JPWO2020218615A1 - Optical materials, polymerizable compositions for optical materials, plastic lenses, eyewear, infrared sensors and infrared cameras - Google Patents

Abstract

The optical material of the present disclosure contains (thio) urethane resin and a near-infrared absorber, and a * is -10 or more in the CIE1976 (L *, a *, b *) color space measured at a thickness of 2 mm. It is 0 or less, L * is 70 or more, and the peak width at the absorbance of 2/3 of the absorbance of the peak peak (Pmax) of the main absorption peak (P) is 150 nm or more and 400 nm or less in the visible light absorption spectroscopic spectrum.

Description

The present disclosure relates to optical materials containing near infrared absorbers, polymerizable compositions for optical materials, plastic lenses, eyewear, infrared sensors and infrared cameras.

Conventionally, spectacle lenses that cut a specific wavelength range have been developed.

Patent Document 1 describes a near-infrared ray cut having a near-infrared reflective film formed by alternately laminating two dielectric layers having different refractive indexes on at least one surface of a transparent substrate containing a cyclic olefin resin and a glass filler. The filter is disclosed.

Patent Document 2 discloses a near-infrared cut filter having a predetermined spectral transmittance of light in a plurality of wavelength ranges. It is described that this near-infrared cut filter contains a transparent resin such as a cyclic olefin resin and a near-infrared absorber such as a phthalocyanine compound.

Patent Documents 3 to 7 disclose resin compositions and the like containing a predetermined phthalocyanine dye and a resin. Patent Document 7 describes that a lens for protective eyeglasses can be obtained from a resin composition.
Patent Documents 8 and 9 disclose a far-infrared cut lens composed of a phthalocyanine dye and a urethane resin or a polythiourethane resin.

Patent Document 1: Japanese Patent Application Laid-Open No. 2009-258362 Patent Document 2: Japanese Patent Application Laid-Open No. 2011-100084 Patent Document 3: Japanese Patent Application Laid-Open No. 11-48612 Patent Document 4: Japanese Patent Application Laid-Open No. 2000-313788 Patent Document 5: Japanese Patent Application Laid-Open No. 2006-228646 Patent Document 6: International Publication No. 2014/208484 Patent Document 7: Japanese Patent Application Laid-Open No. 8-60008 Patent Document 8: Japanese Patent Application Laid-Open No. 2017-529415 Patent Document 9: Japanese Patent Application Laid-Open No. 2018-528829

However, in the conventional technique described in the patent document, there is room for improvement in the following points.

Although the near-infrared cut filters of Patent Documents 1 and 2 can cut near-infrared rays, the filter may become turbid and the transparency may be lowered.

Therefore, when we proceeded with the study of optical materials in which a near-infrared absorber was added to the resin, the near-infrared absorber did not dissolve in the resin, and when the amount added was increased, the optical material became turbid and the transparency decreased. Or, there was a tendency for the color (design) to deteriorate due to coloring. As described above, in the optical material using the near-infrared absorber, the near-infrared ray cutting effect and the designability have a trade-off relationship.

An object to be solved by one embodiment according to the present disclosure is to provide an optical material having a high near-infrared cut rate and excellent design.

As a result of diligent studies, the present inventors have set a high near-infrared cut rate and designability by containing a near-infrared absorber and a predetermined resin and setting L * and a * in a specific range in the CIE1976 color space. We have found that it is possible to achieve both, and completed the invention of the present disclosure.
That is, the aspects according to the present disclosure include the following aspects.

[1] (thio) Urethane resin and
Including near-infrared absorber,
In the CIE1976 (L *, a *, b *) color space measured at a thickness of 2 mm, a * is -10 or more and 0 or less, L * is 70 or more, and the main absorption peak (main absorption peak in the visible light absorption spectroscopic spectrum). An optical material having a peak width of 150 nm or more and 400 nm or less at an absorbance of 2/3 of the absorbance of the peak peak (Pmax) of P).
[2] The optical material according to [1], wherein the spectral transmittance at a wavelength of 900 nm to 1000 nm at a thickness of 2 mm is 10% or more and 80% or less.
[3] The optical material according to [1], which has a visual transmittance of 45% or more at a thickness of 2 mm. [4] The near-infrared absorber has a minimum value of a spectral transmittance curve in a wavelength region of 900 nm to 1000 nm, and the minimum value is a spectral transmittance of less than 50% [1] to [3]. The optical material described in any of.
[5] The optical material according to any one of [1] to [4], wherein the near-infrared absorber contains a phthalocyanine compound.
[6] The phthalocyanine compound has a main absorption peak (P) between 900 nm and 1000 nm in a visible light absorption spectroscopic spectrum measured with a toluene solution, and the peak peak (Pmax: in the peak) of the peak (P). The extinction coefficient (ml / g · cm) of (the point showing the maximum extinction coefficient) is 10,000 or more and 20,000 or less, and the peak width at the absorbance of 1/2 of the absorbance of (Pmax) of the peak (P) is 400 nm or less. The optical material according to [5], wherein the peak width is in the range of 300 nm or less in the absorbance of 2/3 of the absorbance of (Pmax) of the peak (P).
[7] The optical material according to [5] or [6], wherein the phthalocyanine compound contains at least one compound represented by the general formula (1).

(In the general formula (1), X represents a hydrogen atom or a halogen atom, R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, and R ³ represents a hydrogen atom or COR 1. l represents a ^{hydrogen atom or COR 1.} 1 to 7, m represents 0 to 13, n represents 1 to 8, p represents an integer of 1 to 14, z represents an integer of 0 to 13, and 2l + m + z + p = 16. M is a divalent metal atom, trivalent or 4 Represents a valence substitution metal or an oxymetal.)
[8] The optical material according to any one of [1] to [7], which contains the near-infrared absorber at 3 ppm or more and 200 ppm or less.
[9] The (thio) urethane resin is composed of at least one of a constituent unit derived from a polyisocyanate compound, a constituent unit derived from a polythiol compound, and a constituent unit derived from a polyol compound.
The polyisocyanate compound is 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, and the like. m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, At least one selected from the group consisting of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate.
The polythiol compounds include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiane octane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,7-. Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianeundecane, pentaerythritol tetrakis (3- Mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,1,3,3-tetrakis (mercapto) At least one selected from the group consisting of methylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane. And
The polyol compound is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3. The optical material according to any one of [1] to [8], which is at least one selected from the group consisting of −cyclohexanediol and 1,4-cyclohexanediol.
[10] A polymerizable compound composed of a combination of a polyisocyanate compound and at least one of a polythiol compound and a polyol compound.
A near-infrared absorber having a minimum value of the spectral transmittance curve in the wavelength region of 900 nm to 1000 nm and having the minimum value of less than 50% spectral transmittance,
The polymerizable composition for an optical material according to [1].
[11] The polymerizable composition for an optical material according to [10], wherein the near-infrared absorber contains a phthalocyanine compound.



