WO2023229048A1

WO2023229048A1 - Optical material and eyeglass lens

Info

Publication number: WO2023229048A1
Application number: PCT/JP2023/019821
Authority: WO
Inventors: 百合絵石本; 愛美竹中; 伸雄河戸
Original assignee: 三井化学株式会社
Priority date: 2022-05-27
Filing date: 2023-05-26
Publication date: 2023-11-30

Abstract

An optical material comprising an organic pigment A comprising a porphyrin-based compound a represented by formula (A1), an organic pigment B comprising a porphyrin-based compound b represented by formula (B1), and a resin. In formula (A1), M represents a cobalt or vanadium oxide, R1 represents a chlorine atom or bromine atom, n represents 1 or 2, and R2 represents a phenyl group or a phenyl group substituted with an aromatic group or 1-7 carbon aliphatic group. In formula (B1), M represents a divalent metal atom, trivalent substituted metal atom, tetravalent substituted metal atom, hydroxylated metal atom, or oxidized metal atom, and R3 and R4 each represent a hydrogen atom, halogen atom, 3-10 carbon aliphatic groups, or aromatic group that may comprise a halogen atom.

Description

Optical materials and eyeglass lenses

The present disclosure relates to optical materials and spectacle lenses.

In recent years, optical materials have been used for various purposes. As optical materials, for example, optical materials containing polymers and organic dyes are widely known. Specific examples of the optical material include optical filters, lenses, and the like.
Among them, plastic lenses are lighter and more difficult to break than inorganic lenses, so they have rapidly become popular as optical materials for eyeglass lenses, camera lenses, etc. in recent years.

For example, Patent Document 1 describes an optical filter in which, in the transmission spectrum of the optical filter, the minimum value of transmittance in the wavelength range of 550 nm or more and 650 nm or less is 20% or more and 60% or less, and 570 nm or more 620 nm or less, the optical filter includes one or more types of absorption dye, and the absorption dye is a tetraazaporphyrin-based material whose central metal is nickel or cobalt and whose substituent group is fluorobenzo-based. Optical filters that are dyes are described.

For example, Patent Document 2 describes a transmission spectrum that includes a maximum value in a wavelength range of more than 315 nm and less than 400 nm, and a minimum value in a wavelength range of more than 380 nm and less than 500 nm, and the wavelength of the maximum value is shorter than the wavelength of the minimum value. An optical member having the following characteristics is described.

For example, Patent Document 3 states that the transmittance curve when measured at a thickness of 2 mm satisfies (1) to (3) below, and the hue in the CIE1976 (L ^* , a ^* , b ^* ) color space is a. An optical material is described in which ^* is -4 or more and 1 or less, and b ^* is -1 or more and 11 or less. (1) The transmittance curve has a maximum value T1 of transmittance at a wavelength of 400 nm to 445 nm, and the maximum value T1 is 65% or more. (2) The transmittance curve has a transmittance minimum value T2 at a wavelength of 445 nm to 485 m, and the minimum value T2 is 60% or more and 90% or less. (3) The minimum value of the transmittance in the wavelength range of 650 nm to 800 nm is 75% or more, and the average value of the transmittance in the wavelength range of 650 nm to 800 nm is 80% or more.

Patent Document 1: Japanese Patent Application Publication No. 2021-162625 Patent Document 2: International Publication No. 2017-090128 Patent Document 3: International Publication No. 2021-024962

Examples of optical materials include spectacle lenses. As eyeglass lenses, eyeglass lenses having blue light cutting ability are known.
Eyeglass lenses that have blue light blocking ability may deteriorate in blue light blocking ability over a long period of time after being manufactured.
Furthermore, eyeglass lenses that have blue light cutting ability may have an unnatural appearance.

The problem to be solved by an embodiment of the present disclosure is to provide an optical material and an eyeglass lens that can suppress a decline in blue light cutting ability over a long period of time and have a natural color appearance. The goal is to provide the following.

Means for solving the above problems include the following aspects.
<1> Optical material containing an organic dye A containing a porphyrin compound a represented by the following formula (A1), an organic dye B containing a porphyrin compound b represented by the following formula (B1), and a resin. .

In formula (A1), M represents cobalt or vanadium oxide, R ₁ represents a chlorine atom or a bromine atom, n represents 1 or 2, and R ₂ represents a phenyl group, an aromatic group, or a carbon group. Represents a phenyl group substituted with an aliphatic group of numbers 1 to 7.

In formula (B1), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom, and each of R ₃ and R ₄ is hydrogen represents an atom, a halogen atom, an aliphatic group having 3 to 10 carbon atoms, or an aromatic group that may contain a halogen atom.
<2> The optical material according to <1>, wherein in the formula (B1), M is cobalt or vanadium oxide.
<3> The optical material according to <1> or <2>, wherein the porphyrin compound a is a compound represented by the following formula (A2).

In formula (A2), M represents cobalt or vanadium oxide.
<4> The optical system according to any one of <1> to <3>, wherein the porphyrin compound b is a compound represented by the following formula (B2), the following formula (B3), or the following formula (B4). material.

In formula (B2), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.

In formula (B3), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.

In formula (B4), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.
<5> The optical material according to any one of <1> to <4>, wherein the ratio of the content of the organic dye B to the content of the organic dye A is 0.5 to 5.0.
<6> In the spectroscopic spectrum, if the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, and the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b, then the maximum absorption wavelength b The optical material according to any one of <1> to <5>, wherein the value obtained by subtracting the maximum absorption wavelength a from the maximum absorption wavelength a is 100 nm to 160 nm.
<7> In the spectroscopic spectrum, the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b, and the thickness at the maximum absorption wavelength a. When the transmittance at 2 mm is the transmittance T1, and the transmittance at the thickness of 2 mm at the maximum absorption wavelength b is the transmittance T2,
The optical system according to any one of <1> to <6>, wherein the transmittance T1 is within the range of 65%T to 85%T, and the transmittance T2 is within the range of 65%T to 85%T. material.
<8> In the spectroscopic spectrum, if the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, and the transmittance at a thickness of 2 mm at the maximum absorption wavelength a is the transmittance T1,
The optical material according to any one of <1> to <7>, wherein ΔT1, which is the absolute value of the difference in transmittance T1 before and after the following weather resistance test, is 1.0%T or less.
<Weather resistance test>
A test sample having a thickness of 2 mm made of the above optical material is irradiated with a xenon lamp under the conditions of a temperature of 50° C., a humidity of 40% RH, an illuminance of 60 W/m ² and an irradiation time of 150 hours.
<9> In the spectroscopic spectrum, the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b, and the thickness at the maximum absorption wavelength a. When the transmittance at 2 mm is the transmittance T1, and the transmittance at the thickness of 2 mm at the maximum absorption wavelength b is the transmittance T2,
The sum of ΔT1, which is the absolute value of the difference in transmittance T1 before and after the following weather resistance test, and ΔT2, which is the absolute value of the difference in transmittance T2 before and after the following weather resistance test, is 3.0%. The optical material according to any one of <1> to <7>, which is T or less.
<Weather resistance test>
A test sample having a thickness of 2 mm made of the above optical material is irradiated with a xenon lamp under the conditions of a temperature of 50° C., a humidity of 40% RH, an illuminance of 60 W/m ² and an irradiation time of 150 hours.
<10> The optical material according to any one of <1> to <9>, which has a luminous transmittance of 80%T or more.
<11> The optical material according to any one of <1> to <10>, wherein the saturation C ^* is from 0.01 to 4.0.
<12> The optical material according to any one of <1> to <11>, wherein the resin contains polythiourethane or polysulfide.
<13> A spectacle lens comprising the optical material according to any one of <1> to <12>.

