Patent Application
20230116314
The present disclosure relates to a spectacle lens.
In spectacle lenses, cutting light rays in the blue region (wavelength range of 380 to 500 nm) reduces glare and improves visibility and contrast. Furthermore, regarding the eyes' health, it is said that light rays in the blue region (wavelength range of 380 to 500 nm) may cause damage to retinas or the like because such light rays have high energy. The damage by blue light is referred to as a “blue light hazard”. In particular, it is said that the low wavelength side near the wavelength of 380 to 420 nm is the most dangerous, and the light of this region should desirably be cut.
PTL 1 discloses an optical material including at least one UV ray absorber (a) with a maximum absorbing peak within the range of 350 nm or more and 370 nm or less, and the light transmittance measured at a thickness of 2 mm satisfies the following characteristics (1) to (3): (1) the light transmittance at a wavelength of 410 nm is 10% or less; (2) the light transmittance at a wavelength of 420 nm is 70% or less; and (3) the light transmittance at a wavelength of 440 nm is 80% or more.
According to a conventional spectacle lens as shown in PTL 1, the transmittance of light of a wavelength of 410 nm can be reduced by including a specific UV absorber. In general, however, UV absorbers also absorb light of wavelengths near 410 nm when they exhibit light absorption properties at that wavelength. For that reason, when a UV absorber reduces the transmittance of light of a wavelength of 410 nm, light in the visible light region is also absorbed, and coloring issues arise, such as the yellowing of spectacle lenses. Yellow-colored spectacle lenses give an impression of deterioration in appearance. Thus, for example, the inclusion of a coloring agent will give the lens a gray or slightly bluish tint, which increases costs and, in some cases, reduces transmittance. Therefore, suppressing the coloration of spectacle lenses due to UV absorbers by increasing the transmittance of light of a wavelength of 430 nm is focused on.
An embodiment of the present disclosure relates to a spectacle lens that reduces the transmittance of light of a wavelength of 410 nm and shows excellent transmittance of light of 430 nm.
One embodiment according to the present disclosure relates to a spectacle lens including a compound represented by formula (1)
R1 is an alkoxy group having 1 to 20 carbon atoms;
R2 is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms;
R3 is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms;
n is an integer of 1 to 2; and
m is an integer of 0 to 2).
According to an embodiment of the present disclosure, a spectacle lens that reduces the transmittance of light at a wavelength of 410 nm and shows excellent transmittance at a wavelength of 430 nm can be provided.
Hereinafter, embodiments according to the present disclosure will be described in detail with reference to the drawings, as necessary. However, the disclosure is not limited thereto, and various modifications are possible without departing from the gist thereof. It should be noted that, in the drawings, the same symbols are assigned to the same elements and will not be further explained. Unless otherwise specified, positional relationships, such as vertical and horizontal relationships, are based on the positional relationships illustrated in the drawings. Further, the dimensional ratios of the drawings are not limited to those illustrated therein.
It should be noted that, in the present description, for example, the notation of a numerical range of “1 to 100” shall encompass both the lower limit “1” and the upper limit “100”. The same applies to notations of other numerical ranges.
For example, the “cured product of an isocyanate component and an active hydrogen-containing compound component” does not mean excluding other components but means a cured product of a composition containing at least an isocyanate component and an active hydrogen-containing compound component.
The spectacle lens according to the present embodiment includes a compound represented by formula (1):
wherein
R1 is an alkoxy group having 1 to 20 carbon atoms;
R2 is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms;
R3 is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms; and
m is an integer of 0 to 2 (hereinafter referred to as “compound 1”).
According to an embodiment of the present disclosure, a spectacle lens that reduces the transmittance of light at a wavelength of 410 nm and shows excellent transmittance at a wavelength of 430 nm can be provided.
The spectacle lens according to the present embodiment containing a compound 1 represented by formula (1) reduces the transmittance of light at a wavelength of 410 nm and shows excellent transmittance at a wavelength of 430 nm. Light with a wavelength of 410 nm is in the visible light range but has relatively high energy. Thus, such light is harmful to the eyes when visually viewed over a long period of time. The compound 1 has a —COR1 group on the benzotriazole ring, allowing compound 1 to absorb light of a wavelength of 410 nm. Furthermore, it is desirable not to absorb light on the side of wavelengths longer than 410 nm because the inclusion of compounds that absorb light in the visible light region will easily cause coloration. However, when the absorption spectrum is observed, the absorption peak of the compound also absorbs light of the peak wavelength and the surrounding wavelengths thereof, resulting in a peak-shaped spectrum. Therefore, when the absorption of light of a wavelength of 410 nm is increased, the light in the surrounding area of the wavelength of 410 nm is also absorbed, which may easily cause coloration.
Therefore, from the viewpoint of the problem of the coloring of spectacle lenses, or in order to make such coloring less noticeable, using a large amount of coloring agents is required to make the hue a neutral gray, which results in a reduction of the luminous transmittance, etc. Regarding this issue, the compound 1 has a —COR1 group on the benzotriazole ring, which can reduce the absorption at a wavelength of 430 nm.
The site of substitution of —COR1 group may be the 5-position of the benzotriazole ring from the viewpoint of reducing the transmittance of light of a wavelength of 410 nm and reducing the transmittance at a wavelength of 430 nm.
In formula (1), R1 is an alkoxy group having 1 to 20 carbon atoms.
The number of carbon atoms in the alkoxy group in R1 may be 2 to 20, may be 4 to 20, may be 6 to 18, may be 6 to 15, or may be 6 to 12. The increase in the number of carbons in the alkoxy groups increases the solubility of the compound 1 in organic compounds such as isocyanate components and polythiol components. The alkyl group in R1 may be branched or linear, may be a branched alkyl group.
Examples of the alkoxy group in R1 include a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a n-butyloxy group, a sec-butyloxy group, a tert-butyloxy group, a pentyloxy group, a 1-methylpentyloxy group, a 2-methylpentyloxy group, a 3-methylpentyloxy group, a 1-ethylpentyloxy group, a 2-ethylpentyloxy group, a 3-ethylpentyloxy group, a n-hexyloxy group, a 1-methylhexyloxy group, a 2-methylhexyloxy group, a 3-methylhexyloxy group, a 1-ethylhexyloxy group, a 2-ethylhexyloxy group, a 3-ethylhexyloxy group, a n-heptyloxy group, a 1-methylheptyloxy group, a 2-methylheptyloxy group, a 3-methylheptyloxy group, a 1-ethylheptyloxy group, a 2-ethylheptyloxy group, a 3-ethylheptyloxy group, a n-octyloxy group, a 1-methyloctyloxy group, a 2-methyloctyloxy group, a 3-methyloctyloxy group, a 1-ethyloctyloxy group, a 2-ethyloctyloxy group, a 3-ethyloctyloxy group, a n-decyloxy group, a n-dodecyloxy group, a n-dodecyloxy group, a n-tetradecyloxy group, a n-hexadecyloxy group, a n-octadecyloxy group, and a n-icosyloxy group. Among these, the alkoxy group may be a tert-butyloxy group, a hexyloxy group, an n-octyloxy group, or a 2-ethylhexyloxy group, or may be a 2-ethylhexyloxy group.
