythiol compound ratio = 100% × [(C ₁₃ H ₂₈ S ₉ peak area (%)) + (C ₁₅ H ₃₂ S ₁₀ peak area (%))]/(peak area of tetrafunctional polythiol compound) (%))

The peak area (%) used in Equation 1 is the peak area (%) of the compound measured through a high-performance liquid chromatography (HPLC) analysis graph obtained at a wavelength of 230 nm.

Within the ratio range of the sub-polythiol compound represented by Equation 1, the chemical stability of the polythiol composition or the optical product may be improved, and accordingly lens cloudiness and color shift may be effectively suppressed.

For example, when the ratio of the sub-polythiol compound exceeds 5%, high-molecular-weight components in the polythiol composition increase and the purity may decrease. Accordingly, while the yield of optical products is reduced, cloudiness of the lens may be caused.

When the ratio of the sub-polythiol compound is less than 1%, during the synthesis process of the polythiol compound described later, suppression of polysulfide is not sufficiently suppressed, and color change such as yellowing of the lens may occur.

In a preferred embodiment, the ratio of the sub-polythiol compound defined by Formula 1 below may be in the range of 2 to 5% or 3 to 5%.

According to one aspect of the present application, a method for preparing a polythiol composition including polythiol-based compounds is provided. As described above, the polythiol composition may include a tetrafunctional polythiol compound and the aforementioned sub-polythiol compound.

A method for preparing a polythiol composition according to exemplary embodiments may include the following steps, processes, or actions.

S10) Injecting metal sulfide into a preliminary polyol compound to produce a polyol intermediate

S20) Reacting the polyol intermediate with thiourea under acid conditions to produce an isothiouronium salt

S30) Converting the isothiouronium salt to a polythiol compound

For example, in step S10, a polyol intermediate may be produced by reacting a preliminary polyol compound and a metal sulfide.

In one embodiment, the preliminary polyol compound may be obtained through reaction with 2-mercaptoethanol and epihalohydrin as illustrated in Scheme 1 below.

[Scheme 1]

A basic catalyst may be used to promote the reaction of 2-mercaptoethanol and epihalohydrin. Examples of the basic catalyst include tertiary amines such as triethyl amine, quaternary ammonium salts, triphenylphosphine, and trivalent chromium-based compounds. As illustrated in Scheme 1, epichlorohydrin can be used as the epihalohydrin.

The obtained preliminary polyol compound may be, for example, a diol compound containing a sulfide bond.

The reaction temperature for generating the preliminary polyol compound may be, for example, -5 to 15 °C, preferably 0 to 12 °C, and more preferably 5 to 10 °C.

For example, the content of 2-mercaptoethanol may be 0.5 mol to 3 mol, preferably 0.7 mol to 2 mol, and more preferably 0.9 mol to 1.1 mol, based on 1 mol of epihalohydrin. The basic catalyst may be used in an amount of 0.001 mol to 0.1 mol based on 1 mol of epihalohydrin.

In one embodiment, as a reaction catalyst for generating the preliminary polyol compound, a metallic catalyst such as sodium hydroxide or potassium hydroxide may be excluded in order to suppress by-products such as trifunctional thiol.

As illustrated in Scheme 2 below, a polyol intermediate may be formed by adding a metal sulfide to the sulfide bond-containing diol compound obtained as described above.

[Scheme 2]

As illustrated in Scheme 2, a polyol intermediate including a tetrafunctional polyol compound may be obtained by additionally reacting the diol compounds with each other through the metal sulfide.

The metal sulfide includes an alkali metal sulfide, and Na ₂ S may be used as shown in Scheme 2.

According to exemplary embodiments, the ratio of the above-described sub-polythiol compound may be adjusted by adjusting the absorbance of metal sulfide or Na ₂ S.

In some embodiments, as the metal sulfide, one having an absorbance in the range of 0.7 to 2.0 measured for 350 nm wavelength light at 25° C. after being dissolved in distilled water in an amount of 17.3 parts by weight based on 100 parts by weight of distilled water in a 50 mm quartz cell can be used. there is.

When a metal sulfide having an absorbance of less than 0.7 is used, a metal sulfide corresponding to a sufficient reaction equivalent may not be introduced because it is used in a state in which excessive moisture is included. Accordingly, high molecular weight by-products such as oligomers may be generated, and the purity of the synthesized polythiol-based compound may be reduced.