According to an embodiment of the present disclosure, it is possible to suppress a decline in blue light cutting ability over a long period of time, and to provide an optical material and a spectacle lens that have a natural color appearance.

These are spectra of a lens in Comparative Example 3 in which the content of dye (1-A) was changed to 10 ppm before and after 300 hours in a weather resistance test. These are spectra of the lens of Comparative Example 4 in which the content of the dye (3-A) was changed to 10 ppm before the test, after 150 hours, and after 300 hours in the weather resistance test.

Below, the content of the present disclosure will be explained in detail.
Although the description of the constituent elements described below may be made based on typical embodiments of the present disclosure, the present disclosure is not limited to such embodiments.

In the present disclosure, "~" indicating a numerical range is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
In the numerical ranges described in stages in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.

In the present disclosure, compounds that are not specified as being substituted or unsubstituted may have any substituent as long as the effects of the present disclosure are not impaired.
In the present disclosure, when a plurality of substances corresponding to each component are present in the layer, the amount of each component of the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
Note that in the present disclosure, combinations of preferred aspects are more preferred aspects.
In the present disclosure, ppm (parts per million) means ppm on a mass basis.

≪Optical materials≫
The optical material of the present disclosure includes an organic dye A containing a porphyrin compound a represented by the following formula (A1), an organic dye B containing a porphyrin compound b represented by the following formula (B1), and a resin. including.

By including the above configuration, the optical material of the present disclosure can suppress a decrease in blue light cutting ability over a long period of time, and has a natural color appearance.
In the present disclosure, a natural color refers to a color with a gray tone and suppressed saturation.
Eyeglass lenses that have blue light blocking ability may deteriorate in blue light blocking ability over a long period of time after being manufactured.
The reason why the optical material of the present disclosure can suppress the decline in blue light cutting ability over a long period of time is thought to be due to its excellent weather resistance.

<Organic dye A>
Organic dye A contains a porphyrin compound a represented by the following formula (A1).
The organic dye A preferably has a maximum absorption wavelength in a wavelength range of 440 nm to 500 nm.
The wavelength of maximum absorption may be the minimum value of transmittance.

In formula (A1), M represents cobalt or vanadium oxide, R ₁ represents a chlorine atom or a bromine atom, n represents 1 or 2, and R ₂ represents a phenyl group, an aromatic group, or a carbon group. Represents a phenyl group substituted with an aliphatic group of numbers 1 to 7.
A plurality of R ₁ 's in formula (A1) may be the same or different.
A plurality of R ₂ 's in formula (A1) may be the same or different.
R ₁ preferably represents a bromine atom.
R ₂ preferably represents a phenyl group.
In _R2 , the aliphatic group having 1 to 7 carbon atoms includes a straight chain, branched or cyclic alkyl group having 1 to 7 carbon atoms, a straight chain, branched or cyclic alkenyl group, and a straight chain, branched or cyclic alkyl group having 1 to 7 carbon atoms. Examples include alkynyl groups.

Examples of straight chain, branched or cyclic alkyl groups having 1 to 7 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, Isopentyl group, neopentyl group, tert-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 2-methylpentyl group, 4-methylpentyl group, 4-methyl- 2-pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 3-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group Examples include.

Examples of the straight chain, branched or cyclic alkenyl group having 1 to 7 carbon atoms include vinyl group, 1-methylvinyl group, propenyl group, 2-butenyl group, 2-pentenyl group and the like.

Examples of straight chain, branched or cyclic alkynyl groups having 1 to 7 carbon atoms include ethynyl group, propynyl group, butynyl group, 1,3-butadiynyl group, 2-pentynyl group, 2,4-pentadiynyl group, and 2-hexynyl group. , 3,3-dimethyl-1-butynyl group, 3-heptynyl group, and the like.

Examples of the aromatic group in R ₂ include a substituted or unsubstituted phenyl group.

As mentioned above, the central metal of the porphyrin compound a is cobalt or vanadium oxide. This point particularly contributes to improving weather resistance. As a result, it also contributes to suppressing the decline in blue light cutting ability.
It is not clear why the central metal of the porphyrin compound a is cobalt or vanadium oxide, which contributes to suppressing the decline in blue light cutting ability. For example, it is presumed that the use of cobalt or vanadium oxide as the central metal makes it possible to stabilize the electronic state of the complex (dye).
In addition, from the viewpoint of weather resistance, porphyrin compound a is considered to make a greater contribution than porphyrin compound b because it absorbs shorter wavelengths.

In the optical material of the present disclosure, the porphyrin compound a is preferably a compound represented by the following formula (A2).

In formula (A2), M represents cobalt or vanadium oxide.

The content of organic dye A is preferably 0.5 ppm to 10.0 ppm.
When the content of organic dye A is 0.5 ppm or more, blue light cutting ability can be maintained better.
Organic dye A absorbs relatively high energy (that is, short wavelength) light more easily than organic dye B. Therefore, the lower limit of the content of organic dye A has a large contribution to maintaining good blue light cutting ability.
From the above viewpoint, the content of organic dye A is more preferably 1.0 ppm or more, and even more preferably 1.5 ppm or more.
When the content of organic dye A is 10.0 ppm or less, the appearance has a more natural color tone.
From the above viewpoint, the content of organic dye A is more preferably 8.0 ppm or less, and even more preferably 5.0 ppm or less.

<Organic dye B>
Organic dye B contains a porphyrin compound b represented by the following formula (B1).
Organic dye B preferably has a maximum absorption wavelength in a wavelength range of 550 nm to 600 nm.

In formula (B1), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom, and each of R ₃ and R ₄ is hydrogen represents an atom, a halogen atom, an aliphatic group having 3 to 10 carbon atoms, or an aromatic group that may contain a halogen atom.

M is preferably copper, palladium, cobalt or vanadium oxide, more preferably cobalt or vanadium oxide.
Among R ₃ and R ₄ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred.
In the aliphatic group having 3 to 10 carbon atoms, examples of the aliphatic group include a straight chain, branched or cyclic alkyl group, a straight chain, branched or cyclic alkenyl group, a straight chain, branched or cyclic alkynyl group, etc. .

Examples of linear, branched or cyclic alkyl groups as aliphatic groups having 3 to 10 carbon atoms include n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, Isopentyl group, neopentyl group, tert-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 2-methylpentyl group, 4-methylpentyl group, 4-methyl- 2-pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 3-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group Examples include.

Examples of linear, branched or cyclic alkenyl groups as aliphatic groups having 3 to 10 carbon atoms include 1-methylvinyl group, propenyl group, 2-butenyl group, and 2-pentenyl group.

Examples of linear, branched or cyclic alkynyl groups as aliphatic groups having 3 to 10 carbon atoms include propynyl group, butynyl group, 1,3-butadiynyl group, 2-pentynyl group, 2,4-pentadiynyl group, 2 -hexynyl group, 3,3-dimethyl-1-butynyl group, 3-heptynyl group, etc.

