Polymerizable composition, resin, optical member, and composition kit

Abstract

A polymerizable composition containing an isocyanurate (A), a thiol (B) that is a monofunctional to tetrafunctional thiol compound, an acid (C) that is an acid having a pka of 1 or less, and an amine catalyst (D).

Description

Coincidence composition, resin, optical member, and composition kit

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

[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, in addition to the thiol compound and the isocyanate compound, examples containing isocyanurate, which is a modified product (that is, an isocyanurate form) of the isocyanate compound, are also known (see, for example, Patent Documents 1 and 2).

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

[0004] However, it has been found that in a polymerizable composition containing isocyanurate, the pot life may decrease (that is, become shorter). An object of one aspect of the present disclosure is to provide a polymerizable composition that can produce a resin excellent in refractive index and heat resistance and has an excellent pot life, a resin and an optical member excellent in refractive index and heat resistance, and a composition kit that can produce the above polymerizable composition.

[0005] The means for solving the above problems include the following embodiments: <1> A polymerizable composition containing isocyanurate (A), a thiol (B) which is a monofunctional to tetrafunctional thiol compound, an acid (C) which is an acid with a pKa of 1 or less, and an amine catalyst (D). <2> The thiol (B) is 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 The polymerizable composition according to <1>, comprising at least one selected from the group consisting of (1), 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), naphthalenchiol, and naphthalenedithiol. <3> The polymerizable composition according to <1> or <2>, wherein the isocyanurate (A) is an isocyanurate of an isocyanate compound, which is at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. <4> The polymerizable composition according to any one of <1> to <3>, wherein the content of the isocyanurate (A) is 3% by mass to 50% by mass with respect to the total amount of the polymerizable composition. <5> The polymerizable composition according to any one of <1> to <4>, wherein the amine catalyst (D) comprises an alkylammonium salt.<6> The polymerizable composition according to any one of <1> to <5>, wherein the content of the amine catalyst (D) is 20 ppm by mass to 2000 ppm by mass based on the total amount of the polymerizable composition. <7> The polymerizable composition according to any one of <1> to <6>, wherein the acid (C) comprises at least one selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, and polyphosphate. <8> The polymerizable composition according to any one of <1> to <7>, wherein the content of the acid (C) is 50 ppm by mass to 4000 ppm by mass based on the total amount of the polymerizable composition. <9> The polymerizable composition according to any one of <1> to <8>, wherein the acid (C) contains a sulfo group, the amine catalyst (D) contains at least one of an amino group and a quaternary ammonium structure, and the molar ratio of the sulfo group to the sum of the amino group and the quaternary ammonium structure is 0.2 to 1.2. <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> The resin according to <11>, wherein the glass transition temperature is 105°C to 160°C. <13> An optical component comprising the resin according to <11> or <12>. <14> The optical component according to <13>, which is an optical waveguide. <15> A composition kit for producing the polymerizable composition according to any one of <1> to <10>, comprising: a first composition containing the isocyanurate (A), the acid (C), and the amine catalyst (D); and a second composition containing the thiol (B) or the thiol (B).

[0006] According to one aspect of this disclosure, a polymerizable composition is provided that can produce a resin with excellent refractive index and heat resistance and has excellent pot life, as well as a resin and optical component with excellent refractive index and heat resistance, and a composition kit that can produce the above-mentioned polymerizable composition.

[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 isocyanurate (A), thiol (B), which is a monofunctional to tetrafunctional thiol compound, acid (C), which is an acid with a pKa of 1 or less, and an amine catalyst (D).

[0009] The polymerizable composition of this disclosure makes it possible to produce a resin with excellent refractive index and heat resistance. Furthermore, the polymerizable composition of this disclosure has excellent pot life. The effect of the resin's refractive index is obtained by thiol (B). The effect of the resin's heat resistance is obtained by isocyanurate (A). The effect of the pot life is obtained by acid (C).

[0010] The effect of pot life will be explained in more detail. Through the inventors' studies, it has been found that in polymerizable compositions containing isocyanurate (A), thiol (B), and amine catalyst (D), the pot life may decrease (i.e., become shorter). In this regard, according to the polymerizable composition of this disclosure, the decrease in pot life that may occur when containing isocyanurate (A), thiol (B), and amine catalyst (D) can be suppressed by acid (C).

[0011] <Isocyanurate (A)> The polymerizable compositions of this disclosure contain isocyanurate (A). Isocyanurate (A) may be one type of isocyanurate or two or more types of isocyanurates. Isocyanurate is a type of modified isocyanate compound. Isocyanurate can be produced by isocyanurating (e.g., trimerizing) an isocyanate compound. For a method of producing an isocyanate compound, see, for example, International Publication No. 2018 / 190290.

