Polymerizable composition and application thereof

Abstract

Provided is a polymerizable composition which contains an iso(thio)cyanate compound and an active hydrogen compound including a thiol compound, wherein the A / B ratio, which is the ratio of value (A) to value (B), is more than 1.00.　Value (A) = ((the total mass of the iso(thio)cyanate compound) / (the molecular weight of the main compound in the iso(thio)cyanate compound)) × (the number of iso(thio)cyanato groups in each molecule of the main compound in the iso(thio)cyanate compound) Value (B) = ((the total mass of the active hydrogen compound) / (the molecular weight of the main compound in the active hydrogen compound)) × (the number of active hydrogen groups in each molecule of the main compound in the active hydrogen compound)

Description

Polymerizable composition and use thereof

[0001] The present disclosure relates to a polymerizable composition and use thereof.

[0002] Plastic lenses, which are lenses containing a resin, are lighter, more resistant to cracking, and can be dyed compared to inorganic lenses, and thus have rapidly become widespread in recent years in applications such as eyeglass lenses and camera lenses.

[0003] Patent Document 1 discloses, as a method for obtaining a high-refractive-index resin (e.g., a lens) excellent in various physical properties such as transparency, hue, heat resistance, and impact resistance, a method for obtaining a resin by curing the following polymerizable composition. The polymerizable composition disclosed in Patent Document 1 is a composition containing a polythiol compound having a dithioacetal, dithioketal, orthotrithioformate or orthotetrathio carbonate skeleton and having two or more mercapto groups, and a compound having two or more iso(thio)cyanate groups, wherein the molar ratio of mercapto groups to iso(thio)cyanate groups is greater than 1.0 and 3.0 or less, and is a polymerizable composition for high-refractive-index resins.

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-2820

[0005] Resin-containing lenses are produced by processing (e.g., grinding) a resin (or a molded article containing the resin). However, when processing (e.g., grinding) a resin (e.g., a thiourethane resin) formed using a polymerizable composition containing a thiol compound, sulfur odor may be generated. There are cases where reduction of this sulfur odor during processing is required.

[0006] An object to be solved by an embodiment of the present disclosure is to provide a polymerizable composition capable of producing a resin with reduced odor during processing, a resin with reduced odor during processing, and a molded article, an optical material, and a lens containing the resin.

[0007] The means for solving the above problems include the following embodiments: <1> A polymerizable composition containing an iso(thio)cyanate compound and an active hydrogen compound containing a thiol compound, wherein the A / B ratio, which is the ratio of the following value (A) to the following value (B), is greater than 1.00. Value (A) = (Total mass of the iso(thio)cyanate compound / Molecular weight of the main compound in the iso(thio)cyanate compound) × Number of iso(thio)cyanate groups in one molecule of the main compound in the iso(thio)cyanate compound (B) = (Total mass of the active hydrogen compound / Molecular weight of the main compound in the active hydrogen compound) × Number of active hydrogen groups in one molecule of the main compound in the active hydrogen compound <2> The polymerizable composition according to <1>, wherein the A / B ratio is 1.02 or more. <3> The polymerizable composition according to <1> or <2>, wherein the A / B ratio is 1.08 or more. <4> The polymerizable composition according to any one of <1> to <3>, wherein the thiol compound comprises a compound containing an ethylenethio group and a thiol group. <5> The polymerizable composition according to any one of <1> to <4>, wherein the thiol compound comprises at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, bis(2-mercaptoethyl) sulfide, and 2,5-bismercaptomethyl-1,4-dithiane. <6> The polymerizable composition according to any one of <1> to <5>, wherein the iso(thio)cyanate compound comprises at least one selected from the group consisting of xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate.<7> A resin containing a cured product of any one of the polymerizable compositions described in <1> to <6>. <8> A molded article containing the resin described in <7>. <9> An optical material containing the resin described in <7>. <10> A lens containing the resin described in <7>.

[0008] According to one aspect of this disclosure, a polymerizable composition capable of producing a resin with reduced odor during processing, a resin with reduced odor during processing, and a molded article, an optical material, and a lens containing the resin are provided.

[0009] In this disclosure, numerical ranges expressed using "~" mean a range that includes the numbers before and after "~" as the lower and upper limits. In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In this disclosure, the amount of each component in a composition means the total amount of multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In numerical ranges described in steps in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in steps. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. In this disclosure, "*" in a chemical formula means a bond position.

[0010] [Polymerizable Composition] The polymerizable composition of this disclosure contains an iso(thio)cyanate compound and an active hydrogen compound containing a thiol compound, and the A / B ratio, which is the ratio of the value (A) below to the value (B) below, is greater than 1.00.