As stated above, R1 may be an alkoxy group having 4 to 20 carbon atoms, may be a branched alkoxy group having 4 to 20 carbon atoms, may be tert-butyloxy group and 2-ethylhexyloxy group, or may be 2-ethylhexyloxy group.
n is an integer of 1 to 2, or may be 1.
In the formula (1), R2 represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and for the alkyl group and the alkoxy group, the number of carbon atoms may be each independently 1 to 8, may be each independently 2 to 8, or may be each independently 4 to 8. The alkyl group and alkoxy group may be branched or linear. Among alkyl groups and alkoxy groups, in some embodiment, R2 may be alkoxy groups.
Examples of alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an n-octyl group, a 1,1,3,3-tetramethylbutyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
Examples of alkoxy groups include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a sec-butyloxy group, a tert-butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. Among them, in some embodiment the alkoxy group may be a methoxy group or an ethoxy group.
In formula (1), R3 is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Examples of the alkyl group and the alkoxy group in R3 are the same as those listed for R2.
m is an integer of 0 to 2, or may be 0.
Although not particularly limited, specific examples of the compound 1 include 2-ethylhexyl 2-(2-hydroxy-4-methoxyphenyl)-2H-benzotriazole-5-carboxylate (a compound represented by the following formula (1-1)),
2-ethylhexyl 2-(2-hydroxy-4-ethoxyphenyl)-2H-benzotriazole-5-carboxylate (a compound represented by the following formula (1-2)),
Among these compounds 1, one may be used singly, or two or more of them may be used.
Among these, the compound 1 may be 2-ethylhexyl 2-(2-hydroxy-4-methoxyphenyl)-2H-benzotriazole-5-carboxylate or 2-ethylhexyl 2-(2-hydroxy-4-ethoxyphenyl)-2H-benzotriazole-5-carboxylate.
The spectacle lens according to the present embodiment includes, for example, a lens substrate. The spectacle lens according to the present embodiment may include at least one layer selected from the group consisting of a hard coat layer, a base layer, and an anti-reflection layer.
When the lens substrate 11 is a finished lens, a spectacle lens 1 of the present embodiment includes a hard coat layer 21b disposed on the surface 11b side on the eyeball side of the lens substrate 11, a functional layer 31b disposed on the surface 21bb side of the eyeball side of this hard coat layer 21b, and a water repellent layer 41b disposed on the surface 31bb side of the eyeball side of this functional layer 31b.
It should be noted that, although not illustrated, a base layer may be disposed between the lens substrate 11 and the hard coat layer 21f, or between the lens substrate 11 and the hard coat layer 21b.
The lens substrate may contain the compound 1 and a resin.
The spectacle lens may contain 0.05 parts by mass or more and 2.00 parts by mass or less of the compound 1 in relation to 100 parts by mass of the resin in the lens substrate. From the viewpoint of further reducing the transmittance of light of a wavelength of 410 nm and further increasing the transmittance of light of a wavelength of 430 nm, the content of the compound 1 may be 0.10 parts by mass or more and 2.00 parts by mass or less, may be 0.15 parts by mass or more and 1.50 parts by mass or less, or may be 0.20 parts by mass or more and 1.00 parts by mass or less in relation to 100 parts by mass of the resin in the lens substrate.
From the viewpoint of further reducing the transmittance of light of a wavelength of 410 nm, further increasing the transmittance of light of a wavelength of 430 nm, and suppressing the decrease in Abbe's number, the content of the compound 1 may be 0.05 parts by mass or more and 0.60 parts by mass or less, may be 0.10 parts by mass or more and 0.55 parts by mass or less, or may be 0.20 parts by mass or more and 0.50 parts by mass or less in relation to 100 parts by mass of the resin in the lens substrate.
Examples of the resin of the lens substrate include a urethane-based resin, an episulfide resin, a polycarbonate resin, and an acrylic resin.
The resin may be at least one selected from the group consisting of a polythiourethane resin, a polysulfide resin, and a polyurethane resin, or may be at least one selected from the group consisting of a polythiourethane resin and a polysulfide resin.
A urethane-based resin is a cured product of a polymerizable composition containing an isocyanate component and an active hydrogen-containing compound component. Examples of urethane-based resins include a thiourethane resin including a polymerization site of an isocyanate component and a polythiol component; a urethane resin including a polymerization site of an isocyanate component and a polyol component; and, a urethane urea resin having a polythiourethane site that is a polymerization site of an isocyanate component and a polythiol or polyol component and a polyurea site that is a polymerization product of an isocyanate component and a polyamine component.
Examples of isocyanate components include a polyisocyanate compound having an aromatic ring, a polyisocyanate compound having an aliphatic ring, and a linear or branched aliphatic polyisocyanate compound.
Examples of polyisocyanate compounds having an aromatic ring include diisocyanatobenzene, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-methylenebis(2-methylphenylisocyanate), 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′-tetramethylxylylene 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-methyloxy-4-isocyanatophenyl) disulfide, and bis(4-methyloxy-3-isocyanatophenyl) disulfide.
Examples of polyisocyanate compounds having an aliphatic ring include 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 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, and 4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane.
Examples of linear or branched aliphatic polyisocyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 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, 1,5-diisocyanato-2-isocyanatomethyl-3-pentane, 1,2,3-tris(isocyanatomethylthio)propane, 1,2,3-tris(isocyanatoethylthio)propane, 3,5-dithia-1,2,6,7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithia-1,7-heptanediisocyanate, 2,5-diisocyanatomethylthiophene, 4-isocyanatoethylthio-2,6-dithia-1,8-octanediisocyanate, 1,2-diisothiocyanatoethane, and 1,6-diisothiocyanatohexane.
These may be used alone, or two or more thereof may be used in combination.
The isocyanate component may include at least one (hereinafter referred to as a “suitable isocyanate compound”) selected from the group consisting of
Example of bis(isocyanatomethyl)bicyclo[2.2.1]heptane include at least one 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 bis(isocyanatomethyl)bicyclo[2.2.1]heptane may be a mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane.
Example of bis(isocyanatomethyl)cyclohexane include 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane. Among these, bis(isocyanatomethyl)cyclohexane may be 1,3-bis(isocyanatomethyl)cyclohexane.
Examples of bis(isocyanatomethyl)benzene include 1,3-bis(isocyanatomethyl)benzene and 1,4-bis(isocyanatomethyl)benzene. Among these, bis(isocyanatomethyl)benzene may be 1,3-bis(isocyanatomethyl)benzene.
Examples of tolylene diisocyanate include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. Among these, tolylene diisocyanate may be 2,4-tolylene diisocyanate.
Examples of diphenylmethane diisocyanate include 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate.
Examples of dicyclohexylmethane diisocyanate include dicyclohexylethane 4,4′-diisocyanate.
The content of the “suitable isocyanate compound” mentioned above in the isocyanate component may be 80 mass % or more, may be 90 mass % or more, or may be 95 mass % or more and 100 mass % or less.
Examples of active hydrogen-containing compound components include a polythiol component, a polyol component, or a polyamine component.
Examples of polythiol components include an ester compound of a polyol compound and a mercapto group-containing carboxylic acid compound, a linear or branched aliphatic polythiol compound, a polythiol compound having an aliphatic ring, and a polythiol compound having an aromatic ring.
