JP2018168140A - Blue light absorbing compound - Google Patents

Abstract

To provide a blue light absorbing compound having a high effect of blocking harmful blue light of 380-500 nm.SOLUTION: A blue light absorbing compound has one or more trichiocarbonate groups in the molecule represented by formula (1), such as ethylene trithiocarbonate, dibenzyl trithiocarbonate. In the compound, thiocarbonate may form a saturated/unsaturated heterocycle. There is also provided use of a composition and a molding containing the compound.SELECTED DRAWING: None

Description

  The present invention relates to a blue light absorbing compound, a composition for an optical material containing the same, and an optical material thereof.

Conventionally, the adverse effect of ultraviolet rays on the eyes has been regarded as a problem. Furthermore, in recent years, the effects on the eyes, such as eye fatigue and pain, have been a problem due to the blue light contained in natural light, liquid crystal displays of office equipment, and displays of mobile devices such as smartphones and mobile phones. Therefore, it has been desired to reduce the exposure amount of blue light having a wavelength of 380 to 500 nm.
In particular, Non-Patent Document 1 describes the effect of short wavelength blue light of about 420 nm on the eyes.

  In addition, exposure of the eyes to blue light for a long period of time is a cause of eyestrain and stress, and is also considered to be a cause of age-related macular degeneration.

  Patent Document 1 discloses a plastic lens formed by using a plastic lens composition containing a urethane resin material and an ultraviolet absorber having a maximum absorption wavelength in a chloroform solution of 345 nm or more. Patent Document 1 describes that there is no yellowing of the lens, no change in refractive index, and the like due to the addition of the ultraviolet absorber, and that the mechanical strength of the lens does not decrease. Examples of the ultraviolet absorber include benzotriazole compounds.

  Patent Document 2 discloses a polymer material containing an ultraviolet absorber containing a specific compound and a polymer compound. According to Patent Document 2, according to this polymer material, there is no precipitation of an ultraviolet absorber or bleed out due to long-term use, and long wave ultraviolet absorption ability is excellent, and the absorption ability is maintained for a long time. It is described that it is excellent in property.

JP 11-295502 A International Publication No. 2009/123153

The European journal of neuroscience, vol.34, Iss.4, 548-58, (2011)

  Patent Document 1 discloses the spectral transmittance of a plastic lens with respect to light having a wavelength of 400 nm, but there is no description regarding the light transmittance of wavelengths of 420 nm and 440 nm, and the blue light absorption effect of the ultraviolet absorber is not clear. Moreover, the ultraviolet absorber of patent document 2 has the maximum absorption wavelength in the range of 300-400 nm, and a blue light absorption effect is not clear.

  When a lens is prepared from a composition containing a general ultraviolet absorber such as a benzotriazole compound or a triazine compound and an attempt is made to cut a blue light wavelength region of a wavelength of 380 nm to 500 nm, it is necessary to add a large amount of the ultraviolet absorber. is there. For this reason, the ultraviolet absorbent may not be completely dissolved in the resin and may be precipitated, or the cured resin may become cloudy, and there is room for improvement in the appearance such as transparency. Moreover, even if the ultraviolet absorber is dissolved, it is difficult to cut blue light in a long wavelength region exceeding 420 nm.

（一般式（１）中、Ｒ_１およびＲ_２はそれぞれ独立して、炭素数１〜２０の有機残基を表す。また当該有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。Ｒ_３およびＲ_４はそれぞれ独立して、炭素数１〜２０の２価の有機残基を表す。また当該２価の有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。複数存在するＲ_３同士は同一でも異なっていてもよく、複数存在するＲ_４同士は同一でも異なっていてもよい。ｍは、０〜３の整数を表す。Ｒ_１およびＲ_３は結合して環を形成していてもよく、Ｒ_２およびＲ_４は結合して環を形成していてもよい。ｍが０の場合、Ｒ_１およびＲ_２は結合して環を形成していてもよい。）
［３］ 一般式（１）で表される化合物が、下記一般式（２）または下記一般式（３）で表される化合物である、［２］に記載のブルーライト吸収化合物。

（一般式（２）中、Ｒ_１およびＲ_２はそれぞれ独立して、炭素数１〜２０の有機残基を表す。また当該有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。また、Ｒ_１およびＲ_２は結合して環を形成していてもよい。）