Accordingly, the amount of the above-described sub-polythiol compound may be excessively increased, and the ratio of the sub-polythiol compound represented by Formula 1 may exceed 5%.

When a metal sulfide having an absorbance exceeding 2.0 is used, excessive generation of polysulfide compounds may cause discoloration and yellowing of optical products.

When using a commercially purchased metal sulfide, a product within the above-described absorbance range may be selected and used, or additionally processed to have the above-described absorbance range.

In one embodiment, when a metal sulfide product having an absorbance of less than 0.7 is purchased, it may be sufficiently washed with a cleaning solution on the filter and then dried. Thereafter, after dissolving again at 17.3 parts by weight with respect to 100 parts by weight of distilled water, the absorbance of 350 nm wavelength light is measured in a 50 mm quartz cell to confirm that the absorbance in the range of 0.7 to 2.0 is obtained, and then the metal sulfide can be used.

For example, as the cleaning solution, alcohol, water, or an aqueous alcohol solution having a temperature of 10° C. or lower may be used. For example, ethanol may be used as the alcohol.

In one embodiment, when a metal sulfide product having an absorbance of more than 2.0 is purchased, it is uniformly mixed with a product of a metal sulfide having an absorbance of less than 2.0, and an absorbance in the range of 0.7 to 2.0 is obtained according to the absorbance measurement method described above. You can use it after checking your luggage.

For example, in step S20, the polyol intermediate may be reacted with thiourea. Accordingly, according to exemplary embodiments, an isothiouronium salt may be obtained.

Reflux under acid conditions can be used for the production of isothiouronium salts. Acidic compounds such as hydrochloric acid, hydrobromic acid, iodic acid, sulfuric acid, and phosphoric acid may be used to form acid conditions.

The reflux temperature may be 90 to 120°C, preferably 100 to 120°C, and may be performed for about 1 to 10 hours.

For example, in step S30, the isothiouronium salt may be converted into a polythiol-based compound. According to exemplary embodiments, a polythiol-based compound may be produced by hydrolyzing the isothiouronium salt under basic conditions.

The above steps S20 and S30 may include thiolation as exemplified by Scheme 3 below.

[Scheme 3]

For example, hydrolysis can be performed by adding a basic aqueous solution to a reaction solution containing an isothiouronium salt. The basic aqueous solution may include an alkali metal hydroxide and/or an alkaline earth metal hydroxide such as NaOH, KOH, LiOH, Ca(OH) ₂ , and the like.

In one embodiment, after cooling the reaction solution containing the isothiouronium salt to a temperature of 20 to 60 ° C, preferably 25 to 55 ° C, more preferably 25 to 50 ° C, the basic aqueous solution is added. can

In one embodiment, an organic solvent may be added before adding the basic aqueous solution. An organic solvent having a boiling point above the thiolation reaction temperature and having a low or substantially no reactivity can be used to allow a stable thiolation reaction to proceed.

Examples of the organic solvent include toluene, xylene, chlorobenzene, dichlorobenzene, and the like, and toluene may be preferably used in consideration of reaction stability and toxicity from the organic solvent.

The polythiol-based compound obtained as described above may be further purified. For example, impurities included in the polythiol-based compound may be removed by repeatedly performing acid washing and water washing processes, and transparency of an optical material manufactured from the polythiol composition may be improved. Thereafter, additional processes such as drying and filtration may be performed.

According to one aspect of the present application, a polymerizable composition including the polythiol-based compound or polythiol composition prepared as described above is provided. The polymerizable composition may be an optical polymerizable composition for manufacturing optical products such as lenses.

The polymerizable composition may include the polythiol-based compound and the isocyanate-based compound.

The isocyanate-based compound may include a compound that can be used as a monomer for synthesizing polythiourethane. In a preferred embodiment, the isocyanate-based compound may include 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, and the like. . These may be used alone or in combination of two or more.

The polymerizable composition may further include additives such as a release agent, a reaction catalyst, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

Examples of the release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphoric acid ester group; silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphoric acid ester group; alkyl quaternary ammonium salts such as trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, and diethylcyclohexadodecyl ammonium salt; Acidic phosphoric acid ester etc. are mentioned. These may be used alone or in combination of two or more.

