Method for producing optical material, and polymerizable composition for optical material

Abstract

A method for producing an optical material according to the present disclosure comprises: a step for preparing a polymerizable composition for an optical material having a hue in which L * is 70 or more and b * is-30 to 10 (inclusive) in a CIE1976 (L *, a *, b *) color space when measured at a thickness of 10 mm by mixing a resin monomer for an optical material and an additive; and a step for polymerizing and curing the polymerizable composition for optical materials.

Description

[0001] This application is a divisional application of an invention patent application with an application date of March 27, 2020, application number 202080022964.X (PCT / JP2020 / 014270), and invention name “Method for producing optical material, polymerizable composition for optical material”. Technical Field

[0002] The present disclosure relates to a method for producing an optical material and a polymerizable composition for an optical material. Background Art

[0003] Plastic lenses are lighter and less prone to breakage than inorganic lenses, and can be dyed. Therefore, in recent years, plastic lenses have rapidly become popular in optical materials such as eyeglass lenses and camera lenses.

[0004] Resins constituting lenses used as optical materials are required to be less colored and transparent in view of their use.

[0005] Patent Document 1 discloses a method for producing a sulfur-containing monomer for an optical material having a preferred hue by adjusting the hue of a raw material.

[0006] Patent Document 1: Japanese Patent Application Publication No. 2006-284920 Summary of the invention

[0007] Problems to be solved by the invention

[0008] Resins for optical materials are generally prepared by mixing monomers and additives such as ultraviolet absorbers and hue adjusters to prepare a polymerizable composition, and then polymerizing and curing the composition. However, due to the influence of additives, the hue of the polymerizable composition for optical materials may change, and therefore, it may be impossible to produce a resin for optical materials having a desired hue.

[0009] It should be noted that Patent Document 1 does not disclose the influence of additives such as ultraviolet absorbers and hue adjusters on the hue of monomers and polymerizable compositions, nor does it disclose changes in hue during the polymerization and curing process.

[0010] Means for solving problems

[0011] The inventors of the present application conducted in-depth research and found a correlation between the hue of a polymerizable composition for optical materials before polymerization and curing and the hue of a resin for optical materials after polymerization and curing, thereby completing a method for obtaining a resin for optical materials with good hue and a polymerizable composition for optical materials adjusted to a specified hue.

[0012] That is, the present disclosure can be as follows.

[0013] <1> A method for producing an optical material, comprising the following steps:

[0014] A step of mixing an optical material resin monomer and an additive to prepare an optical material polymerizable composition having a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm; and

[0015] A step of polymerizing and curing the optical material polymerizable composition to obtain a cured product having a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0016] <2> A method for producing an optical material, comprising the following steps:

[0017] A step of mixing an optical material resin monomer and an additive to prepare a polymerizable composition for an optical material having a hue of YI of -70 or more and 20 or less; and

[0018] A step of polymerizing and curing the optical material polymerizable composition to obtain a cured product having a hue of -70 or more and 20 or less.

[0019] <3> A method for producing an optical material as described in <2>, wherein the polymerizable composition for optical material has a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm, and for the step of obtaining the cured product, has a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0020] <4> The method for producing an optical material according to any one of <1> to <3>, wherein the additive comprises an ultraviolet absorber and a hue adjuster, and the step of preparing the polymerizable composition for an optical material comprises:

[0021] A step of adjusting the hue of the polymerizable composition for an optical material using the hue adjusting agent.

[0022] <5> The method for producing an optical material according to <4>, wherein the ultraviolet absorber comprises a benzotriazole compound represented by the following general formula (1).

[0023] [Chemical formula 1]

[0024]

[0025] (In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms, or a halogen atom. m represents an integer of 0 to 3, n represents an integer of 0 to 3, p represents an integer of 0 to 1, and p R3 each independently represents a functional group having 2 to 15 carbon atoms including an ester bond.)

[0026] <6> The method for producing an optical material according to <5>, wherein the benzotriazole compound is at least one selected from the group consisting of 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-ethylphenyl)-5-chloro-2H-benzotriazole, 2-(4-ethoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, and 2-(4-butoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole.

[0027] <7> The method for producing an optical material according to any one of <4> to <6>, wherein the hue adjusting agent is a bluing agent.

[0028] <8> The method for producing an optical material according to any one of <1> to <7>, wherein the optical material resin monomer comprises at least one selected from the group consisting of:

[0029] a combination of an isocyanate compound (A) and at least one active hydrogen compound (B) selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, a polyol compound having two or more hydroxyl groups, and an amine compound,

[0030] an episulfide compound (C), and

[0031] A combination of an episulfide compound (C) and a polythiol compound.

[0032] <9> The method for producing an optical material according to <8>, wherein the isocyanate compound (A) comprises at least one selected from the group consisting of aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and aromatic aliphatic isocyanate compounds.

[0033] <10> The method for producing an optical material as described in <9>, wherein the isocyanate compound (A) comprises at least one selected from the group consisting of xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, bis(isocyanatecyclohexyl)methane, 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, and isophorone isocyanate.

[0034] <11> The method for producing an optical material according to <8>, wherein the polythiol compound comprises an ester 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, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2 ,5-bis(mercaptomethyl)-1,4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0035] <12> The method for producing an optical material according to <8>, wherein the episulfide compound (C) is at least one selected from the group consisting of bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide, and bis(2,3-epithiopropylthio)methane.

[0036] <13> The method for producing an optical material as described in any one of <1> to <12>, wherein the polymerizable composition for optical material has a hue of L* of 70 or more and b* of -30 or more and 5 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0037] <14> A method for producing an optical material as described in any one of <1> to <13>, wherein the cured product has a hue of L* greater than 70 and b* greater than -25 and less than 10 in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0038] <15> A polymerizable composition for an optical material, comprising an optical material resin monomer and an additive, wherein the composition has a hue of 70 or more and a b* of -30 or more and 10 or less in the CIE 1976 (L*, a*, b*) color space.

[0039] <16> A polymerizable composition for an optical material, comprising a resin monomer for an optical material and an additive, wherein YI is -70 or more and 20 or less.

[0040] <17> The polymerizable composition for an optical material according to <16>, wherein L* is 70 or more and b* is -30 or more and 10 or less in a CIE1976 (L*, a*, b*) color space.