[0011] Value (A) = (Total mass of isocyanate compound / Molecular weight of the main compound in the isocyanate compound) × Number of isocyanate groups in one molecule of the main compound in the isocyanate compound (B) = (Total mass of active hydrogen compound / Molecular weight of the main compound in the active hydrogen compound) × Number of active hydrogen groups in one molecule of the main compound in the active hydrogen compound

[0012] The polymerizable composition of this disclosure, having an A / B ratio greater than 1.00, can produce a resin with reduced odor during processing (for example, a thiourethane resin with reduced sulfurous odor during processing). This effect is thought to be achieved because an A / B ratio greater than 1.00 reduces the residual sulfur component in the resulting resin.

[0013] <Value (A)> In the formula for calculating Value (A), the total mass of the isocyanate compound is the total mass of the isocyanate compound contained in the polymerizable composition (the total mass if two or more isocyanate compounds are contained). In the formula for calculating Value (A), the principal compound in the isocyanate compound is the compound corresponding to the maximum peak in the gas chromatography analysis of the isocyanate compound. The principal compound in the isocyanate compound may be a mixture of two or more isomers (for example, N2 in the examples described below). The conditions for gas chromatography analysis are GC conditions 1 below.

[0014] (GC Condition 1) Packing material: DB-1 (film thickness) 1.5 μm Column: Inner diameter 0.53 mm x length 60 m (Agilent) Oven temperature: Heating from 130°C to 220°C at 3°C / min, then heating to 300°C at 10°C / min after reaching 220°C. Split ratio: Pulsed splitless method Inlet temperature: 280°C Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ Pressure: 55 kPa, Air pressure: 45 kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2 μL Detection method: FID

[0015] In gas chromatography analysis of isocyanate compounds, the ratio of the peak area of ​​the "main compound" (or the total peak area in the case of two or more compounds) to the total peak area of ​​all peaks is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and even more preferably 80% or more.

[0016] The main compound in the isocyanate compound is preferably an isocyanate compound, more preferably a polyisocyanate compound, and even more preferably a diisocyanate compound. The main compound in the isocyanate compound is appropriately selected from the specific examples described below.

[0017] <Value (B)> In the formula for calculating Value (B), the total mass of the active hydrogen compound is the total mass of the active hydrogen compound contained in the polymerizable composition (the sum of the active hydrogen compounds if two or more are contained). In the formula for calculating Value (B), the principal compound in the active hydrogen compound is the compound corresponding to the maximum peak in the high-performance liquid chromatography analysis of the active hydrogen compound. The principal compound in the active hydrogen compound may be a mixture of two or more isomers. The conditions for the high-performance liquid chromatography analysis are the measurement conditions X below.

[0018] (Measurement Conditions X) The column used is YMC-Pack (registered trademark) ODS-A manufactured by YMC Corporation (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm). The mobile phase is a mixed solution of acetonitrile / 0.01 mol potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol). The measurement solution is a mixed solution of 160 mg of active hydrogen compound and 10 mL of acetonitrile. The detector is an ultraviolet detector with a measurement wavelength of 230 nm. The column temperature is 40°C, the flow rate is 1.0 mL / min, and the injection volume is 2 μL. For example, YMC-Pack ODS-A (manufactured by YMC Corporation) can be used as the above column.

[0019] In high-performance liquid chromatography analysis of active hydrogen compounds, the ratio of the peak area of ​​the "main compound" (or the total peak area in the case of two or more compounds) to the total peak area of ​​all peaks is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and even more preferably 80% or more.

[0020] The active hydrogen compound includes a thiol compound. The main compound in the active hydrogen compound is preferably a thiol compound, and more preferably a polythiol compound. When the main compound in the active hydrogen compound is a thiol compound, the main compound that is a thiol compound may be a mixture of two or more isomers.

[0021] The content of thiol compounds in the active hydrogen compound (total content if there are two or more types; the same applies hereinafter) is preferably 90% by mass or more of the total amount of the active hydrogen compound. The content of thiol compounds in the active hydrogen compound may be 100% by mass.

[0022] When the active hydrogen compound is a thiol compound, the aforementioned value (B) means the following value (B2): Value (B2) = (Total mass of the thiol compound / Molecular weight of the main compound in the thiol compound) × Number of thiol groups in one molecule of the main compound in the thiol compound

[0023] <A / B Ratio> The polymerizable composition of this disclosure contains an iso(thio)cyanate compound and an active hydrogen compound containing a thiol compound, and the A / B ratio, which is the ratio of the above-mentioned value (A) to the above-mentioned value (B) (i.e., ratio [value (A) / value (B)]), is greater than 1.00. This suppresses the odor (for example, the sulfurous odor when processing thiourethane resin) when processing resins produced using the polymerizable composition. From the viewpoint of obtaining this effect more effectively, the above-mentioned A / B ratio is preferably 1.02 or higher, more preferably 1.08 or higher.