As the reaction catalyst, a catalyst used in the polymerization of the polythiourethane-based resin may be used. For example, dialkyl tin halide type catalysts, such as dibutyl tin dichloride and dimethyl tin dichloride; dialkyl tin dicarboxylate-based catalysts such as dimethyl tin diacetate, dibutyl tin dioctanoate, and dibutyl tin dilaurate; dialkyl tin dialkoxide catalysts such as dibutyltin dibutoxide and dioctyltin dibutoxide; dialkyltindithioalkoxide-based catalysts such as dibutyltindi(thiobutoxide); dialkyl tin oxide catalysts such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin)oxide; A dialkyl tin sulfide-based catalyst or the like can be used. These may be used alone or in combination of two or more.

Examples of the UV absorber include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, and oxanilide-based compounds. As examples of the heat stabilizer, metal fatty acid-based, phosphorus-based, lead-based, or organotin-based compounds may be used. These may be used alone or in combination of two or more.

The bluing agent may be included as a color control agent for an optical material made from the polythiourethane resin. For example, the bluing agent may have an absorption band in a wavelength band from orange to yellow in the visible light region.

Examples of the bluing agent include dyes, fluorescent brightening agents, fluorescent pigments, inorganic pigments, and the like, and may be appropriately selected according to physical properties or resin color required for manufactured optical products. When a dye is used as the bluing agent, for example, a dye having a maximum absorption wavelength of 520 nm to 600 nm, preferably 540 nm to 580 nm, may be used. Preferably, an anthraquinone-based dye may be used.

A polythiourethane resin may be produced through a polymerization reaction between the polythiol-based compound and the isocyanate-based compound included in the polythiol composition.

In some embodiments, the polythiol-based compound is about 40 to 60% by weight, the isocyanate-based compound is about 40 to 60% by weight, and the above-mentioned additive is about 0.01 to 1% by weight of the total weight of the polymerizable composition. can be included

According to one aspect of the present application, an optical product manufactured through the above-described polymerizable composition may be provided.

For example, after degassing the polymerizable composition under reduced pressure, it may be injected into a mold for forming an optical material. Mold injection may be performed at a temperature range of 20 to 40° C., for example.

After injection into the mold, the temperature may be gradually raised and the polymerization reaction of the polythiourethane resin may proceed. The polymerization temperature may be 20 to 150 °C, preferably 25 to 125 °C.

After completion of polymerization, an optical product may be obtained by separating the polymerized polythiourethane resin from the mold. The optical product may be manufactured in the form of a spectacle lens, a camera lens, or a light emitting diode according to a mold shape.

The refractive index of the optical product may be adjusted according to the type and/or content ratio of the polythiol-based compound and the isocyanate-based compound used in the polymerizable composition, and may be, for example, adjusted in the range of 1.65 to 1.75.

The optical product may be improved by adding surface treatments such as anti-fouling, color imparting, hard coat, surface polishing, hardness enhancement, and the like.

According to the above-described embodiments, a metal sulfide having an absorbance within the above-described range may be used when synthesizing a polythiol-based compound. Therefore, for example, the purity and yield of the tetrafunctional polythiol compound can be improved, and an optical product suppressing optical defects such as cloudiness and yellowing can be obtained from the polythiol-based compound.

Hereinafter, embodiments provided in the present application will be additionally described with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention, but do not limit the scope of the appended claims, and various changes and modifications to the examples are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, and it goes without saying that these variations and modifications fall within the scope of the appended claims.

Example 1

1) Synthesis of tetrafunctional polythiol compound

After adding 60.0 parts by weight of water, 0.3 parts by weight of triethylamine, and 73.0 parts by weight of 2-mercaptoethanol into the reactor, the temperature was lowered to 0 ° C, and 88.2 parts by weight of epichlorohydrin was slowly added dropwise at a temperature below 15 ° C. It was further stirred at °C for 3 hours. Then, 17.3 parts by weight was dissolved in 100 parts by weight of distilled water, and when the absorbance for 350 nm wavelength light was measured at 25 ° C, the absorbance was _0.75 . 145.8 parts by weight of a 25% sodium sulfide aqueous solution was slowly added dropwise at 20 to 25° C., and further stirred for 3 hours.

Thereafter, 473.2 parts by weight of 36% hydrochloric acid and 177.8 parts by weight of thiourea were added, and stirred for 3 hours while refluxing at 110 ° C. to proceed with the tiuronium chloride reaction.

After cooling the obtained reaction solution to 50 °C, 305.6 parts by weight of toluene and 332.6 parts by weight of 50% NaOH were added thereto, followed by hydrolysis at 40-60 °C for 3 hours.