[12] The polymerizable composition for an optical material according to [11], wherein the phthalocyanine compound contains at least one compound represented by the general formula (1).

(In the general formula (1), X represents a hydrogen atom or a halogen atom, R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, and R ³ represents a hydrogen atom or COR 1. l represents a ^{hydrogen atom or COR 1.} 1 to 7, m represents 0 to 13, n represents 1 to 8, p represents an integer of 1 to 14, z represents an integer of 0 to 13, and 2l + m + z + p = 16. M is a divalent metal atom, trivalent or 4 Represents a valence substitution metal or an oxymetal.)
[13] The polymerizable composition for an optical material according to any one of [10] to [12], which contains the near-infrared absorber at 3 ppm or more and 200 ppm or less.
[14] The polyisocyanate compound is 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1]. -Heptane, m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) ) At least one selected from the group consisting of cyclohexane, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate.
The polythiol compounds include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiane octane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,7-. Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianeundecane, pentaerythritol tetrakis (3- Mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,1,3,3-tetrakis (mercapto) At least one selected from the group consisting of methylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane. And
The polyol compound is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3. The polymerizable composition for an optical material according to any one of [10] to [13], which is at least one selected from the group consisting of −cyclohexanediol and 1,4-cyclohexanediol.
[15] A plastic lens made of the optical material according to any one of [1] to [9].
[16] Eyewear provided with the plastic lens according to [15].
[17] An infrared sensor or an infrared camera provided with the plastic lens according to [15].

According to the present disclosure, it is possible to provide an optical material having a high near-infrared cut rate and excellent design.

The spectral transmittance curve of the flat plate lens obtained in Example 5 is shown. The spectral transmittance curve of the flat plate lens obtained in Comparative Example 3 is shown. The spectral transmittance curve of the flat plate lens obtained in Comparative Example 9 is shown. The spectral transmittance curve of the flat plate lens obtained in Comparative Example 12 is shown.

Hereinafter, embodiments of the present disclosure will be specifically described.
The optical material of the present embodiment includes a (thio) urethane resin and a near-infrared absorber.

The optical material of the present embodiment has a * of -10 or more and 0 or less, L * of 70 or more, preferably a * of-in the CIE1976 (L *, a *, b *) color space measured at a thickness of 2 mm. 8 or more and 0 or less, L * is 73 or more, more preferably a * is -7 or more and 0 or less, L * is 75 or more, further preferably a * is -4 or more and 0 or less, L * is 85 or more, particularly preferably. a * is -3 or more and 0 or less, and L * is 90 or more.
Further, in the visible light absorption spectroscopic spectrum measured at a thickness of 2 mm, the optical material of the present embodiment has a peak width of 150 nm or more and 400 nm at an absorbance of 2/3 of the absorbance of the peak peak (Pmax) of the main absorption peak (P). It is as follows.

In the present embodiment, the near-infrared absorber and the (thio) urethane resin are contained, L * and a * are in the above range in the CIE1976 color space, and the absorbance is 2/3 of the absorbance at the peak peak (Pmax). When the peak width in the above range is in the above range, it is possible to achieve both a high near-infrared cut rate and designability.

From the viewpoint of the effect in the present disclosure, the optical material of the present embodiment has a spectral transmittance of 10% or more and 80% or less, preferably 15% or more and 70% or less, more preferably 20% at a wavelength of 900 nm to 1000 nm at a thickness of 2 mm. More than 60% or less.

Since the optical material of the present embodiment suppresses turbidity and coloring and is excellent in design, the total light transmittance at a thickness of 2 mm is 45% or more, preferably 65% or more, more preferably 70% or more, and further. It can be preferably 75% or more, and further, the visual transmittance can be 45% or more, preferably 65% or more, more preferably 70% or more, still more preferably 75% or more.
In the present disclosure, the measurement of various optical characteristics may be specifically carried out by the method described in the examples.

[Near infrared absorber]
The structure of the near-infrared absorber in the present embodiment is not particularly limited as long as the effect in the present disclosure can be obtained, and the near-infrared absorber can be selected and used from conventionally known near-infrared absorbers.

The near-infrared absorber in the present embodiment has, for example, a minimum value of the spectral transmittance curve in the wavelength region of 900 nm to 1000 nm in order to realize a high near-infrared cut rate, and the minimum value is the spectral transmittance. Those that are less than 50% can be used.
In the present embodiment, by using a near-infrared absorber having such characteristics, a high cut rate can be realized in a wide near-infrared region.
The near-infrared absorber is not particularly limited, but preferably contains a phthalocyanine compound.

The phthalocyanine compound has a main absorption peak (P) between 900 nm and 1000 nm in the visible light absorption spectroscopic spectrum measured with a toluene solution, and the peak peak (Pmax: maximum among the peaks) of the peak (P). The absorption coefficient (ml / g · cm) of the point indicating the absorption coefficient) is 10,000 or more and 20,000 or less, and the peak width at the absorbance of 1/2 of the absorbance of (Pmax) of the peak (P) is 400 nm or less. Moreover, a compound having a peak width in the range of 300 nm or less in the absorbance of 2/3 of the absorbance of (Pmax) of the peak (P) can be used.
The visible light absorption spectroscopic spectrum of the near-infrared absorber is measured using a toluene solution at an optical path length of 10 mm. The concentration of the toluene solution may be appropriately adjusted, and may be, for example, 3.3 mass ppm to 36.5 mass ppm.