[0012] The isocyanurate preferably contains an isocyanuryl ring structure and an isocyanate group. For example, in an isocyanurate obtained by isocyanurating (e.g., trimerizing) an isocyanate compound, an isocyanate group may remain in the formed isocyanurate. Such an isocyanurate can be formed, for example, using a polyisocyanate compound containing two or more isocyanate groups.

[0013] The isocyanurate (A) preferably contains an isocyanurate of an isocyanate compound (hereinafter also referred to as "isocyanate compound (a)") which is at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate (preferably m-xylylene diisocyanate), isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. From the viewpoint of balancing the refractive index and heat resistance of the resulting resin, isocyanurate (A) more preferably contains an isocyanurate of an isocyanate compound selected from the group consisting of xylylene diisocyanate (preferably m-xylylene diisocyanate), bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, and 4,4'-diphenylmethane diisocyanate, and more preferably contains an isocyanurate of xylylene diisocyanate (preferably m-xylylene diisocyanate).

[0014] The isocyanurate (A) content is preferably 1% to 50% by mass, more preferably 5% to 45% by mass, and even more preferably 10% to 40% by mass, based on the total amount of the polymerizable composition.

[0015] <Isocyanate Compounds> The polymerizable compositions of this disclosure may contain at least one isocyanate compound. Preferably, the isocyanate compound is one of the isocyanate compounds (a) described above (i.e., at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate (preferably m-xylylene diisocyanate), isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate).

[0016] The isocyanate compound content is preferably 20% to 77% by mass, more preferably 30% to 75% by mass, and even more preferably 35% to 60% by mass, based on the total amount of the polymerizable composition.

[0017] The total content of isocyanate compounds and isocyanurate (A) is preferably 21% to 80% by mass, more preferably 35% to 80% by mass, and even more preferably 45% to 70% by mass, based on the total amount of the polymerizable composition.

[0018] <Thiol (B)> The polymerizable compositions of this disclosure contain thiol (B). Thiol (B) is a monofunctional to tetrafunctional thiol compound. Thiol (B) may be one thiol compound or two or more thiol compounds.

[0019] Thiol (B) is preferably 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 It comprises at least one selected from the group consisting of -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), naphthalenchiol, and naphthalenedithiol.

[0020] The thiol (B) content is preferably 10% to 80% by mass, more preferably 20% to 65% by mass, based on the total amount of the polymerizable composition.

[0021] In the polymerizable composition of this disclosure, the molar ratio [NCO group / SH group], which is the molar ratio of isocyanate groups to mercapto groups, is preferably 0.3 to 2.5, more preferably 0.7 to 1.5, and even more preferably 0.7 to 1.3.

[0022] If the polymerizable composition of this disclosure contains an isocyanate compound, the molar ratio [NCO group / SH group] is the molar ratio of the total isocyanate groups in isocyanurate (A) and isocyanate groups in the isocyanate compound to the mercapto groups in thiol (B). If the polymerizable composition of this disclosure does not contain an isocyanate compound, the molar ratio [NCO group / SH group] is the molar ratio of isocyanate groups in isocyanurate (A) to mercapto groups in thiol (B).

[0023] <Acid (C)> The polymerizable composition of this disclosure contains acid (C). Acid (C) is an acid with a pKa of 1 or less. Acid (C) may be one type of acid or two or more types of acids.

[0024] 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.

[0025] Examples of sulfonic acids with a pKa of 1 or less 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), and benzenesulfonic acid (pKa: 0.7). Acids with a pKa of 1 or less may form hydrates. The pKa of acids with a pKa of 1 or less may be -4 or higher, or -3 or higher.

[0026] Acid (C) preferably contains at least one selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, and polyphosphate.

[0027] The acid (C) content is preferably 50 ppm to 4000 ppm by mass, more preferably 100 ppm to 3500 ppm by mass, and even more preferably 300 ppm to 3000 ppm by mass, based on the total amount of the polymerizable composition.

[0028] <Amine Catalyst (D)> The polymerizable composition of this disclosure contains an amine catalyst (D). The amine catalyst (D) may consist of one type or two or more types.

[0029] Examples of amine catalysts include ammonium salts, alkylammonium salts, tertiary amine compounds, and nitrogen-containing heterocyclic compounds.

