Polymerizable composition, resin, and optical member

Abstract

This polymerizable composition contains: a polyisocyanate component (A) which is at least one selected from the group consisting of a modified product of a bifunctional or higher-functional isocyanate and a bifunctional or higher-functional isocyanate; and a thiol component (B) which is at least one selected from the group consisting of naphthalenethiol and naphthalenedithiol.

Description

Coincidence composition, resin, and optical member

[0001] The present disclosure relates to a polymerizable composition, a resin, and an optical member.

[0002] As a polymerizable composition for producing an optical member (for example, a lens) made of resin, a polymerizable composition containing a thiol compound and an isocyanate compound may be used. By polymerizing the monomers (that is, the thiol compound and the isocyanate compound) in this polymerizable composition, an optical member containing a resin can be obtained. As the above polymerizable composition, an example containing isocyanurate, which is a modified product (that is, an isocyanurate form) of an isocyanate compound, in addition to a thiol compound and an isocyanate compound is also known (see, for example, Patent Documents 1 and 2).

[0003] International Publication No. 2018 / 079829 International Publication No. 2018 / 190290

[0004] However, there may be a case where it is required to further improve the refractive index and heat resistance of a resin which is a cured product of a polymerizable composition containing a thiol compound and at least one selected from the group consisting of a modified product of an isocyanate compound and an isocyanate compound. An object of one aspect of the present disclosure is to provide a polymerizable composition capable of producing a resin excellent in refractive index and heat resistance, and a resin and an optical member excellent in refractive index and heat resistance.

[0005] Means for solving the above problems include the following embodiments: <1> A polymerizable composition containing a polyisocyanate component (A) which is at least one selected from the group consisting of modified isocyanates with two or more functions and isocyanates with two or more functions, and a thiol component (B) which is at least one selected from the group consisting of naphthalenchiol and naphthalenedithiol. <2> The polymerizable composition according to <1>, wherein the polyisocyanate component (A) comprises at least one isocyanate (XA) selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, naphthalene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and at least one modified form of the isocyanate (XA). <3> The polymerizable composition according to <1> or <2>, wherein the modified isocyanate with two or more functions comprises at least one selected from the group consisting of isocyanurate group, allophanate group, burette group, urethane group, urea group, uretdione group, iminooxadiazinedione group, uretonimine group, and carbodiimide group. <4> The polymerizable composition according to any one of <1> to <3>, wherein the modified isocyanate with two or more functions comprises a trimer of an aromatic ring-containing isocyanate. <5> The polymerizable composition according to any one of <1> to <4>, wherein the thiol component (B) comprises at least one selected from the group consisting of 1-naphthalenchiol, 2-naphthalenchiol, 1,6-naphthalenedithiol, and 1,7-naphthalenedithiol. <6> The polymerizable composition according to any one of <1> to <5>, wherein the thiol component (B) comprises an asymmetric naphthalenedithiol. <7> The polymerizable composition according to any one of <1> to <6>, wherein the thiol component (B) comprises at least one selected from the group consisting of 1,6-naphthalenedithiol and 1,7-naphthalenedithiol. <8> The polymerizable composition according to any one of <1> to <7>, satisfying either condition 1 or condition 2 below.Condition 1: The thiol component (B) contains naphthalenchiol, and the polymerizable composition further contains thiols other than the thiol component (B). Condition 2: The thiol component (B) contains naphthalenedithiol. <9> The thiols other than the thiol component (B) are 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, and pentaerythritol. A polymerizable composition according to <8>, which is at least one selected from the group consisting of tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol bis(3-mercaptopropionate). <10> A polymerizable composition according to any one of <1> to <9>, wherein the molar ratio [NCO group / SH group], which is the molar ratio of isocyanate groups to mercapto groups, is 0.7 to 1.5. <11> A resin which is a cured product of the polymerizable composition according to any one of <1> to <10>. <12> A resin according to <11>, wherein the glass transition temperature is 105°C to 160°C. <13> Refractive index n. ｅ However, the resin described in <11> or <12> is 1.60 to 1.75. <14> An optical component containing the resin described in any one of <11> to <13>. <15> An optical component of <14> that is an optical waveguide.