As the phthalocyanine compound, a compound represented by the general formula (1) can be mentioned, and at least one kind can be used.

In the general formula (1), X represents a hydrogen atom or a halogen atom, R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, and R ³ represents a hydrogen atom or COR ¹ . l represents an integer of 1 to 7, m represents 0 to 13, n represents 1 to 8, p represents 1 to 14, and z represents an integer of 0 to 13, and 2l + m + z + p = 16. M represents a divalent metal atom, a trivalent or tetravalent substituted metal or an oxymetal.

In the phthalocyanine-based compound in the present disclosure, examples of the halogen atom in which X is a halogen atom include a chlorine atom, a bromine atom, a fluorine atom, an iodine atom and the like, but a chlorine atom, a bromine atom or a fluorine atom is preferable, and a chlorine atom is preferable. Is preferable.
As X, a hydrogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable, and a hydrogen atom or a chlorine atom is more preferable.

As the ^{alkyl group of R 1,} a linear or branched alkyl group having 1 to 18 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 16 carbon atoms is more preferable. For example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, n-hexyl group, n- Cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- Examples thereof include a pentadecyl group, a 2-hexylnonanyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group and the like.

As the ^{aryl group of R 1} , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
The R ^2, preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, n-hexyl group, n- Examples thereof include a heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group and an n-dodecyl group.

n is an integer of 1 to 8, but 1 to 5 is preferable, and 1 to 3 is more preferable.
R ³ is a hydrogen atom or COR ¹ , but is preferably a hydrogen atom.
Examples of those in which M is a divalent metal include Cu (II), Zn (II), Fe (II), Ni (II), Ru (II), Rh (II), Pd (II), Mn ( II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pd (II), Sn (II) and the like. Be done.

Examples of mono-substituted trivalent metals in which M is Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-I, Ga-Br, In-Cl, In-Br. , In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C ₆ H ₅ , Al-C ₆ H ₄ (CH ₃ ), In-C ₆ H ₅ , Examples thereof include In-C ₆ H ₄ (CH ₃ ), Al (OH), Mn (OH), Mn (OC ₆ H ₅ ), Mn [OSi (CH ₃ ) ₃ ], Fe-Cl, Ru-Cl and the like. ..

Examples of those in which M is a disubstituted tetravalent metal include CrCl ₂ , SiCl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , GeF ₂ , GeBr ₂ , GeF ₂ , and TiCl _2. , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SnR ₂ , GeR ₂ [R Represents an alkyl group, a phenyl group, a naphthyl group, and derivatives thereof], Si (OR ^' ) ₂ , Sn (OR ^' ) ₂ , Ge (OR ^' ) ₂ , Ti (OR ^' ) ₂ , Cr (OR ^' ) ₂ [R ^'is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkyl alkoxy silyl group and derivatives _{^{thereof], Sn (SR'')}} 2, Ge (SR'') 2 [R'' is Representing an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof] and the like.

Examples of those in which M is an oxymetal include VO, MnO, TiO and the like.
As M, Cu, AlCl, TiO, or VO is preferable, and Cu is more preferable.
Although l is an integer of 1 to 7, 2 to 6 is preferable, 3 to 5 is more preferable, and 4 is even more preferable. Although m is an integer of 0 to 13, 0 to 8 is preferable, 2 to 6 is more preferable, and 4 is even more preferable. Although p is an integer of 1 to 14, 1 to 8 is preferable, 2 to 6 is more preferable, and 4 is further preferable. Although z is an integer of 0 to 13, 0 to 4 is preferable, 0 to 2 is more preferable, and 0 is further preferable. 2l + m + z + p = 16.

Specific examples of preferable phthalocyanine dyes are described in, for example, Table 1 of JP-A-2006-228646. More preferably, it is a compound represented by the chemical formula (1a) described later.

From the viewpoint of the effect in the present disclosure, the phthalocyanine compound represented by the general formula (1) preferably has a weight average molecular weight excluding the central metal M of 900 or more and 5000 or less, and more preferably 1200 or more and 4000 or less. preferable.

By containing the compound selected from the above-mentioned phthalocyanine compounds, the near-infrared ray absorber in the present embodiment can efficiently cut near-infrared rays in a wide range. Although the near-infrared ray absorber in the present embodiment can efficiently cut near-infrared rays in a wide range even if it contains only one compound selected from the above-mentioned phthalocyanine compounds, it can absorb other near-infrared rays. The agent may be further contained.

From the viewpoint of the effect in the present disclosure, the optical material of the present embodiment preferably contains the near-infrared absorber at 3 ppm or more and 200 ppm or less, more preferably 3 ppm or more and 100 ppm or less, still more preferably 3 ppm or more and 80 ppm or less, and particularly preferably 3 ppm or more. It can contain 50 ppm or less.

The optical material of this embodiment contains (thio) urethane resin.
The (thio) urethane resin is composed of at least one of a constituent unit derived from a polyisocyanate compound, a constituent unit derived from a polythiol compound, and a constituent unit derived from a polyol compound.
These compounds will be described later.

<Polymerizable composition for optical materials>
The polymerizable composition for an optical material of the present embodiment contains a near-infrared absorber and a polymerizable compound.
As the near-infrared absorber, those described above can be used, and are preferably 3 ppm or more and 200 ppm or less, more preferably 3 ppm or more and 100 ppm or less, still more preferably 3 ppm or more and 80 ppm or less, and particularly preferably 3 ppm or more and 50 ppm or less in the polymerizable composition. Included in the following amounts:

Examples of the polymerizable compound include a combination of a polyisocyanate compound and at least one of a polythiol compound and a polyol compound.

(Polyisocyanate compound)
Examples of the polyisocyanate compound include an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, a heterocyclic isocyanate compound, an aromatic aliphatic isocyanate compound and the like, and one or a mixture of two or more thereof is used. These isocyanate compounds may include dimers, trimers and prepolymers. Examples of these isocyanate compounds include the compounds exemplified in WO2011 / 0555540.