[0024] Furthermore, the polymerizable composition of this disclosure has the effect of reducing the glass transition temperature (Tg) of the resulting resin by having an A / B ratio greater than 1.00. Reducing the glass transition temperature (Tg) of the resulting resin is advantageous in that it can improve the dyeability of the resin. From the viewpoint of the effect of reducing Tg, the above-mentioned A / B ratio is preferably 1.02 or higher, and more preferably 1.08 or higher.

[0025] On the other hand, from the viewpoint of the heat resistance of the resulting resin (i.e., from the viewpoint of suppressing an excessive reduction in the Tg of the resin), the above-mentioned A / B ratio is preferably 1.25 or less, and more preferably 1.20 or less.

[0026] When the main component of the iso(thio)cyanate compound is m-xylylene diisocyanate (N1, described later), the Tg of the resulting resin is preferably 88.0°C or lower, more preferably 85.0°C or lower. In this case, the lower limits of Tg include, for example, 75.0°C and 80.0°C.

[0027] When the main component of the isocyanate compound is a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane (N2, as described later), the Tg of the resulting resin is preferably 108.0°C or lower, more preferably 105.0°C or lower. In this case, the lower limits of Tg include, for example, 90.0°C and 95.0°C.

[0028] In this disclosure, the Tg of the resin is a value obtained using a thermomechanical analyzer (for example, a Shimadzu TMA-60 thermomechanical analyzer) with a test specimen measuring 10 mm in length, 10 mm in width, and 2 mm in thickness, by the TMA penetration method (50 g load, 0.5 mm diameter pin tip, heating rate of 10 °C / min).

[0029] <Iso(thio)cyanate compounds> The polymerizable compositions of this disclosure contain at least one iso(thio)cyanate compound.

[0030] In this disclosure, "iso(thio)cyanate compound" means "isocyanate compound" or "isothiocyanate compound."

[0031] The iso(thio)cyanate compound in the polymerizable composition of this disclosure is preferably a polyiso(thio)cyanate compound, more preferably a polyisocyanate compound, and even more preferably a diisocyanate compound.

[0032] Examples of polyiso(thio)cyanate compounds include, specifically, aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, and xylylene diisocyanate; Alicyclic polyisocyanate compounds such as 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-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; Heterocyclic polyisocyanate compounds such as 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, and 4,5-bis(isocyanatomethyl)-1,3-dithiolane; aliphatic polyisothiocyanate compounds such as hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, and xylylene diisothiocyanate;Alicyclic polyisothiocyanate compounds such as isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, bis(isothiocyanatocyclohexyl)methane, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 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(isothiocyanatomethyl)tricyclodecane, 4,8-bis(isothiocyanatomethyl)tricyclodecane, and 4,9-bis(isothiocyanatomethyl)tricyclodecane; Examples include aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyl disulfide-4,4-diisothiocyanate; and sulfur-containing heterocyclic polyisothiocyanate compounds such as 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-diisothiocyanato-1,3-dithiolane, and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane. The polyiso(thio)cyanate compound may include at least one selected from these.

[0033] Furthermore, as polyiso(thio)cyanate compounds, halogen-substituted compounds such as chlorine-substituted and bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer-type modified compounds with polyhydric alcohols, carbodiimide-substituted compounds, urea-substituted compounds, biuret-substituted compounds, and dimerization or trimmerization reaction products can also be used.

[0034] The iso(thio)cyanate compound in the polymerizable composition of the present disclosure preferably includes at least one selected from the group consisting of xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate.

[0035] When the polymerizable composition of this disclosure contains a polythiol composition as an active hydrogen compound, the mixing ratio of the polythiol composition and the iso(thio)cyanate compound is not particularly limited. For example, the molar ratio (mercapto group / iso(thio)cyanate group) of the mercapto group (i.e., thiol group) of the polythiol compound contained in the polythiol composition to the iso(thio)cyanate group of the iso(thio)cyanate compound is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3. When the mixing ratio is within the above range, it tends to be possible to satisfy various properties such as refractive index and heat resistance required for plastic lenses, etc., in a well-balanced manner.

[0036] The polymerizable compositions of this disclosure may include an isocyanate composition comprising an isocyanate compound.

[0037] Here, an isocyanate composition means a composition containing at least one isocyanate.

[0038] The isocyanate composition may contain components other than the isocyanate compound as impurities. Preferably, the isocyanate composition contains at least one isocyanate compound as its main component.