[0041] <18> The polymerizable composition for an optical material according to any one of <15> to <17>, wherein the additive includes an ultraviolet absorber and a hue adjuster.

[0042] <19> The polymerizable composition for an optical material according to <18>, wherein the ultraviolet absorber comprises a benzotriazole compound represented by the following general formula (1).

[0043] [Chemical formula 2]

[0044]

[0045] (In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms, or a halogen atom. m represents an integer of 0 to 3, n represents an integer of 0 to 3, p represents an integer of 0 to 1, and p R3 each independently represents a functional group having 2 to 15 carbon atoms including an ester bond.)

[0046] <20> The polymerizable composition for an optical material according to <19>, wherein the benzotriazole compound is selected from 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole At least one of the group consisting of 2-(3-tert-butyl-5-octyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-ethylphenyl)-5-chloro-2H-benzotriazole, 2-(4-ethoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, and 2-(4-butoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole.

[0047] <21> The polymerizable composition for an optical material according to any one of <18> to <20>, wherein the hue adjusting agent is a bluing agent.

[0048] <22> A polymerizable composition for an optical material as described in any one of <15> to <21>, wherein the resin monomer for an optical material comprises an isocyanate compound (A) and at least one active hydrogen compound (B) selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, a polyol compound having two or more hydroxyl groups, and an amine compound.

[0049] <23> The polymerizable composition for an optical material according to <22>, wherein the isocyanate compound (A) comprises at least one selected from the group consisting of aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, and aromatic aliphatic isocyanate compounds.

[0050] <24> The polymerizable composition for an optical material as described in <22> or <23>, wherein the isocyanate compound (A) comprises at least one selected from the group consisting of xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, bis(isocyanatecyclohexyl)methane, 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, and isophorone isocyanate.

[0051] <25> The polymerizable composition for an optical material according to <22>, wherein the polythiol compound comprises a compound 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, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), At least one of the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiacyclohexane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0052] <26> The polymerizable composition for an optical material according to any one of <15> to <25>, which has a hue of L* of 70 or more and b* of -30 or more and 5 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0053] It should be noted that the hue of the polymerizable composition for an optical material in the present disclosure refers to the hue of the polymerizable composition for an optical material before it is polymerized and cured.

[0054] Effects of the Invention

[0055] According to the production method of the present disclosure, an optical material having a good hue can be obtained by using a polymerizable composition for an optical material having a desired hue. DETAILED DESCRIPTION

[0056] In the present disclosure, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0057] In the present disclosure, when the amount of each component in the composition contains a plurality of substances belonging to each component, unless otherwise specified, it means the total amount of the plurality of substances present in the composition.

[0058] In the numerical ranges recorded in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in this disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiments.

[0059] Hereinafter, the method for producing the optical material of the present disclosure will be specifically described with reference to the first embodiment and the second embodiment.

[0060] <First embodiment>

[0061] The method for producing an optical material according to the present embodiment includes the following steps.

[0062] Step 1: An optical material resin monomer and an additive are mixed to prepare an optical material polymerizable composition having a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0063] Step 2: The optical material polymerizable composition is polymerized and cured to obtain a cured product having a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0064] By controlling the hue of the polymerizable composition for an optical material, an optical material having a good hue can be obtained.

[0065] (Process 1)

[0066] In this step, from the viewpoint of the effects of the present disclosure, the polymerizable composition for an optical material has an L* of 70 or more, preferably 75 or more, and more preferably 80 or more in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0067] In this step, from the viewpoint of the effects of the present disclosure, the polymerizable composition for an optical material has a hue of b* of -30 to 10, preferably b* of -30 to 5, more preferably b* of -27 to 3, and even more preferably b* of -10 to 1 in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0068] In order to obtain a polymerizable composition for an optical material having the above-mentioned hue, this step preferably includes a step of mixing an optical material resin monomer and an additive to adjust the hue.

[0069] [additive]

[0070] The additive is not particularly limited as long as it is dispersible or soluble in the resin constituting the lens, and a conventionally known resin additive can be used.

[0071] Examples of additives in this embodiment include polymerization catalysts, internal mold release agents, ultraviolet absorbers, chain extenders, crosslinking agents, light stabilizers, antioxidants, oil-soluble dyes, fillers, and adhesion improvers, and these can be appropriately selected and used as needed.

[0072] In this embodiment, from the viewpoint of suppressing the coloring of the resin due to ultraviolet rays, it is preferable to use an ultraviolet absorber or the like as an additive, and in order to suppress the change in hue of the resin due to the addition of the ultraviolet absorber or the like, it is preferable to use a hue adjuster.

[0073] The ultraviolet absorber (a) can be used in an amount capable of suppressing coloration of the resin, and the hue adjuster (b) can be used to adjust the hue of the resin changed by the addition of the ultraviolet absorber (a) to the above hue.

[0074] Regarding the weight ratio (b / a) of the hue adjuster (b) and the ultraviolet absorber (a) contained in the polymerizable composition for optical materials, although the range varies depending on the resin constituting the lens, the hue adjuster (a) and the ultraviolet absorber (b), the weight ratio (b / a) can be greater than 30 and less than 50,000, preferably greater than 70 and less than 40,000, and more preferably greater than 100 and less than 30,000.

[0075] [Ultraviolet light absorber (a)]

[0076] The ultraviolet absorber (a) can be selected from the known ultraviolet absorbers, as long as it can achieve the effect of the present disclosure. The ultraviolet absorber (a) can include, for example, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, benzotriazole ultraviolet absorbers, etc., preferably benzotriazole ultraviolet absorbers.

[0077] As the benzotriazole-based ultraviolet absorber, from the viewpoint of the effects of the present disclosure, it is preferred that the benzotriazole compound represented by the following general formula (1) is contained.

[0078] [Chemical formula 3]

[0079]

[0080] In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms or a halogen atom. m represents an integer of 0 to 3, n represents an integer of 0 to 3, p represents an integer of 0 to 1, and p R3 each independently represent a functional group having 2 to 15 carbon atoms including an ester bond.