The polyisocyanate compound is 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, and the like. m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, It is preferably at least one selected from the group consisting of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate.
2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, and bis (isocyanatomethyl) ) It is more preferable that it is at least one selected from the group consisting of cyclohexane.

(Polythiol compound)
The polythiol compound is a compound having two or more mercapto groups, and examples thereof include the compounds exemplified in WO2016 / 125736.
In the present embodiment, from the viewpoint of the effect in the present disclosure, the polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiane octane, 5,7-dimercaptomethyl-1,11-dimercapto-3. , 6,9-Trithiandecan, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecan, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6 , 9-Trithiane decane, pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2,5-bis (mercaptomethyl) -1,4- Dithiane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-bis (mercaptomethylthio) ethyl) -1 , 3-It is preferably at least one selected from the group consisting of dithiane.
4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), and 2,5-bis (mercaptomethyl)- More preferably, it is at least one selected from the group consisting of 1,4-dithiane.

The polyol compound may be one or more aliphatic or alicyclic alcohols.
Specific examples thereof include linear or branched aliphatic alcohols and alicyclic alcohols, and alcohols obtained by adding ethylene oxide, propylene oxide, or ε-caprolactone to these alcohols, and specific examples thereof. The compounds exemplified in WO2016 / 125736 can be used.

The polyol compound is preferably ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, and the like. It is at least one selected from the group consisting of 1,3-cyclohexanediol and 1,4-cyclohexanediol.

Examples of the additive include a polymerization catalyst, an internal mold release agent, a brewing agent, an ultraviolet absorber, and the like. In the present embodiment, when polyurethane and polythiourethane are obtained, a polymerization catalyst may or may not be used.

Examples of the internal mold release agent include acidic phosphoric acid esters. Examples of the acidic phosphoric acid ester include phosphoric acid monoester and phosphoric acid diester, which can be used alone or in combination of two or more. Examples of the bluing agent include those having an absorption band in the orange to yellow wavelength range in the visible light region and having a function of adjusting the hue of an optical material made of a resin. More specifically, the bluing agent contains a substance showing a blue color to a purple color.

Examples of the ultraviolet absorber include 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and 2-hydroxy-4-. Benzophenone-based 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) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonyl) Ethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and other triazine-based UV absorbers,

2- (2H-benzotriazole-2-yl) -4-methylphenol, 2- (2H-benzotriazole-2-yl) -4-tert-octylphenol, 2- (2H-benzotriazole-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2-yl) -4,6-di-tert-pentylphenol, 2- (5-chloro-2H-) Benzotriazole-2-yl) -4-methyl-6-tert-butylphenol, 2- (5-chloro-2H-benzotriazole-2-yl) -2,4-tert-butylphenol, 2,2'-methylenebis [ Examples thereof include benzotriazole-based ultraviolet absorbers such as 6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol].
Among the above, the UV absorbers are preferably 2- (2H-benzotriazole-2-yl) -4-tert-octylphenol and 2- (5-chloro-2H-benzotriazole-2-yl) -4-. It is a benzotriazole-based ultraviolet absorber such as methyl-6-tert-butylphenol. These UV absorbers can be used alone or in combination of two or more.
The composition for optical materials can be obtained by mixing the above components by a predetermined method.
The mixing order and mixing method of each component in the composition are not particularly limited as long as each component can be uniformly mixed, and a known method can be used.

[Optical material]
The optical material of the present embodiment can be obtained by polymerizing and curing the composition for an optical material of the present embodiment.
Optical materials include plastic spectacle lenses, goggles, vision correction spectacle lenses, imaging device lenses, LCD projector frennel lenses, wrenchular lenses, contact lenses, infrared sensor lenses, infrared camera lenses, and eyewear (sunglasses, fashion). For various plastic lenses such as lenses, encapsulants for light emitting diodes (LEDs), optical waveguides, optical adhesives (for example, optical adhesives used for joining optical lenses, optical waveguides, etc.), optical lenses, etc. Examples thereof include a near-infrared absorbing film used, a transparent coating used for a liquid crystal display device member (a substrate, a light guide plate, a film, a sheet, etc.), a car front glass, a windshield of a motorcycle helmet, a transparent substrate, and the like.
The optical material of the present embodiment may contain an ultraviolet absorber. As the optical material, a plastic lens, a lens for an infrared sensor, a lens for an infrared camera, eyewear, a near-infrared absorbing film used for these optical lenses and the like are preferable.
Hereinafter, a plastic lens, which is a preferred embodiment of the optical material, will be described in detail.

[Plastic lens]
Examples of the plastic lens include the following configurations.
(A) A plastic lens provided with a lens base material made of the composition for optical material of the present embodiment (b) A lens base material (excluding the lens base material obtained from the composition for optical material of this embodiment) surface. A plastic lens provided with a film or coating layer made of the composition for optical materials of the present embodiment on at least one surface (c) A lens base material (c) on both sides of a film made of the composition for optical materials of the present embodiment. However, a plastic lens in which (excluding the lens base material obtained from the composition for optical materials of the present embodiment) is laminated, these plastic lenses can be preferably used in the present embodiment.
Hereinafter, each embodiment will be described.

(Embodiment a)
The method for producing a plastic lens including the lens substrate made of the composition for optical materials of the present embodiment is not particularly limited, but a preferred production method includes casting polymerization using a lens casting mold. The lens base material can be composed of a polyurethane resin or a polythiourethane resin, and the composition for an optical material of the present embodiment containing a near-infrared absorber and a monomer of these resins (resin monomer for an optical material) can be obtained. Can be used.

Specifically, the composition for an optical material is injected into the cavity of the molding mold held by a gasket, tape or the like. At this time, depending on the physical characteristics required for the obtained plastic lens, it is often preferable to perform defoaming treatment under reduced pressure, filtration treatment such as pressurization and reduced pressure, and the like, if necessary.

Then, after the composition is injected, the lens casting mold is heated by a predetermined temperature program in a heatable device such as in an oven or in water to cure and mold. The resin molded product may be subjected to a treatment such as annealing, if necessary.

