Polymerizable composition for optical material, method for producing same, optical material, and method for producing same

Abstract

This polymerizable composition for an optical material comprises not less than two types of different monomers for optical materials and not less than two types of nitrogen-containing aromatic heterocyclic compound catalysts, wherein the not less than two types of different monomers for optical materials each contains an isocyanate compound having an aromatic ring.

Description

Polymerizable Composition for Optical Materials, Method for Producing the Same, Optical Material, and Method for Producing the Same

[0001] The present disclosure relates to a polymerizable composition for optical materials, a method for producing the same, an optical material, and a method for producing the same.

[0002] As a composition for producing optical materials such as plastic lenses, a polymerizable composition for optical materials containing a monomer for optical materials and a catalyst is known. For example, Patent Document 1 discloses a polymerizable composition for optical materials containing two or more different monomers for optical materials and a polymerization catalyst, wherein at least one of the two or more different monomers for optical materials is an isocyanate compound having an aromatic ring, and the content of the polymerization catalyst with respect to 100 parts by mass in total of the two or more different monomers for optical materials is 0.010 parts by mass to 0.5 parts by mass, and the viscosity measured under the conditions of 25°C and 60 rpm with a B-type viscometer is 10 mPa·s to 1000 mPa·s.

[0003] Patent Document 1: International Publication No. 2021 / 153631

[0004] However, it has been found that when a polymerizable composition for optical materials containing an isocyanate compound containing an aromatic ring is used, the resulting optical material may have a color tone. Also, even when the resulting optical material does not have a color tone when a polymerizable composition for optical materials containing an isocyanate compound containing an aromatic ring is used, it has been found that bubbles may occur in the resulting optical material.

[0005] The problem to be solved by one embodiment of the present disclosure is to provide a polymerizable composition for optical materials capable of producing an optical material with suppressed color tone and bubbles despite containing an isocyanate compound containing an aromatic ring, a method for producing the above polymerizable composition for optical materials, an optical material with suppressed color tone and bubbles, and a method for producing the above optical material.

[0006] Specific means for solving the problem include the following embodiments: <1> A polymerizable composition for optical materials comprising two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts, wherein the two or more different monomers for optical materials each contain an isocyanate compound containing an aromatic ring. <2> The polymerizable composition for optical materials according to <1>, wherein each of the two or more nitrogen-containing aromatic heterocyclic compound catalysts contains a nitrogen-containing aromatic heterocyclic ring having two substituents. <3> The polymerizable composition for optical materials according to <1> or <2>, wherein the two or more nitrogen-containing aromatic heterocyclic compound catalysts each contain 3,5-lutidine and 2,6-lutidine. <4> The polymerizable composition for optical materials according to <3>, wherein the mass ratio of [2,6-lutidine / 3,5-lutidine] is greater than 1. <5> A polymerizable composition for optical materials according to <3> or <4>, wherein the mass ratio of [2,6-lutidine / 3,5-lutidine] is 3 to 20. <6> A polymerizable composition for optical materials according to any one of <1> to <5>, further containing an organic acid with a pKa of 3 or less. <7> A polymerizable composition for optical materials according to any one of <1> to <6>, wherein the viscosity measured by a B-type viscometer at 25°C and 60 rpm is 10 mPa·s to 1000 mPa·s. <8> A polymerizable composition for optical materials according to any one of <1> to <7>, wherein the total content of the two or more nitrogen-containing aromatic heterocyclic compound catalysts per 100 parts by mass of the total amount of the polymerizable composition for optical materials is 0.01 parts by mass to 2.5 parts by mass. <9> A polymerizable composition for optical materials according to any one of <1> to <8>, wherein it does not contain tin, or if it does, the tin content is 10 ppm by mass or less. <10> A polymerizable composition for optical materials according to any one of <1> to <9>, wherein the two or more different monomers for optical materials further comprises at least one active hydrogen compound A selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound.<11> A polymerizable composition for optical materials according to any one of <1> to <10>, wherein the isocyanate compound containing the aromatic ring comprises at least one selected from m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and m-phenylene diisocyanate. <12> A polymerizable composition for optical materials according to any one of <1> to <11>, further comprising a prepolymer which is a polymer containing polymerizable functional groups in at least a portion of the total amount of the two or more different monomers for optical materials. <13> A method for producing a polymerizable composition for optical materials as described in <12>, comprising: a preparation step of preparing a total of 100 parts by mass of two or more different monomers for optical materials and a total of 0.01 to 2.5 parts by mass of two or more nitrogen-containing aromatic heterocyclic compound catalysts; and a prepolymerization step of mixing a portion of the two or more different monomers for optical materials with at least a portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.<14> A method for producing a polymerizable composition for optical materials as described in <12>, comprising: a preparation step of preparing a total of 100 parts by mass of two or more different monomers for optical materials and a total of 0.01 to 2.5 parts by mass of two or more nitrogen-containing aromatic heterocyclic compound catalysts; a first prepolymerization step of mixing a portion of the two or more different monomers for optical materials and a portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a first prepolymer which is a polymer containing polymerizable functional groups, thereby obtaining a first liquid containing the first prepolymer; a second prepolymerization step of mixing the remaining portion of the two or more different monomers for optical materials and the remaining portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the remaining portion of the two or more different monomers for optical materials to obtain a second prepolymer which is a polymer containing polymerizable functional groups, thereby obtaining a second liquid containing the second prepolymer; A method for producing a polymerizable composition for optical materials, comprising the step of mixing the first liquid and the second liquid to obtain the polymerizable composition for optical materials. <15> The method for producing a polymerizable composition for optical materials according to <14>, wherein the two or more nitrogen-containing aromatic heterocyclic compound catalysts include 3,5-lutidine and 2,6-lutidine, the first liquid contains at least a portion of the total amount of 2,6-lutidine, and the second liquid contains at least a portion of the total amount of 3,5-lutidine. <16> An optical material comprising a cured product of the polymerizable composition for optical materials according to any one of <1> to <12>. <17> The optical material according to <16>, which is a lens. <18> A method for producing an optical material as described in <16>, comprising: a casting step of pouring the polymerizable composition for optical materials into a mold; and a curing step of curing the polymerizable composition for optical materials by polymerizing the two or more different monomers for optical materials in the polymerizable composition for optical materials in the mold.