[0081] Examples of the benzotriazole compound represented by the general formula (1) include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(5-octylpropionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(5-methylpropionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-octylpropionate)- 2-(2-hydroxy-5-tert-butylphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-ethylphenyl)-5-chloro-2H-benzotriazole, 2-(4-ethoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(4-butoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(5-tert-octyl-3-(phenylpropane-2- 2-(5-tert-butyl-3-(phenylpropane-2-yl)-2-hydroxyphenyl)benzotriazole, 2-(5-methyl-3-(phenylpropane-2-yl)-2-hydroxyphenyl)benzotriazole, 2-(5-octyl propionate-2-hydroxyphenyl)benzotriazole, 2-(5-tert-octyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, At least one selected from the group consisting of 2-(3,5-bis(phenylpropane-2-yl)-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(4-octyloxy-2-hydroxyphenyl)benzotriazole, 2-(5-methyl-3-n-dodecyl-2-hydroxyphenyl)benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole can be used.

[0082] The benzotriazole compound is preferably at least one selected from the group consisting of 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-ethylphenyl)-5-chloro-2H-benzotriazole, 2-(4-ethoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(4-butoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, and 2-(3-tert-butyl-5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole.

[0083] [Hue Adjuster (b)]

[0084] As the hue adjusting agent (b), any hue adjusting agent can be selected from conventionally known hue adjusting agents as long as it can achieve the effects of the present disclosure.

[0085] Examples of the hue adjusting agent include anthraquinone dyes, perinone dyes, monoazo dyes, disazo dyes, and phthalocyanine dyes, and these dyes may be used alone or in combination of two or more.

[0086] Examples of anthraquinone dyes include Solvent Blue 36 (1,4-bis(isopropylamino)anthracene-9,10-dione), Solvent Blue 63 (1-(methylamino)-4-(m-tolylamino)anthracene-9,10-dione), Solvent Blue 94 (1-amino-2-bromo-4-(phenylamino)anthracene-9,10-dione), Solvent Blue 97 (1,4-bis((2,6-diethyl-4-methylphenyl)amino)anthracene-9,10-dione), Solvent Blue 104 (1,4-bis(mesitylamino)anthracene-9,10-dione), Solvent Violet 13 (1-hydroxy-4-(p-tolylamino)anthracene-9,10-dione), Solvent Green 3 (1,4-bis(p-tolylamino)anthracene-9,10-dione), Solvent Red 52 (3-methyl-6-(p-tolylamino)-3H-naphtho[1,2,3-de]quinoline-2,7-dione), Solvent Red 168 or Plast Red 8320 (1-(cyclohexylamino)anthracene-9,10-dione), Solvent Red 207 (1,5-bis(cyclohexylamino)anthracene-9,10-dione), Disperse Red 22 (1-(phenylamino)anthracene-9,10-dione), Disperse Red 60 (1-amino-4-hydroxy-2-phenoxyanthracene-9,10-dione), Solvent Violet 59 (1,4-diamino-2,3-diphenylanthracene-9,10-dione), Solvent Green 28 (1,4-bis((4-butylphenyl)amino)-5,8-dihydroxyanthracene-9,10-dione), Plast Blue 8514 (1-hydroxy-4-[(4-methylphenyl)amino]-9,10-anthracenedione), etc.

[0087] Among the above, as the anthraquinone dye, Solvent Blue 36, Solvent Blue 94, Plast Red 8320, and Plast Blue 8514 are preferred.

[0088] Examples of perinone dyes include Solvent Orange 60 (12H-isoindole[2,1-a] pyridine-12-one), Solvent Orange 78, Solvent Orange 90, Solvent Red 135 (8,9,10,11-tetrachloro-12H-isoindole[2,1-a] pyridine-12-one), Solvent Red 162, Solvent Red 179 (14H-benzo[4,5]isoquinoline[2,1-a] Pyridine-14-one) etc.

[0089] Examples of the monoazo dye include Solvent Red 195, Fast Orange R, Oil Red, and Oil Yellow.

[0090] Examples of disazo dyes include Chicago Sky Blue. Blue 6B (sodium 6,6'-((1E,1'E)-(3,3'-dimethoxy-[1,1'-biphenyl]-4,4'-diyl)bis(diazene-2,1-diyl))bis(4-amino-5-hydroxynaphthalene-1,3-disulfonic acid)), Evans Blue (sodium 6,6'-((1E,1'E)-(3,3'-dimethyl-[1,1'-biphenyl]-4,4'-diyl)bis(diazene-2,1-diyl))bis(4-amino-5-hydroxynaphthalene-1,3-disulfonic acid)), Direct Blue 15 (3,3'-((1E,1'E)-(3,3'-dimethoxy-[1,1'-biphenyl]-4,4'-diyl)bis(diazene-2,1-diyl))bis(5-amino-4 -hydroxynaphthalene-2,7-disulfonic acid) sodium), trypan blue (3,3'-((1E, 1'E)-(3,3'-dimethyl-[1,1'-biphenyl]-4,4'-diyl)bis(diazene-2,1-diyl))bis(5-amino-4-hydroxynaphthalene-2,7-disulfonic acid) sodium), phenazine 4B (3,3'-((1E, 1'E)-(3,3'-dimethyl-[1,1'-biphenyl]-4,4'-diyl)bis(diazene-2,1-diyl))bis(4-aminonaphthalene-1-sulfonic acid) sodium), Congo red (3,3'-((1E, 1'E)-[1,1'-biphenyl]-4,4'-diylbis(diazene-2,1-diyl))bis(4-aminonaphthalene-1-sulfonic acid) sodium), etc.

[0091] Examples of the phthalocyanine dye include CI Direct Blue 86 and CI Direct Blue 199.

[0092] From the viewpoint of the effects of the present disclosure, the hue adjusting agent (b) preferably comprises at least one selected from the group consisting of Solvent Blue 36, Solvent Blue 94, Solvent Blue 97, Solvent Blue 104, Solvent Violet 59, Solvent Red 195, Disperse Red 60, Solvent Green 28, Solvent Orange 60, Plast Red 8320, and Plast Blue 8514.

[0093] More preferably, at least one selected from the group consisting of Solvent Blue 36, Solvent Blue 94, Plast Red 8320, and Plast Blue 8514 is contained.

[0094] The hue adjusting agents (b) listed above may be used alone or in combination of two or more.

