Isocyanate composition, polymerizable composition, resin, optical material, and spectacle lens

Abstract

An isocyanate composition containing a compound represented by formula (1) and an isocyanate component, a polymerizable composition containing the isocyanate composition, a resin which is a cured product of the polymerizable composition, an optical material containing the resin, and a spectacle lens containing the resin.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an isocyanate composition, a polymerizable composition, a resin, an optical material, and a spectacle lens. BACKGROUND

[0002] At present, a spectacle lens made of plastic is widely known. As a material of a spectacle lens, a polythiourethane resin (for example, Patent Document 1) can be used. Since the polythiourethane resin is a material having an appropriate refractive index, it can become a spectacle lens of an appropriate thickness, and it is easy to ensure processability, impact resistance, and has been widely popularized.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent Application Publication No. 2004-002820 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] An isocyanate used as a raw material of a spectacle lens made of plastic is generally highly reactive, and easily colored due to long-term storage. In the field of optical materials and the like, the colored isocyanate cannot be used.

[0008] One embodiment of the present disclosure relates to an isocyanate composition, a polymerizable composition, a resin, an optical material, and a spectacle lens having high storage stability.

[0009] METHOD FOR SOLVING THE PROBLEM

[0010] One embodiment of the present disclosure relates to an isocyanate composition containing a compound represented by Formula (1) and an isocyanate component.

[0011] [Chemical Formula 1]

[0012]

[0013] One embodiment of the present disclosure relates to a polymerizable composition containing the above-described isocyanate composition and an active hydrogen compound component.

[0014] One embodiment of the present disclosure relates to a resin which is a cured product of the above-described polymerizable composition.

[0015] One embodiment of the present disclosure relates to an optical material containing the above-described resin.

[0016] One embodiment of the present disclosure relates to a spectacle lens containing the above-described resin.

[0017] EFFECT OF THE INVENTION

[0018] According to one embodiment of the present disclosure, it is possible to provide an isocyanate composition, a polymerizable composition, a resin, an optical material, and an eyeglass lens having high storage stability. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is a schematic cross-sectional view of an eyeglass lens 1 of the present embodiment. DETAILED DESCRIPTION

[0020] Hereinafter, the embodiments of the present disclosure will be described in detail as needed while referring to the accompanying drawings, but the present disclosure is not limited thereto and various modifications can be made within the scope of the gist thereof. Note that in the drawings, the same elements are denoted by the same reference symbols, and overlapping descriptions will be omitted. In addition, unless otherwise specified, the positional relationship of up, down, left, right, and the like is based on the positional relationship shown in the drawings. Furthermore, the dimensional proportions of the drawings are not limited to the proportions shown in the drawings.

[0021] Note that in the present specification, for example, the recitation of a numerical range such as "1 to 100" includes both the lower limit value "1" and the upper limit value "100". The same applies to other numerical ranges.

[0022] Note that the "cured product of the isocyanate component and the active hydrogen compound component" refers to a substance obtained by curing a composition containing at least an isocyanate component and an active hydrogen compound component, and does not mean that other components are excluded.

[0023] [Isocyanate composition]

[0024] The isocyanate composition of the present embodiment contains a compound represented by formula (1) (hereinafter also referred to as "DBP") and an isocyanate component.

[0025] [Chemical formula 2]

[0026]

[0027] Based on the above configuration, an isocyanate composition having high storage stability can be obtained.

[0028] The compound represented by formula (1) can improve the storage stability of the isocyanate component by being mixed with the isocyanate component. The compound represented by formula (1) exhibits storage stability equivalent to that of 2,6-di-tert-butyl-p-cresol, which has been used as a storage stabilizer in the past. Therefore, in one embodiment, the isocyanate component can be stabilized even without using 2,6-di-tert-butyl-p-cresol, which exhibits toxicity.

[0029] The content of the compound represented by formula (1) in the isocyanate composition of the present embodiment is preferably 10 to 10,000 mass ppm, more preferably 50 to 5,000 mass ppm, and further preferably 100 to 3,000 mass ppm, relative to the total amount of the isocyanate component.

[0030] (Isocyanate component)

[0031] As the isocyanate component, for example, a polyisocyanate compound having an aromatic ring, a polyisocyanate compound having an aliphatic ring, an aliphatic polyisocyanate compound having a linear or branched chain can be given.