In the aromatic group which may contain a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with fluorine being preferred.
In the aromatic group which may contain a halogen atom, examples of the aromatic group include a substituted or unsubstituted phenyl group.

In the optical material of the present disclosure, the porphyrin compound b is preferably a compound represented by the following formula (B2), the following formula (B3), or the following formula (B4).

In formula (B4), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.

In formulas (B2) to (B4), specific examples and preferred embodiments of M are the same as those of M in formula (B1).

The content of organic dye B is preferably 1.0 ppm to 20.0 ppm.
When the content of organic dye B is 1.0 ppm or more, the lens has a natural tint.
From the above viewpoint, the content of organic dye B is more preferably 2.0 ppm or more, and even more preferably 5.0 ppm or more.
When the content of organic dye B is 20.0 ppm or less, it has a natural color tone, maintains high luminous transmittance, and is bright and easy to see.
From the above viewpoint, the content of organic dye B is more preferably 15.0 ppm or less, even more preferably 10.0 ppm or less, and particularly preferably 8.0 ppm or less.

The total content of organic dye A and organic dye B is preferably 1.0 ppm to 100.0 ppm.
When the total content of organic dye A and organic dye B is 1.0 ppm or more, blue light cutting ability can be maintained better.
From the above viewpoint, the total content of organic dye A and organic dye B is more preferably 3.0 ppm or more, even more preferably 5.0 ppm or more, and particularly preferably 7.0 ppm or more. .
When the total content of organic dye A and organic dye B is 100.0 ppm or less, the appearance has a more natural color tone.
From the above viewpoint, the total content of organic dye A and organic dye B is more preferably 50.0 ppm or less, even more preferably 30.0 ppm or less, and particularly preferably 15.0 ppm or less. .

The ratio of the content of the organic dye B to the content of the organic dye A (organic dye B/organic dye A) is preferably from 0.5 to 5.0.
As mentioned above, organic dye A absorbs relatively high energy (that is, short wavelength) light more easily than organic dye B. Therefore, from the viewpoint of maintaining good blue light cutting ability, it is not necessary to contain a large amount of organic dye A. For example, the ratio of organic dye B/organic dye A is more preferably from 1.0 to 4.5, even more preferably from 1.5 to 4.0, and more preferably from 2.0 to 3.0. Particularly preferred.
Further, it is also preferable that the content of organic dye A is smaller than the content of organic dye B.

<Resin>
The optical material of the present disclosure includes resin.
In the present disclosure, as the resin, a commercially available resin may be used, or a resin obtained from a monomer may be used.
In the present disclosure, the resin can be used without particular limitation, and is preferably a transparent resin.
The resin and the monomer for obtaining the resin will be explained below.

The resin is not particularly limited, and includes, for example, polyurethane, polythiourethane, polysulfide, polycarbonate, poly(meth)acrylate, polyolefin, cyclic polyolefin, polyallyl, polyurethaneurea, polyene-polythiol polymer, ring-opening metathesis polymer, and polyester. , epoxy resin, etc.

Among the above, it is preferable that the resin contains polythiourethane or polysulfide.
One type of resin may be used, or two or more types may be used in combination.

The optical material preferably contains at least one selected from the group consisting of polyurethane, polythiourethane, polysulfide, polycarbonate, and poly(meth)acrylate, and more preferably contains polythiourethane. These resins are highly transparent materials and can be suitably used for optical material applications.

Polyurethane includes structural units derived from polyisocyanate compounds and structural units derived from polyol compounds. Polythiourethane includes a structural unit derived from a polyisocyanate compound and a structural unit derived from a polythiol compound.

Examples of polyisocyanate compounds include 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6- Hexamethylene diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α,α,α′,α′-tetramethylxylylene diisocyanate, bis(isocyanatomethyl)naphthalene , mesityrylene triisocyanate, bis(isocyanatomethyl) sulfide, bis(isocyanatoethyl) sulfide, bis(isocyanatomethyl) disulfide, bis(isocyanatoethyl) disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatomethyl) sulfide Aliphatic polyisocyanate compounds such as natoethylthio)methane, bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane; isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis (isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis (isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis Alicyclic polyisocyanate compounds such as (isocyanatomethyl)tricyclodecane and 4,9-bis(isocyanatomethyl)tricyclodecane; naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate Isocyanate, 2,6-tolylene diisocyanate, biphenyl diisocyanate, diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, benzene triisocyanate, diphenyl sulfide-4,4 - Aromatic polyisocyanate compounds such as diisocyanate; 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl) ) Tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 4,5- Examples include heterocyclic polyisocyanate compounds such as diisocyanato-1,3-dithiolane and 4,5-bis(isocyanatomethyl)-1,3-dithiolane, and at least one selected from these can be used. .

The polyol compound is one or more aliphatic or alicyclic alcohols, specifically linear or branched aliphatic alcohols, alicyclic alcohols, and combinations of these alcohols with ethylene oxide, propylene oxide, ε- Examples include alcohols to which caprolactone is added, and at least one selected from these can be used.

Straight chain or branched chain aliphatic alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3- Propanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1 , 2-pentanediol, 1,3-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1 , 6-hexanediol, 2,5-hexanediol, glycerol, diglycerol, polyglycerol, trimethylolpropane, pentaerythritol, di(trimethylolpropane), and the like.

Examples of alicyclic alcohols include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 3-methyl-1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1 , 4-cyclohexanediol, 4,4'-bicyclohexanol, 1,4-cyclohexanedimethanol, etc., and at least one selected from these can be used.

Compounds obtained by adding ethylene oxide, propylene oxide, or ε-caprolactone to these alcohols may also be used. For example, ethylene oxide adduct of glycerol, ethylene oxide adduct of trimethylolpropane, ethylene oxide adduct of pentaerythritol, propylene oxide adduct of glycerol, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of pentaerythritol, Examples include caprolactone-modified glycerol, caprolactone-modified trimethylolpropane, caprolactone-modified pentaerythritol, and at least one selected from these can be used.

Examples of polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanedithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate) , trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol Tetrakis (3-mercaptopropionate), bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio) Methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2 -bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3- Mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 -dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl ) methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane , 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate), hydroxyethylsulfide bis(2-mercaptoacetate), hydroxyethylsulfide bis(3-mercaptopropionate), hydroxymethyldisulfide bis(2-mercaptopropionate), -mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropinate), 2-mercaptoethyl ether bis(2- mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane , 4,6-bis(mercaptomethylthio)-1,3-dithiane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane; 1,2-dimercaptobenzene, 1,3- Dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis (mercaptoethyl)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(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, Aromatic polythiol compounds such as 2,6-naphthalenedithiol; 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, bismuthiol, 2,5-bis(mercaptomethyl)-1,4 -dithiane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, and other heterocyclic polythiol compounds. At least one selected from these can be used.

Polysulfide can be obtained by ring-opening polymerization of monomers such as polyepithio compounds and polythiethane compounds. The composition for optical materials can contain monomers constituting these resins.

The polyepithio compound can be used without any particular limitation, and for example, those described in Japanese Patent No. 6216383 can be used.
As the polythietane compound, a metal-containing thietane compound or a non-metal thietane compound can be used. Specifically, for example, the one described in Japanese Patent No. 6216383 can be used.