[0095] In the present embodiment, as the hue adjusting agent, a bluing agent is preferably used among these. The bluing agent has an absorption band in the wavelength range from orange to yellow in the visible light region and has a function of adjusting the hue of an optical material formed of a resin.

[0096] Examples of the bluing agent include Plast Blue 8514, Solvent Blue 36, Solvent Blue 94, Solvent Blue 97, Solvent Blue 104, Plast Red 8320, Solvent Red 207, Disperse Red 22, and Disperse Red 60.

[0097] From the viewpoint of the effects of the present disclosure, the bluing agent preferably comprises at least one selected from the group consisting of Plast Blue 8514, Solvent Blue 36, Solvent Blue 94, Solvent Blue 97, Solvent Blue 104, Plast Red 8320, and Disperse Red 22.

[0098] More preferably, at least one selected from the group consisting of Plast Blue 8514, Solvent Blue 94, Solvent Blue 36, and Plast Red 8320 is contained.

[0099] The bluing agents listed above may be used alone or in combination of two or more.

[0100] [Resin monomers for optical materials]

[0101] In the present embodiment, as the resin monomer for optical material, any resin monomer that can achieve the effects of the present disclosure can be selected from conventionally known resin monomers used for optical materials.

[0102] In the present embodiment, the optical material resin monomer preferably comprises at least one selected from the group consisting of: a combination of an isocyanate compound (A) and at least one active hydrogen compound (B) selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, a polyol compound having two or more hydroxyl groups, and an amine compound; an episulfide compound (C); and a combination of an episulfide compound (C) and a polythiol compound.

[0103] Resins obtained from these resin monomers are excellent in transparency and are therefore preferred.

[0104] (Isocyanate compound (A))

[0105] The isocyanate compound (A) includes aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, heterocyclic isocyanate compounds, aromatic aliphatic isocyanate compounds, etc., and one kind or a mixture of two or more kinds can be used. These isocyanate compounds may include dimers, trimers, and prepolymers.

[0106] Examples of these isocyanate compounds include compounds listed in WO2011 / 055540.

[0107] In the present embodiment, from the viewpoint of the effects of the present disclosure, the isocyanate compound (A) preferably includes a diisocyanate selected from the group consisting of xylylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, bis(isocyanate cyclohexyl)methane, 1,6-hexamethylene diisocyanate, 1 ,5-pentane diisocyanate, and at least one of the group consisting of isophorone isocyanate, more preferably comprising at least one selected from the group consisting of xylylene diisocyanate, toluene diisocyanate, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, bis(isocyanate cyclohexyl)methane, 1,6-hexane diisocyanate, and 1,5-pentane diisocyanate.

[0108] (Active hydrogen compound (B))

[0109] In this embodiment, as the active hydrogen compound (B), at least one selected from the group consisting of a polythiol compound having two or more mercapto groups, a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, a polyol compound having two or more hydroxyl groups, and an amine compound can be used.

[0110] Examples of these active hydrogen compounds include compounds listed in WO2016 / 125736.

[0111] From the viewpoint of the effects of the present disclosure, the active hydrogen compound (B) is preferably at least one selected from a polythiol compound having two or more mercapto groups and a hydroxythiol compound having one or more mercapto groups and one or more hydroxyl groups, and more preferably at least one selected from a polythiol compound having two or more mercapto groups.

[0112] The polythiol compound is preferably 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, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)- At least one selected from the group consisting of 1,4-dithiol, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiol, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiene, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithialane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate),

[0113] More preferably, it is 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, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and pentaerythritol tetrakis(3-mercaptopropionate).

[0114] (Episulfide compound (C))

[0115] Examples of the episulfide compound (C) include epithioethylthio compounds, chain aliphatic 2,3-epithiopropylthio compounds, cyclic aliphatic 2,3-epithiopropylthio compounds, aromatic 2,3-epithiopropylthio compounds, chain aliphatic 2,3-epithiopropyloxy compounds, cyclic aliphatic 2,3-epithiopropyloxy compounds, aromatic 2,3-epithiopropyloxy compounds, and the like, and one or more of them may be used in combination. Examples of these episulfide compounds include compounds listed in WO2015 / 137401.

[0116] From the viewpoint of improving the solubility of the ultraviolet absorber in the resin, the episulfide compound is preferably at least one selected from the group consisting of bis(2,3-epithiopropyl)sulfide, bis(2,3-epithiopropyl)disulfide, bis(1,2-epithioethyl)sulfide, bis(1,2-epithioethyl)disulfide, and bis(2,3-epithiopropylthio)methane, and more preferably bis(2,3-epithiopropyl)disulfide.

[0117] In this embodiment, the molar ratio of the active hydrogen group in the active hydrogen compound (B) to the isocyanate group in the isocyanate compound (A) is in the range of 0.8 to 1.2, preferably in the range of 0.85 to 1.15, and more preferably in the range of 0.9 to 1.1. Within the above range, a resin suitable for use as an optical material, especially a plastic lens material for spectacles, can be obtained.

[0118] The polymerizable composition for an optical material can be obtained by mixing an optical material resin monomer, an additive, and other additives as required by a conventionally known method.

[0119] The temperature during mixing is usually 25° C. or lower. From the viewpoint of the pot life of the polymerizable composition for optical materials, a lower temperature may be preferable. However, if the additive has poor solubility in the resin monomer for optical materials, it may be heated in advance to dissolve it.

[0120] The order and method of mixing the components in the composition are not particularly limited, as long as the hue of the polymerizable composition for optical materials is not affected and the components can be uniformly mixed, and the mixing can be carried out by a known method. As a known method, for example, there is a method of preparing a masterbatch containing a predetermined amount of additives and dispersing and dissolving the masterbatch in a solvent.

[0121] (Process 2)

[0122] In this step, from the viewpoint of the effects of the present disclosure, the cured product has an L* of 70 or more, preferably 75 or more, and more preferably 80 or more in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0123] In this step, from the viewpoint of the effects of the present disclosure, the cured product has a hue of b* of -30 to 10, preferably b* of -25 to 10, more preferably b* of -22 to 7, and even more preferably b* of -10 to 5 in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0124] The polymerizable composition for an optical material of the present embodiment can be polymerized to obtain a cured product, and cured products of various shapes can be obtained depending on the shape of the mold. Regarding the polymerization method, conventionally known methods can be mentioned, and the conditions are not particularly limited.