[0006] According to one aspect of this disclosure, a polymerizable composition capable of producing a resin with excellent refractive index and heat resistance is provided, as well as a resin and optical component with excellent refractive index and heat resistance.

[0007] 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 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 stages 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 stages. 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.

[0008] [Polymerizable Composition] The polymerizable composition of this disclosure contains a polyisocyanate component (A) which is at least one selected from the group consisting of modified isocyanates with two or more functions and isocyanates with two or more functions, and a thiol component (B) which is at least one selected from the group consisting of naphthalenchiol and naphthalenedithiol.

[0009] As described above, there are cases where it is desired to further improve the refractive index and heat resistance of a resin that is a cured product of a polymerizable composition containing a thiol compound and at least one selected from the group consisting of modified isocyanate compounds and isocyanate compounds. The polymerizable composition of this disclosure is a polymerizable composition containing a thiol compound and at least one selected from the group consisting of modified isocyanate compounds and isocyanate compounds, and is a polymerizable composition that can produce a resin with excellent refractive index and heat resistance. The effects of the refractive index and heat resistance of the resin are both effects obtained by the thiol component (B). In particular, because the polymerizable composition of the present invention contains a thiol component (B) which is at least one selected from the group consisting of naphthalenchiol and naphthalenedithiol, the heat resistance of the resulting resin is improved compared to a polymerizable composition that does not contain thiol component (B) but contains a thiol compound other than thiol component (B) (for example, the polymerizable composition of Comparative Example 1 described later). In addition, the sulfur atom in the thiol component (B) in the polymerizable composition of the present invention improves the refractive index of the resulting resin.

[0010] <Polyisocyanate component (A)> The polymerizable composition of this disclosure contains a polyisocyanate component (A). The polyisocyanate component (A) is at least one selected from the group consisting of modified isocyanates with two or more functions and isocyanates with two or more functions.

[0011] (Isocyanates with two or more functions) There are no particular limitations on isocyanates with two or more functions, but examples include isocyanates (XA) that are at least one selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, naphthalene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane.

[0012] (Modified isocyanates with two or more functions) Examples of modified isocyanates with two or more functions include the modified isocyanate (XA) mentioned above.

[0013] Modified isocyanates with two or more functions preferably contain at least one selected from the group consisting of isocyanurate group, allophanate group, biuret group, urethane group, urea group, uretdione group, iminooxadiazinedione group, uretonimine group, and carbodiimide group, and more preferably contain an isocyanurate group.

[0014] The modified form of a bifunctional or more isocyanate is preferably a trimer of an aromatic ring-containing isocyanate. The aromatic ring-containing isocyanate is preferably tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, or naphthalene diisocyanate. The trimer of the aromatic ring-containing isocyanate preferably contains an isocyanurate group. That is, the trimer of the aromatic ring-containing isocyanate is preferably the isocyanurate of the aromatic ring-containing isocyanate.

[0015] From the viewpoint of further improving the heat resistance of the resulting resin, the polyisocyanate component (A) preferably contains a modified isocyanate with two or more functionalities. This further improves the heat resistance of the resulting resin.

[0016] The content of polyisocyanate component (A) is preferably 30% to 90% by mass, more preferably 40% to 80% by mass, and even more preferably 50% to 70% by mass, based on the total amount of the polymerizable composition.

[0017] <Thiol component (B)> The polymerizable composition of this disclosure contains thiol component (B). Thiol component (B) is at least one selected from the group consisting of naphthalenthol and naphthalenedithiol.

[0018] The thiol component (B) preferably comprises at least one selected from the group consisting of asymmetric naphthalenthols and asymmetric naphthalenedithiols, and more preferably comprises at least one selected from the group consisting of 1-naphthalenthol, 2-naphthalenthol, 1,6-naphthalenedithiol, and 1,7-naphthalenedithiol. This further improves the heat resistance of the resulting resin. This is thought to be because the structure of the compound is asymmetric (i.e., neither line-symmetric nor point-symmetric), resulting in superior miscibility with the polyisocyanate component (A).