[0007] According to one embodiment of the present disclosure, a polymerizable composition for optical materials is provided that can produce an optical material in which color and bubbles are suppressed despite containing an isocyanate compound containing an aromatic ring, a method for producing the polymerizable composition for optical materials, an optical material in which color and bubbles are suppressed, and a method for producing the optical material are provided.

[0008] 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. 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 their intended purpose is achieved.

[0009] [Polymerizable Composition for Optical Materials] The polymerizable composition for optical materials of the present disclosure contains two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts, wherein the two or more different monomers for optical materials contain isocyanate compounds containing aromatic rings.

[0010] As mentioned above, it has been found that when a polymerizable composition for optical materials containing an isocyanate compound containing an aromatic ring is used, the resulting optical material may have a discoloration. Furthermore, it has been found that even when a polymerizable composition for optical materials containing an isocyanate compound containing an aromatic ring does not produce a discoloration in the resulting optical material, bubbles may form in the resulting optical material. In response to these problems, the polymerizable composition for optical materials of this disclosure (hereinafter also simply referred to as "polymerizable composition") makes it possible to produce an optical material in which discoloration and bubbles are suppressed, despite containing an isocyanate compound containing an aromatic ring. The reason for this effect is thought to be the inclusion of two or more nitrogen-containing aromatic heterocyclic compound catalysts.

[0011] <Two or more different monomers for optical materials> The polymerizable composition of this disclosure contains two or more different monomers for optical materials. The two or more different monomers for optical materials include isocyanate compounds containing an aromatic ring.

[0012] For monomers used in optical materials, refer to International Publication No. 2021 / 153631 as appropriate.

[0013] The monomer for optical materials may be, for example, a monomer used to produce an optical material having any of the following properties. The optical material obtained using the monomer for optical materials may have a total light transmittance of 10% or more. The total light transmittance of the optical material may be measured in accordance with JIS K 7361-1 (1997). The optical material obtained using the monomer for optical materials may have a haze (i.e., total haze) of 10% or less, preferably 1% or less, and more preferably 0.5% or less. The haze of the optical material is the value measured at 25°C using a haze measuring instrument [(Tokyo Denshoku Co., Ltd., TC-HIII DPK)] in accordance with JIS-K7105. The optical material obtained using the monomer for optical materials may have a refractive index of preferably 1.58 or more. The refractive index of the optical material obtained using the monomer for optical materials may be 1.80 or less, or 1.75 or less. The refractive index of the optical material may be measured in accordance with JIS K7142 (2014).

[0014] The shape of the optical material obtained using the monomer for optical materials is not particularly limited and may be plate-shaped, cylindrical, rectangular, or the like.

[0015] Two or more different monomers for optical materials include isocyanate compounds containing aromatic rings. Preferably, the isocyanate compounds containing aromatic rings include at least one selected from m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and m-phenylene diisocyanate.

[0016] Two or more different monomers for optical materials may or may not contain an isocyanate compound that does not contain an aromatic ring. Examples of isocyanate compounds that do not contain an aromatic ring include isophorone diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate. When two or more different monomers for optical materials contain an isocyanate compound that does not contain an aromatic ring and an isocyanate compound that contains an aromatic ring, the proportion of the isocyanate compound containing an aromatic ring in the total isocyanate compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0017] Two or more different monomers for optical materials may include at least one selected from the group consisting of isocyanate compounds that do not contain aromatic rings, polythiol compounds having two or more mercapto groups, hydroxythiol compounds containing one or more mercapto groups and one or more hydroxyl groups, polyol compounds containing two or more hydroxyl groups, and amine compounds. Examples of isocyanate compounds that do not contain aromatic rings include aliphatic isocyanate compounds, alicyclic isocyanate compounds, and heterocyclic isocyanate compounds.

[0018] Preferably, the two or more different monomers for optical materials include, in addition to an isocyanate compound containing an aromatic ring, at least one active hydrogen compound A selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound.

[0019] Among the above, it is preferable that the active hydrogen compound A contains a polythiol compound having two or more mercapto groups, from the viewpoint of improving the heat resistance and refractive index of the cured product. The content of the polythiol compound having two or more mercapto groups is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the active hydrogen compound A.

[0020] In active hydrogen compound A, the total content of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and pentaerythritol tetrakis(3-mercaptopropionate) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total amount of active hydrogen compound A.

[0021] Furthermore, when two or more different monomers for optical materials contain a polythiol compound (as active hydrogen compound A), the total content of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and pentaerythritol tetrakis (3-mercaptopropionate) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the polythiol compound.