[0032] As the polyisocyanate compound having an aromatic ring, for example, phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylphenyl triisocyanate, phenyl triisocyanate, diphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-methylenebis(2-methylphenyl isocyanate), bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, 1,3-bis(isocyanatomethyl)benzene, 1,4-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, α,α,α',α'-tetramethylbenzyl diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethylphenyl)ether, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis(4-isocyanatophenyl) sulfide, bis(4-isocyanatomethylphenyl) sulfide, bis(4-isocyanatophenyl) disulfide, bis(2-methyl-5-isocyanatophenyl) disulfide, bis(3-methyl-5-isocyanatophenyl) disulfide, bis(3-methyl-6-isocyanatophenyl) disulfide, bis(4-methyl-5-isocyanatophenyl) disulfide, bis(3-methoxy-4-isocyanatophenyl) disulfide, bis(4-methoxy-3-isocyanatophenyl) disulfide can be given.

[0033] As the polyisocyanate compound having an alicyclic ring, there can be mentioned, for example, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, 4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane.

[0034] As the linear or branched aliphatic polyisocyanate compound, there can be mentioned, for example, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 4-isocyanatomethyloctane-1,8-diisocyanate, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, lysine diisocyanatomethyl ester, lysine triisocyanate, bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfide, bis(isocyanatomethyl)sulfone, bis(isocyanatomethyl)disulfide, bis(isocyanatoethyl)disulfide, bis(isocyanatopropyl)disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane, bis(isocyanatomethylthio)ethane, bis(isocyanatoethylthio)ethane, 2-isocyanatomethyl-3-pentane-1,5-diisocyanate, 1,2,3-tris(isocyanatomethylthio)propane, 1,2,3-tris(isocyanatoethylthio)propane, 3,5-dithio-1,2,6,7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithio-1,7-heptanediiisocyanate, 2,5-diisocyanato-methylthiophene, 4-isocyanatoethylthio-2,6-dithio-1,8-octanediisocyanate, 1,2-diisothiocyanatoethane, 1,6-diisothiocyanatohexane.

[0035] These can be used singly or two or more kinds in combination.

[0036] The isocyanate component preferably contains at least one selected from the group consisting of bis(isocyanatomethyl)bicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)benzene, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate (hereinafter also referred to as "preferred isocyanate compounds").

[0037] The bis(isocyanatomethyl)bicyclo[2.2.1]heptane can be exemplified by, for example, one or more selected from the group consisting of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, and preferably a mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane.

[0038] As the bis(isocyanatomethyl)cyclohexane, for example, 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane can be exemplified. Among them, 1,3-bis(isocyanatomethyl)cyclohexane is preferred.

[0039] As the bis(isocyanatomethyl)benzene, for example, 1,3-bis(isocyanatomethyl)benzene and 1,4-bis(isocyanatomethyl)benzene can be exemplified. Among them, 1,3-bis(isocyanatomethyl)benzene is preferred.

[0040] As the toluene diisocyanate, for example, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate can be exemplified. Among them, 2,4-toluene diisocyanate is preferred.

[0041] As the diphenylmethane diisocyanate, for example, 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate can be exemplified.

[0042] As the dicyclohexylmethane diisocyanate, for example, dicyclohexylmethane-4,4'-diisocyanate can be exemplified.

[0043] In the isocyanate component, the content of the above-described "preferred isocyanate compounds" is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more and 100% by mass or less.

[0044] (Phenolic antioxidant)

[0045] The isocyanate composition of the present embodiment can contain a phenolic antioxidant. By using the compound represented by Formula (1), even when used in combination with a phenolic antioxidant, excellent storage stability is exhibited.

[0046] As the phenol-based antioxidant, for example, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,6-di-tert-butyl-p-cresol (hereinafter also referred to as "BHT"), phenol can be given. Among them, 2,6-di-tert-butyl-p-cresol or phenol is preferable.

[0047] The content of the phenol-based antioxidant in the isocyanate composition of the present embodiment is preferably 10 to 10,000 mass ppm, more preferably 30 to 1,000 mass ppm, and further preferably 50 to 500 mass ppm, relative to the total amount of the isocyanate component.

[0048] [Polymerizable composition]

[0049] The polymerizable composition of the present embodiment contains the above-described isocyanate composition and an active hydrogen compound component.

[0050] (Active hydrogen compound component)

[0051] As the active hydrogen compound component, for example, a polythiol component, a polyol component, or a polyamine component can be given.

[0052] (Polythiol component)

[0053] As the polythiol component, for example, an ester compound formed from a polyol compound and a mercapto carboxylic acid compound, a linear or branched aliphatic polythiol compound, a polythiol compound having an aliphatic ring, a polythiol compound having an aromatic ring can be given.

[0054] In the ester compound formed from a polyol compound and a mercapto carboxylic acid compound, as the polyol compound, a compound having 2 or more hydroxyl groups in the molecule can be given. Here, as the polyol compound, for example, ethylene glycol, diethylene glycol, propylene glycol, glycerol, butanediol, trimethylolpropane, bis(2-hydroxyethyl)disulfide, pentaerythritol, dipentaerythritol can be given.