In the ester compound of a polyol compound and a mercapto group-containing carboxylic acid compound, examples of polyol compounds include compounds having two or more hydroxyl groups in a molecule. Here, examples of polyol compounds include ethylene glycol, diethylene glycol, propanediol, propanetriol, butanediol, trimethylolpropane, bis(2-hydroxyethyl) disulfide, pentaerythritol, and dipentaerythritol.
Examples of mercapto group-containing carboxylic acid compounds include thioglycolic acid, mercaptopropionic acid, a thiolactic acid compound, and thiosalicylic acid.
Examples of ester compounds of a polyol compound and a mercapto group-containing carboxylic acid compound include ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(2-mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(2-mercaptoacetate), and dipentaerythritol hexakis(3-mercaptopropionate).
Examples of linear or branched aliphatic polythiol compounds include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethyloxybutane-1,2-dithiol, 2,3-dimercapto-1-propanol, 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, dimercaptoethyl ether, 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,1,2,2-tetrakis(mercaptoethylthio)ethane, 1,1,3,3-tetrakis(mercaptoethylthio)propane, 3-mercaptomethyl-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-mercaptopropane, 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, and 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol.
Examples of polythiol compounds 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.
Examples of polythiol compounds 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, 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-di(p-methyloxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane.
These may be used alone, or two or more thereof may be used in combination.
Examples of polyol components include ethylene glycol, diethylene glycol, propanediol, propanetriol, butanediol, trimethylolpropane, bis(2-hydroxyethyl) disulfide, pentaerythritol, and dipentaerythritol.
Examples of polyamine components include polymethylenediamine, polyetherdiamine, diethylenetriamine, iminobis(propylamine), bis(hexamethylenetriamine), diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, pentaethylenehexamine, dimethylaminopropylamine, aminoethylethanolamine, methyliminobis(propylamine), diaminomethane, N-aminomethylpiperazine, 1,3-diaminocyclohexane, isophoronediamine, m-xylenediamine, tetrachloro-p-xylenediamine, m-phenylenediamine, 4,4′-methylenedianiline, diaminodiphenylsulfone, benzidine, diaminodiphenyl ether, 4,4′-thiodianiline, 4,4′-bis(o-toluidine)dianisidine, o-phenylenediamine, 2,4-toluenediamine, 2,5-toluenediamine, methylenebis(o-chloroaniline), diaminoditolyl 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, pyrazine, 2,4,6-tris(dimethylaminomethylol)phenol, N-methylpiperazine, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldimethoxysilane.
The active hydrogen-containing compound component may include at least one selected from the group consisting of toluenediamine, pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(mercaptopropionate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), bis(mercaptoethylthio)mercaptopropane, bis(mercaptomethyl)-3,6,9-trithiaundecanedithiol, dimercaptoethyl sulfide, bis(mercaptomethyl)dithiane, dimercaptoethyl ether, and diethylene glycol.
Examples of toluenediamine include 2,4-toluenediamine and 2,5-toluenediamine.
Examples of pentaerythritol tetrakis(mercaptoacetate) include pentaerythritol tetrakis(2-mercaptoacetate).
Examples of pentaerythritol tetrakis(mercaptopropionate) include pentaerythritol tetrakis(3-mercaptopropionate).
Examples of trimethylolpropane tris(mercaptoacetate) include trimethylolpropane tris(2-mercaptoacetate).
Examples of trimethylolpropane tris(mercaptopropionate) include trimethylolpropane tris(3-mercaptopropionate).
Examples of bis(mercaptoethylthio)mercaptopropane include 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane.
Examples of bis(mercaptomethyl)-3,6,9-trithiaundecanedithiol include 4,7-bis(mercaptomethyl)-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. Bis(mercaptomethyl)-3,6,9-trithiaundecanedithiol may be 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, and 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol.
The active hydrogen-containing compound component may be a polythiol component.
The polythiol component
may include at least one selected from the group consisting of 2,5-bis(mercaptomethyl)-1,4-dithiane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 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-mercaptopropionate), butanediol bis(2-mercaptoacetate), butanediol bis(3-mercaptopropionate), dipentaerythritol hexakis(2-mercaptoacetate), and dipentaerythritol hexakis (3-mercaptopropionate);
may include 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-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, and pentaerythritol tetrakis(2-mercaptoacetate);
may include 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, and 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol; and may include 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, and 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol.
The amount of the polythiol components mentioned above may be 50 mass % or more, more may be 70 mass % or more, may be 90 mass % or more, or may be 95 mass % or more, and 100 mass % or less in the polythiol component.
The equivalent ratio (mercapto groups/isocyanato groups) between the mercapto groups of the polythiol component and the isocyanato group of the polyisocyanate component may be 40/60 or more, may be 43/57 or more, or may be 45/55 or more, and may be 60/40 or less, may be 55/45 or less, or may be 53/47 or less.
The total amount of the polythiol component and the polyisocyanate component may be 80 mass % or more, may be 90 mass % or more, or may be 95 mass % or more, and 100 mass % or less in the polymerizable composition.
The episulfide resin is a cured product of a polymerizable composition of an epithio compound. Here, the polymerizable composition may contain other monomers.
The epithio compound is a compound having an episulfide group (an epithio group).
Examples of epithio compounds include an episulfide compound having a linear or branched aliphatic skeleton, an episulfide compound having an alicyclic skeleton, an episulfide compound having an aromatic skeleton, and an episulfide compound having a dithiane ring skeleton.
Examples of episulfide compounds having a linear or branched aliphatic skeleton include bis(β-epithiopropyl) sulfide, bis((3-epithiopropyl) disulfide, 2-(2-β-epithiopropylthioethylthio)-1,3-bis(β-epithiopropylthio)propane, 1,2-bis[(2-β-epithiopropylthioethyl)thio]-3-(β-epithiopropylthio)propane, tetrakis(β-epithiopropylthiomethyl)methane, and 1,1,1-tris(β-epithiopropylthiomethyl)propane.
Examples of episulfide compounds having an alicyclic skeleton include 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, and bis[4-(β-epithiopropylthio)cyclohexyl]sulfide.
Examples of episulfide compounds having an aromatic skeleton include 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfine, and 4,4-bis(β-epithiopropylthio)biphenyl.
Examples of episulfide compounds having a dithiane ring skeleton include 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethyl)-1,4-dithiane, and 2,3,5-tri(β-epithiopropylthioethyl)-1,4-dithiane.
In addition to the epithio compound, other polymerizable components such as the polyisocyanate component and the polythiol component, which were mentioned above, may be added.
Among these, the episulfide compound may be an episulfide compound having a linear or branched aliphatic skeleton, or may be bis(β-epithiopropyl) sulfide or bis(β-epithiopropyl) disulfide.
The content of the epithio compound may be 50 mass % or more, may be 60 mass % or more, may be 70 mass % or more, may be 80 mass % or more, or may be 90 mass % or more, and may be 98 mass % or less or may be 96 mass % or less in the polymerizable composition.
The polymerizable composition may further contain sulfur or a polythiol compound in combination with an epithio compound.