[0019] From the viewpoint of further improving the heat resistance of the resulting resin, the thiol component (B) more preferably includes an asymmetric naphthalenedithiol, and more preferably includes at least one selected from the group consisting of 1,6-naphthalenedithiol and 1,7-naphthalenedithiol.

[0020] The content of thiol component (B) is preferably 10% to 70% by mass relative to the total amount of the polymerizable composition.

[0021] <Other Thiols> The polymerizable compositions of this disclosure may contain at least one other thiol (i.e., a thiol other than thiol component (B)). When the polymerizable compositions of this disclosure contain other thiols, the yellowness of the resulting resin can be further suppressed. The yellowness of the resulting resin is evaluated, for example, using the yellowness index (YI) of the resin as an indicator. The other thiols are preferably monofunctional to tetrafunctional thiols, and more preferably difunctional to tetrafunctional thiols.

[0022] Other thiols include, specifically, 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, and pentaeri. Examples include at least one selected from the group consisting of thritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol bis(3-mercaptopropionate). When the polymerizable composition of this disclosure contains these compounds as other thiols, the yellowing of the resulting resin can be further suppressed.

[0023] If the polymerizable composition of this disclosure contains other thiols, the content of the other thiols is preferably 10% to 40% by mass, more preferably 10% to 30% by mass, based on the total amount of the polymerizable composition.

[0024] In the polymerizable composition of this disclosure, the total thiol content (i.e., the total content of other thiols and thiol component (B) if other thiols are included; if other thiols are not included, the content of thiol component (B)) is preferably 20% to 70% by mass, more preferably 30% to 60% by mass, based on the total amount of the polymerizable composition.

[0025] In the polymerizable composition of this disclosure, the molar ratio [NCO group / SH group], which is the molar ratio of isocyanate groups (i.e., NCO groups) to mercapto groups (i.e., SH groups), is preferably 0.3 to 2.5, more preferably 0.7 to 1.5, and even more preferably 0.7 to 1.3.

[0026] If the polymerizable composition of this disclosure contains other thiols, the molar ratio [NCO group / SH group] is the molar ratio of isocyanate groups in polyisocyanate component (A) to mercapto groups in thiol (B) and the other thiols. If the polymerizable composition of this disclosure does not contain other thiols, the molar ratio [NCO group / SH group] is the molar ratio of isocyanate groups in polyisocyanate component (A) to mercapto groups in thiol (B).

[0027] <Catalyst> The polymerizable composition of this disclosure may contain at least one catalyst. The catalyst functions, for example, as a catalyst for the polymerization reaction when curing the polymerizable composition of this disclosure to obtain a resin. Known polymerization catalysts such as organometallic compounds, amines, and quaternary onium salts can be used as catalysts. Examples of organometallic compounds include compounds containing tin, zinc, copper, etc. Specifically, examples of organometallic compounds include: organotin compounds such as tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dimethyltin dichloride (hereinafter also referred to as "dimethyltin dichloride"), and dibutyltin dichloride; organozinc compounds such as zinc naphthenate; organocouple compounds such as copper octenoate; and so on.

[0028] Examples of amines include: triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, trioctylamine, triallylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, dimethyldipropylenetriamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, N-methylmorpholine, N,N'-dimethylpiperazine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, bicyclooctanediamine (DABCO), 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chlorpyridine, and other tertiary amines; Examples include imidazoles such as imidazole, 1,2-dimethylimidazole, N-benzyl-2-methylimidazole, and 2-ethyl-4-imidazole; and pyrazoles such as pyrazole and 3,5-dimethylpyrazole.

[0029] Examples of quaternary ammonium salts include quaternary ammonium salts and phosphonium salts. Examples of quaternary ammonium salts include tetrabutylammonium bromide and tetraethylammonium hydroxide. Examples of phosphonium salts include tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrahexylphosphonium chloride, tetraoctylphosphonium chloride, ethyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, butyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, methoxymethyltriphenylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylphosphonium bromide, tetrabutylphosphonium bromide, and tetrahexylphosphonium bromide. Examples of phosphonium salt compounds include tetraoctylphosphonium bromide, ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium bromide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium iodide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetraphenylphosphonium tetrakis(4-methylphenyl) borate, tetraphenylphosphonium tetraphenyl borate, and tetrabutylphosphonium-o,o-diethylphosphorodithioate.