[0055] As the mercapto carboxylic acid compound, for example, mercapto acetic acid, mercapto propionic acid, thiolactic acid compound, thiosalicylic acid can be given.

[0056] As the ester compound formed from the polyhydric alcohol compound and the mercapto carboxylic acid compound, for example, ethylene glycol bis (2-mercapto acetate), ethylene glycol bis (3-mercapto propionate), diethylene glycol bis (2-mercapto acetate), diethylene glycol bis (3-mercapto propionate), 1, 4-butanediol bis (2-mercapto acetate), 1, 4-butanediol bis (3-mercapto propionate), trimethylol propane tris (2-mercapto acetate), trimethylol propane tris (3-mercapto propionate), pentaerythritol tetra (2-mercapto acetate), pentaerythritol tetra (3-mercapto propionate), dipentaerythritol hexa (2-mercapto acetate), dipentaerythritol hexa (3-mercapto propionate) can be given.

[0057] As the straight chain or branched chain aliphatic polythiol compound, for example, 1, 2-ethanedithiol, 1, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2, 2-propanedithiol, 1, 6-hexanedithiol, 1, 2, 3-propanetriol, 2, 2-dimethylpropane-1, 3-dithiol, 3, 4-dimethoxybutane-1, 2-dithiol, 2, 3-dimercapto-1-propanol, 1, 2-dimercapto propyl methyl ether, 2, 3-dimercapto propyl methyl ether, dimercaptoethyl ether, 2- (2-mercaptoethylthio) propane-1, 3-dithiol, 2, 2-bis (mercapto methyl) -1, 3-propanedithiol, bis (mercapto methylthio) methane, tris (mercapto methylthio) methane, bis (2-mercaptoethylthio) methane, 1, 2-bis (mercapto methylthio) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 1, 3-bis (mercapto methylthio) propane, 1, 3-bis (2-mercaptoethylthio) propane, 1, 1, 2, 2-tetrakis (mercaptoethylthio) ethane, 1, 1, 3, 3-tetrakis (mercaptoethylthio) propane, 3-mercapto methyl-1, 5-dimercapto-2, 4-dithiapentane, tetrakis (mercaptoethylthio) propane, bis (2-mercaptoethyl) ether, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 1, 2-bis (2-mercaptoethylthio) -3-mercapto propane, 4, 7-bis (mercapto methyl) -3, 6, 9-trithiaundecane-1, 11-dithiol, 4, 8-bis (mercapto methyl) -3, 6, 9-trithiaundecane-1, 11-dithiol, 5, 7-bis (mercapto methyl) -3, 6, 9-trithiaundecane-1, 11-dithiol can be given.

[0058] Examples of the polythiol compound having an aliphatic ring include 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, methylcyclohexanedithiol, bis(mercaptomethyl)cyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 2,5-bis(mercaptomethyl)-1,4-dithiane, and 4,8-bis(mercaptomethyl)-1,3-dithiane.

[0059] Examples of the polythiol compound having an aromatic ring include 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 4,4'-dimercaptobiphenyl, and 4,4'-dimercaptobibenzyl. , 2,5-toluenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-bis(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-bis(p-mercaptophenyl)pentane.

[0060] These may be used alone or in combination of two or more.

[0061] (Polyol component)

[0062] Examples of the polyol component include ethylene glycol, diethylene glycol, propylene glycol, glycerol, butylene glycol, trimethylolpropane, bis(2-hydroxyethyl)disulfide, pentaerythritol, and dipentaerythritol.

[0063] (Polyamine ingredient)

[0064] Examples of the polyamine component include polymethylenediamine, polyetherdiamine, diethylenetriamine, iminobispropylamine, bishexamethylenetriamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, pentaethylenehexamine, dimethylaminopropylamine, aminoethylethanolamine, methyliminobispropylamine, alkylenediamines, N-aminomethylpiperazine, 1,3-diaminocyclohexane, isophorone diamine, m-xylylenediamine, tetrachloro-p-xylylenediamine, m-phenylenediamine, 4,4'- methylenedianiline, diamino diphenyl sulfone, benzidine, diamino diphenyl ether, 4,4'- thiodianiline, 4,4'-bis(o-toluidine)dianisidine, o-phenylenediamine, 2,4-toluenediamine, 2,5- toluenediamine, methylenebis(o-chloroaniline), diamino diphenyl sulfone, bis(3,4- diaminophenyl)sulfone, 2,6-diaminopyridine, 4-chloro-o-phenylenediamine, 4-methoxy-6- methyl-m-phenylenediamine, m-aminobenzylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethyl-p-phenylenediamine, tetramethylguanidine, 2-dimethylamino-2- hydroxypropane, piperazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methylpiperazine, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane.