[0125] In this embodiment, the method for producing the cured product is not particularly limited, and cast polymerization can be cited as a preferred method. First, the polymerizable composition for optical material is injected into a molding die held by a gasket or tape. At this time, according to the physical properties required for the obtained cured product, it is often preferred to perform degassing treatment under reduced pressure, filtration treatment such as pressurization or reduced pressure, etc. as needed.

[0126] The polymerization conditions are not limited because they vary depending on the type and amount of the optical material resin monomer and additives, the type and amount of the catalyst, the shape of the mold, etc., but are usually carried out at a temperature of -50 to 150° C. for 1 to 50 hours. Depending on the circumstances, it is preferred to maintain or slowly increase the temperature within a range of 10 to 150° C. for 1 to 25 hours to cure.

[0127] The cured product of the present embodiment may be subjected to treatment such as annealing as necessary. The treatment temperature is usually 50 to 150°C, preferably 90 to 140°C, and more preferably 100 to 130°C.

[0128] In addition, in this embodiment, the cured product obtained by heat-curing the polymerizable composition for optical material can be used as an optical material, for example, and can constitute a part of the optical material. Since the cured product of this embodiment has excellent hue and excellent design, it can be used as various optical materials by forming the cured product into a desired shape and forming a coating layer, other components, etc. as needed.

[0129] <Second embodiment>

[0130] The method for producing an optical material according to the present embodiment includes the following steps.

[0131] Step a: A resin monomer for an optical material and an additive are mixed to prepare a polymerizable composition for an optical material having a hue of YI of -70 or more and 20 or less.

[0132] Step b: polymerizing and curing the polymerizable composition for an optical material to obtain a cured product having a hue of -70 or more and 20 or less.

[0133] By controlling the hue of the polymerizable composition for an optical material, an optical material having a good hue can be obtained.

[0134] Hereinafter, description of the same configurations and conditions as those of the first embodiment will be appropriately omitted.

[0135] (Process a)

[0136] In this step, a polymerizable composition for an optical material having a hue of YI of -70 to 20, preferably -40 to 15, and more preferably -20 to 10 can be prepared.

[0137] By using the polymerizable composition for an optical material having the above-mentioned hue, an optical material having good hue can be obtained.

[0138] In this step, from the viewpoint of the effects of the present disclosure, the polymerizable composition for an optical material has an L* of 70 or more, preferably 75 or more, and more preferably 80 or more in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0139] In this step, from the viewpoint of the effects of the present disclosure, the polymerizable composition for an optical material has a hue of b* of -30 to 10, preferably b* of -30 to 5, more preferably b* of -27 to 3, and even more preferably b* of -10 to 1 in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0140] In order to obtain a polymerizable composition for an optical material having the above-mentioned hue, this step preferably includes a step of mixing the optical material resin monomer and the additive to adjust the hue.

[0141] Regarding the resin monomers and additives for optical materials, the same optical material resin monomers and additives as those in the first embodiment can be used. From the viewpoint of suppressing the coloring of the resin due to ultraviolet rays, it is preferred to use an ultraviolet absorber, etc. In addition, in order to suppress the hue change of the resin caused by the addition of an ultraviolet absorber, etc., it is preferred to use a hue regulator.

[0142] The ultraviolet absorber (a) can be used in an amount capable of suppressing coloration of the resin, and the hue adjuster (b) can be used to adjust the hue of the resin changed by the addition of the ultraviolet absorber (a) to the above hue.

[0143] Regarding the weight ratio (b / a) of the hue adjuster (b) and the ultraviolet absorber (a) contained in the polymerizable composition for optical materials, although the range varies depending on the resin constituting the lens, the hue adjuster (a) and the ultraviolet absorber (b), the weight ratio (b / a) can be greater than 30 and less than 50,000, preferably greater than 70 and less than 40,000, and more preferably greater than 100 and less than 30,000.

[0144] In step a, a polymerizable composition for an optical material can be obtained in the same manner as in step 1 of the first embodiment.

[0145] (Process b)

[0146] In this step, the polymerizable composition for an optical material is polymerized and cured to obtain a cured product having a hue of YI of -70 to 20, preferably -40 to 15, and more preferably -20 to 10.

[0147] In this step, from the viewpoint of the effects of the present disclosure, the cured product has an L* of 70 or more, preferably 75 or more, and more preferably 80 or more in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0148] In this step, from the viewpoint of the effects of the present disclosure, the cured product has a hue of b* of -30 to 10, preferably b* of -25 to 10, more preferably b* of -22 to 7, and even more preferably b* of -10 to 5 in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

[0149] Regarding the points other than those described above, step b is the same as step 2 in the first embodiment, and thus the description thereof will be omitted.

[0150] <Optical Materials>

[0151] As the optical material of the present embodiment obtained by the above method, plastic lens, camera lens, light emitting diode (LED), prism, optical fiber, information recording substrate, optical filter, light emitting diode, etc. can be cited. In particular, it is preferably used as an optical material and optical element such as plastic lens, camera lens, light emitting diode, etc.

[0152] For the plastic lens comprising the cured product of the present embodiment, as required, a coating layer can be applied to one or both sides of the lens substrate formed by the cured product and used. As the coating layer, a primer layer, a hard coat layer, an anti-reflection film layer, an anti-fog coating film layer, an anti-pollution layer, a hydrophobic layer, etc. can be cited. These coating layers can be used separately, or multiple coating layers can be formed into multiple layers and used. When the coating layers are applied to both sides, the same coating layer can be applied to each side, or different coating layers can be applied.

[0153] For these coating layers, infrared absorbers for protecting eyes from infrared rays, light stabilizers and antioxidants for improving the weather resistance of lenses, dyes and pigments for improving the fashionability of lenses, photochromic dyes and photochromic pigments, antistatic agents, and other known additives for improving the performance of lenses can be used together. Coatings such as hard coatings and anti-reflection coatings or primers can also be provided.

[0154] The plastic lens including the cured product of the present embodiment can be dyed using a pigment suitable for the purpose for the purpose of imparting fashionability, photochromic properties, etc. The lens can be dyed using a known dyeing method.

[0155] In addition, the method for producing the optical material of the present embodiment includes, for example, a step of cast-polymerizing the polymerizable composition for an optical material of the present embodiment.