[0030] From the viewpoint of reducing environmental impact, non-metallic catalysts may be used as catalysts. Examples of non-metallic catalysts include amines (particularly preferably imidazoles), phosphonium salts, and acids. These catalysts themselves may be compounds derived from plants.

[0031] If the polymerizable composition of this disclosure contains a catalyst, the catalyst content is preferably 20 ppm to 2000 ppm by mass, more preferably 50 ppm to 1500 ppm by mass, and even more preferably 50 ppm to 1000 ppm by mass, based on the total amount of the polymerizable composition.

[0032] <UV absorbers> The polymerizable composition of this disclosure may contain at least one UV absorber.Examples of UV absorbers include: benzophenone-based UV absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and 2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone; 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy] Triazine-based UV absorbers such as -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; 2-(2H-benzotriazole-2-yl)-4-methylphenol, 2-(2H-benzotriazole-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol, 2-(5-chloro-2H-benzotriazole-2-yl)-4-methyl-6- Benzotriazole-based ultraviolet absorbers such as tert-butylphenol, 2-(5-chloro-2H-benzotriazole-2-yl)-2,4-tert-butylphenol, 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and 2-(2H-benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol are examples.

[0033] The amount of ultraviolet absorber in the polymerizable composition of this disclosure is preferably 100 ppm to 50,000 ppm by mass, more preferably 500 ppm to 20,000 ppm by mass, and even more preferably 1,000 ppm to 10,000 ppm by mass, based on the total amount of the polymerizable composition.

[0034] <Release Agent> The polymerizable composition of this disclosure may contain at least one release agent. For example, an acidic phosphate ester can be used as the release agent. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more.

[0035] Commercially available acidic phosphate esters include ZelecUN from STEPAN, the JP series from Johoku Chemical Industry, the Phosphanol series from Toho Chemical Industry, and the AP and DP series from Daihachi Chemical Industry. Furthermore, from the viewpoint of solubility in polymerizable compositions and transparency of the resin, ZelecUN and JP-506H are preferred, with JP-506H being particularly preferred.

[0036] The release agent content in the polymerizable composition of this disclosure is preferably 100 ppm to 5,000 ppm by mass, more preferably 200 ppm to 30,000 ppm by mass, and even more preferably 500 ppm to 2,000 ppm by mass, based on the total amount of the polymerizable composition.

[0037] <Acid> The polymerizable composition of this disclosure may contain at least one acid. Preferably, the acid is an acid with a pKa of 1 or less.

[0038] Examples of acids with a pKa of 1 or less include hydrochloric acid (pKa: -3.7), sulfuric acid (pKa: -3.0), nitric acid (pKa: -1.4), sulfonic acid with a pKa of 1 or less, and polyphosphate with a pKa of 1 or less. From the viewpoint of the pot life of the composition, sulfonic acid with a pKa of 1 or less is preferred.

[0039] Examples of sulfonic acids with pKa1 or lower include methanesulfonic acid (pKa: -2.6), p-toluenesulfonic acid (pKa: -2.8), dodecylbenzenesulfonic acid (pKa: 0.9), 10-camphorsulfonic acid (pKa: 1.2), vinylsulfonic acid (pKa: -2.7), benzenesulfonic acid (pKa: 0.7), and the like. The acid with pKa1 or lower may form a hydrate. The pKa of the acid with pKa1 or lower may be -4 or higher or -3 or higher.

[0040] The acid preferably contains at least one selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, and polyphosphoric acid.

[0041] When the polymerizable composition of the present disclosure contains an acid, the content of the acid is preferably 50 ppm by mass to 4000 ppm by mass, more preferably 100 ppm by mass to 3500 ppm by mass, still more preferably 300 ppm by mass to 3000 ppm by mass, based on the total amount of the polymerizable composition.