[0030] Examples of tertiary amine compounds 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, and bicyclooctanediamine (DABCO). Examples of nitrogen-containing heterocyclic compounds include 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chlorpyridine, imidazole, 1,2-dimethylimidazole, N-benzyl-2-methylimidazole, 2-ethyl-4-imidazole, pyrazole, and 3,5-dimethylpyrazole.

[0031] Examples of counteranions in ammonium salts and alkylammonium salts include halide ions and hydroxide ions. Examples of alkylammonium salts include tetrabutylammonium bromide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.

[0032] The amine catalyst (D) preferably contains an alkylammonium salt. The number of carbon atoms per alkyl group in the alkylammonium salt is preferably 1 to 20, more preferably 1 to 10. Tetraalkylammonium salts are preferred as the alkylammonium salt.

[0033] The content of the amine catalyst (D) is preferably 20 ppm to 2000 ppm by mass, more preferably 50 ppm to 1500 ppm by mass, even more preferably 55 ppm to 1500 ppm by mass, and even more preferably 100 ppm to 1000 ppm by mass, relative to the total amount of the polymerizable composition.

[0034] From the viewpoint of extending the pot life of the polymerizable composition, in the polymerizable composition of this disclosure, the acid (C) contains a sulfo group (for example, the aforementioned sulfonic acid with a pKa of 1 or less), the amine catalyst (D) contains a quaternary nitrogen atom, and the molar ratio [sulfo group / quaternary nitrogen atom], which is the molar ratio of sulfo group to quaternary nitrogen atom, is preferably 0.2 to 1.2, and more preferably 0.5 to 1.2. Here, the sulfo group is, for example, contained in a sulfonic acid with a pKa of 1 or less, which is a preferred embodiment of the acid (C), and the quaternary nitrogen atom is, for example, contained in an alkylammonium salt, which is a preferred embodiment of the amine catalyst (D).

[0035] <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.

[0036] 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.

[0037] <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.

[0038] 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.

[0039] 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.

[0040] The polymerizable compositions of this disclosure may contain other components besides those described above. Examples of other components include light stabilizers, antioxidants, color inhibitors, dyes, bluing agents, and resin modifiers.

[0041] <Initial Viscosity of Polymerizable Composition> The initial viscosity of the polymerizable composition of this disclosure (viscosity within 5 minutes from the completion of preparation; the same applies hereinafter) is preferably 500 mPa·s or less, more preferably 400 mPa·s or less, and even more preferably 300 mPa·s or less, from the viewpoint of pot life. The lower limit of the initial viscosity of the polymerizable composition is, for example, 50 mPa·s or 100 mPa·s.

[0042] In the present disclosure, the viscosity of the composition is measured using a B-type viscometer and spindle No. 2 under the conditions of 25°C and 100 rpm (revolutions per minute).

[0043] <Viscosity of the Polymerizable Composition of the Present Disclosure after 3 Hours at 25°C> The polymerizable composition of the present disclosure has excellent pot life. As an index of pot life, the viscosity of the polymerizable composition after 3 hours at 25°C (that is, the viscosity at the time when the polymerizable composition is allowed to stand at 25°C for 3 hours) can be mentioned. The lower the viscosity after 3 hours at 25°C, the better the pot life (that is, the longer the pot life). The viscosity of the polymerizable composition after 3 hours at 25°C is preferably 2000 mPa·s or less, more preferably 1500 mPa·s or less, and still more preferably 1000 mPa·s or less. The lower limit of the viscosity of the polymerizable composition after 3 hours at 25°C is, for example, 100 mPa·s or 200 mPa·s.

[0044] <Method for Producing Polymerizable Composition> The polymerizable composition of the present disclosure is obtained by mixing the above-described respective components (raw materials). There is no particular limitation on the order of mixing the respective components (raw materials). All of the raw materials may be put into a container at once and mixed, or the raw materials may be put into the container in multiple portions and mixed. Also, at an intermediate stage of mixing, a part of the monomers (that is, isocyanurate (A) and thiol (B), and an isocyanate compound if contained) in the polymerizable composition of the present disclosure may polymerize to form a prepolymer.

[0045] From the viewpoint of lengthening the pot life of the polymerizable composition, the order of mixing is preferably such that first, the components other than thiol (B) are mixed, and then a composition containing thiol (B) alone or thiol (B) is added thereto. According to this order, an unintended reaction between isocyanurate (A) and / or the isocyanate compound and thiol (B) is suppressed at a stage prior to producing a resin which is a cured product of the polymerizable composition, so that the pot life of the polymerizable composition is lengthened. In order to carry out the mixing in the above-described preferred order, the polymerizable composition of the present disclosure may be produced using the composition kit of the present disclosure shown below.