Polycarbonate can be obtained by reacting alcohol and phosgene, or by reacting alcohol and chloroformate, or by transesterifying a carbonic acid diester compound, but generally available commercially available polycarbonate resins can be used. It is also possible to use As a commercially available product, Panlite series manufactured by Teijin Kasei Co., Ltd., etc. can be used. The optical material composition of the present disclosure can contain polycarbonate as a resin material.

The poly(meth)acrylate can be used without any particular limitation, and for example, those described in Japanese Patent No. 6216383 can be used.

The polyolefin can be used without any particular limitation, and for example, the specific examples, cyclic polyolefin, olefin polymerization reaction, and polyolefin manufacturing method described in Japanese Patent No. 6216383 can be used.

Polyallyl is produced by polymerizing at least one allyl group-containing monomer selected from allyl group-containing monomers in the presence of a known radical-generating polymerization catalyst.
As allyl group-containing monomers, allyl diglycol carbonate and diallyl phthalate are generally commercially available, and these can be suitably used.

Polyurethane urea is a reaction product of a polyurethane prepolymer and a diamine curing agent and is manufactured by PPG Industries, Inc. under the trademark TRIVEX. A typical example is the one sold by. Polyurethane urea is a highly transparent material and can be suitably used.

Polyene-polythiol polymers are resins produced by addition polymerization and ethylene chain polymerization, consisting of a polyene compound having two or more ethylenic functional groups in one molecule and a polythiol compound having two or more thiol groups in one molecule. It is a product.

As the polyene compound in the polyene-polythiol polymer, for example, those described in Japanese Patent No. 6216383 can be used.

A ring-opening metathesis polymer is a resin formed by ring-opening polymerization of cyclic olefins using a catalyst. As the cyclic olefins that can be subjected to ring-opening polymerization, for example, those described in Japanese Patent No. 6216383 can be used.

Polyester is condensed and polymerized in the presence of known polyester production catalysts such as Lewis acid catalysts typified by antimony and germanium compounds, organic acids, and inorganic acids. Specifically, one or more selected from polyhydric carboxylic acids including dicarboxylic acids and their ester-forming derivatives and one or more selected from polyhydric alcohols including glycol; or hydroxycarboxylic acids and their ester-forming derivatives, or cyclic esters.

As the dicarboxylic acid and glycol, for example, those described in Japanese Patent No. 6216383 can be used.

As the polyester, for example, those described in Japanese Patent No. 6216383 can be used.

Epoxy resin is a resin formed by ring-opening polymerization of an epoxy compound, and as the epoxy compound, for example, those described in Japanese Patent No. 6216383 can be used.

(Additive)
The optical material of the present disclosure may contain additives as components other than those mentioned above.
Examples of the additives include polymerization catalysts, internal mold release agents, dyes, and ultraviolet absorbers. In the present disclosure, when obtaining polyurethane and polythiourethane, a polymerization catalyst may or may not be used.
Internal mold release agents include acidic phosphate esters. Examples of acidic phosphoric acid esters include phosphoric acid monoesters and phosphoric acid diesters, each of which can be used alone or in combination of two or more types. For example, an internal mold release agent illustrated in WO2021/132559 can be used.

As ultraviolet absorbers, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, 2-hydroxy-4- Benzophenone UV absorbers such as acryloyloxy-2',4'-dichlorobenzophenone, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2, 4dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2 ,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3, Triazine UV absorbers such as 5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine , 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl) -4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(5-chloro-2H -benzotriazol-2-yl)-4-methyl-6-tert-butylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, 2,2'-methylenebis Examples include benzotriazole UV absorbers such as [6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], but preferably 2-( Benzotriazole UV absorbers such as 2H-benzotriazol-2-yl)-4-tert-octylphenol and 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol are Can be mentioned. These ultraviolet absorbers can be used alone or in combination of two or more.

Commercially available products may be used as the ultraviolet absorber. Examples of the commercially available products include Tinuvin326 (manufactured by BASF Japan Co., Ltd.) and Viosorb583 (manufactured by Kyodo Yakuhin Co., Ltd.).

The optical material of the present disclosure may contain a color tone adjusting agent. When the optical material contains a tone adjusting agent, the content of the tone adjusting agent may be 3 ppm to 50 ppm, or 5 ppm to 40 ppm.

Examples of the color tone adjusting agent include those having an absorption band in the wavelength range from orange to yellow in the visible light region and having the function of adjusting the hue of optical materials containing resin. Examples of the color tone adjusting agent include bluing agents. Examples of the bluing agent include those that have an absorption band in the wavelength range from orange to yellow in the visible light region and have the function of adjusting the hue of an optical material made of a resin material. The bluing agent may contain a substance that exhibits a blue to purple color.

(Luminous transmittance)
From the viewpoint of visibility, the optical material of the present disclosure preferably has a luminous transmittance of 75%T or more, more preferably 78%T or more, and even more preferably 80%T or more.
The luminous transmittance can be measured using a spectrophotometer (for example, CM-5 manufactured by Konica Minolta) using an optical material having a thickness of 2 mm in accordance with ISO 8980-3.

(Preferred spectral characteristics)
Preferred spectral properties of the optical material of the present disclosure are shown below.
The following preferred spectral characteristics are in the spectral spectrum:
The maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a,
The maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b,
Let the transmittance at a thickness of 2 mm at the maximum absorption wavelength a be the transmittance T1,
This is a spectral characteristic when the transmittance at a thickness of 2 mm at the maximum absorption wavelength b is defined as the transmittance T2.

The above spectroscopic spectrum is measured using a 2 mm thick test sample made of the optical material of the present disclosure and a spectrophotometer (for example, UV-visible spectrophotometer UV-1800, manufactured by Shimadzu Corporation).

The value obtained by subtracting the maximum absorption wavelength a from the maximum absorption wavelength b (ie, the difference [maximum absorption wavelength b - maximum absorption wavelength a]) is preferably 100 nm to 160 nm, more preferably 100 nm to 140 nm.
When the difference [maximum absorption wavelength b−maximum absorption wavelength a] is 100 nm to 160 nm, the effect of having a natural color appearance is more excellent.

The transmittance T1 is preferably within the range of 60%T to 95%T, more preferably within the range of 65%T to 85%T.
When the transmittance T1 is within the range of 60%T to 95%T, the effect of having a natural color appearance is more excellent.
Transmittance T2 is preferably within the range of 60%T to 95%T, more preferably within the range of 65%T to 85%T.
When the transmittance T2 is within the range of 60%T to 95%T, the effect of having a natural color appearance is more excellent.

(Weather resistance test)
In the optical material of the present disclosure, ΔT1, which is the absolute value of the difference in transmittance T1 before and after the following weather resistance test, is preferably 2.5%T or less, more preferably 2.0%T or less, and even more preferably is 1.0%T or less.
When ΔT1 is 2.5%T or less, the effect of suppressing the decline in blue light cutting ability over a long period of time is excellent.

Here, the light resistance test was performed on a 2 mm thick test sample made of the optical material of the present disclosure using a xenon lamp under the conditions of a temperature of 50° C., a humidity of 40% RH, an illumination intensity of 60 W/m ² , and an irradiation time of 150 hours. This is a test in which irradiation is performed.
Irradiation with a xenon lamp is performed using, for example, a weather resistance acceleration tester (for example, Xenon Weather Meter NX75, manufactured by Suga Test Instruments Co., Ltd.).