[0039] The iso(thio)cyanate compound preferably contains xylylene diisocyanate (XDI).

[0040] Hereinafter, an iso(thio)cyanate compound containing xylylene diisocyanate is also referred to as an XDI composition. It is preferable that the XDI composition contains xylylene diisocyanate as a main component.

[0041] It is preferable that the XDI composition contains at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).

[0042]

[0043] Hereinafter, preferred aspects of the XDI composition are shown from the viewpoint of improving the stability of the iso(thio)cyanate composition and the transparency of a resin formed using the iso(thio)cyanate composition.

[0044] When the XDI composition contains the compound (N1), the peak area of the compound (N1 in gas chromatography measurement under the following GC condition 1 is preferably 0.20 ppm or more relative to a peak area of 1 for xylylene diisocyanate. - GC Condition 1 - Filler; DB-1 (film thickness) 1.5 µm Column; inner diameter 0.53 mm × length 60 m (manufactured by Agilent) Oven temperature; temperature increased from 130°C to 220°C at 3°C / min, and after reaching 220°C, temperature increased to 300°C at 10°C / min Split ratio; pulsed splitless method Inlet temperature; 280°C Detector temperature; 300°C Carrier gas; N ２ 158 kPa, H ２ 55 kPa, Air 45 kPa (constant pressure control) Solvent; chloroform Sample concentration: 2.0 mass% chloroform solution Injection volume; 2 µL Detection method; FID

[0045] The peak area of the above compound (N1) is more preferably 5.0 ppm or more, still more preferably 50 ppm or more, and still more preferably 100 ppm or more, relative to a peak area of 1 for xylylene diisocyanate. The peak area of the above compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, still more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and still more preferably 1000 ppm or less, relative to a peak area of 1 for xylylene diisocyanate. The peak area of the above compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0046] When the XDI composition contains the compound (N2), it is preferable that the peak area of the compound (N2) in gas chromatography measurement under the following GC conditions 2 is 0.05 ppm or more relative to a peak area of 1 for xylylene diisocyanate. - GC Conditions 2 - Column; HP-50+, inner diameter 0.25 mm × length 30 m × film thickness 0.25 μm (manufactured by Hewlett-Packard Company) Oven temperature; heating from 50°C to 280°C at a rate of 10°C / min, holding for 6 minutes after reaching 280°C. Split ratio; pulsed splitless method Inlet temperature; 200°C Detector temperature; 280°C Carrier gas; He Carrier gas flow rate; 1.0 ml / min (constant flow control) Sample concentration: 1.0 mass% dichloromethane solution Injection volume; 1.0 μL Detection method; SIM (monitoring ions: m / z 180, 215) (Content ratio of xylylene diisocyanate (XDI))

[0047] The peak area of ​​the above compound (N2) is more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and still more preferably 0.6 ppm or more, relative to the peak area 1 of xylylene diisocyanate. The peak area of ​​the above compound (N2) is more preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and still more preferably 60 ppm or less, relative to the peak area 1 of xylylene diisocyanate. The peak area of ​​the above compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.

[0048] When the XDI composition contains compound (N3), it is preferable that the peak area of ​​compound (N3) in the gas chromatography measurement under the aforementioned GC condition 1 is 0.10 ppm or more relative to the peak area 1 of xylylene diisocyanate. The peak area of ​​compound (N3) is more preferably 0.1 ppm or more, even more preferably 3.0 ppm or more, and even more preferably 5.0 ppm or more, relative to the peak area 1 of xylylene diisocyanate. The peak area of ​​compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, even more preferably 100 ppm or less, and even more preferably 75 ppm or less, relative to the peak area 1 of xylylene diisocyanate. The peak area of ​​compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0049] The acidity of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm. The lower limit of the acidity of the XDI composition is not particularly limited, but the lower limit is, for example, 1 ppm. The acidity of the XDI composition can be measured in accordance with the method described in paragraph 0091 of International Publication No. 2021 / 256417. The XDI composition may also contain stabilizers.

[0050] <Active Hydrogen Compounds> The polymerizable compositions of this disclosure contain at least one active hydrogen compound, which includes a thiol compound. In this disclosure, an active hydrogen compound means a compound containing an active hydrogen group. Examples of active hydrogen groups include thiol groups (i.e., mercapto groups), hydroxyl groups, and amino groups.

[0051] The active hydrogen compound contains at least one thiol compound (i.e., a compound containing a thiol group, which is an active hydrogen group). Preferably, the active hydrogen compound contains a thiol compound as its main component. The active hydrogen compound may also contain a thiol composition containing a thiol compound as its main component.