[0022] In the polymerizable compositions of this disclosure, the molar ratio ((OH group + SH group) / NCO group) of the total sum of hydroxyl groups (OH group) and mercapto groups (SH group) in the active hydrogen compound A to the isocyanate group (NCO group) in the isocyanate compound (i.e., an isocyanate compound containing an aromatic ring, and an isocyanate compound without an aromatic ring if present; the same applies hereinafter) is preferably 0.8 or more, more preferably 0.85 or more, and even more preferably 0.9 or more. In the polymerizable compositions of this disclosure, the molar ratio ((OH group + SH group) / NCO group) of the total sum of hydroxyl groups (OH group) and mercapto groups (SH group) in the active hydrogen compound A to the isocyanate group (NCO group) in the isocyanate compound is preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.1 or less.

[0023] In the polymerizable composition of this disclosure, the total content of two or more different monomers for optical materials per 100 parts by mass of the total amount of the polymerizable composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more.

[0024] When the polymerizable composition of this disclosure contains a prepolymer as described later, the total content of two or more different monomers for optical materials and the prepolymer, relative to 100 parts by mass of the total amount of the polymerizable composition, is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more.

[0025] <Prepolymer> The polymerizable composition of this disclosure preferably contains a prepolymer, which is a polymer of at least some of the two or more different monomers for optical materials described above, and which is a polymer containing polymerizable functional groups. This makes it possible to further shorten the time required to form a cured product of the polymerizable composition. It also makes it possible to further suppress striations in the resulting cured product and optical material.

[0026] Examples of prepolymers include polymers obtained by polymerizing two types of monomers for optical materials at an equivalence ratio other than 1:1 (i.e., an unbalanced equivalence ratio). Polymerizable functional groups in prepolymers are functional groups that can polymerize with other polymerizable functional groups, and specifically include functional groups having active hydrogen, such as isocyanate groups and mercapto groups. Polymerization at an equivalence ratio of 1:1 means, for example, when polymerizing using an isocyanate compound and a polythiol compound, polymerizing in amounts such that the isocyanate group of the isocyanate compound and the mercapto group of the polythiol compound are in a molar ratio of 1:1.

[0027] <Nitrogen-containing aromatic heterocyclic compound catalyst> The polymerizable composition of this disclosure contains two or more nitrogen-containing aromatic heterocyclic compound catalysts. This suppresses color and bubbles in optical materials produced using the polymerizable composition.

[0028] Preferably, each of the two or more nitrogen-containing aromatic heterocyclic compound catalysts contains a nitrogen-containing aromatic heterocyclic ring having two substituents.

[0029] Preferably, each of the two or more nitrogen-containing aromatic heterocyclic compound catalysts contains a compound represented by the following formula (1).

[0030]

[0031] In formula (1), R １ R represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom, and there are multiple Rs. １ They may be the same or different. Q represents a carbon atom or a nitrogen atom. m represents an integer from 0 to 5.

[0032] In formula (1), m is preferably an integer from 1 to 5, more preferably an integer from 2 to 5, and even more preferably 2.

[0033] Examples of two or more nitrogen-containing aromatic heterocyclic compound catalysts include 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-collidine, 3-chlorpyridine, quinoline, quinaldine, 1,2-dimethylimidazole, and 1-benzyl-2-methylimidazole.

[0034] The catalyst comprises two or more nitrogen-containing aromatic heterocyclic compounds, preferably including 3,5-lutidine and 2,6-lutidine. In the embodiment in which the catalyst comprises two or more nitrogen-containing aromatic heterocyclic compounds including 3,5-lutidine and 2,6-lutidine, the color (e.g., redness) of the resulting optical material is more suppressed compared to the embodiment in which the catalyst comprises two or more nitrogen-containing aromatic heterocyclic compounds including 3,5-lutidine and not including 2,6-lutidine. Furthermore, in the embodiment in which the catalyst comprises two or more nitrogen-containing aromatic heterocyclic compounds including 3,5-lutidine and 2,6-lutidine, bubbles in the resulting optical material are more suppressed compared to the embodiment in which the catalyst comprises two or more nitrogen-containing aromatic heterocyclic compounds including 2,6-lutidine and not including 3,5-lutidine. Furthermore, in embodiments in which the catalyst includes two or more nitrogen-containing aromatic heterocyclic compound catalysts, 3,5-lutidine and 2,6-lutidine, the resulting optical material exhibits even greater suppression of striations and improved mold release properties compared to embodiments in which the catalyst includes 2,6-lutidine but does not include 3,5-lutidine. Here, the effects of using 3,5-lutidine as a catalyst—suppression of bubbles, suppression of striations, and improvement of mold release properties—are considered to be due to 3,5-lutidine further promoting the polymerization reaction of monomers for optical materials in polymerizable compositions.

[0035] In embodiments in which two or more nitrogen-containing aromatic heterocyclic compound catalysts include 3,5-lutidine and 2,6-lutidine, the mass ratio of [2,6-lutidine / 3,5-lutidine] (i.e., the ratio of the content of 2,6-lutidine to the content of 3,5-lutidine) in the polymerizable composition is not particularly limited. From the viewpoint of more effectively achieving both color suppression and bubble suppression in the resulting optical material, the mass ratio of [2,6-lutidine / 3,5-lutidine] is preferably greater than 1, more preferably 3 to 20, and even more preferably 3 to 10.

[0036] In the polymerizable composition of this disclosure, the total content of two or more nitrogen-containing aromatic heterocyclic compound catalysts per 100 parts by mass of the total amount of polymerizable composition is preferably 0.01 to 2.5 parts by mass, more preferably 0.01 to 1 part by mass, even more preferably 0.01 to 0.50 parts by mass, and even more preferably 0.01 to 0.2 parts by mass.