In the present embodiment, when molding the resin, in addition to the above-mentioned "arbitrary additive", a chain extender, a cross-linking agent, a light stabilizer, and an antioxidant, as in the case of a known molding method depending on the purpose. , Oil-soluble dyes, fillers, adhesion improvers and the like may be added.

Further, the plastic lens in the present embodiment may have various coating layers on the lens base material made of the composition for optical materials of the present embodiment according to the purpose and use thereof. The coating layer can contain a near infrared absorber. The coating layer containing the near-infrared absorber can be prepared by using a coating material (composition) containing the near-infrared absorber, or after forming the coating layer, the near-infrared absorber is dispersed in water or a solvent. It can be prepared by immersing a plastic lens with a coating layer in the dispersion liquid thus obtained and impregnating the coating layer with a near-infrared absorber.

(Embodiment b)
The plastic lens of the present embodiment may be provided with a film or layer made of the composition for optical materials of the present embodiment on at least one surface of the surface of the lens substrate. The lens base material does not have to be formed from the composition for optical materials of the present embodiment, and various lens base materials can be used.

As a method for manufacturing a plastic lens in the present embodiment, for example, (b-1) a lens base material is manufactured, and then the composition for an optical material of the present embodiment is formed on at least one surface of the lens base material. A method of laminating a film or a sheet, (b-2) In a cavity of a molding mold held by a gasket or tape as described later, one of the molds is a film or a sheet made of the composition for an optical material of the present embodiment. A method of arranging the composition along the inner wall of the lens and then injecting the composition for an optical material into the cavity and curing the composition can be mentioned.

The film or sheet made of the composition for optical materials of the present embodiment used in the method (b-1) is not particularly limited and can be obtained by a known molding method.
The lens base material can be obtained from a known optical resin, and various optical resins can be used.
A known method can be used as a method of bonding the film or sheet made of the composition for optical materials of the present embodiment on the surface of the lens base material.

The casting polymerization in the method (b-2) can be carried out in the same manner as the method for the plastic lens in the embodiment a, and the composition used for the casting polymerization is a composition containing a resin monomer for an optical material ( (Does not contain near-infrared absorber).

Further, the plastic lens in the present embodiment may have various coating layers on a lens base material or a "film or layer" made of a composition for an optical material, depending on the purpose and use thereof. Similar to the plastic lens in embodiment a, the coating layer may contain a near infrared absorber.

(Embodiment c)
In the plastic lens of the present embodiment, a lens base material (excluding the lens base material obtained from the optical material composition of the present embodiment) is laminated on both sides of a film made of the optical material composition of the present embodiment. You may.

As a method for manufacturing a plastic lens in the present embodiment, for example, (c-1) a method of manufacturing a lens base material and laminating it on both sides of a film or a sheet made of the composition for an optical material of the present embodiment, (c). -2) In the cavity of the molded mold held by a gasket or tape, the film or sheet made of the composition for optical material of the present embodiment is placed in a state of being separated from the inner wall of the mold, and then the optical is placed in the cavity. Examples thereof include a method of injecting a composition for a material and curing it.

The film or sheet made of the composition for optical material of the present embodiment and the lens base material used in the method (c-1) are the same as the method of the plastic lens (b-1) in the embodiment b. Things can be used.
A known method can be used as a method of bonding the film or sheet made of the composition for optical materials of the present embodiment on the surface of the lens base material.
The method (c-2) can be specifically carried out as follows.

In the space of the lens casting mold used in the method for manufacturing a plastic lens in the embodiment a, a film or a sheet made of the composition for an optical material of the present embodiment is placed on the inner surface of the mold on the front side where both sides face each other. Install so that it is parallel to.

Next, in the space of the lens casting mold, a composition containing a resin monomer for an optical material (not containing a near-infrared absorber) in two gaps between the mold and the polarizing film by a predetermined injection means. Inject.

Then, after the composition is injected, the lens casting mold is heated by a predetermined temperature program in a heatable device such as in an oven or in water to cure and mold. The resin molded product may be subjected to a treatment such as annealing, if necessary.

Further, the plastic lens in the present embodiment may have various coating layers on the lens base material according to its purpose and application. Similar to the plastic lens in embodiment a, the coating layer may contain a near infrared absorber.

[Plastic spectacle lens]
A plastic spectacle lens can be obtained by using the plastic lens of the present embodiment. If necessary, a coating layer may be applied to one side or both sides.

Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an anti-fog coat layer, an anti-contamination layer, and a water-repellent layer. Each of these coating layers can be used alone, or a plurality of coating layers can be used in layers. When the coating layers are applied to both surfaces, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.

Each of these coating layers is a near-infrared absorber used in the present embodiment, an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer or an antioxidant for the purpose of improving the weather resistance of the lens, and fashionability of the lens. Dyes and pigments, photochromic dyes and photochromic pigments, antistatic agents, and other known additives for enhancing the performance of lenses may be used in combination for the purpose of enhancing the temperature. For the layer to be coated by coating, various leveling agents for the purpose of improving the coatability may be used.

The primer layer is usually formed between the hard coat layer described later and the lens. The primer layer is a coating layer for the purpose of improving the adhesion between the hard coat layer formed on the primer layer and the lens, and it is also possible to improve the impact resistance in some cases. Any material can be used for the primer layer as long as it has high adhesion to the obtained lens, but usually a primer containing urethane resin, epoxy resin, polyester resin, melamine resin, or polyvinyl acetal as the main components. Compositions and the like are used. The primer composition may use an appropriate solvent that does not affect the lens for the purpose of adjusting the viscosity of the composition. Of course, it may be used without a solvent.

The primer layer can be formed by either a coating method or a dry method. When the coating method is used, the primer composition is applied to the lens by a known coating method such as spin coating or dip coating, and then solidified to form a primer layer. When it is carried out by a dry method, it is formed by a known dry method such as a CVD method or a vacuum vapor deposition method. When forming the primer layer, the surface of the lens may be subjected to pretreatment such as alkali treatment, plasma treatment, and ultraviolet treatment, if necessary, for the purpose of improving adhesion.
The hard coat layer is a coating layer for the purpose of imparting functions such as scratch resistance, abrasion resistance, moisture resistance, temperature water resistance, heat resistance, and weather resistance to the lens surface.