[0052] The thiol compound preferably includes a compound containing an ethylenethio group and a thiol group.

[0053] The thiol compound more preferably includes at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakiss(2-mercaptoacetate), pentaerythritol tetrakiss(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol bis(3-mercaptopropionate) (hereinafter also referred to as "thiol T"). Thiol compounds more preferably contain thiol T as the main component.

[0054] More specific embodiments of the thiol compound include, for example: an embodiment mainly comprising 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "thiol T1"); an embodiment mainly comprising at least one selected from the group consisting of 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 (hereinafter also referred to as "thiol T2"); an embodiment mainly comprising pentaerythritol tetrakiss (3-mercaptopropionate) (hereinafter also referred to as "thiol T3"); and an embodiment mainly comprising thiol T1 and thiol T3. Embodiments comprising thiol T2 and thiol T3 as main components; and so on.

[0055] In this case, the thiol compound may contain at least one other component besides thiol T (for example, other thiol compounds, components other than thiol compounds, etc.).

[0056] Other thiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 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.

[0057] When a thiol compound contains thiol T as its main component, the thiol compound may also contain the following compound (XB). Compound (XB) is a compound in which at least one of the mercapto groups in the aforementioned thiol T is replaced with a group represented by the following formula (XB-1).

[0058]

[0059] In equation (XB-1), * indicates a bonding position.

[0060] Examples of compound (XB) are shown below, but compound (XB) is not limited to these examples.

[0061]

[0062] When a thiol compound contains thiol T as its main component, the thiol compound may also contain the following compound (C1).

[0063]

[0064] In compound (C1), X is -CH ２ - Or represents a sulfur atom.

[0065] In the polymerizable composition of this disclosure, the total content of the iso(thio)cyanate compound and the active hydrogen compound described above is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the polymerizable composition.

[0066] In the polymerizable composition of this disclosure, the total content of the iso(thio)cyanate compound and the thiol compound described above is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the polymerizable composition.

[0067] The polymerizable compositions of this disclosure may contain other components besides polyiso(thio)cyanate compounds and active hydrogen compounds for the purpose of improving the various physical properties of the resin, handling properties, polymerization reactivity of the polymerizable composition, etc. Examples of other components include polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and other bluing agents.

[0068] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0069] As an internal release agent, an acidic phosphate ester can be used. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more types.

[0070] Examples of resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, and olefin compounds including (meth)acrylate compounds. The polymerizable composition of this disclosure can be obtained by mixing the above components.

[0071] [Resin, Molded Article] The resin of this disclosure includes a cured product of the polymerizable composition of this disclosure. The molded article of this disclosure includes the resin of this disclosure. The method for producing the molded article of this disclosure is not particularly limited, but a preferred method is casting polymerization. First, the polymerizable composition is injected between molds held together by a gasket or tape. At this time, depending on the physical properties required of the resulting plastic lens, it is often preferable to perform degassing treatment under reduced pressure, filtration treatment under pressure or reduced pressure, etc., as necessary.

[0072] Polymerization conditions are not limited to specific conditions, as they 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, polymerization is carried out at a temperature of -50°C to 150°C for 1 to 50 hours. In some cases, it is preferable to maintain the temperature in the range of 10°C to 150°C or gradually raise the temperature and cure it for 1 to 48 hours.

[0073] The molded article may be subjected to treatments such as annealing, if necessary. Annealing is usually carried out at a temperature between 50°C and 150°C, preferably between 90°C and 140°C, and more preferably between 100°C and 130°C.

[0074] <Applications> The resin obtained from the polymerizable composition of this disclosure can be used as a material for manufacturing molded articles of various shapes by changing the type of mold used during casting polymerization.

[0075] [Optical Materials] The optical materials of this disclosure include the resin of this disclosure. Molded articles obtained from the polymerizable composition of this disclosure can be made of a material with reduced yellowness without impairing transparency. Furthermore, molded articles obtained from a polymerizable composition containing the polythiol composition of the first embodiment can be made of a material that also possesses excellent devitrification. Therefore, it can be used in various optical materials such as plastic lenses.

[0076] [Lenses] The lenses of this disclosure include the resin of this disclosure. Lenses are particularly preferred as optical materials. Examples of lenses include plastic spectacle lenses and plastic polarizing lenses.

[0077] <Plastic Eyeglass Lenses> Plastic eyeglass lenses using a lens substrate made from the molded product of the present disclosure may have a coating layer applied to one or both sides as needed. The plastic eyeglass lenses of the present disclosure comprise a lens substrate containing a cured product of the polymerizable composition described above, and a coating layer.

[0078] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers can be used individually or in multiple layers. When applying coating layers to both surfaces, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.