[0042] The polymerizable composition of the present disclosure may contain other components in addition to the above-described components. Examples of the other components include a light stabilizer, an antioxidant, a colorant inhibitor, a dye, a bluing agent, a resin modifier, and the like.

[0043] <Preferred embodiments of the polymerizable composition (Condition 1 and Condition 2)> As preferred embodiments of the polymerizable composition of the present disclosure, embodiments that satisfy at least one (i.e., one or both) of the following Condition 1 and Condition 2 are exemplified. However, the polymerizable composition of the present disclosure is not limited to the following preferred embodiments. Condition 1... The thiol component (B) contains naphthalenethiol, and the polymerizable composition further contains a thiol other than the thiol component (B). Condition 2... The thiol component (B) contains naphthalenedithiol.

[0044] When the polymerizable composition of the present disclosure satisfies Condition 1, it is advantageous in terms of suppressing the yellowness of the resulting resin. From the viewpoint of further reducing the yellowness of the resulting resin, thiols other than the thiol component (B) in Condition 1 are preferably 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 tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, diethylene glycol bis(3-mercaptopropionate). In Condition 1, from the viewpoint of further improving the heat resistance of the resulting resin, the naphthalenethiol contained in the thiol component (B) is preferably an asymmetric naphthalenethiol, more preferably at least one selected from the group consisting of 1-naphthalenethiol and 2-naphthalenethiol.

[0045] In the polymerizable composition of the present disclosure when Condition 1 is satisfied, when the polyisocyanate component (A) contains a modified product of a bifunctional or higher-functional isocyanate, the heat resistance of the resulting resin is further improved.

[0046] The polymerizable composition of the present disclosure when Condition 1 is satisfied may further satisfy Condition 2. That is, in the polymerizable composition of the present disclosure when Condition 1 is satisfied, the thiol component (B) may further contain naphthalenedithiol.

[0047] When the polymerizable composition of the present disclosure satisfies Condition 2, it is advantageous in terms of improving the heat resistance of the resulting resin.

[0048] In the polymerizable composition of the present disclosure when condition 2 is satisfied, from the viewpoint of further improving the heat resistance of the resulting resin, the thiol component (B) preferably includes an asymmetric naphthalenedithiol, and more preferably includes at least one selected from the group consisting of 1,6-naphthalenedithiol and 1,7-naphthalenedithiol.

[0049] When condition 2 is satisfied, the polymerizable composition of this disclosure may or may not contain thiols other than thiol component (B). When the polymerizable composition of this disclosure satisfies condition 2 and contains thiols other than thiol component (B), it is advantageous in terms of suppressing the yellowing of the resulting resin. Specific examples of thiols other than thiol component (B) are the same as in the case of condition 1.

[0050] In the polymerizable composition of this disclosure that satisfies condition 2, the heat resistance of the resulting resin is further improved if the polyisocyanate component (A) includes a modified isocyanate with two or more functionalities.

[0051] A polymerizable composition of the present disclosure that satisfies condition 2 may further satisfy condition 1. That is, in a polymerizable composition of the present disclosure that satisfies condition 2, the thiol component (B) may further contain naphthalenchiol, and the polymerizable composition may further contain thiols other than thiol component (B).

[0052] <Method for Producing Polymerizable Composition> The polymerizable composition of this disclosure is obtained by mixing the above-mentioned components (raw materials). There are no particular restrictions on the order in which the components (raw materials) are mixed; all of the raw materials may be added to the container at once and mixed, or the raw materials may be added to the container in multiple stages and mixed. Furthermore, during the mixing process, some of the monomers in the polymerizable composition of this disclosure (i.e., polyisocyanate (A) and thiol component (B), and other thiols if present) may polymerize to form a prepolymer.

[0053] From the viewpoint of extending the pot life of the polymerizable composition, it is preferable to first mix the components other than thiols (i.e., thiol component (B), and other thiols if present; the same applies hereinafter), and then add the thiol alone or the composition containing thiols. This order suppresses unintended reactions between the polyisocyanate component (A) and thiols in the pre-production stage of manufacturing the resin, which is the cured product of the polymerizable composition, thus extending the pot life of the polymerizable composition.