[0065] The active hydrogen compound component preferably contains at least one selected from the group consisting of toluene diamine, pentaerythritol tetramercaptoacetate, pentaerythritol tetramercapto propionate, trimethylolpropane trimercaptoacetate, trimethylolpropane trimercapto propionate, bis(mercaptoethylthio)mercaptopropane, bis(mercaptomethyl)-3,6,9-trithiaundecanedithiol, dimercaptoethyl sulfide, bis(mercaptomethyl)dithiane, dimercaptoethyl ether, and diethylene glycol.

[0066] As the toluene diamine, for example, 2,4-toluenediamine, 2,5-toluenediamine can be given.

[0067] As the pentaerythritol tetramercaptoacetate, for example, pentaerythritol tetra(2- mercaptoacetate) can be given.

[0068] As the pentaerythritol tetramercapto propionate, for example, pentaerythritol tetra(3- mercapto propionate) can be given.

[0069] As the trimethylolpropane trimercaptoacetate, for example, trimethylolpropane tri(2- mercaptoacetate) can be given.

[0070] As the trimethylolpropane trimercapto propionate, for example, trimethylolpropane tri(3- mercapto propionate) can be given.

[0071] As the bis(mercaptoethylthio)mercaptopropane, for example, 1,2-bis(2- mercaptoethylthio)-3-mercaptopropane can be given.

[0072] As the bis(mercaptomethyl)-3,6,9-trithiaundecane dithiol, for example, 4,7- bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9- trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol can be given. The bis(mercaptomethyl)-3,6,9-trithiaundecane dithiol is preferably a mixture of 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9- trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol.

[0073] The active hydrogen compound component is preferably a polythiol component.

[0074] For the polythiol component,

[0075] preferably contains at least one selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3- mercaptopyropropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9- trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3- mercaptopyropropionate), butanediol bis(2-mercaptoacetate), butanediol bis(3- mercaptopyropropionate), dipentaerythritol hexakis(2-mercaptoacetate), and dipentaerythritol hexakis(3-mercapto pyropropionate),

[0076] more preferably contains at least one selected from the group consisting of 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(3- mercaptopyropropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, and pentaerythritol tetrakis(2-mercaptoacetate),

[0077] Further preferably, at least one selected from the group consisting of 4,7-bis(mercapto- methyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercapto-methyl)-3,6,9-trithiaundecane- 1,11-dithiol, and 5,7-bis(mercapto-methyl)-3,6,9-trithiaundecane-1,11-dithiol is contained.

[0078] Further preferably, a mixture of 4,7-bis(mercapto-methyl)-3,6,9-trithiaundecane-1,11- dithiol, 4,8-bis(mercapto-methyl)-3,6,9-trithiaundecane-1,11-dithiol, and 5,7-bis(mercapto- methyl)-3,6,9-trithiaundecane-1,11-dithiol is contained.

[0079] The amount of the above-mentioned preferred polythiol component is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and still further preferably 95% by mass or more, and 100% by mass or less, in the polythiol component.

[0080] The equivalent ratio of the mercapto group of the polythiol component to the isocyanate group of the polyisocyanate component (mercapto / isocyanate) is preferably 40 / 60 or more, more preferably 43 / 57 or more, and further preferably 45 / 55 or more, and is preferably 60 / 40 or less, more preferably 55 / 45 or less, and further preferably 53 / 47 or less.

[0081] The total content of the polythiol component and the polyisocyanate component is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more, and 100% by mass or less, in the polymerizable composition.

[0082] The polymerizable composition of the present embodiment can contain ultraviolet absorbers, colorants, antioxidants, anticolorants, optical brighteners, and other additives. One or two or more of these can be used.

[0083] [Resin]

[0084] The resin of the present embodiment is a cured product of the above-mentioned polymerizable composition. The cured product is formed by polymerizing the polymerizable composition.

[0085] The polymerization conditions can be appropriately set according to the polymerizable composition. The polymerization start temperature is preferably 0°C or more, and more preferably 10°C or more, and is preferably 50°C or less, and more preferably 40°C or less. Preferably, the temperature is increased from the polymerization start temperature, and then heating and curing are performed. For example, the temperature increase maximum temperature is typically 110°C or more and 130°C or less.

[0086] The resin can be used as, for example, an optical material. The optical material contains the above-mentioned resin. In the optical material, use as a spectacle lens is preferred.

[0087] [eyeglass lens]

[0088] The eyeglass lens of the present embodiment, for example, has a lens substrate containing the resin of the present embodiment. The eyeglass lens of the present embodiment can have at least one layer selected from a hard coat layer, a base layer, and an antireflection layer.