The hard coat layer is generally an organic silicon 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. A hard coat composition containing one or more of the oxide fine particles of the above and at least one of the fine particles composed of a composite oxide of two or more elements selected from these element groups is used. ..

In addition to the above components, the hard coat composition comprises amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, perchloric acid salts, acids, metal chlorides and polyfunctional epoxy compounds. It is preferred to include at least one selected from the group. A suitable solvent that does not affect the lens may be used for the hard coat composition, or a solvent-free solvent may be used.

The hard coat layer is usually formed by applying a hard coat composition by a known coating method such as spin coating or dip coating and then curing it. Examples of the curing method include heat curing and a curing method by irradiation with energy rays (ultraviolet rays, visible light, etc.). In order to suppress the occurrence of interference fringes, the refractive index of the hard coat layer is preferably in the range of ± 0.1 in the difference in refractive index from the lens.

The antireflection layer is usually formed on the hardcourt layer as needed. The antireflection layer includes an inorganic type and an organic type. In the case of the inorganic type, _{an inorganic oxide such as SiO 2} or TiO ₂ is used, and a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, or a CVD method is used. It is formed by a dry method such as. In the case of an organic system, it is formed by a wet process using a composition containing an organosilicon compound and silica-based fine particles having internal cavities.

The antireflection layer has a single layer and a multilayer, and when used as a single layer, it is preferable that the refractive index is at least 0.1 or more lower than the refractive index of the hard coat layer. In order to effectively exhibit the antireflection function, it is preferable to use a multilayer antireflection film, in which case the low refractive index film and the high refractive index film are alternately laminated. In this case as well, the difference in refractive index between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high-refractive index film include films such as ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , and Ta ₂ O _5, and examples of the low-refractive index film include SiO _{2 film.} ..

An anti-fog layer, an anti-contamination layer, and a water-repellent layer may be formed on the anti-reflection layer, if necessary. The method for forming the anti-fog layer, the anti-fouling layer, the water-repellent layer, etc. is not particularly limited as long as it does not adversely affect the antireflection function, and the treatment method, treatment material, etc. are not particularly limited, and known anti-fog layers are known. Treatment methods, antifouling treatment methods, water repellent treatment methods, materials and the like can be used.
For example, in the anti-fog treatment method or the anti-fouling treatment method, a method of covering the surface with a surfactant, a method of adding a hydrophilic film to the surface to make it water-absorbent, and a method of covering the surface with fine irregularities to improve water absorption. , A method of making water absorbent by utilizing photocatalytic activity, a method of applying superhydrophobic treatment to prevent the adhesion of water droplets, and the like. Further, in the water-repellent treatment method, a method of forming a water-repellent treatment layer by vapor deposition, sputtering, etc. of a fluorine-containing silane compound, a method of dissolving a fluorine-containing silane compound in a solvent and then coating the water-repellent treatment layer to form a water-repellent treatment layer. And so on.

Although the embodiments of the present disclosure have been described above, these are examples of the present disclosure, and various configurations other than the above can be adopted as long as the effects in the present disclosure are not impaired.

Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited thereto. The evaluation methods and materials used in the examples of the present disclosure are as follows.

[Measurement method of spectral transmittance and visual transmittance]
A Shimadzu spectrophotometer UV-1800 manufactured by Shimadzu Corporation was used as a measuring device, and the ultraviolet-visible light spectrum was measured using a flat plate lens with a thickness of 2 mm to obtain a spectral transmittance curve. The visual transmittance was calculated based on the obtained spectral transmittance curve.

[Measurement method of L *, a *, b *]
Using a spectrophotometer (CM-5 manufactured by Konica Minolta), under the following measurement conditions, L *, a *, in the CIE1976 (L *, a *, b *) color system of a 2 mm thick flat plate lens. b * was measured.
~Measurement condition~
Light source: C Light source Measurement method: Transmission measurement Measurement area: Circular viewing angle with a diameter of 30 mm: 2 ° field of view [YI measurement method]
YI was measured with a 2 mm thick flat lens with a spectrophotometer CM-5 manufactured by Konica Minolta.

[Haze and total light transmittance measurement method]
The haze and total light transmittance of a 2 mm thick flat lens were measured with a HazeMeter NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

In the examples, the near-infrared absorber shown below was used.

・ Near infrared absorber A

In the visible light absorption spectroscopic spectrum measured with a toluene solution of the near-infrared absorber A represented by the chemical formula (1a), it has a main absorption peak (P) at 935 nm, and the peak peak (Pmax::) of the peak (P). extinction coefficient of the point showing the maximum absorption coefficient) in the peak (ml / g · cm) is 1.58 × 10 ^4, and peaks at half the absorbance of the absorbance of the peak of the (P) (Pmax) The width was 379 nm, and the peak width at the absorbance of 2/3 of the (Pmax) absorbance of the peak (P) was 252 nm.
The visible light absorption spectroscopic spectrum was measured using a toluene solution having an optical path length of 10 mm and a mass of 36.5 mass ppm.

・ Near infrared absorber B

In the visible light absorption spectroscopic spectrum measured with a toluene solution of the near-infrared absorber B represented by the chemical formula (b), it has a main absorption peak (P) at 720 nm, and the peak peak (Pmax::) of the peak (P). extinction coefficient of the point showing the maximum absorption coefficient) in the peak (ml / g · cm) is 1.57 × 10 ^5, the peak width at half the absorbance of the absorbance of the peak of the (P) (Pmax) Was 28 nm, and the peak width at the absorbance of 2/3 of the (Pmax) absorbance of the peak (P) was 20 nm.
The visible light absorption spectroscopic spectrum was measured using a toluene solution of 3.7 mass ppm at an optical path length of 10 mm.