[0079] These coating layers may each contain known additives such as infrared absorbers to protect the eyes from infrared rays, light stabilizers and antioxidants to improve the weather resistance of the lenses, photochromic compounds, dyes, and pigments to enhance the fashionability of the lenses, and antistatic agents to improve the performance of the lenses. For layers coated by application, various leveling agents may be used to improve the applicability. In addition, an anti-fog layer, an anti-stain layer, and a water-repellent layer may be formed on top of the anti-reflective layer as needed.

[0080] The embodiments described above are examples of this disclosure, and various other configurations can be adopted as long as they do not impair the effects of this disclosure.

[0081] The following are examples of the embodiments of this disclosure, but this disclosure is not limited to the following embodiments.

[0082] [Example 1] <Preparation of Polymerizable Composition> 41.9 parts by mass of m-xylylene diisocyanate (hereinafter referred to as "N1") as an iso(thio)cyanate compound was added to 0.10 parts by mass of JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.) as an internal mold release agent, and the mixture was stirred for 5 minutes to dissolve it and obtain Solution 1. 33.6 parts by mass of a thiol composition [active hydrogen compound] mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter referred to as "T1") as a thiol compound was added to 0.0105 parts by mass of dimethyl thysuzin dichloride as a polymerization catalyst, and the mixture was dissolved to obtain Mixture 1. Mixture 1 was added to Solution 1 to obtain a polymerizable composition.

[0083] <Value (A), Value (B), A / B Ratio> In the obtained polymerizable composition, Value (A), Value (B), and A / B ratio are as follows. Here, the main compound in the iso(thio)cyanate compound is m-xylylene diisocyanate (molecular weight 188.2), and the main compound in the active hydrogen compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (molecular weight 260.5). Value (A) = (Total mass of isocyanate compound / Molecular weight of the main compound in the isocyanate compound) × Number of isocyanate groups in one molecule of the main compound in the isocyanate compound = (41.9 / 188.2) × 2 = 0.445 Value (B) = (Total mass of active hydrogen compound / Molecular weight of the main compound in the active hydrogen compound) × Number of active hydrogen groups in one molecule of the main compound in the active hydrogen compound = (33.6 / 260.5) × 3 = 0.387 A / B ratio = 1.15 The A / B ratio (= 1.15) is shown in Table 1.

[0084] <Manufacturing of Molded Articles> The polymerizable composition was stirred and degassed for 30 minutes at a reduced pressure of 400 Pa or less and a temperature between 10°C and 20°C, and then filtered using a 1.0 μm PTFE filter. The polymerizable composition obtained as filtrate was injected between a pair of glass molds fixed with tape, and then this pair of glass molds was placed in an oven and the oven temperature was set to 20°C. Next, the oven temperature was raised from 20°C to 130°C over 16 hours. Here, the size and shape of each of the pair of glass molds was a circle with a diameter of 78 mm, and the distance between the pair of glass molds (i.e., the thickness of the space into which the polymerizable composition is injected) was 2 mm. Through the above process, the monomers in the polymerizable composition (i.e., iso(thio)cyanate compounds and polythiol compositions) were polymerized, and a molded article containing thiourethane resin (hereinafter also simply referred to as "resin") (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. Then, the molded bodies were removed from the pair of glass molds to obtain resin-containing molded bodies. The size and shape of the obtained molded bodies were disc-shaped with a diameter of 78 mm and a thickness of 2 mm. The obtained molded bodies were annealed by leaving them at 120°C for 2 hours.

[0085] <Measurement of the glass transition temperature (Tg) (°C) of the resin> A test piece measuring 10 mm in length, 10 mm in width, and 2 mm in thickness was cut from the molded body after annealing. The glass transition temperature (Tg) (°C) of the thiourethane resin in the cut test piece was measured using the TMA penetration method (50 g load, 0.5 mm diameter pin tip, heating rate 10°C / min) with a Shimadzu TMA-60 thermomechanical analyzer. The results are shown in Table 1.

[0086] <Odor Evaluation> After annealing, a molded body (specifically, a disc-shaped molded body with a diameter of 78 mm and a thickness of 2 mm) was subjected to abrasive grinding until its diameter was 40 mm, without spraying cooling water. The abrasive grinding was performed using a processing machine equipped with a grinding wheel chamber for abrasive grinding (specifically, a NIDEK Le1000 Express patternless edger), with the grinding wheel chamber cover closed. After the abrasive grinding, the grinding wheel chamber cover was opened, and five evaluators checked for sulfurous odor. Each of the five evaluators assigned a score from 1 to 4 based on the results of the sulfurous odor check. The average score from the five evaluators was used as the evaluation result for that example. The results are shown in Table 1. A score of 1 indicates the best suppression of odor.