The content of sulfur may be 1 mass % or more, may be 5 mass % or more, or may be 10 mass % or more, and may be 30 mass % or less or may be 20 mass % or less in the polymerizable composition.
Examples of polythiol compounds include the compounds listed above.
When a polythiol compound is used in combination with an epithio compound, the content of the polythiol compound may be 2 mass % or more or may be 4 mass % or more, and may be 50 mass % or less, may be 40 mass % or less, may be 30 mass % or less, may be 20 mass % or less, or may be 10 mass % or less in the polymerizable components.
When the polymerizable composition contains a polyisocyanate component and a polythiol component, or an epithio compound, the composition may contain a polymerization catalyst.
Examples of polymerization catalysts include tin compounds and nitrogen-containing compounds.
Examples of tin compounds include alkyltin compounds and alkyltin halide compounds.
Examples of alkyltin compounds include dibutyltin diacetate and dibutyltin dilaurate.
Examples of alkyltin halide compounds include dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, and dimethyltin dibromide.
Among these, the polymerization catalyst may be dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, or dimethyltin dichloride, or may be dimethyltin dichloride.
Examples of nitrogen-containing compounds include a tertiary amine, a quaternary ammonium salt, an imidazole-based compound, and a pyrazole-based compound. The tertiary amine may be a hindered amine.
Examples of tertiary amines include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, N-methylmorpholine, N,N′-dimethylpiperazine, N,N,N′,N′-tetramethylethylenediamine, and 1,4-diazabicyclo[2.2.2]octane (DABCO).
Examples of hindered amines include 1,2,2,6,6-pentamethyl-4-piperidinol, 1,2,2,6,6-pentamethyl-4-hydroxyethyl-4-piperidinol, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, a mixture of methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate.
Examples of quaternary ammonium salts include tetraethylammonium hydroxide.
Examples of imidazole-based compounds include imidazole, 1-methyl-2-mercapto-1H-imidazole, 1,2-dimethyl imidazole, benzyl methyl imidazole, and 2-ethyl-4-imidazole.
Examples of pyrazole-based compounds include pyrazole and 3,5-dimethylpyrazole.
Among these, the nitrogen-containing compound may be a tertiary amine such as a hindered amine, an imidazole-based compound, and a pyrazole-based compound, or may be an imidazole-based compound, or may be 1-methyl-2-mercapto-1H-imidazole.
When the polymerizable composition contains an isocyanate component and an active hydrogen-containing compound component, the amount of polymerization catalysts added in the polymerizable composition may be 0.001 parts by mass or more, may be 0.005 parts by mass or more, or may be 0.007 parts by mass or more, and may be 2 parts by mass or less, may be 1 part by mass or less, or may be 0.5 parts by mass or less in relation to 100 parts by mass of the total amount of the isocyanate component and the active hydrogen-containing compound component.
When the polymerizable composition contains an epithio compound, the amount of polymerization catalysts added in the polymerizable composition may be 0.001 parts by mass or more, may be 0.005 parts by mass or more, or may be 0.007 parts by mass or more, and may be 2 parts by mass or less, may be 1 part by mass or less, or may be 0.5 parts by mass or less in relation to 100 parts by mass of the total amount of polymerizable components.
The polycarbonate resin may be a cured product of a polymerizable composition containing diethylene glycol bis(allyl carbonate).
Monomers may include a monomer having two or more polymerizable unsaturated bonds in a molecule in order to obtain a three dimensionally-crosslinked optical resin.
Examples of polymerizable unsaturated bonds include a (meth)acrylate group, an allyl group, a vinyl group, and the like. It should be noted that a (meth)acrylate group is at least one selected from a methacrylate group and an acrylate group.
Among these, the polymerizable unsaturated bond may be at least one selected from the group consisting of a methacrylate group and an allyl group.
As the monomer having two or more polymerizable unsaturated bonds in a molecule, diethylene glycol bis(allyl carbonate) may be included, and diethylene glycol bis(allyl carbonate), benzyl methacrylate, diallyl phthalate, and alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group may be included.
The mixing amount of diethylene glycol bis(allyl carbonate) may be 5 mass % or more, may be 10 mass % or more, or may be 20 mass % or more, and may be 100 mass % or less, may be 80 mass % or less, may be 50 mass % or less, or may be 40 mass % or less in relation to the total amount of monomers.
When diethylene glycol bis(allyl carbonate) is used in combination with benzyl methacrylate, diallyl phthalate, and alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group, the mixing amount of the diethylene glycol bis(allyl carbonate) may be 5 mass % or more, may be 10 mass % or more, or may be 20 mass % or more, and may be 40 mass % or less or may be 35 mass % or less in relation to the total amount of monomers.
The mixing amount of benzyl methacrylate may be 5 mass % or more, may be 10 mass % or more, or may be 15 mass % or more, and may be 40 mass % or less, may be 30 mass % or less, or may be 25 mass % or less in relation to the total amount of monomers.
As a diallyl phthalate, one or two selected from the group consisting of diallyl isophthalate and diallyl terephthalate may be mentioned.
The mixing amount of diallyl phthalate may be 14 mass % or more, may be 20 mass % or more, or may be 30 mass % or more, and may be 88 mass % or less, may be 70 mass % or less, or may be 60 mass % or less in relation to the total amount of monomers.
Examples of alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group include at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, iso-butyl methacrylate, and tert-butyl methacrylate.
The content of the alkyl methacrylate may be 1 mass % or more, may be 2 mass % or more, or may be 3 mass % or more, and may be 6 mass % or less or may be 5 mass % or less in relation to the total amount of monomers.
Examples of radical initiators used in polymerization include 1,1-azobis(cyclohexanecarbonate), diisopropyl peroxycarbonate, 1,1′-azobis(cyclohexanenitrate), di-tert-butyl peroxide, and the like.
The mixing amount of the radical initiator may be 0.1 parts by mass or more, may be 0.5 parts by mass or more, or may be 1.0 part by mass or more, and may be 10 parts by mass or less, may be 8 parts by mass or less, or may be 5 parts by mass or less in relation to 100 parts by mass of monomers.
An acrylic resin is a cured product of a polymerizable composition containing an acrylic compound. Here, the polymerizable composition may contain other monomers.
Examples of acrylic compounds include a multifunctional (meth)acrylate compound having an aromatic ring, polyalkylene glycol di(meth)acrylate, a monofunctional acrylate, and the like.
Among these, the acrylic compound may be a multifunctional (meth)acrylate compound having an aromatic ring or polyalkylene glycol di(meth)acrylate.
Examples of multifunctional (meth)acrylate compounds having an aromatic ring include an alkylene oxide-modified bisphenol A having (meth)acryloyl groups at both ends and alkylene oxide-modified and urethane-modified bisphenol A having (meth)acryloyl groups at both ends.
Among these, the multifunctional (meth)acrylate compound may be an alkylene oxide-modified bisphenol A having (meth)acryloyl groups at both ends.
An example of the alkylene oxide-modified bisphenol A having (meth)acryloyl groups at both ends may be a compound represented by formula (2):
wherein R51 is an ethylene group or a propylene group; R52 is hydrogen or a methyl group; X is an oxygen or sulfur atom and may be an oxygen atom; m and n each represent an average number of moles added; and m+n is 1.5 to 6 and may be 2 to 4.