・ Near infrared absorber C

In the visible light absorption spectroscopic spectrum measured with a toluene solution of the near-infrared absorber C represented by the chemical formula (c), it has a main absorption peak (P) at 830 nm, and the peak peak (Pmax::) of the peak (P). extinction coefficient of the point showing the maximum absorption coefficient) in the peak (ml / g · cm) is 1.11 × 10 ^5, the peak width at half the absorbance of the absorbance of the peak of the (P) (Pmax) Was 47 nm, and the peak width at the absorbance of 2/3 of the (Pmax) absorbance of the peak (P) was 35 nm.
The visible light absorption spectroscopic spectrum was measured with an optical path length of 10 mm using a 5.2 mass ppm toluene solution.

・ Near infrared absorber D

In the visible light absorption spectroscopic spectrum measured with a toluene solution of the near-infrared absorber D represented by the chemical formula (d), it has a main absorption peak (P) at 1005 nm, and the peak peak (Pmax::) of the peak (P). extinction coefficient of the point showing the maximum absorption coefficient) in the peak (ml / g · cm) is 7.22 × 10 ^4, the peak width at half the absorbance of the absorbance of the peak of the (P) (Pmax) Was 112 nm, and the peak width at the absorbance of 2/3 of the (Pmax) absorbance of the peak (P) was 81 nm.
The visible light absorption spectroscopic spectrum was measured using a toluene solution of 8.0 mass ppm at an optical path length of 10 mm.

・ Near infrared absorber E

In the visible light absorption spectroscopic spectrum measured with a toluene solution of the near-infrared absorber E represented by the chemical formula (e), it has a main absorption peak (P) at 780 nm, and the peak peak (Pmax::) of the peak (P). extinction coefficient of the point showing the maximum absorption coefficient) in the peak (ml / g · cm) is 1.75 × 10 ^5, the peak width at half the absorbance of the absorbance of the peak of the (P) (Pmax) Was 24 nm, and the peak width at the absorbance of 2/3 of the (Pmax) absorbance of the peak (P) was 17 nm.
The visible light absorption spectroscopic spectrum was measured using a toluene solution having an optical path length of 10 mm and a mass of 3.3 mass ppm.

[Example 1]
0.035 parts by mass of dibutyltin (II) dichloride, 0.1 parts by mass of MR internal mold release agent manufactured by Mitsui Chemicals, 1.5 parts by mass of UV absorber Tinuvin329, 2,5-bis (isosianatomethyl) bicyclo- [ 2.2.1] -Heptane and 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -Heptane mixture 50.6 parts by mass, near infrared absorber A 0.0020 parts by mass A mixed solution was prepared by charging. The mixed solution was stirred at 25 ° C. for 1 hour to completely dissolve. Then, 25.5 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and 23.9 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were added to this preparation solution. Was stirred at 25 ° C. for 30 minutes to prepare a uniform solution. This solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and then poured into a flat glass mold having a center thickness of 2 mm and a diameter of 77 mm. The temperature of this glass mold was raised from 25 ° C. to 120 ° C. over 16 hours. After cooling to room temperature, the lens was removed from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120 ° C. for 2 hours.
The physical characteristics of the flattened lens subjected to this annealing treatment were measured. The results are shown in Table 1.

[Examples 2 to 5]
A flat plate lens was obtained in the same manner as in Example 1 except that the amount of the near infrared absorber A added was the amount shown in Table 1. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens. Further, the spectral transmittance curve of the flat plate lens of Example 5 is shown in FIG.

[Comparative Examples 1 to 7]
A flat plate lens was obtained in the same manner as in Example 1 except that the near-infrared absorber A was changed to the near-infrared absorber B and the amount added thereof was the amount shown in Table 1. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens. Further, the spectral transmittance curve of the flat plate lens of Comparative Example 3 is shown in FIG.

[Comparative Examples 8 to 10]
A flat plate lens was obtained in the same manner as in Example 1 except that the near-infrared absorber A was changed to the near-infrared absorber C and the amount added thereof was the amount shown in Table 1. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens. Further, the spectral transmittance curve of the flat plate lens of Comparative Example 9 is shown in FIG.

[Comparative Examples 11 to 13]
A flat plate lens was obtained in the same manner as in Example 1 except that the near-infrared absorber A was changed to the near-infrared absorber D and the amount added thereof was the amount shown in Table 1. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens. Further, the spectral transmittance curve of the flat plate lens of Comparative Example 12 is shown in FIG.

[Comparative Example 14]
The near-infrared absorber A was changed to the near-infrared absorber E, and the mixture was stirred at 25 ° C. for 1 hour in the same manner as in Example 1 except that the addition amount was 0.00165 parts by mass. However, the near-infrared absorber E did not dissolve.

[Example 6]
0.452 parts by mass of dimethyltin (II) dichloride, 0.18 parts by mass of JP-506H manufactured by Johoku Chemical Industry Co., Ltd., 1 part by mass of the ultraviolet absorber Tinuvin 329, and 48 parts by mass of 1,3-bis (isocyanatemethyl) cyclohexane. A mixed solution was prepared by charging 0.01825 parts by mass of the near-infrared absorber A. The mixed solution was stirred at 25 ° C. for 1 hour to completely dissolve. Then, 26.7 parts by mass of pentaerythritol tetrakis (2-mercaptoacetate) and 26.24 parts by mass of 2,5-bis (mercaptomethyl) -1,4-dithiane were added to this preparation solution, and 25 parts by mass thereof was added. The mixture was stirred at ° C. for 30 minutes to obtain a uniform solution. This solution was defoamed at 400 Pa for 1 hour, filtered through a 1 μm PTFE filter, and then poured into a flat glass mold having a center thickness of 2 mm and a diameter of 77 mm. The temperature of this glass mold was raised from 25 ° C. to 120 ° C. over 16 hours. After cooling to room temperature, the lens was removed from the glass mold to obtain a flat lens. The obtained flat lens was further annealed at 120 ° C. for 2 hours.
The physical characteristics of the flattened lens subjected to this annealing treatment were measured. The results are shown in Table 1.

[Comparative Example 15]
A flat plate lens was obtained in the same manner as in Example 6 except that the near-infrared absorber A was changed to the near-infrared absorber B and the amount added was 0.00184 parts by mass. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens.

[Comparative Example 16]
A flat plate lens was obtained in the same manner as in Example 6 except that the near-infrared absorber A was changed to the near-infrared absorber C and the amount added was 0.0026 parts by mass. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens.