[0054] [Resin] The resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure. That is, the resin of the present disclosure can be produced by curing the polymerizable composition of the present disclosure as described above, more specifically by polymerizing and curing the monomers in the polymerizable composition of the present disclosure.

[0055] One method for polymerizing the monomers in the polymerizable composition of the present disclosure is casting polymerization. By casting polymerization, a molded article of the present disclosure is obtained, which contains the resin of the present disclosure (i.e., a cured product of the polymerizable composition of the present disclosure).

[0056] In casting polymerization, first, a polymerizable composition according to an example of the present disclosure is injected between a pair of molds held together by a gasket or tape. At this time, degassing, filtration, etc. may be performed as necessary. Next, the monomers in the composition injected between the molds are polymerized to cure the composition between the molds and obtain a cured product. Then, the cured product is removed from the molds to obtain a cured product. The polymerization of the monomers may also be carried out by heating the polymerizable composition of the present disclosure. This heating can be carried out, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, etc.

[0057] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition of this disclosure are set appropriately, taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, the shape of the mold, etc. Examples of polymerization temperatures include -50°C to 150°C and 10°C to 150°C. Examples of polymerization times include 1 hour to 200 hours and 1 hour to 80 hours.

[0058] The resin of this disclosure may be obtained by polymerizing monomers and then subjecting them to treatments such as annealing. Examples of annealing temperatures include 50°C to 150°C, 90°C to 140°C, 100°C to 130°C, and so on.

[0059] The resin of this disclosure is a cured product of the polymerizable composition of this disclosure and therefore exhibits excellent refractive index and heat resistance. Regarding heat resistance, the glass transition temperature (Tg) of the resin of this disclosure is preferably greater than 100°C and 200°C or less, more preferably 105°C to 180°C, and even more preferably 105°C to 160°C. Here, Tg is measured by the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10°C / min).

[0060] With respect to the refractive index, the refractive index of the resin of this disclosure is preferably 1.60 to 1.75. The refractive index referred to herein is the refractive index n at a wavelength of 546.1 nm (mercury e line). ｅ That is the case.

[0061] [Optical Components] The optical components of this disclosure include the resin of this disclosure as described above. The optical components of this disclosure may be manufactured, for example, by casting polymerization as described above.

[0062] The optical component of this disclosure may consist of the resin of this disclosure, or may include the resin of this disclosure and other elements. Other elements include other components, a coating layer provided on the resin of this disclosure, and the like.

[0063] Examples of optical components of this disclosure include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses, etc.), light-emitting diodes (LEDs), optical waveguides (e.g., optical waveguides for AR (Augmented Reality) lenses or optical waveguides for VR (Virtual Reality) lenses), optical fibers, display components, etc. Since the optical components of this disclosure contain a resin with excellent refractive index and heat resistance, optical waveguides (e.g., optical waveguides for AR lenses or optical waveguides for VR lenses) are particularly preferred.

[0064] The following are examples of the present disclosure, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts," "%," and "ppm" all refer to mass.