Examples of alkylene oxide-modified bisphenol A having (meth)acryloyl groups at both ends include 2,2-bis[4-[2-((meth)acryloyloxy)ethoxy]phenyl]propane and 2,2-bis[4-[2-((meth)acryloyloxy)ethoxy]-3,5-dibromophenyl]propane.
The content of the multifunctional (meth)acrylate compound having an aromatic ring may be 40 mass % or more, may be 50 mass % or more, or may be 55 mass % or more, and may be 90 mass % or less, may be 80 mass % or less, or may be 70 mass % or less in the polymerizable composition.
Examples of polyalkylene glycol di(meth)acrylate include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, dibuthylene glycol di(meth)acrylate, tributhylene glycol di(meth)acrylate, and tetrabuthylene glycol di(meth)acrylate.
The content of the polyalkylene glycol di(meth)acrylate may be 10 mass % or more, may be 20 mass % or more, or may be 30 mass % or more, and may be 60 mass % or less, may be 50 mass % or less, or may be 45 mass % or less in the polymerizable composition.
Examples of monofunctional (meth)acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenyl phenyl (meth)acrylate, 4-phenylphenyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, 3-(4-phenylphenyl)-2-hydroxypropyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenyl-di(oxyethyl) (meth)acrylate, and 2,4,6-tribromobenzyl (meth)acrylate.
The total amount of polymerizable components may be 80 mass % or more, may be 85 mass % or more, or may be 90 mass % or more, and may be 99 mass % or less and may be 95 mass % or less in the polymerizable composition.
When the polymerizable composition contains an acrylic compound, the composition may contain a radical polymerization initiator.
Examples of radical polymerization initiators include energy ray-sensitive polymerization initiators and heat-sensitive polymerization initiators.
Examples of energy ray-sensitive polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxycyclohexyl phenyl ketone, methyl phenylglyoxylate, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of heat-sensitive polymerization initiators include organic peroxide and azo compounds.
Examples of organic peroxide include peroxy esters such as tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxyacetate, cumyl peroxyneodecanoate, tert-butyl peroxyoxtoate, tert-butyl peroxyisopropylcarbonate, cumyl peroxyoxtoate, tert-hexyl peroxyneodecanoate, tert-hexyl peroxypivalate, and tert-butyl peroxyneohexanoate; peroxy ketals such as 1,1-bis(tert-butyl peroxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)octane, and 2,2-bis(tert-butylperoxy)butane; diacyl peroxides such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and m-toluoyl peroxide; and peroxydicarbonates such as diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate.
Examples of azo compounds include 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis(isobutyrate), and 2,2′-azobis(2,4,4-trimethylpentane).
The amount of the radical polymerization initiator added may be 0.01 parts by mass or more, may be 0.1 parts by mass or more, may be 0.5 parts by mass or more, and may be 10 parts by mass or less, may be 5 parts by mass or less, or may be 3 parts by mass or less in relation to 100 parts by mass of the total amount of acrylic compounds.
The lens substrate may include other additives such as a release agent, a coloring agent, an antioxidant, a coloring prevention agent, and a fluorescent whitening agent. These may be used alone, or two or more thereof may be used in combination.
Examples of release agents include phosphate ester compounds such as isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, nonyl acid phosphate, decyl acid phosphate, isodecyl acid phosphate, isodecyl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, propylphenyl acid phosphate, butylphenyl acid phosphate, butoxyethyl acid phosphate, and the like. The phosphoric acid ester compound may be either a phosphoric acid monoester compound or a phosphoric acid diester compound, but it may be a mixture of a phosphate monoester compound and a phosphate diester compound.
The amount of the release agent added may be 0.01 part by mass or more, or may be 0.05 parts by mass or more, and may be 1.00 part by mass or less, or may be 0.50 parts by mass or less in relation to 100 parts by mass of the total amount of resins.
The lens substrate may contain a coloring agent within the range that does not impair the luminous transmittance, which will be described later.
From the viewpoint of making the coloring due to the addition of the compound 1 less noticeable, the lens substrate may contain a coloring agent L having a largest maximum absorption wavelength within the range of 550 nm or more and 600 nm or less in a 20-ppm by mass toluene solution (hereinafter also simply referred to as “coloring agent L”).
From the viewpoint of making the coloring due to the addition of the compound 1 less noticeable, the lens substrate may contain a coloring agent S having a largest maximum absorption wavelength within the range of 500 nm or more and less than 550 nm in a 20-ppm by mass toluene solution (hereinafter also simply referred to as “coloring agent S”).
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the coloring agent L has a largest maximum absorption wavelength of 550 nm or more and 600 nm or less in a 20-ppm by mass toluene solution. The 20-ppm by mass toluene solution means a ratio of a solute to the total toluene solution.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the largest maximum absorption wavelength of the coloring agent L may be 550 nm or more, may be 560 nm or more, or may be 580 nm or more. From the viewpoint of obtaining a resin composition with a slightly bluish and good color tone, the largest maximum absorption wavelength of the coloring agent L may be 600 nm or less, and may be 590 nm or less.
Examples of the coloring agent L include C.I. Solvent Violet 11, 13, 14, 26, 31, 33, 36, 37, 38, 45, 47, 48, 51, 59, and 60; C.I. Disperse Violet 26, 27, and 28. Among these, the coloring agent L may be C.I. Disperse Violet 27 and C.I. Solvent Red 13 and 31, or from the viewpoint of high stability and small changes in color tone in the polymerization of the polymerizable composition, may be C.I. Disperse Violet 27, C.I. Solvent Violet 13, or may be C.I. Disperse Violet 27.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the amount of the coloring agent L added may be 10,000 ppb by mass or less, may be 3,000 ppb by mass or less, and still may be 1,500 ppb by mass or less in relation to resins. From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the amount of the coloring agent L added may be 200 ppb by mass or more, may be 300 ppb by mass or more, and still may be 400 ppb by mass or more.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the coloring agent S has a largest maximum absorption wavelength of 500 nm or more and less than 550 nm in a 20-ppm by mass toluene solution.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the largest maximum absorption wavelength of the coloring agent S may be 500 nm or more, may be 510 nm or more, or may be 530 nm or more. Further, from the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the largest maximum absorption wavelength of the coloring agent L may be 545 nm or less.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, examples of the coloring agent S include C.I. Solvent Red 24, 49, 52, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, and 247; and C.I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, and 289. Among these, the coloring agent S may be C.I. Solvent Red 52 or 146, from the viewpoint of high stability and small changes in color tone in the polymerization of the polymerizable composition, may be C.I. Solvent Red 52.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the amount of the coloring agent S added may be 500 ppb by mass or less, may be 100 ppb by mass or less, or may be 50 ppb by mass or more in relation to the resin. From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the amount of the coloring agent S added may be 1 ppb by mass or more, may be 3 ppb by mass or more, or may be 5 ppb by mass or more.
From the viewpoint of obtaining a lens substrate with a slightly bluish and good color tone, the mass ratio between the coloring agent L and the coloring agent S [(mass of coloring agent L)/(mass of coloring agent S)] is 5 or more and 500 or less.