[0037] <Other Catalysts> The polymerizable compositions of this disclosure may contain catalysts other than nitrogen-containing aromatic heterocyclic compound catalysts. Examples of other catalysts include tertiary amine compound catalysts and organometallic catalysts. For other catalysts, refer to the description in International Publication No. 2021 / 153631 as appropriate.

[0038] The polymerizable composition of this disclosure preferably does not contain tin, or if it does, the tin content is 10 ppm by mass or less based on the total amount of the polymerizable composition.

[0039] <Organic acids with a pKa of 3 or less> From the viewpoint of further suppressing early release (i.e., the phenomenon of peeling off the mold earlier than expected (for example, during polymerization of monomers for optical materials)), the polymerizable composition of this disclosure preferably contains at least one organic acid with a pKa of 3 or less.

[0040] Examples of organic acids with a pKa of 3 or less include hydrochloric acid (pKa: -3.7), sulfuric acid (pKa: -3.0), nitric acid (pKa: -1.4), and sulfonic acids with a pKa of 3 or less. Examples of sulfonic acids with a pKa of 3 or less include 10-camphor sulfonic acid (pKa: 1.2), methanesulfonic acid (pKa: -2.6), p-toluenesulfonic acid (pKa: -2.8), vinylsulfonic acid (pKa: -2.7), and benzenesulfonic acid (pKa: 0.7). Among these, 10-camphor sulfonic acid, methanesulfonic acid, or p-toluenesulfonic acid are preferred.

[0041] The content of organic acids with a pKa of 3 or less in the polymerizable composition is preferably 0.005% to 1% by mass, more preferably 0.01% to 0.5% by mass, and even more preferably 0.01% to 0.2% by mass, based on the total amount of the polymerizable composition.

[0042] <Other Components> The polymerizable composition of the present disclosure may contain other components in addition to the components described above. Examples of other components include a release agent, an ultraviolet absorber, a bluing agent, a photochromic compound, and the like.

[0043] (Release Agent) Examples of the release agent include an acidic phosphate ester. Examples of the acidic phosphate ester include a phosphoric acid monoester and a phosphoric acid diester, and they can be used alone or in combination of two or more. The content of the release agent in the polymerizable composition is preferably 0.005% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and still more preferably 0.01% by mass to 0.2% by mass with respect to the total amount of the polymerizable composition.

[0044] (Ultraviolet Absorber) Examples of the ultraviolet absorber include, for example: benzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone; triazine-based ultraviolet absorbers such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-4-methylphenol and 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol; and the like. Preferably, benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol and 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol are mentioned. These ultraviolet absorbers can be used alone or in combination of two or more. The content of the ultraviolet absorber in the polymerizable composition is preferably 0.01% by mass to 8% by mass, more preferably 0.1% by mass to 6% by mass, and still more preferably 0.2% by mass to 4% by mass with respect to the total amount of the polymerizable composition.

[0045] (Bluing agent) As the bluing agent, those having an absorption band in the wavelength range from orange to yellow in the visible light region and having a function of adjusting the hue of an optical material made of resin can be mentioned. More specifically, the bluing agent includes substances showing blue to purple.

[0046] (Photochromic compound) A photochromic compound is a compound whose molecular structure changes reversibly by irradiation with light of a specific wavelength, and accordingly, its light absorption characteristics (absorption spectrum) change. Examples of the photochromic compound include compounds whose light absorption characteristics (absorption spectrum) change with respect to light of a specific wavelength.

[0047] The viscosity of the polymerizable composition of the present disclosure, when measured by a B-type viscometer under the conditions of 25°C and 60 rpm, is preferably 10 mPa·s to 1000 mPa·s, more preferably 100 mPa·s to 900 mPa·s, and still more preferably 400 mPa·s to 800 mPa·s. When the viscosity is 10 mPa·s or more, it is advantageous in that the curing time of the polymerizable composition can be further shortened. When the polymerizable composition contains the aforementioned prepolymer, the viscosity of the polymerizable composition is more likely to increase. When the viscosity is 1000 mPa·s or less, it is advantageous in terms of the handling of the polymerizable composition (for example, ease of casting into a mold).

[0048] Here, the viscosity of the polymerizable composition means the viscosity measured within 30 minutes from the time when all the materials for producing the polymerizable composition are mixed for 5 minutes under the conditions of 25°C and 60 rpm.

[0049] <Method for producing polymerizable composition> The method for producing the polymerizable composition of the present disclosure is not particularly limited, and a known method of putting each component into a container and mixing them can be applied.

[0050] (Production method A) Hereinafter, a preferred production method when the polymerizable composition of the present disclosure contains a prepolymer is shown as production method A.

[0051] Method A comprises a preparation step of preparing a total of 100 parts by mass of two or more different monomers for optical materials and a total of 0.01 to 2.5 parts by mass (more preferably 0.01 to 1 part by mass, even more preferably 0.01 to 0.5 parts by mass, and even more preferably 0.01 to 0.2 parts by mass) of two or more nitrogen-containing aromatic heterocyclic compound catalysts, and a prepolymerization step of mixing a portion of the two or more different monomers for optical materials with at least a portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

[0052] The preparation steps in Method A involve two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts, which are as described above. The preparation steps in Method A may also involve the preparation of materials other than two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts. These materials may refer to the components in the polymerizable composition already described.