[0087] - Odor Evaluation Criteria (Score) - 1: No sulfurous odor can be detected 2: A slight sulfurous odor can be detected 3: A sulfurous odor can be clearly detected 4: A sulfurous odor can be detected at an unbearable level

[0088] [Examples 2 and 3, Comparative Examples 1 and 2] The same procedure as in Example 1 was followed, except that the A / B ratio was changed by changing the amount of N1 (i.e., m-xylylene diisocyanate) as shown in Table 1. The results are shown in Table 1.

[0089] [Example 101] The same procedure as in Example 1 was carried out, except that N1 (i.e., m-xylylene diisocyanate) (41.9 parts by mass) was replaced with 40.3 parts by mass of an isocyanate composition [iso(thio)cyanate compound] mainly composed of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane (hereinafter referred to as "N2"), and the amount of the thiol composition [active hydrogen compound] mainly composed of T1 (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane) (33.6 parts by mass) was changed to 29.5 parts by mass. The results are shown in Table 2.

[0090] <Value (A), Value (B), A / B Ratio> In the polymerizable composition of Example 101, the values ​​(A), (B), and A / B ratio are as follows. Here, the main compound in the isocyanate compound is N2 (i.e., a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane (molecular weight 206.2)), and the main compound in the active hydrogen compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (molecular weight 260.5). Value (A) = (Total mass of isocyanate compound / Molecular weight of the main compound in the isocyanate compound) × Number of isocyanate groups in one molecule of the main compound in the isocyanate compound = (40.3 / 206.2) × 2 = 0.391 Value (B) = (Total mass of active hydrogen compound / Molecular weight of the main compound in the active hydrogen compound) × Number of active hydrogen groups in one molecule of the main compound in the active hydrogen compound = (29.5 / 260.5) × 3 = 0.340 A / B ratio = 1.15 The A / B ratio (= 1.15) is shown in Table 2.

[0091] [Examples 102 and 103, Comparative Examples 101 and 102] The same procedure as in Example 1 was followed, except that the A / B ratio was changed by changing the amount of N2, as shown in Table 2. The results are shown in Table 2.

[0092]

[0093]

[0094] As shown in Table 1, Examples 1 to 3, which used polymerizable compositions containing an iso(thio)cyanate compound and an active hydrogen compound including a thiol compound, and in which the A / B ratio (the ratio of value (A) to value (B)) was greater than 1.00, showed suppressed odor during resin processing compared to Comparative Examples 1 and 2, which used polymerizable compositions with an A / B ratio of 1.00 or less. Furthermore, it was confirmed that Examples 1 to 3 were advantageous for the dyeability of the resin because they had a lower glass transition temperature (Tg) compared to Comparative Example 1.

[0095] As shown in Table 2, Examples 101 to 103, which used polymerizable compositions containing an iso(thio)cyanate compound and an active hydrogen compound including a thiol compound, and in which the A / B ratio (the ratio of value (A) to value (B)) was greater than 1.00, showed suppressed odor during resin processing compared to Comparative Examples 101 and 102, which used polymerizable compositions with an A / B ratio of 1.00 or less. Furthermore, it was confirmed that Examples 101 to 103 had a lower glass transition temperature (Tg) compared to Comparative Example 101, which was advantageous for the dyeability of the resin.

[0096] [Examples 201-203, Comparative Examples 201 and 202] The same procedure as in Example 1 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 3, and the amounts of iso(thio)cyanate compound and active hydrogen compound charged were adjusted so that the A / B ratio was the value shown in Table 3. The results are shown in Table 3. N3 is 1,3-bis(isocyanatomethyl)cyclohexane.

[0097]

[0098] As shown in Table 3, the same trends as those observed in Examples 201-203 and Comparative Examples 201 and 202 were also observed in the series of Examples 1-3 and Comparative Examples 1 and 2.

[0099] [Examples 301-303, Comparative Examples 301 and 302] The same procedure as in Example 1 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 4, and the amounts of iso(thio)cyanate compound and active hydrogen compound charged were adjusted so that the A / B ratio was the value shown in Table 4. The results are shown in Table 4. N4 is isophorone diisocyanate.

[0100]

[0101] As shown in Table 4, the same trends as those observed in Examples 301-303 and Comparative Examples 301 and 302 were also observed in the series of Examples 1-3 and Comparative Examples 1 and 2.