[0156] As mentioned above, although this disclosure was demonstrated based on this embodiment, various structures can be adopted in the range which does not impair the effect in this disclosure.

[0157] Example

[0158] Hereinafter, the present disclosure will be further described in detail by way of examples, but the present disclosure is not limited thereto. It should be noted that the evaluation methods and materials used in the examples of the present disclosure are as follows.

[0159] [Measurement method of L*, a*, b*]

[0160] The polymerizable composition for an optical material was placed in a 10 mm thick cell using a spectrocolorimeter (CM-5 manufactured by MINOLTA), and L*, a*, and b* in the CIE 1976 (L*, a*, b*) color system were measured.

[0161] [Measurement method of YI]

[0162] The polymerizable composition for an optical material was placed in a sample cell having a thickness of 10 mm, and YI was measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc.

[0163] In the examples, the following ultraviolet absorbers and hue adjusters were used.

[0164] [Ultraviolet light absorber]

[0165] Viosorb 583 (product name, manufactured by Kyodo Pharmaceutical Co., Ltd.): 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole

[0166] TINUVIN 326 (product name, manufactured by BASF): 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole

[0167] ·TINUVIN PS (product name, manufactured by BASF): 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole

[0168] Eversorb 109 (product name, manufactured by Everlight Chemical Co., Ltd.): 2-(3-tert-butyl-5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole

[0169] [Hue Adjuster]

[0170] In the examples, the hue adjusting agents shown below were used.

[0171] ·Plast Blue 8514 (manufactured by Arimoto Chemical Industry Co., Ltd., anthraquinone dye)

[0172] ·Plast Red 8320 (manufactured by Arimoto Chemical Industry Co., Ltd., anthraquinone dye)

[0173] Solvent Blue 36 (manufactured by Arimoto Chemical Industry Co., Ltd., anthraquinone dye, 1,4-bis(isopropylamino)anthracene-9,10-dione)

[0174] Solvent Blue 94 (manufactured by Arimoto Chemical Industry Co., Ltd., anthraquinone dye, 1-amino-2-bromo-4-(phenylamino)anthracene-9,10-dione)

[0175] [Example 1]

[0176] 0.01 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of ZelecUN manufactured by Stepan Company, 52 parts by mass of m-xylylene diisocyanate, 1.5 parts by mass of Viosob583 as a UV absorber, and 0.00005 parts by mass of Plast Blue8514 were added to prepare a mixed solution. The mixed solution was stirred at 25°C for 1 hour to completely dissolve it. Then, 48 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithia-octane was added to the prepared solution and stirred at 25°C for 30 minutes to obtain a uniform solution (polymerizable composition for optical materials). According to the above method, the L*, a*, b*, and YI values ​​in the CIE1976 (L*, a*, b*) color system of the polymerizable composition for optical materials were measured.

[0177] The polymerizable composition for optical material was degassed at 600 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 16 hours. After cooling to room temperature, it was taken out from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours. According to the above method, the L*, a*, b*, and YI values ​​of the CIE1976 (L*, a*, b*) color system of the flat lens were measured.

[0178] The evaluation results are shown in Table-1.

[0179] [Examples 2 to 9, Comparative Example 1]

[0180] A polymerizable composition for an optical material and a flat lens were prepared in the same manner as in Example 1 except that the amount of Plast Blue 8514 added as a hue adjuster was changed to the amount shown in Table 1. The evaluation results are shown in Table 1.

[0181] [Example 10]

[0182] 0.01 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of ZelecUN manufactured by Stepan Company, 52 parts by mass of m-xylylene diisocyanate, 0.5 parts by mass of Tinuvin 326 as an ultraviolet absorber, 0.0006 parts by mass of Plast Blue 8514, and 0.0003 parts by mass of Plast Red 8320 were added to prepare a mixed solution. The mixed solution was stirred at 25°C for 1 hour to completely dissolve it. Then, 48 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithia-octane was added to the prepared solution, and it was stirred at 25°C for 30 minutes to obtain a uniform solution (polymerizable composition for optical materials). According to the above method, the L*, a*, b*, and YI values ​​of the polymerizable composition for optical materials in the CIE1976 (L*, a*, b*) color system were measured.

[0183] The polymerizable composition for optical material was degassed at 600 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 16 hours. After cooling to room temperature, it was taken out from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours. According to the above method, the L*, a*, b*, and YI values ​​of the CIE1976 (L*, a*, b*) color system of the flat lens were measured.

[0184] The evaluation results are shown in Table-1.

[0185] [Comparative Example 2]

[0186] A polymerizable composition for an optical material and a flat lens were prepared in the same manner as in Example 10 except that Plast Blue 8514 and Plast Red 8320 as hue adjusters were not added. The evaluation results are shown in Table 1.

[0187] [Example 11]

[0188] 0.035 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of ZelecUN manufactured by Stepan Company, 50.6 parts by mass of a mixture of 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 1.0 parts by mass of Tinuvin 326 as an ultraviolet absorber, 0.0006 parts by mass of Plast Blue 8514, and 0.0003 parts by mass of Plast Red 8320 were added to prepare a mixed solution. The mixed solution was stirred at 25° C. for 1 hour to completely dissolve the mixed solution. Then, 25.5 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were added to the prepared solution, and the mixture was stirred at 25° C. for 30 minutes to obtain a uniform solution (polymerizable composition for optical material). According to the above method, the L*, a*, b*, and YI values ​​of the polymerizable composition for optical material in the CIE1976 (L*, a*, b*) color system were measured.

[0189] The polymerizable composition for optical material was degassed at 600 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 16 hours. After cooling to room temperature, it was taken out from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours. According to the above method, the L*, a*, b*, and YI values ​​of the CIE1976 (L*, a*, b*) color system of the flat lens were measured.

[0190] The evaluation results are shown in Table-1.

[0191] [Comparative Example 3]

[0192] A polymerizable composition for an optical material and a flat lens were prepared in the same manner as in Example 11 except that Plast Blue 8514 and Plast Red 8320 as hue adjusters were not added. The evaluation results are shown in Table 1.