[0053] The prepolymerization step in manufacturing method A is a step of obtaining a mixture containing a prepolymer by mixing a portion of two or more different monomers for optical materials and at least a portion of two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a prepolymer. The mixing time for obtaining the prepolymer (i.e., the prepolymerization time) is preferably 0.1 hours to 10 hours, more preferably 0.2 hours to 5 hours, and even more preferably 0.5 hours to 2 hours. The temperature of the mixture during mixing to obtain the prepolymer (i.e., the prepolymerization temperature) is preferably 30°C to 80°C, more preferably 35°C to 60°C, and even more preferably 40°C to 50°C.

[0054] Here, a portion of two or more different optical material monomers may be the sum of portions of each type of optical material monomer, or it may be the sum of a portion of one or more optical material monomers and the total amount of the remaining types of optical material monomers. The same applies to a portion of two or more nitrogen-containing aromatic heterocyclic compound catalysts.

[0055] (Manufacturing Method XA) Next, we will describe Manufacturing Method XA, which is a more preferred embodiment of Manufacturing Method A. Method XA comprises: a preparation step of preparing a total of 100 parts by mass of two or more different monomers for optical materials and a total of 0.01 to 2.5 parts by mass of two or more nitrogen-containing aromatic heterocyclic compound catalysts; a first prepolymerization step of mixing a portion of the two or more different monomers for optical materials and a portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a first prepolymer which is a polymer containing polymerizable functional groups, thereby obtaining a first liquid containing the first prepolymer; a second prepolymerization step of mixing the remaining portion of the two or more different monomers for optical materials and the remaining portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the remaining portion of the two or more different monomers for optical materials to obtain a second prepolymer which is a polymer containing polymerizable functional groups, thereby obtaining a second liquid containing the second prepolymer; and a step of mixing the first liquid and the second liquid to obtain a polymerizable composition for optical materials. Includes.

[0056] Method XA involves dividing the materials prepared in the preparation step into two parts (i.e., dividing two or more different monomers for optical materials into a "partial amount" and a "remainder," and dividing two or more nitrogen-containing aromatic heterocyclic compound catalysts into a "partial amount" and a "remainder"), and then carrying out a prepolymerization step on each of the two divided materials to produce a first liquid and a second liquid containing a prepolymer, respectively, and then mixing the first liquid and the second liquid to obtain a polymerizable composition (see Table 1 in the Examples below for specific examples).

[0057] According to manufacturing method XA, polymerizable compositions containing prepolymers are easier to produce. Furthermore, the cured product of the resulting polymerizable composition exhibits reduced air bubbles and discoloration.

[0058] The preparation steps in manufacturing method XA are the same as those in manufacturing method A.

[0059] The first prepolymerization step and the second prepolymerization step in manufacturing method XA are the same as the prepolymerization step in manufacturing method A.

[0060] In manufacturing method XA, it is preferable that the catalyst comprises two or more nitrogen-containing aromatic heterocyclic compound catalysts, including 3,5-lutidine and 2,6-lutidine, with the first solution containing at least a portion of the total amount of 2,6-lutidine and the second solution containing at least a portion of the total amount of 3,5-lutidine.

[0061] Here, the total amount of 2,6-lutidine refers to the total amount of 2,6-lutidine prepared in the preparation step. Similarly, the total amount of 3,5-lutidine refers to the total amount of 3,5-lutidine prepared in the preparation step.

[0062] The first solution preferably contains 2,6-lutidine. In this case, the first solution may or may not contain 3,5-lutidine. If the first solution contains 3,5-lutidine, the amount of 2,6-lutidine in the first solution is preferably greater than the amount of 3,5-lutidine, and the mass ratio of [3,5-lutidine / 2,6-lutidine] is more preferably less than 0.5, and even more preferably less than 0.1.

[0063] The second solution preferably contains 3,5-lutidine. In this case, the second solution may or may not contain 2,6-lutidine.

[0064] The first solution preferably contains at least one of an isocyanate compound and a polythiol compound as an optical material monomer. In this case, the mass content of the isocyanate compound in the first solution is preferably greater than the mass content of the polythiol compound, and the mass ratio [polythiol compound / isocyanate compound] is more preferably less than 0.8, and even more preferably less than 0.5.

[0065] The second liquid preferably contains at least one of an isocyanate compound and a polythiol compound as an optical material monomer. In this case, the content of the polythiol compound in the second liquid is preferably greater than the content of the isocyanate compound, and the content mass ratio [isocyanate compound / polythiol compound] is more preferably less than 0.8, and even more preferably less than 0.5.

[0066] The preparation step in manufacturing method XA may involve preparing materials other than two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts. These materials can refer to the components in the polymerizable composition already described. These materials may be included in either the first liquid or the second liquid, or in both.

[0067] [Optical Materials] The optical materials of this disclosure include cured products of the polymerizable compositions of this disclosure. The shape of the optical materials is not particularly limited and may be plate-shaped, cylindrical, rectangular, etc. Examples of optical materials include lenses (i.e., plastic lenses), prisms, optical fibers, information recording substrates, filters, light-emitting diodes, etc. Among these, lenses are preferred, and spectacle lenses are more preferred.

[0068] <Method for Manufacturing Optical Materials> There are no particular limitations on the method for manufacturing the optical materials of this disclosure. A cured polymerizable composition of this disclosure can be obtained, for example, by curing the polymerizable composition of this disclosure (i.e., polymerizing the monomers for optical materials in the polymerizable composition).