[0089] Figure 1 A schematic cross-sectional view of the eyeglass lens 1 of the present embodiment. The eyeglass lens 1 of the present embodiment has a lens substrate 11, a hard coat layer 21f provided on the object side of the surface 11a side of the lens substrate 11, a functional layer 31f provided on the object side of the surface 21fa side of the hard coat layer 21f, and a water-repellent layer 41f provided on the object side of the surface 31fa side of the functional layer 31f.

[0090] In addition, in the case where the lens substrate 11 is a finished lens, the eyeglass lens 1 of the present embodiment further has a hard coat layer 21b provided on the eyeball side of the surface 11b side of the lens substrate 11, a functional layer 31b provided on the eyeball side of the surface 21bb side of the hard coat layer 21b, and a water-repellent layer 41b provided on the eyeball side of the surface 31bb side of the functional layer 31b.

[0091] Note that although not shown in the drawings, a base layer can be provided between the lens substrate 11 and the hard coat layer 21f, or between the lens substrate 11 and the hard coat layer 21b.

[0092] <lens substrate>

[0093] The lens substrate can contain the resin of the present embodiment.

[0094] The surface shape of the lens substrate is not particularly limited, and can be any shape such as a plane, a convex surface, a concave surface, or the like.

[0095] The lens substrate can be for any use such as a single-vision lens, a multifocal lens, a progressive addition lens, or the like. For example, as an example, for a progressive addition lens, generally, a near-use portion region (near-use portion) and a progressive portion region (intermediate region) are contained in the above lower region, and a far-use portion region (far-use portion) is contained in the upper region.

[0096] As the lens substrate, a colorless lens substrate is generally used, but a lens substrate that has been colored within a range that does not impair transparency can also be used.

[0097] The lens substrate is preferably a meniscus type. The "meniscus type" lens substrate refers to a lens substrate in which curved surfaces are formed on both surfaces. By causing the meniscus type lens substrate to contain the above compound 1, it is possible to suppress astigmatism.

[0098] The optical center thickness of the lens base material is not particularly limited, and is preferably 0.5 mm or more and 10.0 mm or less, more preferably 0.5 mm or more and 5.0 mm or less, further preferably 0.5 mm or more and 3.0 mm or less, further preferably 0.5 mm or more and 2.0 mm or less.

[0099] The diameter of the lens base material is not particularly limited, and is usually about 50 to 100 mm.

[0100] The refractive index ne of the lens base material is preferably 1.52 or more, more preferably 1.53 or more, further preferably 1.55 or more, further preferably 1.58 or more, further preferably 1.60 or more.

[0101] From the viewpoint of improving the effect of increasing the Abbe number by the presence of Compound 1, the refractive index ne of the lens base material is preferably 1.70 or more, more preferably 1.74 or more.

[0102] Note that the upper limit of the refractive index ne of the lens base material is not particularly limited, and can be, for example, 1.80 or less.

[0103] [Method for producing lens base material]

[0104] The lens base material is not particularly limited, and can be obtained, for example, by a production method including the following steps:

[0105] a step of curing the above-described polymerizable composition, and

[0106] a step of performing annealing treatment on the cured resin.

[0107] The polymerization is preferably cast polymerization. The lens base material can be obtained, for example, by injecting the polymerizable composition into a mold obtained by combining a glass or metal mold with a belt or a gasket, and performing polymerization.

[0108] The polymerization conditions can be appropriately set depending on the polymerizable composition. The polymerization start temperature is preferably 0°C or higher, more preferably 10°C or higher, and is preferably 50°C or lower, more preferably 40°C or lower. It is preferable to warm up from the polymerization start temperature, and then perform heating and curing. For example, the maximum temperature of the warm-up is usually 110°C or higher and 130°C or lower.

[0109] After the polymerization is completed, the lens base material can be demolded, and annealing treatment can be performed. The temperature of the annealing treatment is preferably 100 to 150°C.

[0110] [Hard coat layer]

[0111] The hard coat layer is, for example, a cured film formed from a curable composition containing an inorganic oxide and a silicon compound. The curable composition preferably further contains a multifunctional epoxy compound.

[0112] As the inorganic oxide, for example, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide, zinc oxide, tin oxide, beryllium oxide, antimony oxide, a composite oxide formed of two or more kinds of inorganic oxides among these can be given. These can be used singly one kind or in combination of two or more kinds. Among these inorganic oxides, silicon oxide is preferred. Note that, as the inorganic oxide, colloidal silica can also be used.

[0113] The content of the inorganic oxide in the solid component of the curable composition is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 70% by mass or less, and further preferably 25% by mass or more and 50% by mass or less.