Thereafter, after layer separation was performed for 1 hour, the aqueous layer was discarded and the obtained 120 parts by weight of 36% hydrochloric acid was added to the toluene solution, and acid washing was performed once at 33 to 40°C for 30 minutes. After pickling, 250 parts by weight of degassed water (dissolved oxygen concentration: 2 ppm) was added, and washing was performed four times at 35 to 45°C for 30 minutes. After removing toluene and residual moisture under reduced pressure by heating, 140 parts by weight of a tetrafunctional polythiol compound represented by Chemical Formula 1-1 was obtained by filtration under reduced pressure with a PTFE-type membrane filter.

2) Preparation of polymerizable composition for optics and lens

After uniformly mixing 49.3 parts by weight of the polythiol compound prepared as described above, 50.7 parts by weight of xylene diisocyanate, 0.01 part by weight of dibutyl tin chloride, and 0.1 part by weight of a phosphate release agent from ZELEC® UN Stepan, degassing at 600Pa for 1 hour. By proceeding with the process, a polymerizable composition for optics was prepared.

Thereafter, the composition filtered through a 3 μm Teflon filter was injected into a mold including a glass mold and a tape. The temperature of the mold was slowly raised from 25 °C to 120 °C at a rate of 5 °C per minute, and polymerization was performed at 120 °C for 18 hours. After the polymerization was completed, the mold was separated from the mold, and further cured at 120° C. for 4 hours to prepare a lens sample.

Examples 2-8 and Comparative Examples

As shown in Table 1 below, tetrafunctional polythiol compounds and lens samples were prepared in the same manner as in Example 1, except that the absorbance of Na ₂ S used in the synthesis of the polythiol-based compound was changed.

In Examples 5 and 6, the purchased Na ₂ S was washed and dried with 0 ° C ethanol, and then used after measuring and confirming the absorbance again.

Experimental example

(1) Na ₂ S absorbance measurement

Obtained or purchased Na ₂ S was dissolved in 100 parts by weight of degassed water containing less than 10 ppm dissolved oxygen at a content of 17.3 parts by weight, put into a quartz cell with an optical path length of 50 mm, and then measured at 350 nm using a spectrophotometer (Lambda-365, perkinelmer). Absorbance for wavelength light was measured.

(2) HPLC analysis content analysis

In the polythiol compositions according to Examples and Comparative Examples, the peak area % of the polythiol compound included in the composition was measured through HPLC analysis performed under the following conditions, and the sub-polythiol compound ratio according to Formula 1 was Calculated.

<HPLC analysis conditions>

i) Equipment: Agilent 1260 Infinity II

ii) Column: ZORBAX Eclipse Plus C18, 5um 4.6×250mm

iii) Mobile phase gradient: Acetonitrile (0.1% Formic Acid): Water (0.01M Ammonium Formate) = 35~100: 65~0

iv) Solvent: Acetonitrile (0.1% Formic Acid)

v) Wavelength: 230nm/ Flow rate: 1.0ml/min / Injection amount: 20μl/sample pretreatment: sample: solvent = 0.1g: 10g

Specific compounds corresponding to peaks in the HPLC graph were identified through liquid chromatography-mass spectrometry (LC-MS). The specific conditions of LC-MS analysis are as follows.

<LC-MS analysis conditions>

i) Equipment: Thermo Hypersil Gold C18, 3um, 2.1×100mm

ii) Mobile phase condition: 5mM Ammonium Formate in Water : 0.1% Formic Acid in ACN = 65~50% : 35~50%

iii) column temperature 35°C / flow rate 0.3 ml / min / injection amount: 2 μl

iv) Detector: UV 230/254nm, Negative/Positive MS 100~1,500Da

v) Sample pretreatment: sample : solvent (ACN) = 0.1g : 10g

Specifically, the tetrafunctional polythiol compound corresponding to Chemical Formula 1-1 was measured in the HPLC analysis graph with a retention time (RT) of 25.0 to 27.0 min, and the subpolythiol compound corresponding to Chemical Formula 2-1 had a retention time of 29.5 to 30.5 min, and the subpolythiol compound corresponding to Chemical Formula 2-2 was measured in the retention time range of 31.0 to 32.5 min.

(3) Thiol value (SHV) evaluation

About 0.1 g of the polythiol composition prepared in Examples and Comparative Examples was added to a beaker, and 25 mL of chloroform was added thereto, followed by stirring for 10 minutes. Thereafter, 10 mL of methyl alcohol MeOH was added, and the solution stirred again for 10 minutes was titrated using 0.1N iodine standard solution, and SHV was measured according to Equation 1 below (theoretical value: 91.7).