[0046] [Composition Kit] The composition kit of the present disclosure is a composition kit for producing the polymerizable composition of the present disclosure, and includes a first composition containing isocyanurate (A), acid (C), and amine catalyst (D), and a second composition containing thiol (B) or thiol (B). The production of the polymerizable composition using the composition kit of the present disclosure is carried out, for example, by mixing the first composition and the second composition or thiol (B) prior to producing a resin that is a cured product of the polymerizable composition (e.g., immediately before producing the resin). At this time, other components may be further mixed to adjust the composition of the polymerizable composition. By producing the polymerizable composition using the composition kit of the present disclosure, as described above, the unintended reaction between isocyanurate (A) and / or isocyanate compound and thiol (B) is suppressed at the stage prior to producing a resin that is a cured product of the polymerizable composition, so that the pot life of the polymerizable composition is prolonged.

[0047] Specific embodiments of the composition kit of the present disclosure include the following embodiment X, the following embodiment Y, the following embodiment Z, and the following embodiment W. Embodiment X of the composition kit of the present disclosure is an embodiment including a first composition containing all of the isocyanurate (A), all of the acid (C), and all of the amine catalyst (D), and all of the thiol (B). Embodiment Y of the composition kit of the present disclosure is an embodiment including a first composition containing all of the isocyanurate (A), a partial amount of the acid (C), and a partial amount of the amine catalyst (D), and a second composition containing all of the thiol (B), the remaining amount of the acid (C), and the remaining amount of the amine catalyst (D) or all of the thiol (B). Embodiment Z of the composition kit of the present disclosure is an embodiment including a first composition containing all of the isocyanurate (A), all of the acid (C), and a partial amount of the amine catalyst (D), and a second composition containing all of the thiol (B) and the remaining amount of the amine catalyst (D). Embodiment W of the composition kit of the present disclosure is an embodiment including a first composition containing all of the isocyanurate (A), a partial amount of the acid (C), and all of the amine catalyst (D), and a second composition containing all of the thiol (B) and the remaining amount of the acid (C).

[0048] [Resins] The resins of the present disclosure are cured products of the polymerizable compositions of the present disclosure. That is, the resins of the present disclosure can be produced by curing the polymerizable compositions of the present disclosure as described above, more specifically by polymerizing and curing the monomers in the polymerizable compositions of the present disclosure (i.e., isocyanurate (A) and thiol (B), and isocyanate compounds if present).

[0049] 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).

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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).

[0054] 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.

[0055] [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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] [Preparation of mixture A1 of m-xylylenediisocyanurate and m-xylylenediisocyanate] A mixture A1 of m-xylylenediisocyanurate as isocyanurate (A) and m-xylylenediisocyanate as an isocyanate compound was prepared. Details are shown below. In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser, 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, in order to adjust the acidity, an m-xylylene diisocyanate composition with an acidity of 2400 ppm was added stepwise, and then the mixture was cooled to below 50°C to obtain a mixture A1 of m-xylylene diisocyanurate and m-xylylene diisocyanate (mass ratio [m-xylylene diisocyanurate / m-xylylene diisocyanate] = 30 / 70) as a reaction solution with an amine equivalent of 145.9 g / mol.

[0060] [Examples 1-8, Comparative Examples 1-2] <Preparation of Polymerizable Composition> All components except thiol (B) shown in Table 1 were mixed and degassed at 600 Pa for 1 hour. Then thiol (B) was added and degassed at 600 Pa for 1 hour to prepare polymerizable compositions having the composition shown in Table 1. The amounts of each component shown in Table 1 are the amounts contained in relation to the total amount of polymerizable composition. In Examples 1-8 and Comparative Example 2, a mixture A1 of m-xylylene diisocyanurate and m-xylylene diisocyanate described above was used as the source of isocyanurate (A) and isocyanate compound. In Comparative Example 1, mixture A1 was not used, and m-xylylene diisocyanate was used as the isocyanate compound. In Table 1, "NCO group / SH group" represents the molar ratio of the total isocyanate groups in isocyanurate (A) (nurate in the example) and isocyanate groups in the isocyanate compound (isocyanate in the example) to the mercapto groups in thiol (B) in the final polymerizable composition. In Table 1, "sulfo group / quaternary nitrogen atom" represents the molar ratio of sulfo groups in acid (C) to quaternary nitrogen atoms in amine catalyst (D) in the final polymerizable composition. Details of the components in Table 1 are as follows.