[0114] The silicon compound is, for example, a silicon compound having a hydrolyzable group such as an alkoxy group. The silicon compound is preferably a silane coupling agent having an organic group bonded to a silicon atom and a hydrolyzable group. The organic group bonded to the silicon atom is preferably an organic group having a functional group such as an epoxypropoxy group, an epoxy group, a vinyl group, a methacryloyloxy group, an acryloyloxy group, a mercapto group, an amino group, a phenyl group, and the like, and more preferably an organic group having an epoxy group. Note that, the silicon compound optionally has an alkyl group bonded to silicon.

[0115] As the commercially available product of the above-mentioned silane coupling agent, for example, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be given.

[0116] The content of the silicon compound in the solid component of the curable composition is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 75% by mass or less, and further preferably 50% by mass or more and 75% by mass or less.

[0117] The multifunctional epoxy compound is preferably a multifunctional epoxy compound containing 2 or more epoxy groups in one molecule, and more preferably a multifunctional epoxy compound containing 2 or 3 epoxy groups in one molecule. As commercially available products of the multifunctional epoxy compound, there are, for example, EX-201, EX-211, EX-212, EX-252, EX-313, EX-314, EX-321, EX-411, EX-421, EX-512, EX-521, EX-611, EX-612, EX-614, EX-614B, etc. of the "Denacol" series manufactured by Nagase Chemtex Corporation.

[0118] The content of the multifunctional epoxy compound in the solid components of the curable composition is preferably 0 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 40 mass% or less, and further preferably 15 mass% or more and 30 mass% or less.

[0119] The curable composition described above can be prepared by mixing, as necessary, an organic solvent, a leveling agent, a curing catalyst, etc. in addition to the components described above.

[0120] The hard coat layer described above can be formed by applying the curable composition to a substrate and performing a curing treatment (thermal curing, photocuring, etc.). As the application method of the curable composition, a method generally performed such as dipping, spin coating, spraying, etc. can be applied. For the curable composition containing the multifunctional epoxy compound, the curing treatment is generally performed by heating. The heating curing treatment can be performed, for example, by placing the lens coated with the curable composition described above in an environment having a gas atmosphere temperature of 50 to 150°C for 30 minutes to 3 hours or so.

[0121] <Substrate Layer>

[0122] The substrate layer described above can be formed, for example, from an aqueous resin composition containing resin particles of at least one resin selected from the group consisting of a polyurethane resin, an acrylic resin, an epoxy resin, etc.

[0123] As the above-mentioned aqueous resin composition, a commercially available aqueous polyurethane can be used directly, or can be used after being diluted with an aqueous solvent as needed. As the commercially available aqueous polyurethane, for example, "Evafanol" series manufactured by Nikka Chemical Co., Ltd., "SuperFlex" series manufactured by the First Industrial Co., Ltd., "ADEKA Bontighter" series manufactured by ADEKA Corporation, "Olester" series manufactured by Mitsui Chemicals, Inc., "Bondic" series manufactured by Dainippon Ink and Chemicals, Incorporated, "Hydran" series, "Impranil" series manufactured by Bayer Corporation, "Sofuranate(" ")" series manufactured by Japan Sofuran Co., Ltd., "POIZ" series manufactured by Showa Highpolymer Co., Ltd., "SUNPRENE" series manufactured by Sanyo Chemical Industries, Ltd., "Aizelux( ")" series manufactured by Hokuetsu Chemical Industry Co., Ltd., "NeoRez" series manufactured by Zeneca Corporation can be mentioned.

[0124] The base layer can be formed, for example, by applying the above-mentioned aqueous resin composition to the surface of a substrate and drying it.

[0125] <Functional layer>

[0126] As the above-mentioned functional layer, for example, an antireflection layer, an ultraviolet absorbing layer, an infrared absorbing layer, a photochromic layer, an antistatic layer, an antifogging layer can be mentioned. These functional layers can be used singly or in combination of two or more. As to these functional layers, the publicly known technology related to eyeglass lenses can be applied. Among them, an antireflection layer is preferred.

[0127] (Antireflection layer)

[0128] The antireflection layer has, for example, low refractive index layers and high refractive index layers arranged alternately. The number of layers of the antireflection layer is preferably 4 to 11 layers, more preferably 5 to 8 layers.

[0129] The refractive index of the low refractive index layer is preferably 1.35 to 1.80, more preferably 1.45 to 1.50, at a wavelength of 500 to 550 nm. The low refractive index layer is formed of an inorganic oxide, preferably of silicon oxide.

[0130] The high refractive index layer preferably has a refractive index of 1.90 to 2.60, more preferably 2.00 to 2.40, at a wavelength of 500 to 550 nm. The high refractive index layer is formed of, for example, an inorganic oxide. The inorganic oxide used for the high refractive index layer is preferably at least one selected from the group consisting of zirconium oxide, tantalum oxide, yttrium oxide, titanium oxide, niobium oxide, and aluminum oxide, more preferably at least one selected from the group consisting of zirconium oxide and tantalum oxide.