[0193] [Example 12]

[0194] 0.035 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of ZelecUN manufactured by Stepan Company, 50.6 parts by mass of a mixture of 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 1.5 parts by mass of Viosob583 as an ultraviolet absorber, and 0.00005 parts by mass of Plast Blue 8514 were added to prepare a mixed solution. The mixed solution was stirred at 25°C for 1 hour to completely dissolve it. Then, 25.5 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) were added to the prepared solution, and stirred at 25°C for 30 minutes to obtain a uniform solution (polymerizable composition for optical materials). According to the above method, the L*, a*, b*, and YI values ​​of the polymerizable composition for optical material in the CIE1976 (L*, a*, b*) color system were measured.

[0195] The polymerizable composition for optical material was degassed at 600 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 16 hours. After cooling to room temperature, it was taken out from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours. According to the above method, the L*, a*, b*, and YI values ​​of the CIE1976 (L*, a*, b*) color system of the flat lens were measured.

[0196] The evaluation results are shown in Table-1.

[0197] [Examples 13 to 15]

[0198] A polymerizable composition for an optical material and a flat lens were prepared in the same manner as in Example 12 except that the amount of Plast Blue 8514 added as a hue adjuster was changed to the amount described in Table 1.

[0199] The evaluation results are shown in Table-1.

[0200] [Example 16]

[0201] 0.035 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of ZelecUN manufactured by Stepan Company, 50.6 parts by mass of a mixture of 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2.0 parts by mass of Eversorb 109 as a UV absorber, 0.0006 parts by mass of Plast Blue 8514, and 0.0003 parts by mass of Plast Red 8320 were added to prepare a mixed solution. The mixed solution was stirred at 25° C. for 1 hour to completely dissolve the mixed solution. Then, 25.5 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were added to the prepared solution, and the mixture was stirred at 25° C. for 30 minutes to obtain a uniform solution (polymerizable composition for optical material). According to the above method, the L*, a*, b*, and YI values ​​of the polymerizable composition for optical material in the CIE1976 (L*, a*, b*) color system were measured.

[0202] The polymerizable composition for optical material was degassed at 600 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 16 hours. After cooling to room temperature, it was taken out from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours. According to the above method, the L*, a*, b*, and YI values ​​of the CIE1976 (L*, a*, b*) color system of the flat lens were measured.

[0203] The evaluation results are shown in Table-1.

[0204] [Example 17]

[0205] 0.035 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of ZelecUN manufactured by Stepan Company, 50.6 parts by mass of a mixture of 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 1.5 parts by mass of Tinuvin PS as an ultraviolet absorber, and 0.00005 parts by mass of Plast Blue 8514 were added to prepare a mixed solution. The mixed solution was stirred at 25°C for 1 hour to completely dissolve it. Then, 25.5 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) were added to the prepared solution, and the mixture was stirred at 25°C for 30 minutes to obtain a uniform solution (polymerizable composition for optical materials). According to the above method, the L*, a*, b*, and YI values ​​of the polymerizable composition for optical material in the CIE1976 (L*, a*, b*) color system were measured.

[0206] The polymerizable composition for optical material was degassed at 600 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 16 hours. After cooling to room temperature, it was taken out from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours. According to the above method, the L*, a*, b*, and YI values ​​of the CIE1976 (L*, a*, b*) color system of the flat lens were measured.

[0207] The evaluation results are shown in Table-1.

[0208] [Examples 18 and 19]

[0209] A uniform solution (polymerizable composition for optical material) and a flat lens were obtained by the same method as in Example 10 except that the type and amount of the ultraviolet absorber and the type and amount of the hue adjuster were changed as described in Table 1. The L*, a*, b*, and YI values ​​of the polymerizable composition for optical material and the flat lens in the CIE1976 (L*, a*, b*) color system were measured according to the above method.

[0210] The evaluation results are shown in Table-1.

[0211] [Examples 20 and 21]

[0212] A uniform solution (polymerizable composition for optical material) and a flat lens were obtained by the same method as in Example 11 except that the type and amount of the ultraviolet absorber and the type and amount of the hue adjuster were changed as described in Table 1. The L*, a*, b*, and YI values ​​of the polymerizable composition for optical material and the flat lens in the CIE1976 (L*, a*, b*) color system were measured according to the above method.

[0213] The evaluation results are shown in Table-1.

[0214] [Examples 22 and 23]

[0215] 90.9 parts by mass of bis(2,3-epithiopropyl)disulfide, 0.02 parts by mass of N,N-dimethylcyclohexylamine, 0.1 parts by mass of N,N-dicyclohexylmethylamine, 9.1 parts by mass of a mixture of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, an ultraviolet absorber described in Table 1 in the amount described in Table 1, and a hue adjuster described in Table 1 in the amount described in Table 1 were charged, and the mixture was stirred at 20° C. for 15 minutes to obtain a uniform solution (polymerizable composition for an optical material). According to the above method, the L*, a*, b*, and YI values ​​of the polymerizable composition for optical material in the CIE1976 (L*, a*, b*) color system were measured.

[0216] The solution was degassed at 400 Pa for 1 hour, filtered with a 1 μm PTFE filter, and then injected into a flat glass mold with a center thickness of 10 mm and a diameter of 78 mm. The glass mold was heated from 25°C to 120°C over 20 hours. After cooling to room temperature, the solution was taken out of the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120°C for 2 hours.

[0217] According to the above method, the L*, a*, b*, and YI values ​​of the flat lens in the CIE 1976 (L*, a*, b*) color system are measured.

[0218] The evaluation results are shown in Table-1.

[0219] [Table 1]

[0220]

[0221] [Table 2]

[0222]

[0223] [Table 3]

[0224] Table-1(Continued)

[0225]

[0226] The compounds listed in Table-1 are as follows.

[0227] a1: m-xylylene diisocyanate

[0228] a2: A mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane

[0229] b1: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiooctane

[0230] b2: Pentaerythritol tetrakis (3-mercaptopropionate)

[0231] b3: Bis(2,3-epithiopropyl) disulfide (also known as ETDS)

[0232] b4: A mixture 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 (also called FSH)

[0233] c1: Viosob583

[0234] c2: Tinuvin326

[0235] c3: Eversorb109

[0236] c4:TinuvinPS

[0237] d1: Plast Blue 8514

[0238] d2: Plast Red 8320

[0239] d3: Solvent Blue 36

[0240] d4: Solvent Blue 94

[0241] The results of the Examples show that an optical material having a good hue can be obtained by using a polymerizable composition for an optical material having a desired hue.