[0069] The following method is preferred for manufacturing the optical material of the present disclosure. Specifically, the preferred manufacturing method includes a casting step of pouring the polymerizable composition of the present disclosure into a mold, and a curing step of curing the polymerizable composition by polymerizing two or more different monomers for optical materials in the polymerizable composition in the mold.

[0070] For preferred manufacturing conditions, refer to International Publication No. 2021 / 153631 as appropriate.

[0071] For example, heating of the polymerizable composition is not necessarily required in the curing process, but it may be done. That is, the polymerizable composition can be cured by letting it stand during the curing process.

[0072] The environment in which the curing process is carried out is not particularly limited, and the mold can be heated and cured from outside the mold. However, from the viewpoint of improving optical quality such as striations and polymerization in a short time, it is preferable to cure the polymerizable composition by leaving it to stand in a closed system space. By leaving the polymerizable composition to stand in a closed system space, the heat generated by the self-heating of the polymerizable composition can be prevented from being released to the outside. As a result, the heat generated by self-heating can be retained in the closed system space, so the polymerization reaction can be promoted more efficiently and optical materials can be manufactured in a shorter time. An example of a closed system space is an insulated environment. An insulated environment refers to an environment in which heat is retained inside and heat conduction between the inside and outside is suppressed. An environment in which heat conduction between the inside and outside is suppressed means an environment in which, when the polymerizable composition is left to stand in a closed system space, the heat conductivity between the inside and outside of the closed system space is sufficient to cure the polymerizable composition.

[0073] An insulating environment can be created, for example, using insulating materials. That is, by placing a polymerizable composition in an insulating container made of insulating material, heat can be retained inside the insulating container, and heat conduction between the inside and outside can be suppressed.

[0074] The thermal conductivity of the insulating material is preferably 0.5 W / mK or less, more preferably 0.1 W / mK or less, and even more preferably 0.05 W / mK or less.

[0075] The density of the insulation material is 10 kg / m³. ３ Preferably, it is 15 kg / m ３ It is more preferable that the amount be greater than or equal to 20 kg / m ３ It is even more preferable that the above conditions are met.

[0076] In the aforementioned "thermal insulation" or "thermal insulation environment," it is preferable to heat the adiabatic reaction vessel to maintain a constant temperature (constant temperature reaction vessel) within a range that does not hinder the polymerization reaction due to the reaction heat of the polymerizable composition or excessively accelerate the polymerization reaction of the polymerizable composition by external heating. This allows the ambient temperature inside the reaction vessel (constant temperature reaction vessel) where the mold is placed to be maintained at a constant temperature or warmed state, depending on the temperature rise due to the self-heating of the monomer for optical materials, thereby promoting the polymerization reaction more effectively.

[0077] As an insulating environment, for example, an adiabatic reaction vessel or a constant-temperature reaction vessel can be used. For example, when a mold into which monomer has been injected is placed in a vacuum vessel which is an adiabatic reaction vessel, adiabatic polymerization in an insulating environment using an adiabatic reaction vessel (constant-temperature reaction vessel) can be carried out by the following procedure. The inner surface of the vacuum vessel is covered with a material that has insulating and heat-retaining properties such as urethane foam or cork, and the mold into which the monomer has been injected is wrapped in a material such as a cloth as needed. Then, the mold into which the monomer has been injected is placed in the vacuum vessel.

[0078] The curing step may be a process in which the polymerizable composition is cured by allowing it to stand without external heating. As mentioned above, heating of the polymerizable composition is not necessarily required in curing. Furthermore, the curing step may involve both curing in an insulated environment and heat curing.

[0079] The curing step is preferably a step in which the polymerizable composition is cured by letting it stand for 1 to 10 hours (more preferably 1 to 8 hours).

[0080] In the curing process, a microwave irradiation step may be provided, if necessary, in which the polymerizable composition is irradiated with microwaves for a predetermined time.

[0081] One embodiment of the curing process includes the following steps a and b: Step a: The polymerizable composition is injected (cast) into the mold (into the cavity of the mold). Step b: The mold containing the polymerizable composition is left to stand in a closed space for a predetermined time to undergo adiabatic polymerization.

[0082] (Step a) First, the polymerizable composition is injected into a molding mold (casting mold) held in place by a gasket or tape. At this time, depending on the physical properties required of the resulting optical material, it is preferable to perform degassing treatment under reduced pressure, filtration treatment under pressure or reduced pressure, etc., as necessary.

[0083] (Step b) The polymerization conditions are not limited, but it is preferable to adjust them as appropriate depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc. Polymerization may also be carried out by leaving the mold into which the polymerizable composition has been injected in an insulated environment for 1 to 4 hours.

[0084] In step b, if necessary, a heating step may be added after the adiabatic polymerization process, in which the mold into which the polymerizable composition is injected is left to stand in an adiabatic environment for a certain period of time. In step b, if necessary, in parallel with the step of leaving the mold into which the polymerizable composition is injected in an adiabatic environment (adiabatic polymerization), the mold into which the polymerizable composition is injected may be heated continuously or intermittently at a temperature that does not exceed the self-heating generated by the polymerizable composition in the adiabatic polymerization process, or the inside of the adiabatic reaction vessel may be heated to maintain the ambient temperature inside the adiabatic reaction vessel.

[0085] <Annealing Step> The method for producing the optical material of the present disclosure may optionally include an annealing step of annealing the cured polymerizable composition (i.e., the cured product). The temperature for annealing is usually 50 to 150°C, but is preferably 90 to 140°C, and more preferably 100 to 130°C.