[0131] The antireflection layer can be formed by alternately stacking the low refractive index layer and the high refractive index layer by a vacuum deposition method.

[0132] <water repellent layer>

[0133] The water repellent layer is formed using a water repellent material composition described later. The water repellent layer can be formed on the hard coat layer, on the functional layer, or preferably on the antireflection layer. Also, the water repellent layer is preferably located on the most surface.

[0134] As shown above, the present specification discloses the following embodiments.

[0135] <1>

[0136] An isocyanate composition containing a compound represented by formula (1) and an isocyanate component

[0137] .

[0138] <2>

[0139] The isocyanate composition according to <1> or <2>, wherein

[0140] The compound represented by formula (1) is contained in an amount of 10 to 10,000 mass ppm relative to the isocyanate component.

[0141] <3>

[0142] The isocyanate composition according to <1> or <2>, wherein

[0143] The isocyanate component contains at least one selected from the group consisting of bis(isocyanatomethyl)dicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)benzene, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate.

[0144] <4>

[0145] The isocyanate composition according to <1> to <3>, containing a phenolic antioxidant.

[0146] <5>

[0147] The isocyanate composition according to <4>, wherein

[0148] The phenolic antioxidant contains 2,6-di-tert-butyl-p-cresol or phenol.

[0149] <6>

[0150] The isocyanate composition according to <4> or <5>, wherein

[0151] The blending amount of the phenolic antioxidant is 10 to 10,000 mass ppm relative to the isocyanate component.

[0152] <7>

[0153] A polymerizable composition containing:

[0154] The isocyanate composition according to any one of <1> to <6>, and

[0155] An active hydrogen compound component.

[0156] <8>

[0157] The polymerizable composition according to <7>, wherein

[0158] The active hydrogen compound component contains at least one selected from the group consisting of toluene diamine, pentaerythritol tetra mercaptoacetate, pentaerythritol tetra mercaptopropionate, trimethylolpropane tri mercaptoacetate, trimethylolpropane tri mercaptopropionate, bis(mercaptoethylthio)mercaptopropane, bis(mercapto methyl)-3,6,9-trithiaundecane dithiol, dimercaptoethyl sulfide, bis(mercapto methyl)ditetrahydrothiophene, dimercaptoethyl ether, and diethylene glycol.

[0159] <9>

[0160] The polymerizable composition according to <8>, wherein

[0161] The bis(mercapto methyl)-3,6,9-trithiaundecane dithiol is a mixture of 4,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, and 5,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol.

[0162] <10>

[0163] A resin which is a cured product of the polymerizable composition according to <8> or <9>.

[0164] <11>

[0165] An optical material comprising <10> The resin.

[0166] <12>

[0167] A spectacle lens comprising <10> or <11> The resin.

[0168] Example

[0169] Hereinafter, this embodiment will be described in more detail using examples and comparative examples. It should be noted that the present invention is not limited to the following examples.

[0170] [Hazen color number (APHA)]

[0171] The Hazen color number (APHA) of the polymerizable composition was measured by the method of JIS K0071-1:1998.

[0172] <Example 1>

[0173] To a mixture of 2,5-bis(isocyanatemethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatemethyl)bicyclo[2.2.1]heptane (hereinafter also referred to as "I-1") as isocyanate components, 1000 ppm by mass of dibutyl phosphate (a compound represented by formula (1), hereinafter also referred to as "DBP") was added relative to the isocyanate components to produce an isocyanate composition. The APHA of the resulting isocyanate composition was evaluated, and the results are shown in Table 1 as Day 0. The compositions were stored at 40°C, and the APHA values ​​were measured after 7, 14, and 21 days, respectively, as shown in Table 1.

[0174] <Example 2>

[0175] An isocyanate composition was obtained in the same manner as in Example 1 except that 50 ppm by mass of 2,6-di-tert-butyl-p-cresol (hereinafter also referred to as "BHT") was further added to the isocyanate component.

[0176] <Example 3>

[0177] An isocyanate composition was obtained in the same manner as in Example 1 except that 100 ppm by mass of BHT was further added to the isocyanate component.