The optical material of the present disclosure has ΔT1, which is the absolute value of the difference in the transmittance T1 before and after the weather resistance test, and ΔT2, which is the absolute value of the difference in the transmittance T2 before and after the weather resistance test. , (ie, ΔT1+ΔT2) is preferably 6.0%T or less, more preferably 3.0%T or less.
When ΔT1+ΔT2 is 6.0%T or less, long-term weather resistance is better.

(Saturation C ^* )
The optical material of the present disclosure preferably has a chroma C ^* of 4.0 or less.
When the saturation C ^* is 4.0 or less, the optical material has excellent appearance.
The saturation C ^* is more preferably 3.5 or less, even more preferably 2.5 or less, and particularly preferably 1.5 or less.
There is no particular restriction on the lower limit value of the saturation C ^* . For example, the saturation C ^* may be greater than 0, or may be greater than or equal to 0.01.
The saturation C ^* is preferably, for example, 0.01 to 4.0.

The method for measuring chroma C ^* is as follows.
Using an optical material with a thickness of 2 mm, a spectrophotometer CM-5 (manufactured by Konica Minolta Co., Ltd.) was used to measure L ^* a ^* b ^{* a} in color space (CIE 1976) under the conditions of a C light source and a viewing angle of 2°. ^* , b ^* were measured. The saturation C ^* was calculated using the following formula.

<Composition for optical materials>
The optical material can be manufactured using, for example, the composition for optical materials described below.
The composition for optical materials includes, for example, an organic dye A containing a porphyrin compound a represented by the above formula (A1), and an organic dye B containing a porphyrin compound b expressed by the above formula (B1). , and the monomers described above.
The monomer is a monomer that can be cured to produce the above-mentioned resin.

In the present disclosure, the composition for optical materials can be obtained by mixing the above components in a predetermined method.
The mixing order, mixing method, etc. of each component in the composition are not particularly limited, and any known method can be used. Known methods include, for example, preparing a masterbatch containing a predetermined amount of additives, and dispersing and dissolving this masterbatch in a solvent. For example, in the case of polyurethane resin, there is a method of preparing a masterbatch by dispersing and dissolving additives in a polyisocyanate compound.

<Aspects of optical material>
Embodiments of the optical material of the present disclosure include an optical material consisting of a base material, an optical material consisting of a base material and a coating layer, and the like.
Examples of the base material include lens base materials.

Examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water repellent layer. These coating layers can be used alone or in a multilayered form of a plurality of coating layers. When coating layers are applied to both sides, the same or different coating layers may be applied to each side.

For example, a molded object (for example, a lens base material) is prepared using a composition for optical materials that does not contain a dye, and then the molded object is immersed in a dispersion obtained by dispersing the dye in water or a solvent. The dye may be impregnated into the molded article, and the dye-impregnated molded article may be dried. Optical materials can be prepared using the molded product thus obtained.

Furthermore, after preparing the optical material, the optical material can be impregnated with a porphyrin compound. In addition, a spectacle lens including a lens base material and a coating layer laminated as necessary can be immersed in a dispersion containing a pigment to impregnate the lens with the pigment.

The amount of dye impregnated may be adjusted to a desired amount depending on the concentration of the dye in the dispersion, the temperature of the dispersion, and the time for immersing the molded object, optical material, etc. The amount of impregnation increases as the concentration increases, the temperature increases, and the immersion time increases. If the amount of impregnation is to be adjusted more precisely, it may be carried out by repeating immersion multiple times under conditions where the amount of impregnation is small.
Furthermore, a pigment-containing coating layer may be formed on an optical material such as a plastic lens by using a composition for an optical material containing a pigment as a coating material.

An optical material having such a configuration can be suitably used as a lens, preferably a spectacle lens.
Note that the present disclosure is not limited to the above-described embodiments, and can take various forms without impairing the effects of the present invention.

<Applications of optical materials>
Applications of the optical material of the present disclosure include, for example;
Lenses such as eyeglass lenses, goggles, eyeglass lenses for vision correction, lenses for imaging devices, Fresnel lenses for LCD projectors, lenticular lenses, contact lenses, and lenses for wearable devices;
Encapsulant for light emitting diodes (LEDs);
Optical waveguide;
optical lens;
Optical adhesive used for joining optical waveguides, etc.;
Anti-reflection coatings used for optical lenses, etc.;
Transparent coating used for liquid crystal display device components (substrates, light guide plates, films, sheets, etc.);
Windshields used for car windshields, motorcycle helmets, etc.;
Transparent substrate;
A film that is attached to the cover of a lighting fixture, the irradiation surface of a lighting fixture, etc. (i.e., a film as an optical material (for example, an optical filter));
Films to be applied to windows (i.e. films as optical materials (e.g. optical filters));
Films attached to lenses (i.e. films as optical materials (e.g. optical filters));
etc. can be mentioned.

(lens)
The lens of the present disclosure is a lens using the optical material of the present disclosure.
That is, the lens of the present disclosure includes the optical material of the present disclosure. The lens of the present disclosure may include a lens base material made of an optical material, and may include a coating layer on one or both surfaces of the lens base material.
The lens of the present disclosure may be any of the various lenses exemplified in the above-mentioned applications of optical materials, and is preferably a spectacle lens.

Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, a water repellent layer, and the like. These coating layers can be used alone or in a multilayered form of a plurality of coating layers. When coating layers are applied to both sides, the same or different coating layers may be applied to each side.

These coating layers include dyes, infrared absorbers, light stabilizers, antioxidants, etc., dyes, pigments, etc., photochromic dyes, photochromic pigments, etc., antistatic agents, and other ingredients used in the present disclosure to enhance the performance of the lens. It may also contain other known additives.
For layers to be coated by coating, various leveling agents may be used for the purpose of improving coating properties.

A primer layer is usually formed between a hard coat layer and a lens base material, which will be described later. The primer layer is a coating layer that aims to improve the adhesion between the hard coat layer formed thereon and the lens base material, and can also improve impact resistance in some cases. The primer layer may be of any material as long as it has high adhesion to the obtained lens base material. For example, a primer composition containing urethane resin, epoxy resin, polyester resin, melamine resin, or polyvinyl acetal as a main component may be used. Used to form a primer layer. In preparing the primer composition, a solvent that does not affect the lens substrate may be used or no solvent may be used for the purpose of adjusting the viscosity of the composition.

The primer layer can be formed by either a coating method or a dry method. When using a coating method, a primer layer is formed by applying a primer composition to a lens substrate by a known coating method such as spin coating or dip coating, and then solidifying the primer composition. When a dry method is used, it is formed by a known dry method such as a CVD method or a vacuum evaporation method. When forming the primer layer, the surface of the lens base material may be subjected to pretreatment such as alkali treatment, plasma treatment, ultraviolet treatment, etc., if necessary, for the purpose of improving adhesion.

The hard coat layer is a coating layer intended to impart functions such as scratch resistance, abrasion resistance, moisture resistance, hot water resistance, heat resistance, and weather resistance to the lens surface.
To form the hard coat layer, an organosilicon compound having curability and an element selected from the element group of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In and Ti are used. A hard coat composition containing one or more types of oxide fine particles may be used,
A composite oxide containing a curable organosilicon compound and two or more elements selected from the element group Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti. A hard coat composition containing one or more of the following fine particles may be used.