[Equation 1] SHV (g / eq.) = Sample weight (g) / {0.1x amount of iodine consumed (L)}

(3) liquid refractive index

The refractive index of the polythiol compositions synthesized in Examples and Comparative Examples was measured at 25° C. using a liquid refractometer (RA-600 (Kyoto Electronics)).

(4) GPC purity

Purity of the polythiol compositions synthesized in Examples and Comparative Examples was measured through gel chromatography analysis performed under the following conditions using an APC system (Waters).

i) Column: Acquity APC XT Column 45A (4.6*150mm)x2,

ii) mobile phase: THF

iii) flow rate: 0.5 mL/min;

iv) Total driving time: 10 minutes;

v) Injection volume: 10 μl

vi) Detector: RID 40℃

(5) stria evaluation

As described above, a lens sample having a diameter of 75 mm and -4.00D was prepared using the polymerizable composition according to Examples and Comparative Examples, and a mercury lamp light source was transmitted through the prepared lens sample, and the transmitted light was projected onto a white plate. The presence or absence of striae was determined by the presence or absence of contrast. The evaluation criteria are as follows.

○: Striae not observed

×: Striae clearly observed with the naked eye

(6) Evaluation of lens cloudiness

With respect to the lens samples of Examples and Comparative Examples prepared as described above, the presence or absence of haze and opaque material was visually confirmed by irradiating the lenses with a projector in a dark room.

The evaluation criteria are as follows.

○: no haze

△: Partial haze observed

×: Haze observed entirely

(7) Measurement of Yellow Index (Y.I.)

For the lens samples of Examples and Comparative Examples, Y.I was measured using a color difference meter (Cinko, Inc., Colormate). Specifically, a lens sample having a thickness of 9 mm and φ 75 mm was prepared and chromaticity coordinates x and y were measured. Based on the measured values of x and y, Y.I was calculated by Equation 2 below.

[Equation 2]

Y.I=(234 × x + 106 × y + 106)/y

The evaluation results are shown together in Table 1 below.

_Na2S
absorbance Absorbance after washing with ethanol of Equation 1
ratio(%) Polythiol composition properties lens properties SHV
(g/ea) liquid
refractive index GPC
Purity (%) striae cloudy YI
(Yellow Index) Example 1 0.75 - 4.8 96.5 1.6465 84 ○ ○ 19 Example 2 1.12 - 4.4 96.2 1.6459 84 ○ ○ 20 Example 3 1.45 - 3.8 96.2 1.6458 82 ○ ○ 22 Example 4 1.94 - 3.0 96.1 1.6468 82 ○ ○ 23 Example 5 0.68 0.83 4.6 96.5 1.6466 83 ○ ○ 19 Example 6 0.55 0.88 4.4 96.4 1.6468 83 ○ ○ 19 Example 7 1.96 - 2.0 96.0 1.6467 82 ○ ○ 23 Example 8 1.99 - 1.1 95.8 1.6466 81 ○ ○ 23 Comparative Example 1 0.68 - 5.2 98.2 1.6475 76 ○ × 20 Comparative Example 2 0.55 - 5.5 98.9 1.6479 74 ○ × 20 Comparative Example 3 2.07 - 0.8 97.2 1.6465 79 ○ △ 26 Comparative Example 4 2.51 - 0.7 97.3 1.6466 78 ○ △ 28

Referring to Table 1, in the examples in which Na ₂ S of a predetermined absorbance range was used and the ratio of the sub-polythiol compound of Formula 1 was adjusted to the range of 1 to 5%, while preventing cloudiness and discoloration, a high-purity polythiol compound and A lens product was obtained.