The mass ratio of the coloring agent L and the coloring agent S may be 5 or more, may be 10 or more, may be 15 or more, or may be 20 or more. The mass ratio of the coloring agent L and the coloring agent S may be 500 or less, may be 200 or less, may be 100 or less, or may be 80 or less.
The lens substrate may be either a finished lens or a semi-finished lens.
The surface shape of the lens substrate is not particularly limited and may be any of a flat surface, a convex surface, a concave surface, or the like.
The lens substrate may be used for any purpose, such as single vision lenses, multifocal lenses, progressive power lenses, etc. For example, as an example, regarding a progressive power lens, a near portion region (near portion) and a progressive portion region (intermediate region) are normally included in the lower region as described above, and a distance portion region (distance portion) is normally included in an upper region.
As the lens substrate, a colorless substrate is usually used, but a colored one can be used as long as transparency is not impaired.
The lens substrate may be a meniscus type. The “meniscus-type” lens substrate means a lens substrate in which curved surfaces are formed on both surfaces. A meniscus-type lens substrate containing the compound 1 described above can suppress astigmatism.
Although not particularly limited, the optical center thickness of the lens substrate may be 0.5 mm or more and 10.0 mm or less, may be 0.5 mm or more and 5.0 mm or less, may be 0.5 mm or more and 3.0 mm or less, or may be 0.5 mm or more and 2.0 mm or less.
The diameter of the lens substrate is not particularly limited and generally about 50 to 100 mm.
The refractive index ne of the lens substrate may be 1.52 or more, may be 1.53 or more, may be 1.55 or more, may be 1.58 or more, or may be 1.60 or more.
From the viewpoint of enhancing the effect of improving Abbe's number by including the compound 1, the refractive index ne of the lens substrate may be 1.70 or more or may be 1.74 or more.
The refractive index ne of the lens substrate is not particularly limited and, for example, 1.80 or less.
From the viewpoint of reducing the blue light hazard, the transmittance of light with a wavelength of 410 nm in the lens substrate may be 5% or less, may be 3% or less, or may be 1.0% or less. The lower limit of the transmittance of light with a wavelength of 410 nm is not particularly limited and, for example, 0.0% or more.
The transmittance of light with a wavelength of 430 nm in the lens substrate may be 70% or more, may be 72% or more, or may be 75% or more. A lens substrate that has a transmittance of light with a wavelength of 410 nm mentioned above and also has a transmittance of light with a wavelength of 430 nm as above can suppress coloring or save the amount used of the dyeing agent described above while reducing the blue light hazard. The upper limit of the transmittance of light with a wavelength of 430 nm is not particularly limited and, for example, 90% or less.
From the viewpoint of reducing the transmission of UV rays that are harmful to the eyes, the transmittance of light with a wavelength of 400 nm in the lens substrate may be 3% or less, may be 1% or less, or may be 0.0% or less.
The transmittance of light of a wavelength of 420 nm in the lens substrate may be 50% or less, may be 30% or less, or may be 20% or less. A lens substrate that has a transmittance of light with a wavelength of 410 nm mentioned above and also has a transmittance of light with a wavelength of 420 nm as above can reduce the blue light hazard. The lower limit of the transmittance of light with a wavelength of 420 nm is not particularly limited and, for example, 0% or more.
The transmittance of light with a wavelength of 440 nm in the lens substrate may be 70% or more, may be 72% or more, or may be 75% or more. A lens substrate that has a transmittance of light with a wavelength of 440 nm as above can suppress coloring or save the amount used of the dyeing agent described above. The upper limit of the transmittance of light with a wavelength of 440 nm is not particularly limited and, for example, 95% or less.
The transmittance of light with a wavelength of 450 nm in the lens substrate may be 70% or more, may be 72% or more, or may be 75% or more. A lens substrate that has a transmittance of light with a wavelength of 450 nm as above can suppress coloring or the amount used of the dyeing agent described above. The upper limit of the transmittance of light with a wavelength of 450 nm is not particularly limited and, for example, 95% or less.
The transmittance of light with a wavelength of 550 nm in the lens substrate may be 70% or more, may be 80% or more, or may be 85% or more. The upper limit of the transmittance of light with a wavelength of 550 nm is not particularly limited and, for example, 95% or less.
The luminous transmittance of the lens substrate may be 70% or more, may be 80% or more, may be 85% or more, or may be 90% or more.
The upper limit of the luminous transmittance is not particularly limited and, for example, 100% or less and may be 95% or less.
The transmittance described above is a transmittance at the optical center of a lens substrate and can be measured using a spectrophotometer. As the spectrophotometer, for example, “U-4100” (trade name, manufactured by Hitachi, Ltd) may be used. The transmittance described above can be achieved by adjusting the content of the compound 1 according to the thickness of the lens substrate.
Although not particularly limited, the lens substrate is obtained by, for example,
a step of curing the polymerizable composition described above and
a step of annealing a cured resin.
The polymerization may be performed by a cast polymerization method. The lens substrate can be obtained, for example, by injecting the polymerizable composition into a mold die which is a combination of a glass or metal mold and a tape or a gasket and performing polymerization.
The polymerization conditions can be appropriately set according to the polymerizable composition. The polymerization starting temperature may be 0° C. or higher and may be 10° C. or higher, and may be 50° C. or lower or may be 40° C. or lower. It may raise the temperature from the polymerization starting temperature, and then perform heating, curing, and forming.
For example, the raised maximum temperature is generally 110° C. or higher and 130° C. or lower.
After completion of the polymerization, the lens substrate may be released, and annealing treatment may be performed. The temperature of the annealing treatment may be 100° C. to 150° C.
A hard coat layer is, for example, a cured film from a curable composition containing an inorganic oxide and a silicon compound. The curable composition may further include a multifunctional epoxy compound.
Examples of inorganic oxides include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide, zinc oxide, tin oxide, beryllium oxide, antimony oxide, and a composite oxide of two or more inorganic oxides among these. These may be used singly or in a combination of two or more thereof. Among these, inorganic oxides may be silicon oxide. Colloidal silica may be used as the inorganic oxide.
The content of inorganic oxides may be 20 mass % or more and 80 mass % or less, may be 25 mass % or more and 70 mass % or less, or may be 25 mass % or more and 50 mass % or less in the solid contents in the curable composition.
A silicon compound is, for example, a silicon compound having a hydrolyzable group such as an alkoxy group. The silicon compound may be a silane coupling agent having an organic group that bonds to a silicon atom and a hydrolyzable group. The organic group that bonds to a silicon atom may be an organic group having a functional group, including an epoxy group such as a glycidoxy group, a vinyl group, a methacryloxy group, an acryloxy group, a mercapto group, an amino group, and a phenyl group and may be an organic group having an epoxy group. The silicon compound may have an alkyl group that bonds to silicon.
Examples of commercialized products of the silane coupling agent described above include the trade names 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.
The content of the silicon compound may be 20 mass % or more and 90 mass % or less, may be 30 mass % or more and 75 mass % or less, or may be 50 mass % or more and 75 mass % or less in the solid contents in the curable composition.
A multifunctional epoxy compound is a multifunctional epoxy compound having two or more epoxy groups in a molecule and may be a multifunctional epoxy compound having two or three epoxy groups in a molecule. Examples of commercialized products of multifunctional epoxy compounds include the trade names “DENACOL” series 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, and the like, manufactured by Nagase ChemteX Corporation.