[0061] (Thiol (B)) ・B1 … 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 ・B2 … 2,2-bis(mercaptomethyl)-1,3-propanedithiol ・B3 … Pentaerythritol tetrakis(3-mercaptopropionate) ・B4 … 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane ・B5 … 1,6-naphthalenedithiol

[0062] (Acid (C)) ・C1 … 10-Camphorsulfonic acid (pKa 1.2) ・C2 … Dodecylbenzenesulfonic acid (pKa 0.9) ・C3 … Paratoluenesulfonic acid monohydrate (pKa -2.8)

[0063] (Amine catalyst (D)) ・D1 … Tetrabutylammonium hydroxide

[0064] (Other) - UV absorber: viosorb583 (manufactured by Kyodo Yakuhin Co., Ltd.) - Release agent: JP-506H (manufactured by Johoku Chemical Industry Co., Ltd.)

[0065] <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.

[0066] <Evaluation> The following evaluations were conducted on the polymerizable compositions and resins described above. The results are shown in Table 1.

[0067] (Initial viscosity of polymerizable composition) The initial viscosity of the polymerizable composition (viscosity within 5 minutes of completion of preparation; the same applies hereinafter) was measured using a B-type viscometer and spindle No. 2 under conditions of 25°C and 100 rpm (revolutions per minute).

[0068] (Viscosity of polymerizable composition after 3 hours at 25°C) The viscosity of the polymerizable composition after standing at 25°C for 3 hours was measured as the viscosity after 3 hours at 25°C. The viscosity after 3 hours at 25°C was measured using the same method as the initial viscosity. The lower the viscosity of the polymerizable composition after 3 hours at 25°C, the better the pot life of the polymerizable composition.

[0069] (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.

[0070] (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.

[0071]

[0072] As shown in Table 1, in each example using a polymerizable composition containing isocyanurate (A), a monofunctional to tetrafunctional thiol compound thiol (B), an acid (C) with a pKa of 1 or less, and an amine catalyst (D), resins with excellent refractive index and heat resistance (i.e., Tg) were produced. Furthermore, in each example, the viscosity of the polymerizable composition after 3 hours at 25°C was reduced, and the pot life of the polymerizable composition was excellent. In contrast, in Comparative Example 1, which used a polymerizable composition that did not contain isocyanurate (A), the heat resistance (i.e., Tg) of the resin decreased. Also, in Comparative Example 2, which used a polymerizable composition that did not contain acid (C), the viscosity of the polymerizable composition after 3 hours at 25°C was too high (i.e., the pot life of the polymerizable composition was poor), and therefore, resin could not be produced.

[0073] The disclosure of Japanese Patent Application No. 2025-005789, 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 containing isocyanurate (A), a thiol (B) which is a monofunctional to tetrafunctional thiol compound, an acid (C) which is an acid with a pKa of 1 or less, and an amine catalyst (D).

2. The thiol (B) is 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) The polymerizable composition according to claim 1, comprising at least one selected from the group consisting of (t), 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), naphthalenchiol, and naphthalenedithiol.

3. The polymerizable composition according to claim 1, wherein the isocyanurate (A) comprises an isocyanurate of an isocyanate compound, which is at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

4. The polymerizable composition according to claim 1, wherein the content of isocyanurate (A) is 3% by mass to 50% by mass based on the total amount of the polymerizable composition.

5. The polymerizable composition according to claim 1, wherein the amine catalyst (D) comprises an alkylammonium salt.

6. The polymerizable composition according to claim 1, wherein the content of the amine catalyst (D) is 20 ppm by mass to 2000 ppm by mass based on the total amount of the polymerizable composition.

7. The polymerizable composition according to claim 1, wherein the acid (C) comprises at least one selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, and polyphosphate.

8. The polymerizable composition according to claim 1, wherein the content of the acid (C) is 50 ppm by mass to 4000 ppm by mass based on the total amount of the polymerizable composition.

9. The polymerizable composition according to claim 1, wherein the acid (C) contains a sulfo group, the amine catalyst (D) contains a quaternary nitrogen atom, and the molar ratio [sulfo group / quaternary nitrogen atom], which is the molar ratio of the sulfo group to the quaternary nitrogen atom, is 0.2 to 1.

2.

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

14. The optical component according to claim 13, which is an optical waveguide.

15. A composition kit for producing a polymerizable composition according to any one of claims 1 to 10, comprising: a first composition containing the isocyanurate (A), the acid (C), and the amine catalyst (D); and a second composition containing the thiol (B) or the thiol (B).

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