In addition to the above components, the hard coat composition also contains amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, acids, metal chlorides, and polyfunctional epoxy compounds. Preferably, it includes at least one selected from the group.
The hard coat composition may contain a solvent that does not affect the lens substrate, or may not contain a solvent.

The hard coat layer is usually formed by applying a hard coat composition using a known coating method such as spin coating or dip coating, and then curing the composition. Examples of the curing method include irradiation with energy rays such as ultraviolet rays and visible light, and thermosetting. From the viewpoint of suppressing the occurrence of interference fringes, it is preferable that the refractive index of the hard coat layer has a difference in refractive index from that of the lens base material within a range of ±0.1.

Antireflection layers include inorganic and organic types.
The inorganic antireflection layer is formed using an inorganic oxide such as SiO ₂ or TiO ₂ by a dry method such as a vacuum evaporation method, a sputtering method, an ion plating method, an ion beam assist method, or a CVD method.
The organic antireflection layer is formed by a wet method using a composition containing an organosilicon compound and silica-based fine particles having internal cavities.
The antireflection layer may be formed on the hard coat layer as necessary.

The antireflection layer may be multilayer or single layer.
From the viewpoint of effectively expressing the antireflection function, the antireflection layer is preferably multilayered, and in that case, it is preferable to alternately laminate low refractive index layers and high refractive index layers. Moreover, it is preferable that the refractive index difference between the low refractive index layer and the high refractive index layer is 0.1 or more.
Examples of the high refractive index layer include layers such as ZnO, TiO ₂ , CeO ₂ , Sb2O ₅ , SnO ₂ , ZrO ₂ , and Ta ₂ O ₅ , and examples of the low refractive index layer include layers such as SiO ₂ .
When used as a single layer, the refractive index is preferably at least 0.1 lower than the refractive index of the hard coat layer.

On the antireflection layer, an antifogging coat layer, an antifouling layer, a water repellent layer, etc. may be formed as necessary. Methods for forming the antifogging layer, antifouling layer, water repellent layer, etc. are not particularly limited, and conventionally known methods can be applied.

Hereinafter, the present disclosure will be explained in more detail with reference to Examples, but the present disclosure is not limited to the following Examples unless the gist thereof is exceeded. Note that unless otherwise specified, "parts" are based on mass.

(Preparation of porphyrin compound)
(Synthesis Example 1: Preparation of (1-A))
17.0 g of the compound represented by the following structural formula (1-a) was dissolved in 170 ml of N,N-dimethylformamide, and 35.8 g of bromine was added dropwise thereto at 10° C. to 20° C. After stirring at room temperature for 4 hours, the mixture was poured into 800 g of ice water and neutralized with an aqueous sodium hydroxide solution. The precipitate was collected by filtration, washed with water, washed with methanol, and dried to obtain a compound represented by the following structural formula (1-A) (hereinafter also referred to as (1-A) compound).

(Synthesis Example 2: Preparation of (2-A))
(Synthesis example In the same manner as in 1), a compound represented by the following structural formula (2-A) (hereinafter also referred to as (2-A) compound) was obtained.

(Synthesis Example 3: Preparation of (3-A))
30.0 g of the compound represented by the following structural formula (3-a) was dispersed in 150 g of 1,1,2-trichloroethane and 60 g of water, and 58.7 g of bromine and 1,2,2- A solution containing 60 g of trichloroethane was added dropwise. After stirring at 50°C to 55°C for 3 hours, the mixture was cooled to room temperature. An aqueous sodium sulfite solution (4.2 g of sodium sulfite, 21 g of water) was added to the reaction solution, and the mixture was stirred at room temperature for 15 minutes. Next, an aqueous sodium hydroxide solution (16.2 g of sodium hydroxide, 162 g of water) was added, and the mixture was stirred at room temperature for 30 minutes. The precipitate was collected by filtration, washed with water, washed with methanol, and dried to obtain 45.6 g of a compound represented by the following structural formula (3-A) (hereinafter also referred to as (3-A) compound).

(Synthesis Example 4: Preparation of (1-B2))
18 g of 2-fluorobenzyl cyanide, 16.7 g of pivaloyl cyanide and 700 mL of dichloromethane were mixed and cooled to -10°C. Subsequently, 82 g of titanium tetrachloride was added dropwise over 70 minutes at the same temperature, and then 88 g of N-methylmorpholine was added dropwise over 2 hours, followed by stirring at room temperature for 15 hours. The reaction solution was poured into water, chloroform was added thereto, the mixture was stirred, and the insoluble matter was filtered. The obtained filtrate was washed successively with aqueous sodium bicarbonate and water, and concentrated. The column-purified product was dissolved in 400 mL of acetonitrile, stirred at room temperature for 94 hours while irradiated with an ultraviolet fluorescent lamp, concentrated, and then separated and purified by silica gel column chromatography to obtain a compound represented by the following structural formula (1-b). Ta.
2 g of the compound represented by structural formula (1-b) and 20 mL of 1-pentanol were mixed, and the mixture was purged with nitrogen. After adding 0.33 g of formamide and 0.38 g of vanadium (III) chloride, 0.83 g of potassium tert-butoxide was added little by little. Thereafter, the reaction solution was heated to 105° C. and stirred for 15 hours. After the stirring was completed, the reaction solution was cooled and discharged into 80 mL of methanol. 40 mL of ion-exchanged water was added dropwise thereto, and the precipitated crystals were separated by filtration and dried at 100°C. The obtained crystals were dissolved in toluene, activated clay and silica gel were added and stirred, insoluble matter was filtered off, and the filtrate was concentrated. The obtained solid content was washed with methanol and dried to obtain 0.91 g of a compound represented by the following structural formula (1-B2) (hereinafter also referred to as (1-B2) compound).

(Synthesis Example 5: Preparation of (2-B2))
A compound represented by the following structural formula (2-B2) (hereinafter also referred to as (2-B2) compound) was prepared in the same manner as in (Synthesis Example 4) except that vanadium (III) chloride was changed to cobalt (II) chloride anhydride. ) was obtained.

(Synthesis Example 6: Preparation of (1-B4))
1.57 g of vanadium (III) chloride and 5.38 g of a compound represented by the following structural formula (2-b) were charged to 50 g of 1-pentanol, and 1.02 g of ammonia gas was introduced over 1 hour at 20°C. . Ammonia gas was introduced into the reaction solution, and heat generation occurred during the introduction of ammonia. After stirring at 20°C to 30°C for 1 hour, the temperature was raised to 125°C. After the temperature was raised, stirring was continued for 6 hours at 125°C. Then, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water at a mass ratio of 1:1 was charged. The precipitated compound was collected by filtration and dried to obtain 5.00 g of a compound represented by the following structural formula (1-B4) (hereinafter also referred to as (1-B4) compound).

(Synthesis Example 7: Preparation of (3-B4))
A compound represented by the following structural formula (3-B4) (hereinafter also referred to as (3-B4) compound) was produced in the same manner as in (Synthesis Example 6) except that vanadium (III) chloride was changed to palladium (II) chloride. ) was obtained.