The content of the multifunctional epoxy compound may be 0 mass % or more and 50 mass % or less, may be 10 mass % or more and 40 mass % or less, or may be 15 mass % or more and 30 mass % or less in the solid contents in the curable composition.
The curable composition described above may be prepared by mixing the components as explained above and, if necessary, optional ingredients such as an organic solvent, a leveling agent, and a curing catalyst.
The hard coat layer described above may be formed by applying the curable composition to a substrate and curing the composition (by heat-curing, photo-curing, etc.). As means for applying the curable composition, commonly performed methods, such as a dipping method, a spin coating method, a spray method, and the like, can be applied. The curing of a curable composition containing a multifunctional epoxy compound is normally performed by heating. For example, curing by heating may be performed by placing a lens on which the curable composition described above is applied under an ambient temperature environment of 50° C. to 150° C. for about 30 minutes to 3 hours.
The base layer described above may be formed, for example, from a waterborne resin composition containing resin particles of at least one selected from the group consisting of a polyurethane resin, an acrylic resin, an epoxy resin, and the like.
As the waterborne resin composition described above, a commercially available waterborne polyurethane may be used as is, or, if necessary, after being diluted with a waterborne solvent. Examples of commercially available waterborne polyurethanes include the trade name “EVAFANOL” series manufactured by Nicca Chemical Co., Ltd., the trade name “SUPERFLEX” series manufactured by DKS CO. Ltd., the trade name “ADEKA BONTIGHTER” series manufactured by ADEKA Corporation, the trade name “OLESTAR” series manufactured by Mitsui Chemicals, Inc., the trade names “VONDIC” series and “HYDRAN” series manufactured by Dainippon Ink and Chemicals, Inc., the trade name “IMPRANIL” series manufactured by Bayer AG, the trade name “SOFLANNATE” series manufactured by Nippon Soflan Co., Ltd., the trade name “POIZ” series manufactured by Kao Corporation, the trade name “SANPLENE” series manufactured by Sanyo Chemical Industries Ltd., the trade name “AIZELAX” series manufactured by Hodogaya Chemical Co., Ltd., and the trade name “NeoRez” series manufactured by Zeneca Co., Ltd.
The base layer may be formed, for example, by applying the waterborne resin composition described above to a surface of a substrate and drying the composition.
Examples of the functional layer described above include an anti-reflection layer, a UV ray absorbing layer, an infrared ray absorbing layer, a photochromic layer, an antistatic layer, and an anti-fogging layer. These functional layers may be used singly or in a combination of two or more thereof. A known technique relating to spectacle lenses can be applied to these functional layers. Among these, spectacle lenses may be provided an anti-reflection layer.
An anti-reflection layer has, for example, low refractive index layers and high refractive index layers arranged alternately. The number of layers in an anti-reflection layer may be 4 to 11 layers and, may be 5 to 8 layers.
The refractive index of the low refractive index layer may be from 1.35 to 1.80, or may be from 1.45 to 1.50 in the wavelengths within the range of 500 to 550 nm. The low refractive index layer is composed of inorganic oxides and may be composed of silicon oxide.
The refractive index of the high refractive index layer may be from 1.90 to 2.60, or may be from 2.00 to 2.40 in the wavelengths within the range of 500 to 550 nm. The high refractive index layer is composed of, for example, an inorganic oxide. Inorganic oxide used in the high refractive index layer may be at least one selected from the group consisting of zirconium oxide, tantalum oxide, yttrium oxide, titanium oxide, niobium oxide, and aluminum oxide, or may be at least one selected from the group consisting of zirconium oxide and tantalum oxide.
The anti-reflection layer may be formed by alternately stacking low refractive index layers and high refractive index layers by vacuum deposition.
A water repellent layer is formed using a water repellent material composition, which will be described below. The water repellent layer may be formed on the hard coat layer or the functional layer, and may be on the anti-reflection layer. The water repellent layer may be positioned on the outermost layer.
From the viewpoint of reducing the blue light hazard, the transmittance of light with a wavelength of 410 nm in the entire spectacle lens may be 5% or less, may be 3% or less, or may be 1.0% or less. The lower limit of the transmittance of light with a wavelength of 410 nm is not particularly limited and, for example, 0.0% or more.
The transmittance of light with a wavelength of 430 nm in the entire spectacle lens may be 70% or more, may be 72% or more, or may be 75% or more. A lens substrate that has a transmittance of light with a wavelength of 410 nm mentioned above and also has a transmittance of light with a wavelength of 430 nm as above can suppress coloring or save the amount used of the dyeing agent described above while reducing the blue light hazard. The upper limit of the transmittance of light with a wavelength of 430 nm is not particularly limited and, for example, 90% or less.
From the viewpoint of reducing the transmission of UV rays that are harmful to the eyes, the transmittance of light with a wavelength of 400 nm in the entire spectacle lens may be 3% or less, may be 1% or less, or may be 0.0% or less.
The transmittance of light of a wavelength of 420 nm in the entire spectacle lens may be 50% or less, may be 30% or less, or may be 20% or less. A lens substrate that has a transmittance of light with a wavelength of 410 nm mentioned above and also has a transmittance of light with a wavelength of 420 nm as above can reduce the blue light hazard. The lower limit of the transmittance of light with a wavelength of 420 nm is not particularly limited and, for example, 0% or more.
The transmittance of light with a wavelength of 440 nm in the entire spectacle lens may be 70% or more, may be 72% or more, or may be 75% or more. A lens substrate that has a transmittance of light with a wavelength of 440 nm as above can suppress coloring or save the amount used of the dyeing agent described above. The upper limit of the transmittance of light with a wavelength of 440 nm is not particularly limited and, for example, 95% or less.
The transmittance of light with a wavelength of 450 nm in the entire spectacle lens may be 70% or more, may be 72% or more, or may be 75% or more. A lens substrate that has a transmittance of light with a wavelength of 450 nm as above can suppress coloring or save the amount used of the dyeing agent described above. The upper limit of the transmittance of light with a wavelength of 450 nm is not particularly limited and, for example, 95% or less.
The transmittance of light with a wavelength of 550 nm in the entire spectacle lens may be 70% or more, may be 80% or more, or may be 85% or more. The upper limit of the transmittance of light with a wavelength of 550 nm is not particularly limited and, for example, 95% or less.
The luminous transmittance of the spectacle lens may be 70% or more, may be 80% or more, may be 85% or more, or may be 90% or more. The upper limit of the luminous transmittance is not particularly limited and, for example, 100% or less and 95% or less.
The transmittance described above is a transmittance at the optical center of a spectacle lens and can be measured using a spectrophotometer. As the spectrophotometer, for example, “U-4100” (trade name, manufactured by Hitachi, Ltd) can be used. The transmittance described above can be achieved by adjusting the content of the compound 1 according to the thickness of the spectacle lens.
Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples. It should be noted that the present disclosure is not limited to these examples.
The transmittance of light of each wavelength was measured using a spectrophotometer “U-4100” (trade name, manufactured by Hitachi, Ltd). The measured point of the transmittance was set to the optical center of the spectacle lens and lens substrate.