[0065] [Preparation of mixture A2 of m-xylylenediisocyanurate and m-xylylenediisocyanate] A mixture A2 of m-xylylenediisocyanurate, which is the isocyanurate of m-xylylenediisocyanate, and m-xylylenediisocyanate was prepared. Details are shown below. In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, under a nitrogen atmosphere, 97.18 parts by mass of m-xylylenediisocyanate and 0.02 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (hindered phenol antioxidant, trade name: Irganox 1076, manufactured by Ciba Japan) were mixed at 63°C to 65°C to obtain a mixture. 2.12 parts by mass of 1,3-butanediol were added to the obtained mixture at 70°C to 75°C and mixed to carry out a urethane reaction to obtain a urethane reaction solution. To the obtained urethane reaction solution, a propylene glycol methyl ether acetate solution (solid content concentration 3.7% by mass) of tetrabutylammonium hydroxide (isocyanurate catalyst, TBAOH (37% methanol solution)) was added. The amount added was adjusted so that TBAOH was 0.03 parts by mass as the active ingredient. Next, while mixing the urethane reaction solution, the m-xylylene diisocyanate was subjected to an isocyanurate reaction at 70°C to 76°C to obtain an isocyanurate reaction solution containing m-xylylene diisocyanurate, which is the isocyanurate of m-xylylene diisocyanate. To the obtained isocyanurate reaction solution, a propylene glycol methyl ether acetate solution (active ingredient concentration 50% by mass) of dodecylbenzenesulfonic acid (DDBSA, catalyst deactivator) was added, with the DDBSA addition ratio being 500 ppm relative to the isocyanurate reaction solution, to stop the isocyanurate reaction. Next, the resulting isocyanurate reaction solution was stirred at 70°C to 75°C for 30 minutes.Next, to adjust the acidity, m-xylylene diisocyanate with an acidity of 2400 ppm was added in stages, and then the mixture was cooled to below 50°C to obtain a reaction solution with an amine equivalent of 145.9 g / mol, which is a mixture A2 of m-xylylene diisocyanurate and m-xylylene diisocyanate (mass ratio [m-xylylene diisocyanurate / m-xylylene diisocyanate] = 30 / 70).

[0066] [Examples 1-5, Comparative Example 1] <Preparation of Polymerizable Composition> All components except thiol component (B) shown in Table 1 were mixed and stirred at 25°C, degassed at 600 Pa for 1 hour, then thiol component (B) was added and mixed and stirred at 45°C, and degassed at 600 Pa for 1 hour to prepare a polymerizable composition having the composition shown in Table 1. The amounts (parts by mass) of polyisocyanate component (A), thiol component (B), and other thiols shown in Table 1 are substantially the content (mass%) relative to the total amount of polymerizable composition. The amounts (ppm) of catalyst, ultraviolet absorber, and mold release agent shown in Table 1 are the content (mass ppm) relative to the total amount of polymerizable composition. Details of the components in Table 1 are as follows.

[0067] (Polyisocyanate component (A)) ・A1 … m-xylylene diisocyanate ・A2 … A mixture of m-xylylene diisocyanurate and m-xylylene diisocyanate as described above (Thiol component (B)) ・B1 … 1,6-naphthalenedithiol ・B2 … 2-naphthalenthol (Other thiols) ・XB1 … 2,2-bis(mercaptomethyl)-1,3-propanedithiol ・XB2 … At least one selected from the group consisting of 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-trithiaundecane

[0068] (Other) ・Catalyst: Dimethyltin dichloride (product name: Nestin P, manufactured by Honjo Chemical Co., Ltd.) ・UV absorber: viosorb583 (manufactured by Kyodo Yakuhin Co., Ltd.) ・Release agent: JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.)

[0069] <Preparation of Resin> The obtained polymerizable composition was poured into a mold having a diameter of 76 mm and a thickness of 2 mm through a static mixer and a filter with a mesh size of 10 μm. Next, the mold containing the polymerizable composition was placed in an oven and heated at 120°C for 2 hours to cure the polymerizable composition in the mold and produce a resin, which is the cured product of the polymerizable composition. Then, the resin was released from the mold to obtain a resin with a diameter of 76 mm and a thickness of 2 mm. The obtained resin was annealed at 120°C for 2 hours.

[0070] <Evaluation> The following evaluation was conducted on the resins mentioned above. The results are shown in Table 1.

[0071] (Glass transition temperature (Tg) (°C) of resin) The glass transition temperature (Tg) (°C) of the resin after annealing as described above was measured using the TMA penetration method (50g load, pin tip 0.5mmφ, heating rate 10°C / min) with a Shimadzu TMA-60 thermomechanical analyzer. The higher the Tg, the better the heat resistance of the resin.

[0072] (Refractive index n of resin) ｅ ) The refractive index (n) of the resin after annealing as described above was measured using a Shimadzu KPR-3000 Pulfrich refractometer at a wavelength of 546.1 nm (mercury e line). ｅ ) was measured.

[0073] (Yellowness) The yellowness (YI (Yellow Index)) of the resin after annealing as described above was measured using a Konica Minolta CM-5 spectrophotometer.