[0178] <Example 4>

[0179] To the isocyanate component, PhOH 50 mass ppm was further added, and otherwise, the isocyanate composition was obtained similarly to Example 1. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0180] <Example 5>

[0181] To the isocyanate component, PhOH 100 mass ppm was further added, and otherwise, the isocyanate composition was obtained similarly to Example 1. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0182] <Comparative Example 1>

[0183] BHT 50 mass ppm was added instead of DBP with respect to the isocyanate component, and otherwise, the isocyanate composition was obtained similarly to Example 1. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0184] <Comparative Example 2>

[0185] Acid phosphoxybutyl ethyl ester "JP-506H" (trade name, manufactured by Jouno Chemical Industry Co., Ltd.) 1000 mass ppm was added instead of DBP with respect to the isocyanate component, and otherwise, the isocyanate composition was obtained similarly to Example 1. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0186] <Comparative Example 3>

[0187] To the isocyanate component, BHT 50 mass ppm was further added, and otherwise, the isocyanate composition was obtained similarly to Comparative Example 2. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0188] <Comparative Example 4>

[0189] To the isocyanate component, BHT 100 mass ppm was further added, and otherwise, the isocyanate composition was obtained similarly to Comparative Example 2. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0190] <Comparative Example 5>

[0191] To the isocyanate component, PhOH 50 mass ppm was further added, and otherwise, the isocyanate composition was obtained similarly to Comparative Example 2. The isocyanate composition was evaluated for APHA similarly to Example 1.

[0192] <Comparative Example 6>

[0193] For the isocyanate component, PhOH 100 mass ppm was further added, and otherwise, the isocyanate composition was obtained in the same manner as in Comparative Example 2. The isocyanate composition was evaluated for APHA in the same manner as in Example 1.

[0194]

[0195] In the table, various abbreviations are as described below.

[0196] I-1: mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6- bis(isocyanatomethyl)bicyclo[2.2.1]heptane

[0197] DBP: dibutyl phosphate (compound represented by formula (1))

[0198] BHT: 2,6-di-tert-butyl-p-cresol

[0199] JP-506H: butoxyethyl acid phosphate

[0200] Amount (mass ppm): amount of addition (unit: mass ppm) with respect to the isocyanate component

[0201] <Example 6>

[0202] To 50.28 parts by mass of the isocyanate composition of Example 1, 0.06 parts by mass of dimethyltin dichloride as a catalyst, 0.15 parts by mass of butoxyethyl acid phosphate "JP-506H" (trade name, manufactured by JONOH CHEMICAL CO., LTD.) as a release agent, and 0.55 parts by mass of "Seesorb 701" (trade name, manufactured by SHIPRO KASEI KAISHA) as an ultraviolet absorber were added, and stirred and mixed. Then, 25.50 parts by mass of pentaerythritol tetra(3-mercaptopropionate) and 24.22 parts by mass of 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane were further added, and stirred and mixed under reduced pressure of 10 mmHg for 30 minutes, and a curable composition was prepared. Subsequently, the curable composition was injected into a lens molding mold (set to 0.00 D, thickness 1.6 mm) formed of a glass mold and a resin gasket prepared in advance, and polymerization was performed at 20°C to 120°C for 24 hours in an electric furnace. After the end of the polymerization, the gasket and the mold were removed, and then heat treatment was performed at 120°C for 2 hours, and a lens substrate was obtained.

Claims

1. An isocyanate composition containing a compound represented by formula (1) and an isocyanate component 。 2. The isocyanate composition according to claim 1, wherein, the blending amount of the compound represented by formula (1) is 10 to 10,000 mass ppm relative to the isocyanate component.

3. The isocyanate composition according to claim 1, wherein, the isocyanate component contains at least one selected from the group consisting of bis(isocyanatomethyl)bicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)benzene, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate.

4. The isocyanate composition according to claim 1, containing a phenolic antioxidant.

5. The isocyanate composition according to claim 4, wherein, the phenolic antioxidant contains 2,6-di-tert-butyl-p-cresol or phenol.

6. The isocyanate composition according to claim 4, wherein, the blending amount of the phenolic antioxidant is 10 to 10,000 mass ppm relative to the isocyanate component.

7. A polymerizable composition containing: the isocyanate composition according to any one of claims 1 to 6, and an active hydrogen compound component.

8. The polymerizable composition according to claim 7, wherein, the active hydrogen compound component contains at least one selected from the group consisting of toluene diamine, pentaerythritol tetra mercaptoacetate, pentaerythritol tetra mercaptopropionate, trimethylolpropane tri mercaptoacetate, trimethylolpropane tri mercaptopropionate, bis(mercaptoethylthio)mercaptopropane, bis(mercapto methyl)-3,6,9-trithiaundecane dithiol, dimercaptoethyl sulfide, bis(mercapto methyl)ditetrahydrothiophene, dimercaptoethyl ether, and diethylene glycol.

9. The polymerizable composition according to claim 8, wherein, the bis(mercapto methyl)-3,6,9-trithiaundecane dithiol is a mixture of 4,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol, and 5,7-bis(mercapto methyl)-3,6,9-trithiaundecane-1,11-dithiol.

10. A resin which is a cured product of the polymerizable composition according to claim 8.

11. An optical material containing the resin according to claim 10.

12. A spectacle lens containing the resin according to claim 10.

Images