[0102] [Examples 401-403, Comparative Examples 401 and 402] The same procedure as in Example 1 was followed, except that the type of active hydrogen compound was changed as shown in Table 5, and the amount of iso(thio)cyanate compound and active hydrogen compound charged was adjusted so that the A / B ratio was the value shown in Table 5. The results are shown in Table 5. T2 is the aforementioned thiol T2 (i.e., at least one selected from the group consisting of 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).

[0103]

[0104] As shown in Table 5, the same trends as those observed in Examples 401-403 and Comparative Examples 401 and 402 were also observed in the series of Examples 1-3 and Comparative Examples 1 and 2.

[0105] [Examples 501-503, Comparative Examples 501 and 502] The same procedure as in Example 401 was followed, except that the type of active hydrogen compound was changed as shown in Table 6, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 6. The results are shown in Table 6. N2 is as described above.

[0106]

[0107] As shown in Table 6, the same trend as in the series of Examples 501-503 and Comparative Examples 501 and 502 was observed.

[0108] [Examples 601-603, Comparative Examples 601 and 602] The same procedure as in Example 401 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 7, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 7. The results are shown in Table 7. N3 is as described above.

[0109]

[0110] As shown in Table 7, the same trend as in the series of Examples 601-603 and Comparative Examples 601 and 602 was observed.

[0111] [Examples 701-703, Comparative Examples 701 and 702] The same procedure as in Example 401 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 8, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 8. The results are shown in Table 8. N4 is as described above.

[0112]

[0113] As shown in Table 8, the same trend as in the series of Examples 701-703 and Comparative Examples 701 and 702 was observed.

[0114] [Examples 801-803, Comparative Examples 801 and 802] The same procedure as in Example 1 was followed, except that the type of active hydrogen compound was changed as shown in Table 9, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 9. The results are shown in Table 9. T3 is pentaerythritol tetrakis (3-mercaptopropionate).

[0115]

[0116] As shown in Table 9, the same trends as those observed in Examples 801-803 and Comparative Examples 801 and 802 were also observed in the series of Examples 1-3 and Comparative Examples 1 and 2.

[0117] [Examples 901-903, Comparative Examples 901 and 902] The same procedure as in Example 801 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 10, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 10. The results are shown in Table 10. N2 is as described above.

[0118]

[0119] As shown in Table 10, the same trend as in the series of Examples 901-903 and Comparative Examples 901 and 902 was observed.

[0120] [Examples 1001-1003, Comparative Examples 1001 and 1002] The same procedure as in Example 801 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 11, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 11. The results are shown in Table 11. N3 is as described above.

[0121]

[0122] As shown in Table 11, the same trend as in the series of Examples 1001-1003 and Comparative Examples 1001 and 1002 was observed.

[0123] [Examples 1101-1103, Comparative Examples 1101 and 1102] The same procedure as in Example 801 was followed, except that the type of iso(thio)cyanate compound was changed as shown in Table 12, and the amounts of iso(thio)cyanate compound and active hydrogen compound were adjusted so that the A / B ratio was the value shown in Table 12. The results are shown in Table 12. N4 is as described above.

[0124]

[0125] As shown in Table 12, the same trend as in the series of Examples 1101-1103 and Comparative Examples 1101 and 1102 was observed.

[0126] The disclosure of Japanese Patent Application No. 2025-052535, filed on 26 March 2025, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A polymerizable composition containing an iso(thio)cyanate compound and an active hydrogen compound containing a thiol compound, wherein the A / B ratio, which is the ratio of the value (A) below to the value (B) below, is greater than 1.

00. Value (A) = (Total mass of the iso(thio)cyanate compound / Molecular weight of the main compound in the iso(thio)cyanate compound) × Number of iso(thio)cyanate groups in one molecule of the main compound in the iso(thio)cyanate compound (B) = (Total mass of the active hydrogen compound / Molecular weight of the main compound in the active hydrogen compound) × Number of active hydrogen groups in one molecule of the main compound in the active hydrogen compound 2. The polymerizable composition according to claim 1, wherein the A / B ratio is 1.02 or greater.

3. The polymerizable composition according to claim 1, wherein the A / B ratio is 1.08 or greater.

4. The polymerizable composition according to claim 1, wherein the thiol compound comprises a compound containing an ethylenethio group and a thiol group.

5. The polymerizable composition according to claim 1, wherein the thiol compound comprises at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, bis(2-mercaptoethyl) sulfide, and 2,5-bismercaptomethyl-1,4-dithiane.

6. The polymerizable composition according to claim 1, wherein the iso(thio)cyanate compound comprises at least one selected from the group consisting of xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate.

7. A resin comprising a cured product of the polymerizable composition according to claim 1.

8. A molded article comprising the resin described in claim 7.

9. An optical material comprising the resin described in claim 7.

10. A lens comprising the resin described in claim 7.

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