[0242] The entire disclosure of Japanese Patent Application No. 2019-066203 filed on March 29, 2019 is incorporated into this specification by reference.

[0243] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

Claims

1. A method for producing an optical material, comprising the following steps: A step of mixing an optical material resin monomer and an additive to prepare an optical material polymerizable composition having a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm; and The step of polymerizing and curing the optical material polymerizable composition to obtain a cured product having a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm, The additives include ultraviolet absorbers and hue adjusters, The ultraviolet absorber comprises a benzotriazole compound represented by the following general formula (1): In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms, or a halogen atom; m represents an integer from 0 to 3, n represents an integer from 0 to 3, p represents an integer from 0 to 1, and p R3 each independently represents a functional group having 2 to 15 carbon atoms including an ester bond, The hue adjusting agent is a bluing agent, The optical material resin monomer is composed of an isocyanate compound (A) and at least one active hydrogen compound (B), The isocyanate compound (A) is 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, and the at least one active hydrogen compound (B) is selected from the group consisting of a polythiol compound having two or more thiol groups and a hydroxythiol compound having one or more thiol groups and one or more hydroxyl groups.

2. A method for producing an optical material, comprising the following steps: A step of mixing an optical material resin monomer and an additive to prepare a polymerizable composition for an optical material having a hue of YI of -70 or more and 20 or less; and The step of polymerizing and curing the optical material polymerizable composition to obtain a cured product having a hue of -70 or more and 20 or less, The additives include ultraviolet absorbers and hue adjusters, The ultraviolet absorber comprises a benzotriazole compound represented by the following general formula (1): In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms, or a halogen atom; m represents an integer from 0 to 3, n represents an integer from 0 to 3, p represents an integer from 0 to 1, and p R3 each independently represents a functional group having 2 to 15 carbon atoms including an ester bond, The hue adjusting agent is a bluing agent, The optical material resin monomer is composed of an isocyanate compound (A) and at least one active hydrogen compound (B), The isocyanate compound (A) is 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, and the at least one active hydrogen compound (B) is selected from the group consisting of a polythiol compound having two or more thiol groups and a hydroxythiol compound having one or more thiol groups and one or more hydroxyl groups.

3. The method for producing an optical material according to claim 2, wherein: The polymerizable composition for an optical material has a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm, The cured product has a hue of L* of 70 or more and b* of -30 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

4. The method for producing an optical material according to any one of claims 1 to 3, wherein: The process of preparing the polymerizable composition for optical material comprises: A step of adjusting the hue of the polymerizable composition for an optical material using the hue adjusting agent.

5. The method for producing an optical material according to any one of claims 1 to 3, wherein: The benzotriazole compound is at least one selected from the group consisting of 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-ethylphenyl)-5-chloro-2H-benzotriazole, 2-(4-ethoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, and 2-(4-butoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole.

6. The method for producing an optical material according to any one of claims 1 to 3, wherein: The polythiol compound comprises 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, , 4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

7. The method for producing an optical material according to any one of claims 1 to 3, wherein: The polymerizable composition for an optical material has a hue of L* of 70 or more and b* of -30 or more and 5 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

8. The method for producing an optical material according to any one of claims 1 to 3, wherein: The cured product has a hue of L* of 70 or more and b* of -25 or more and 10 or less in the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm.

9. A polymerizable composition for an optical material, comprising a resin monomer for an optical material and an additive, wherein, in terms of hue, in the CIE1976 (L*, a*, b*) color space, L* is 70 or more, b* is -30 or more and 10 or less, The additives include ultraviolet absorbers and hue adjusters, The ultraviolet absorber comprises a benzotriazole compound represented by the following general formula (1): In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms, or a halogen atom; m represents an integer from 0 to 3, n represents an integer from 0 to 3, p represents an integer from 0 to 1, and p R3 each independently represents a functional group having 2 to 15 carbon atoms including an ester bond, The hue adjusting agent is a bluing agent, The optical material resin monomer is composed of an isocyanate compound (A) and at least one active hydrogen compound (B), The isocyanate compound (A) is 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, and the at least one active hydrogen compound (B) is selected from the group consisting of a polythiol compound having two or more thiol groups and a hydroxythiol compound having one or more thiol groups and one or more hydroxyl groups.

10. A polymerizable composition for an optical material, comprising a resin monomer for an optical material and an additive, wherein the YI is -70 or more and 20 or less. The additives include ultraviolet absorbers and hue adjusters, The ultraviolet absorber comprises a benzotriazole compound represented by the following general formula (1): In the general formula (1), m R1 and n R2 each independently represent an alkyl group having 1 to 8 carbon atoms, or a halogen atom; m represents an integer from 0 to 3, n represents an integer from 0 to 3, p represents an integer from 0 to 1, and p R3 each independently represents a functional group having 2 to 15 carbon atoms including an ester bond, The hue adjusting agent is a bluing agent, The optical material resin monomer is composed of an isocyanate compound (A) and at least one active hydrogen compound (B), The isocyanate compound (A) is 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, and the at least one active hydrogen compound (B) is selected from the group consisting of a polythiol compound having two or more thiol groups and a hydroxythiol compound having one or more thiol groups and one or more hydroxyl groups.

11. The polymerizable composition for an optical material according to claim 10, wherein In the CIE1976 (L*, a*, b*) color space, L* is 70 or more, and b* is -30 or more and 10 or less.

12. The polymerizable composition for an optical material according to any one of claims 9 to 11, wherein The benzotriazole compound is at least one selected from the group consisting of 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-octyl propionate-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-ethylphenyl)-5-chloro-2H-benzotriazole, 2-(4-ethoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, and 2-(4-butoxy-2-hydroxyphenyl)-5-chloro-2H-benzotriazole.

13. The polymerizable composition for an optical material according to any one of claims 9 to 11, wherein The polythiol compound comprises 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, , 4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

14. The polymerizable composition for an optical material according to any one of claims 9 to 11, wherein In the CIE1976 (L*, a*, b*) color space when measured at a thickness of 10 mm, the film has a hue of L* of 70 or more and b* of -30 or more and 5 or less.

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