(Synthesis Example 8: Preparation of (4-B4))
A compound represented by the following structural formula (4-B4) (hereinafter also referred to as (4-B4) compound) was prepared in the same manner as in (Synthesis Example 6) except that vanadium (III) chloride was changed to anhydrous copper (II) chloride. ) was obtained.

(Example 1 to Example 3, Example 6 to Example 10, Comparative Example 1 to Comparative Example 4, Comparative Example 6)
(Preparation of lens)
Organic pigments A (porphyrin pigments) listed in Tables 1 to 3 are added in the amounts listed in Tables 1 to 3, and organic pigments B (porphyrin pigments) listed in Tables 1 to 3 are added in the amounts listed in Tables 1 to 3. In the stated amounts, 0.020 parts by mass of dibutyltin dichloride as a polymerization catalyst, 0.1 parts by mass of an internal mold release agent for MR (manufactured by Mitsui Chemicals, Inc.) as an internal mold release agent, and Viosorb 583 (Kyodo Yakuhin) as an ultraviolet absorber. Co., Ltd.), 1.5 parts by mass of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2. 1] - 50.6 parts by mass of a composition containing heptane was stirred at 25°C to completely dissolve each component.
Thereafter, 25.5 parts by mass of a composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of a composition containing pentaerythritol tetrakis (3-mercaptopropionate) were added. The mixture was added and stirred at 25° C. for 30 minutes to prepare a homogeneous solution.
This solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE (polytetrafluoroethylene) filter, and then poured into a 4C plano glass mold with a center thickness of 2 mm and a diameter of 77 mm. This glass mold was heated from 25°C to 120°C over 16 hours.
Thereafter, the plano lens was cooled to room temperature and released from the glass mold. The obtained plano lens was further annealed at 120° C. for 2 hours. Thereby, a lens with a thickness of 2 mm was obtained.

Note that in Comparative Examples 3, 4, and 6 in Table 3, "-" means that the corresponding organic dye was not contained.

(Example 4)
Organic dye A (porphyrin dye) listed in Table 1 was used in the amount listed in Table 1, organic dye B (porphyrin dye) listed in Table 1 was used in the amount listed in Table 1, and dibutyltin dichloride was used as a polymerization catalyst in an amount of 0. m - 52.0 parts by mass of a composition containing xylylene diisocyanate was stirred at 25°C to completely dissolve each component.
Thereafter, 48.0 parts by mass of a composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added and stirred at 25° C. for 30 minutes to prepare a homogeneous solution.
This solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE (polytetrafluoroethylene) filter, and then poured into a 4C plano glass mold with a center thickness of 2 mm and a diameter of 77 mm. This glass mold was heated from 25°C to 120°C over 16 hours.
Thereafter, the plano lens was cooled to room temperature and released from the glass mold. The obtained plano lens was further annealed at 120° C. for 2 hours. Thereby, a lens with a thickness of 2 mm was obtained.

(Example 5)
Organic dye A (porphyrin dye) listed in Table 1 was used in the amount listed in Table 1, organic dye B (porphyrin dye) listed in Table 1 was used in the amount listed in Table 1, and dibutyltin dichloride was used as a polymerization catalyst in an amount of 0. m - 50.6 parts by mass of a composition containing xylylene diisocyanate was stirred at 25°C to completely dissolve each component.
Thereafter, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 49.4 parts by mass of a composition containing 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and stirred at 25°C for 30 minutes to form a homogeneous solution. Created.
This solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE (polytetrafluoroethylene) filter, and then poured into a 4C plano glass mold with a center thickness of 2 mm and a diameter of 77 mm. This glass mold was heated from 25°C to 120°C over 16 hours.
Thereafter, the plano lens was cooled to room temperature and released from the glass mold. The obtained plano lens was further annealed at 120° C. for 2 hours. Thereby, a lens with a thickness of 2 mm was obtained.

(Comparative example 5)
Without adding organic dye B (2-B2), 0.00084 parts by mass of blueing agent Plast Blue 8514 (manufactured by Arimoto Chemical Industry Co., Ltd.) and Plast Red 8320 (manufactured by Arimoto Chemical Industry Co., Ltd.) were added. 0.00034 parts by mass was added, and 0.95 parts by mass of Tinuvin 326 (manufactured by BASF Japan Co., Ltd.) was added as an ultraviolet absorber.
A lens with a thickness of 2 mm was obtained in the same manner as in Example 1 except for the above changes.

<Evaluation>
The following evaluations were performed on lenses with a thickness of 2 mm produced in each Example and each Comparative Example.
The results are shown in Tables 1 to 3.

(Measurement of maximum absorption wavelength a, transmittance T1, maximum absorption wavelength b, and transmittance T2)
Spectral spectra were measured for each lens with a thickness of 2 mm produced in each Example and each Comparative Example using a spectrophotometer (UV-Visible Spectrophotometer UV-1800, manufactured by Shimadzu Corporation).
Based on the obtained spectroscopic spectrum,
maximum absorption wavelength a, which is the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm;
maximum absorption wavelength b, which is the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm;
Transmittance T1, which is the transmittance at a thickness of 2 mm at the maximum absorption wavelength a, and
Transmittance T2, which is the transmittance at a thickness of 2 mm at the maximum absorption wavelength b
were measured respectively.

(Luminous transmittance)
Luminous transmittance was calculated from the measurement data of the above spectroscopic spectrum in accordance with ISO 8980-3.

(Initial blue light cut rate)
From the measurement data of the above spectroscopic spectrum, the blue light absorption rate of 380 nm to 500 nm was determined in accordance with EN ISO12312-1:2013.

(Saturation C ^* )
The chroma C ^* of the 2 mm thick lenses produced in each Example and each Comparative Example was measured by the method described above.

(Lens hue)
The hue of the 2 mm thick lenses produced in each Example and each Comparative Example was evaluated by five panelists based on the following evaluation criteria.
〔standard〕
A: The color of the lens was gray and had a natural hue.
B: A slight yellowish or bluish tint was felt.
C: It had a clear yellow or blue color, had a strong color tinge, and had an unnatural hue.

(Weather resistance test)
The lenses with a thickness of 2 mm produced in each example and each comparative example were subjected to a weather resistance test (i.e., under the conditions of temperature 50°C, humidity 40% RH, illumination intensity 60 W/m ² , and irradiation time 150 hours) by the method described above. A test using xenon lamp irradiation was conducted.
The weather resistance test was conducted using an accelerated weather resistance tester, Xenon Weather Meter NX75 (manufactured by Suga Test Instruments Co., Ltd.).
The above-mentioned spectra were measured before and after the weather resistance test.
Based on the obtained spectroscopic spectrum,
ΔT1, which is the absolute value of the difference in transmittance T1 before and after the above weather resistance test;
ΔT2, which is the absolute value of the difference in transmittance T2 before and after the weather resistance test, and
The sum of ΔT1 and ΔT2 (i.e. ΔT1+ΔT2)
were calculated respectively.
ΔT1 and ΔT1+ΔT2 were evaluated according to the following evaluation criteria.
Regarding ΔT1, the rank A is the most effective in suppressing the decline in blue light cutting ability over a long period of time.
Regarding ΔT1+ΔT2, the rank A is the best in long-term weather resistance.