[0086] Hereinafter, an embodiment of the present disclosure will be specifically described by reference to examples, but the present disclosure is not limited to these examples. Hereinafter, "catalyst" means a nitrogen-containing aromatic heterocyclic compound catalyst, "polymerizable composition" means a polymerizable composition for optical materials, and "monomer" means a monomer for optical materials.

[0087] [Example 1] <Production of Polymerizable Composition> (Production of the First Solution) A mixture was prepared by charging 0.13 parts by mass of "JP-506H" (butoxyethyl acid phosphate) [internal release agent] manufactured by Johoku Chemical Industry Co., Ltd., 1.5 parts by mass of Tinuvin 329 [ultraviolet absorber, benzotriazole type], and 46.8 parts by mass of m-xylylene diisocyanate (XDI) [monomer]. This mixture was stirred at 25°C for 1 hour to completely dissolve the substances. Then, 10.56 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter referred to as "thiol T1") [monomer] into this mixture and stirring at 25°C for 5 minutes to obtain a homogeneous solution. Furthermore, the obtained homogeneous solution was mixed with the catalyst described in Table 1 in the amount described in Table 1 (specifically, parts by mass per 100 parts by mass of monomer in the first liquid) and stirred at 40°C for 1 hour to polymerize a portion of the monomer and obtain a mixture 1 containing a prepolymer. The refractive index and viscosity of the mixture containing the prepolymer are shown in Table 1. The formation of the prepolymer was confirmed by using a liquid refractometer RA600 manufactured by Kyoto Electronics Manufacturing Co., Ltd., and confirming that the refractive index of the prepolymer was 1.59. Next, the mixture 1 containing the prepolymer was degassed at 400 Pa and 25°C for 1 hour to obtain the first liquid.

[0088] (Preparation of the second solution) 5.2 parts by mass of m-xylylene diisocyanate (XDI) [monomer] and 37.44 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (thiol T1) [monomer] were stirred at 25°C for 5 minutes to obtain a homogeneous solution. Furthermore, the catalysts listed in Table 1 were added to the obtained homogeneous solution in the amounts listed in Table 1 (specifically, parts by mass per 100 parts by mass of monomer in the second solution) and stirred at 40°C for 1 hour to polymerize a portion of the monomer for optical materials, thereby obtaining a mixture 2 containing a prepolymer. The refractive index and viscosity of the mixture containing the prepolymer are shown in Table 1. The formation of the prepolymer was confirmed by using a liquid refractometer RA600 manufactured by Kyoto Electronics Manufacturing Co., Ltd., and confirming that the refractive index of the prepolymer was 1.64. Next, the mixture 2 containing the prepolymer was degassed at 400 Pa and 25°C for 1 hour to obtain the second solution.

[0089] (Preparation of Polymerizable Composition) The first liquid and the second liquid described above were mixed for 5 minutes at 25°C and 60 rpm to obtain a polymerizable composition. The viscosity of the obtained polymerizable composition was measured using a B-type viscometer at 25°C and 60 rpm. The viscosity measurement was performed within 30 minutes from the time the first liquid and the second liquid were mixed for 5 minutes at 25°C and 60 rpm.

[0090] <Manufacturing of Cured Products> The polymerizable composition whose viscosity was measured above was stirred in a stationary mixer at 25°C and 60 rpm for 5 minutes, and then transferred to a casting mold (i.e., a mold) while continuing to stir. Specifically, this transfer was carried out by injecting the polymerizable composition into the cavity of the casting mold at a rate of 5 g / second while filtering it through a 1 μm PTFE filter. The mold used consisted of a 78 mm diameter, 4-curve glass upper mold and a 78 mm diameter, 4-curve glass lower mold, and had a cavity for lens production with a center thickness of 10 mm. The mold into which the polymerizable composition was poured (hereinafter referred to as "cast product") was heated and subjected to thermal polymerization at 120°C for 4 hours. Next, the cured polymerizable composition was released from the mold, and the removed cured product was annealed at 120°C for 2 hours to obtain a lens, which was an annealed cured product.

[0091] <Evaluation> The following evaluations were conducted on the obtained lenses or during the lens manufacturing process. The results are shown in Table 1.

[0092] (Color) The lens was visually inspected to confirm its color.

[0093] (Structure) The lens was projected using an ultra-high pressure mercury lamp (light source model OPM-252HEG: manufactured by Ushio Inc.), and the transmitted image was observed visually and evaluated according to the following criteria: A: No striae were observed, or striae were not clearly observed. B: Slight striae were observed, but the product was generally acceptable. C: Many striae were observed, and the product was unacceptable.

[0094] (Air bubbles in the lens) The lens was visually inspected, and the amount of air bubbles in the lens was evaluated according to the following evaluation criteria. In the following evaluation criteria, rank A represents the best suppression of air bubble generation. -Evaluation criteria for air bubbles in the lens- A. No air bubbles were observed throughout the entire lens. B. Air bubbles were observed in the peripheral part of the lens, but not in the center of the lens. C. Air bubbles were observed throughout the entire lens.

[0095] (Release Properties) The release properties of the hardened material when removing it from the casting mold were evaluated according to the following criteria: A: It peeled off without applying any force. B: It peeled off when force was applied. C: It peeled off when force was applied, but there was a possibility of damage to the casting mold or the hardened material. D: It did not peel off even when force was applied, and the hardened material could not be removed.