<Largest Maximum Absorption Wavelength (λmax)>
The largest maximum absorption wavelength (λmax) of the coloring agent was measured under the following conditions using a spectrophotometer “U-4100” (trade name, manufactured by Hitachi, Ltd).
Sample: toluene solution (coloring agent content: 20 ppm by mass)
Measurement mode: Transmittance
Optical path length: 10 mm
The luminous transmittance was measured according to JIS T 7333:2005. The measured point of the transmittance was set to the optical center of the spectacle lens and lens substrate.
The refractive index of a spectacle lens was measured using a precision refractometer “KPR-2000” (manufactured by Kalnew Optical Industries) at 25° C. with F′ line (488.0 nm), C′ line (643.9 nm), and e line (546.1 nm). Then, the Abbe's number was calculated using the following formula.
Abbe's number νe=(ne−1)/(nF′−nC′)
The ne represents a refractive index measured with the e line, nF′ represents a refractive index measured with the F′ line, and nC′ represents a refractive index measured with the C′ line.
Laser light was applied to the optical center of a spectacle lens from a laser pointer (LP) having an emitting wavelength of 405±10 nm (output<1 mW), thereby observing whether the laser light passes through or not.
◯: Laser light was greatly reduced.
Δ: Laser light was slightly reduced.
x: Laser light passed.
To 50.28 parts by mass of a mixture of 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 0.06 parts by mass of dimethyltin dichloride as a catalyst, 0.15 parts by mass of an acidic phosphate ester, “JP 506H” (trade name, manufactured by Johoku Chemical Industry Co., Ltd.) as a mold release agent, 0.55 parts by mass of 2-ethylhexyl 2-(2-hydroxy-4-ethoxyphenyl)-2H-benzotriazole-5-carboxylate, 0.1037 parts by mass of Disperse Violet 27 (largest maximum absorption wavelength in a toluene solution of 20 ppm by mass: 586 nm) and 0.0013 parts by mass of Solvent Red 52 (largest maximum absorption wavelength in a 20-ppm by mass toluene solution: 543 nm) were added, and the mixture was stirred and mixed. Thereafter, 25.50 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) and 24.22 parts by mass of 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane were added, and the resultant mixture was stirred for 30 minutes under reduced pressure at 10 mmHg to prepare a curable composition. The curable composition was then injected into a mold for molding lenses (0.00 D, the wall thickness was set to 1.6 mm), which was composed of a glass mold and a resin gasket and had been prepared in advance, and polymerization was conducted in an electric furnace from 20° C. to 120° C. over a period of 24 hours.
After completion of the polymerization, the gasket and the mold were removed, followed by heat treatment for 2 hours at 120° C. to obtain a lens substrate. The optical properties and spectral transmittance of the obtained lens substrate were measured. The results are shown in Table 2. The luminous transmittance was 88.6%.
Lens substrates were obtained in the same manner as in Example 1, except that the composition of raw materials was as shown in Table 1. The optical properties and spectral transmittance of the obtained lens substrate were measured. The results are shown in Table 2. The luminous transmittance of the lens substrate of Example 3 was 88.0%.
A 300-mL eggplant flask was charged with 79.92 parts by mass of bis-(β-epithiopropyl) sulfide, 14.00 parts by mass of sulfur, and 0.25 parts by mass of compound 1-1, and degassed for 60 minutes while heating the flask at 60° C. Then, 0.467 parts by mass of 1-methyl-2-mercapto-1H-imidazole was added thereto, and while stirring the resultant mixture, a preliminary reaction was performed for 60 minutes at 60° C. in a sealed state at ordinary pressure. After that, the mixture was cooled to 20° C., and 0.13 parts by mass of dibutyltin dichloride was added to terminate the preliminary reaction.
In a separate container, 6.08 parts by mass of bis(2-mercaptoethyl) sulfide, 0.001 parts by mass of an acidic phosphate ester, “JP 506H” (trade name, manufactured by Johoku Chemical Industry Co., Ltd.), 0.020 parts by mass of tetrabutylphosphonium bromide, and as a bluing agent, 1050 ppb by mass of Disperse Violet 27 (largest maximum absorption wavelength in a 20-ppm by mass toluene solution: 586 nm) and 450 ppb by mass of Solvent Red 52 (largest maximum absorption wavelength in a toluene solution of 20 ppm by mass: 543 nm) were charged and mixed to prepare a solution, The resultant solution was added to the pre-reacted mixture, and the resultant mixture was degassed while stirring at 20° C. to form a homogeneous solution.
Next, the homogeneous solution was injected into a mold for molding lenses (0.00 D, the wall thickness was set to 2.00 mm), which was composed of a glass mold and a resin gasket, while filtrating the solution through a 3-micron polyethylene terephthalate filter. Finally, the mold was placed in an oven, and the temperature therein was raised from 30° C. to 100° C. over 24 hours to polymerize and cure the material, and then the mold was removed, thereby preparing a lens substrate. The optical properties and spectral transmittance of the obtained lens substrate were measured. The results are shown in Table 4. The luminous transmittance was 84.2%.
Lens substrates were obtained in the same manner as in Example 9, except that the composition of raw materials was as shown in Table 3. The optical properties and spectral transmittance of the obtained lens substrate were measured. The results are shown in Table 4.
In a 300-mL eggplant flask, 95.00 parts by mass of bis(β-epithiopropyl) disulfide, 5.00 parts by mass of 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, and 5,7-bis(mercaptomethyl)-3,6,9-trithiaoundecane-1,1-dithiol, 0.40 parts by mass of the compound 1-1, 0.001 parts by mass of an acidic phosphate ester, “JP 506H” (trade name, manufactured by Johoku Chemical Industry Co., Ltd.), and as a bluing agent, 1400 ppb by mass of Disperse Violet 27 (largest maximum absorption wavelength in a toluene solution of 20 ppm by mass: 586 nm), 600 ppb by mass of Solvent Red 52 (largest maximum absorption wavelength in a 20-ppm by mass toluene solution: 543 nm), and 0.10 parts by mass of dicyclohexylmethylamine were charged and degassed at 20° C. for 60 minutes to form a homogeneous solution.
Next, the homogeneous solution was injected into a mold for molding lenses (0.00 D, the wall thickness was set to 2.00 mm), which was composed of a glass mold and a resin gasket, while filtrating the solution through a 3-micron polyethylene terephthalate filter. Finally, the mold was placed in an oven, and the temperature therein was raised from 30° C. to 100° C. over 24 hours to polymerize and cure the material, and then the mold was removed, thereby preparing a lens substrate. The optical properties and spectral transmittance of the obtained lens substrate were measured. The results are shown in Table 4.
A lens substrate was obtained in the same manner as in Example 6, except that the composition of raw materials was as shown in Table 3. The optical properties and spectral transmittance of the obtained lens substrate were measured.
The results are shown in Table 4.
The abbreviations in Table 1 are as follows.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-164980 | Sep 2020 | JP | national |
This application is a continuation of International Application No. PCT/JP2021/036102, filed on Sep. 30, 2021, which claims priority to Japanese Patent Application No. 2020-164980, and the contents of which are incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2021/036102 | Sep 2021 | US |
| Child | 18080392 | US |