[Comparative Example 17]
A flat plate lens was obtained in the same manner as in Example 6 except that the near-infrared absorber A was changed to the near-infrared absorber D and the amount added was 0.00399 parts by mass. Table 1 shows the measurement results of the physical characteristics of the obtained flat lens.

[Comparative Example 18]
The near-infrared absorber A was changed to the near-infrared absorber E, and the mixture was stirred at 25 ° C. for 1 hour in the same manner as in Example 6 except that the addition amount was 0.00165 parts by mass. However, the near-infrared absorber E did not dissolve.

The monomer types shown in Table 1 are as follows.
a1: 2,5-Bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane a2: 1,3-Bis (isocyananatemethyl) cyclohexane b1: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane b2: pentaerythritol tetrakis (3-mercaptopropionate)
b3: Pentaerythritol tetrakis (2-mercaptoacetate)
b4: 2,5-bis (mercaptomethyl) -1,4-dithiane

The disclosure of Japanese Patent Application No. 2019-086172 filed April 26, 2019 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (17)

(Chio) Urethane resin and
Including near-infrared absorber,
In the CIE1976 (L *, a *, b *) color space measured at a thickness of 2 mm, a * is -10 or more and 0 or less, L * is 70 or more, and the main absorption peak (main absorption peak in the visible light absorption spectroscopic spectrum). An optical material having a peak width of 150 nm or more and 400 nm or less at an absorbance of 2/3 of the absorbance of the peak peak (Pmax) of P). The optical material according to claim 1, wherein the spectral transmittance at a wavelength of 900 nm to 1000 nm at a thickness of 2 mm is 10% or more and 80% or less. The optical material according to claim 1, wherein the visual transmittance at a thickness of 2 mm is 45% or more. One of claims 1 to 3, wherein the near-infrared absorber has a minimum value of a spectral transmittance curve in a wavelength region of 900 nm to 1000 nm, and the minimum value is less than 50% of the spectral transmittance. The optical material according to item 1. The optical material according to any one of claims 1 to 4, wherein the near-infrared absorber contains a phthalocyanine compound. The phthalocyanine compound has a main absorption peak (P) between 900 nm and 1000 nm in the visible light absorption spectroscopic spectrum measured with a toluene solution, and the peak peak (Pmax: maximum absorbance in the peak) of the peak (P). The absorption coefficient (ml / g · cm) of the point indicating the coefficient) is 10,000 or more and 20,000 or less, the peak width at the absorbance of 1/2 of the absorbance of (Pmax) of the peak (P) is 400 nm or less, and The optical material according to claim 5, wherein the peak width in the absorbance of 2/3 of the absorbance of the peak (P) (Pmax) is in the range of 300 nm or less. The optical material according to claim 5 or 6, wherein the phthalocyanine compound contains at least one compound represented by the general formula (1).

(In the general formula (1), X represents a hydrogen atom or a halogen atom, R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, and R ³ represents a hydrogen atom or COR 1. l represents a ^{hydrogen atom or COR 1.} 1 to 7, m represents 0 to 13, n represents 1 to 8, p represents an integer of 1 to 14, z represents an integer of 0 to 13, and 2l + m + z + p = 16. M is a divalent metal atom, trivalent or 4 Represents a valence substitution metal or an oxymetal.) The optical material according to any one of claims 1 to 7, wherein the near-infrared absorber is contained in an amount of 3 ppm or more and 200 ppm or less. The (thio) urethane resin is composed of at least one of a constituent unit derived from a polyisocyanate compound, a constituent unit derived from a polythiol compound, and a constituent unit derived from a polyol compound.
The polyisocyanate compound is 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, and the like. m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, At least one selected from the group consisting of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate.
The polythiol compounds include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiane octane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,7-. Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianeundecane, pentaerythritol tetrakis (3- Mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,1,3,3-tetrakis (mercapto) At least one selected from the group consisting of methylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane. And
The polyol compound is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3. The optical material according to any one of claims 1 to 8, which is at least one selected from the group consisting of −cyclohexanediol and 1,4-cyclohexanediol. A polymerizable composition used for producing the optical material according to any one of claims 1 to 9.
A polymerizable compound composed of a combination of a polyisocyanate compound and at least one of a polythiol compound and a polyol compound,
A near-infrared absorber having a minimum value of the spectral transmittance curve in the wavelength region of 900 nm to 1000 nm and having the minimum value of less than 50% spectral transmittance,
A polymerizable composition for an optical material containing. The polymerizable composition for an optical material according to claim 10, wherein the near-infrared absorber contains a phthalocyanine compound. The polymerizable composition for an optical material according to claim 11, wherein the phthalocyanine compound contains at least one compound represented by the general formula (1).

(In the general formula (1), X represents a hydrogen atom or a halogen atom, R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, and R ³ represents a hydrogen atom or COR 1. l represents a ^{hydrogen atom or COR 1.} 1 to 7, m represents 0 to 13, n represents 1 to 8, p represents an integer of 1 to 14, z represents an integer of 0 to 13, and 2l + m + z + p = 16. M is a divalent metal atom, trivalent or 4 Represents a valence substitution metal or an oxymetal.) The polymerizable composition for an optical material according to any one of claims 10 to 12, wherein the near-infrared absorber is contained in an amount of 3 ppm or more and 200 ppm or less. The polyisocyanate compound is 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, and the like. m-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, At least one selected from the group consisting of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, and 1,5-pentamethylene diisocyanate.
The polythiol compounds include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiane octane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,7-. Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecan, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithianeundecane, pentaerythritol tetrakis (3- Mercaptopropionate), bis (mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,1,3,3-tetrakis (mercapto) At least one selected from the group consisting of methylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, and 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithiane. And
The polyol compound is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3. The polymerizable composition for an optical material according to any one of claims 10 to 13, which is at least one selected from the group consisting of −cyclohexanediol and 1,4-cyclohexanediol. A plastic lens made of the optical material according to any one of claims 1 to 9. Eyewear comprising the plastic lens according to claim 15. An infrared sensor or an infrared camera comprising the plastic lens according to claim 15.

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