[0096] [Examples 2-3, Comparative Examples 1-2] The same procedure as in Example 1 was followed, except that the composition of at least one of the first and second solutions and the polymerization time were changed as shown in Table 1. The results are shown in Table 1.

[0097] In Table 1, CSA, which is an organic acid, refers to 10-camphor sulfonic acid (pKa: 1.2).

[0098]

[0099] As shown in Table 1, in Examples 1 to 3, where the polymerizable composition contained two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts, and two or more different monomers for optical materials contained isocyanate compounds containing aromatic rings, an optical material (in this case, a lens) with suppressed color and bubbles was obtained as the cured product of the polymerizable composition. In contrast, in Comparative Examples 1 and 2, where the polymerizable composition contained only one nitrogen-containing aromatic heterocyclic compound catalyst, color or bubbles occurred in the resulting lenses. In Comparative Example 1, striations also occurred, and the release properties were reduced.

[0100] The disclosure of Japanese Patent Application No. 2025-008235, filed on 21 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 for optical materials comprising two or more different monomers for optical materials and two or more nitrogen-containing aromatic heterocyclic compound catalysts, wherein the two or more different monomers for optical materials include isocyanate compounds containing aromatic rings.

2. The polymerizable composition for optical materials according to claim 1, wherein each of the two or more nitrogen-containing aromatic heterocyclic compound catalysts comprises a nitrogen-containing aromatic heterocyclic ring having two substituents.

3. The polymerizable composition for optical materials according to claim 1, wherein the two or more nitrogen-containing aromatic heterocyclic compound catalysts include 3,5-lutidine and 2,6-lutidine.

4. The polymerizable composition for optical materials according to claim 3, wherein the mass ratio of [2,6-lutidine / 3,5-lutidine] is greater than 1.

5. The polymerizable composition for optical materials according to claim 3, wherein the mass ratio of [2,6-lutidine / 3,5-lutidine] is 3 to 20.

6. The polymerizable composition for optical materials according to claim 1, further comprising an organic acid with a pKa of 3 or less.

7. The polymerizable composition for optical materials according to claim 1, wherein the viscosity measured by a B-type viscometer at 25°C and 60 rpm is 10 mPa·s to 1000 mPa·s.

8. The polymerizable composition for optical materials according to claim 1, wherein the total content of the two or more nitrogen-containing aromatic heterocyclic compound catalysts per 100 parts by mass of the total amount of the polymerizable composition for optical materials is 0.01 parts by mass to 2.5 parts by mass.

9. The polymerizable composition for optical materials according to claim 1, which does not contain tin element, or if it does contain tin element, the tin element content is 10 ppm by mass or less.

10. The polymerizable composition for optical materials according to claim 1, wherein the two or more different monomers for optical materials further comprises at least one active hydrogen compound A selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound containing one or more mercapto groups and one or more hydroxyl groups, a polyol compound containing two or more hydroxyl groups, and an amine compound.

11. The polymerizable composition for optical materials according to claim 1, wherein the isocyanate compound containing the aromatic ring comprises at least one selected from m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and m-phenylene diisocyanate.

12. The polymerizable composition for optical materials according to claim 1, further comprising a prepolymer which is a polymer containing polymerizable functional groups in at least a portion of the total amount of the two or more different monomers for optical materials.

13. A method for producing a polymerizable composition for optical materials according to claim 12, comprising: a preparation step of preparing a total of 100 parts by mass of two or more different monomers for optical materials and a total of 0.01 to 2.5 parts by mass of two or more nitrogen-containing aromatic heterocyclic compound catalysts; and a prepolymerization step of mixing a portion of the two or more different monomers for optical materials with at least a portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a prepolymer, thereby obtaining a mixture containing the prepolymer.

14. A method for producing a polymerizable composition for optical materials according to claim 12, comprising: a preparation step of preparing a total of 100 parts by mass of two or more different monomers for optical materials and a total of 0.01 to 2.5 parts by mass of two or more nitrogen-containing aromatic heterocyclic compound catalysts; a first prepolymerization step of mixing a portion of the two or more different monomers for optical materials and a portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the portion of the two or more different monomers for optical materials to obtain a first prepolymer which is a polymer containing polymerizable functional groups, thereby obtaining a first liquid containing the first prepolymer; a second prepolymerization step of mixing the remaining portion of the two or more different monomers for optical materials and the remaining portion of the two or more nitrogen-containing aromatic heterocyclic compound catalysts, and polymerizing at least a portion of the remaining portion of the two or more different monomers for optical materials to obtain a second prepolymer which is a polymer containing polymerizable functional groups, thereby obtaining a second liquid containing the second prepolymer; A method for producing a polymerizable composition for optical materials, comprising the step of mixing the first liquid and the second liquid to obtain the polymerizable composition for optical materials.

15. The method for producing a polymerizable composition for optical materials according to claim 14, wherein the two or more nitrogen-containing aromatic heterocyclic compound catalysts include 3,5-lutidine and 2,6-lutidine, the first liquid contains at least a portion of the total amount of 2,6-lutidine, and the second liquid contains at least a portion of the total amount of 3,5-lutidine.

16. An optical material comprising a cured product of a polymerizable composition for optical materials according to any one of claims 1 to 12.

17. The optical material according to claim 16, which is a lens.

18. A method for producing an optical material according to claim 16, comprising: a casting step of pouring the polymerizable composition for optical materials into a mold; and a curing step of curing the polymerizable composition for optical materials by polymerizing the two or more different monomers for optical materials in the polymerizable composition for optical materials in the mold.

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