- ΔT1 standard -
A: ΔT1 is 1.0%T or less B: ΔT1 is more than 1.0%T and less than 2.5%T C: ΔT1 is more than 2.5%T

- Criteria for ΔT1 + ΔT2 -
A: ΔT1 + ΔT2 is 3.0%T or less B: ΔT1 + ΔT2 is over 3.0%T and 6.0%T or less C: ΔT1 + ΔT2 is over 6.0%T

The evaluation results for the lenses of each Example and each Comparative Example are shown in Tables 1 to 3 below.
In Tables 1 to 3, "-" means that the corresponding component is not included or that there is no evaluation target. In Tables 1 to 3, explanations of each component are as follows.
C1: 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane C2: m-xyly Diisocyanate D1: Pentaerythritol tetrakis (3-mercaptopropionate)
D2: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane D3: 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercapto Methyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane

As shown in Tables 1 to 3, organic dye A containing porphyrin compound a represented by formula (A1), organic dye B containing porphyrin compound b represented by formula (B1), and resin. Examples using optical materials containing , had excellent weather resistance test results. Therefore, the reduction in blue light cutting ability could be suppressed over a long period of time (at least 150 hours under xenon conditions of 50° C., 40% RH, and 60 W/m ² ). Furthermore, by limiting the central metal of the porphyrin compound b to cobalt or vanadium oxide, the weather resistance of the lens was improved.
Further, the value of chroma C ^* was small, and the hue evaluation of the lens was also excellent. Therefore, the lens had a gray appearance and a natural color.
On the other hand, Comparative Examples 1, 2, and 4 in which the central metal of organic dye A was not cobalt or vanadium oxide had poor weather resistance test results. Therefore, the effect of suppressing the decline in blue light cutting ability over a long period of time (at least 150 hours) was inferior.
Furthermore, Comparative Examples 3 to 5, which did not contain organic dye B, had inferior lens hues. Therefore, the lens had a yellowish or bluish appearance and did not have a natural color.
Furthermore, Comparative Example 6, which did not contain organic dye A, had poor lens hue. Therefore, the lens had a yellowish or bluish appearance and did not have a natural color.

In addition, the spectra of the lens in which the dye (1-A) content was changed to 10 ppm in Comparative Example 3 and the lens in which the dye (3-A) content was changed to 10 ppm in Comparative Example 4 are shown in Figures 1 and 2, respectively. Shown below. In this disclosure, ppm is on a mass basis.
FIG. 1 shows the spectra of the lens of Comparative Example 3 in which the pigment (1-A) content was changed to 10 ppm before and after 300 hours in the weather resistance test.
FIG. 2 shows the spectra of the lens of Comparative Example 4 in which the content of the dye (3-A) was changed to 10 ppm before the test, after 150 hours, and after 300 hours in the weather resistance test.
Organic dye A used in Comparative Example 3 corresponds to porphyrin compound a represented by formula (A1) in the present application. As shown in FIG. 1, the lens of Comparative Example 3 shows almost no change in transmittance around 460 nm even after 300 hours in the weather resistance test described above.
On the other hand, organic dye A used in Comparative Example 4 has a central metal of palladium, and does not correspond to the porphyrin compound a represented by formula (A1) in the present application.
As shown in FIG. 2, the lens of Comparative Example 4 showed a large increase in transmittance around 460 nm after 150 hours and 300 hours in the above-mentioned weather resistance test. In other words, the blue light cutting ability is significantly reduced.
It can be understood that the use of the porphyrin compound a represented by formula (A1) in the present application contributes to suppressing the decline in blue light cutting ability.

The disclosure of Japanese Patent Application No. 2022-086829 filed on May 27, 2022 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

Claims

An organic dye A containing a porphyrin compound a represented by the following formula (A1),
An organic dye B containing a porphyrin compound b represented by the following formula (B1),
resin and
Optical materials including.

In formula (A1), M represents cobalt or vanadium oxide, R 1 represents a chlorine atom or a bromine atom, n represents 1 or 2, and R 2 represents a phenyl group, an aromatic group, or a carbon group. Represents a phenyl group substituted with an aliphatic group of numbers 1 to 7.

In formula (B1), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom, and each of R 3 and R 4 is hydrogen represents an atom, a halogen atom, an aliphatic group having 3 to 10 carbon atoms, or an aromatic group that may contain a halogen atom.
The optical material according to claim 1, wherein in the formula (B1), M is cobalt or vanadium oxide.
The optical material according to claim 1, wherein the porphyrin compound a is a compound represented by the following formula (A2).

In formula (A2), M represents cobalt or vanadium oxide.
The optical material according to claim 1, wherein the porphyrin compound b is a compound represented by the following formula (B2), the following formula (B3), or the following formula (B4).

In formula (B2), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.

In formula (B3), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.

In formula (B4), M represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, a hydroxide metal atom, or an oxidized metal atom.
The optical material according to claim 1, wherein the ratio of the content of the organic dye B to the content of the organic dye A is 0.5 to 5.0.
In the spectroscopic spectrum, when the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, and the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b,
The optical material according to claim 1, wherein the value obtained by subtracting the maximum absorption wavelength a from the maximum absorption wavelength b is 100 nm to 160 nm.
In the spectroscopic spectrum, the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b, and the maximum absorption wavelength at the maximum absorption wavelength a of 2 mm. When the transmittance is T1, and the transmittance at a thickness of 2 mm at the maximum absorption wavelength b is T2,
The optical material according to claim 1, wherein the transmittance T1 is within the range of 65%T to 85%T, and the transmittance T2 is within the range of 65%T to 85%T.
In the spectroscopic spectrum, if the maximum absorption wavelength in the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, and the transmittance at a thickness of 2 mm at the maximum absorption wavelength a is the transmittance T1,
The optical material according to claim 1, wherein ΔT1, which is the absolute value of the difference in transmittance T1 before and after the following weather resistance test, is 1.0%T or less.
<Weather resistance test>
A test sample having a thickness of 2 mm made of the above optical material is irradiated with a xenon lamp under the conditions of a temperature of 50° C., a humidity of 40% RH, an illuminance of 60 W/m 2 and an irradiation time of 150 hours.
In the spectroscopic spectrum, the maximum absorption wavelength within the wavelength range of 440 nm to 500 nm is the maximum absorption wavelength a, the maximum absorption wavelength within the wavelength range of 550 nm to 600 nm is the maximum absorption wavelength b, and the maximum absorption wavelength at the maximum absorption wavelength a of 2 mm. When the transmittance is T1, and the transmittance at a thickness of 2 mm at the maximum absorption wavelength b is T2,
The sum of ΔT1, which is the absolute value of the difference in transmittance T1 before and after the following weather resistance test, and ΔT2, which is the absolute value of the difference in transmittance T2 before and after the following weather resistance test, is 3.0%. The optical material according to claim 1, which is T or less.
<Weather resistance test>
A test sample having a thickness of 2 mm made of the above optical material is irradiated with a xenon lamp under the conditions of a temperature of 50° C., a humidity of 40% RH, an illuminance of 60 W/m 2 and an irradiation time of 150 hours.
The optical material according to claim 1, which has a luminous transmittance of 80%T or more.
The optical material according to claim 1, having a chroma C * of 0.01 to 4.0.
The optical material according to claim 1, wherein the resin contains polythiourethane or polysulfide.
A spectacle lens comprising the optical material according to any one of claims 1 to 12.