[0074]

[0075] As shown in Table 1, in each example using a polymerizable composition containing a polyisocyanate component (A) selected from the group consisting of modified isocyanates with two or more functions and isocyanates with two or more functions, and a thiol component (B) selected from the group consisting of naphthalenchiol and naphthalenedithiol, a resin with excellent refractive index and heat resistance (i.e., Tg) was produced. In contrast, in Comparative Example 1, which used a polymerizable composition that did not contain thiol component (B) but contained thiol compounds other than thiol component (B), the heat resistance (i.e., Tg) of the resin decreased.

[0076] A comparison between Example 1 and Example 2 shows that when polyisocyanate component (A) contains a modified isocyanate with two or more functions (Example 2), the heat resistance of the resin is improved compared to when polyisocyanate component (A) does not contain a modified isocyanate with two or more functions (Example 1). Similarly, a comparison between Example 3 and Example 4 shows that when polyisocyanate component (A) contains a modified isocyanate with two or more functions (Example 4), the heat resistance of the resin is improved compared to when polyisocyanate component (A) does not contain a modified isocyanate with two or more functions (Example 3).

[0077] A comparison of Example 2 and Example 5 shows that when the polymerizable composition contains thiols other than thiol component (B) (Example 5), the yellowness (i.e., degree of yellowness) of the resin is more suppressed compared to when the polymerizable composition does not contain thiols other than thiol component (B) (Example 2).

[0078] The disclosure of Japanese Patent Application No. 2025-005790, filed on 15 January 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 comprising: a polyisocyanate component (A) which is at least one selected from the group consisting of modified isocyanates with two or more functions and isocyanates with two or more functions; and a thiol component (B) which is at least one selected from the group consisting of naphthalenchiol and naphthalenedithiol.

2. The polymerizable composition according to claim 1, wherein the polyisocyanate component (A) comprises at least one isocyanate (XA) selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, bis(isocyanatomethyl)cyclohexane, naphthalene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and at least one modified form of the isocyanate (XA).

3. The polymerizable composition according to claim 1, wherein the modified isocyanate comprising at least one selected from the group consisting of isocyanurate group, allophanate group, burette group, urethane group, urea group, uretdione group, iminooxadiazinedione group, uretonimine group, and carbodiimide group.

4. The polymerizable composition according to claim 1, wherein the modified product of the bifunctional or more isocyanates is a trimer of an aromatic ring-containing isocyanate.

5. The polymerizable composition according to claim 1, wherein the thiol component (B) comprises at least one selected from the group consisting of 1-naphthalenchiol, 2-naphthalenchiol, 1,6-naphthalenedithiol, and 1,7-naphthalenedithiol.

6. The polymerizable composition according to claim 1, wherein the thiol component (B) comprises an asymmetric naphthalenedithiol.

7. The polymerizable composition according to claim 1, wherein the thiol component (B) comprises at least one selected from the group consisting of 1,6-naphthalenedithiol and 1,7-naphthalenedithiol.

8. A polymerizable composition according to claim 1, satisfying either condition 1 or condition 2 below. Condition 1: The thiol component (B) comprises naphthalenthil, and the polymerizable composition further comprises a thiol other than the thiol component (B). Condition 2: The thiol component (B) comprises naphthalenedithiol.

9. Thiols other than the thiol component (B) are 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 The polymerizable composition according to claim 8, which is at least one selected from the group consisting of trakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol bis(3-mercaptopropionate).

10. The polymerizable composition according to claim 1, wherein the molar ratio [NCO group / SH group], which is the molar ratio of isocyanate groups to mercapto groups, is 0.7 to 1.

5.

11. A resin which is a cured product of a polymerizable composition according to any one of claims 1 to 10.

12. The resin according to claim 11, wherein the glass transition temperature is 105°C to 160°C.

13. Refractive index n ｅ The resin according to claim 11, wherein the ratio is 1.60 to 1.

75.

14. An optical component comprising the resin described in claim 11.

15. The optical component according to claim 14, which is an optical waveguide.

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