Claims (11)

tetrafunctional polythiol compounds; and
A subpolythiol compound including a compound represented by C ₁₃ H ₂₈ S ₉ having a structure of Formula 2-1 and a compound represented by C ₁₅ H ₃₂ S ₁₀ having a structure of Formula 2-2 below, A polythiol composition having a ratio of 3.8 to 4.8% of a sub-polythiol compound represented by Formula 1 below:
[Equation 1]
Subpolythiol compound ratio = 100% × [(C ₁₃ H ₂₈ S ₉ peak area (%)) + (C ₁₅ H ₃₂ S ₁₀ peak area (%))]/(peak area of tetrafunctional polythiol compound) (%))
(In Formula 1, the peak area (%) is the peak area (%) of the compound measured through a high-performance liquid chromatography (HPLC) analysis graph obtained at a wavelength of 230 nm)
[Formula 2-1]

[Formula 2-2]
. The polythiol composition according to claim 1, wherein the tetrafunctional polythiol compound comprises at least one of tetrafunctional polythiol compounds represented by the following Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]
. delete delete Injecting a metal sulfide into a preliminary polyol compound to produce a polyol intermediate; and
Converting the polyol intermediate into a polythiol-based compound through thiolation,
The polythiol-based compound includes a tetrafunctional polythiol compound and a subpolythiol compound having a higher molecular weight or higher functional number than the tetrafunctional polythiol compound, and the ratio of the subpolythiol compound represented by the following formula 1 is 3.8 to 4.8 is %,
The subpolythiol compound includes a compound represented by C ₁₃ H ₂₈ S ₉ having a structure of Formula 2-1 and a compound represented by C ₁₅ H ₃₂ S ₁₀ having a structure of Formula 2-2 below,
The metal sulfide is dissolved in distilled water in an amount of 17.3 parts by weight based on 100 parts by weight of distilled water, and then the absorbance measured for 350 nm wavelength light in a quartz cell with an optical path length of 50 mm is 0.75 to 1.45. Method for producing a polythiol composition:
[Equation 1]
Subpolythiol compound ratio = 100% × [(C ₁₃ H ₂₈ S ₉ peak area (%)) + (C ₁₅ H ₃₂ S ₁₀ peak area (%))]/(peak area of tetrafunctional polythiol compound) (%))
(In Formula 1, the peak area (%) is the peak area (%) of the compound measured through a high-performance liquid chromatography (HPLC) analysis graph obtained at a wavelength of 230 nm)
[Formula 2-1]

[Formula 2-2]
. delete The method according to claim 5, further comprising the step of treating the metal sulfide so that the absorbance of the metal sulfide has a range of 0.75 to 1.45 through washing and drying with alcohol, water or an alcohol aqueous solution when the absorbance of the metal sulfide is less than 0.75. A method for preparing a thiol composition. The method of claim 5 , wherein the metal sulfide comprises Na ₂ S. A sub-group comprising a tetrafunctional polythiol compound, a compound represented by C ₁₃ H ₂₈ S ₉ having a structure of Formula 2-1 and a compound represented by C ₁₅ H ₃₂ S ₁₀ having a structure of Formula 2-2 below A polythiol composition comprising a polythiol compound and having a ratio of 3.8 to 4.8% of a sub-polythiol compound represented by Formula 1 below; and
A polymerizable composition comprising an isocyanate-based compound:
[Equation 1]
Subpolythiol compound ratio = 100% × [(C ₁₃ H ₂₈ S ₉ peak area (%)) + (C ₁₅ H ₃₂ S ₁₀ peak area (%))]/(peak area of tetrafunctional polythiol compound) (%))
(In Formula 1, the peak area (%) is the peak area (%) of the compound measured through a high-performance liquid chromatography (HPLC) analysis graph obtained at a wavelength of 230 nm)
[Formula 2-1]

[Formula 2-2]
. A polythiol composition and a polymer of an isocyanate-based compound,
The polythiol composition includes a tetrafunctional polythiol compound, a compound represented by C ₁₃ H ₂₈ S ₉ having a structure of Formula 2-1 below, and a compound represented by C ₁₅ H ₃₂ S ₁₀ having a structure of Formula 2-2 below An optical product comprising a subpolythiol compound comprising a compound, wherein the ratio of the subpolythiol compound represented by Formula 1 is 3.8 to 4.8%:
[Equation 1]
Subpolythiol compound ratio = 100% × [(C ₁₃ H ₂₈ S ₉ peak area (%)) + (C ₁₅ H ₃₂ S ₁₀ peak area (%))]/(peak area of tetrafunctional polythiol compound) (%))
(In Formula 1, the peak area (%) is the peak area (%) of the compound measured through a high-performance liquid chromatography (HPLC) analysis graph obtained at a wavelength of 230 nm)
[Formula 2-1]

[Formula 2-2]
. 11. The optical article according to claim 10, further comprising at least one additive selected from the group consisting of release agents, reaction catalysts, heat stabilizers, ultraviolet absorbers and blueing agents.