（一般式（３）中、Ｒ_１およびＲ_２はそれぞれ独立して、炭素数１〜２０の有機残基を表す。また当該有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。Ｒ_３およびＲ_４はそれぞれ独立して、炭素数１〜２０の２価の有機残基を表す。また当該２価の有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。また、Ｒ_１およびＲ_３は結合して環を形成していてもよく、Ｒ_２およびＲ_４は結合して環を形成していてもよい。）
［４］ 一般式（２）で表される化合物が、下記一般式（４）で表される化合物である［３］に記載のブルーライト吸収化合物。

（一般式（４）中、Ｒ_５およびＲ_６はそれぞれ独立して、水素原子、ハロゲン原子、水酸基、メルカプト基、シアノ基、炭素数１〜２０の有機残基を表す。また当該有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。Ｒ_５およびＲ_６は結合して環を形成していてもよい。）
［５］ 一般式（２）で表される化合物が、下記一般式（５）で表される化合物である、［３］に記載のブルーライト吸収化合物。

（一般式（５）中、Ｒ_７およびＲ_８はそれぞれ独立して、水素原子、ハロゲン原子、水酸基、メルカプト基、シアノ基、炭素数１〜２０の有機残基を表す。また当該有機残基はヘテロ原子を含んでいてもよく、水素原子の一部がハロゲン原子、水酸基、メルカプト基、およびシアノ基から選択される少なくとも一種で置換されていてもよい。Ｒ_７およびＲ_８は結合して環を形成していてもよい。）
［６］ 一般式（５）で表される化合物が、下記一般式（６）で表される化合物である、［５］に記載のブルーライト吸収化合物。

（一般式（６）中、Ｑはハロゲン原子、水酸基、メルカプト基、およびシアノ基を表す。）
［７］ 一般式（３）で表される化合物が、下記一般式（７）で表される化合物である、［３］に記載のブルーライト吸収化合物。

（一般式（７）中、Ｒ_９は水素原子、炭素数１〜４のアルキル基、またはフェニル基を表す。ｐおよびｑはそれぞれ独立して０〜１０の整数を表す。）
［８］ 下記一般式（８）で表される、［１］に記載のブルーライト吸収化合物。

（一般式（８）中、Ｍはニッケル、パラジウム、プラチナ、亜鉛、銅、銀、および金から選択される金属原子を表す。Ａは、窒素原子またはリン原子を表す。Ｙ_１〜Ｙ_４はそれぞれ独立して炭素数１〜１０のアルキル基、または炭素数３〜１０のアリール基を表す。ｒは１または２を表す。）
［９］ ［１］〜［８］のいずれかに記載のブルーライト吸収化合物を含む、ブルーライト吸収剤。
［１０］ ［１］〜［８］のいずれかに記載のブルーライト吸収化合物と、樹脂または重合性化合物とを含む、光学材料用組成物。
［１１］ 前記ブルーライト吸収化合物を３０重量％以下の範囲で含む、［１０］に記載の光学材料用組成物。
［１２］ 前記重合性化合物が、ポリイソ(チオ)シアネート化合物、(チオ)エポキシ化合物、オキセタニル化合物、チエタニル化合物、（メタ）アクリロイル化合物、（メタ）アリル化合物、アリルカーボネート化合物、アルケン化合物、アルキン化合物、二官能以上の活性水素化合物、酸無水物、アルコキシシラン化合物およびその加水分解物から選択される少なくとも一種である、［１０］または［１１］に記載の光学材料用組成物。
［１３］ 前記樹脂は、ポリエステル樹脂、ポリカーボネート樹脂、ポリオレフィン樹脂、ポリ（メタ）アクリレート樹脂、およびポリシロキサン樹脂よりなる群から選択される少なくとも一種である、［１０］または［１１］に記載の光学材料用組成物。
［１４］ ［１０］〜［１３］のいずれかに記載の光学材料用組成物を硬化した成形体。
［１５］ 前記ブルーライト吸収化合物を３０重量％以下の範囲で含む、［１４］に記載の成形体。
［１６］ ［１］〜［８］のいずれかに記載のブルーライト吸収化合物を３０重量％以下の範囲で含む、成形体。
［１７］ 厚さ１．６ｍｍにおいて、３８０〜５００ｎｍの範囲にあるブルーライト光の何れかの波長を５％以上カットする、［１４］〜［１６］のいずれかに記載の成形体。
［１８］ ポリ（チオ）ウレタン樹脂、ポリ（メタ）アクリレート樹脂、ポリアリルカーボネート樹脂、ポリ(チオ)エーテル樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリオレフィン樹脂、およびポリシロキサン樹脂よりなる群から選択される少なくとも一種を含んでなる、［１４］または［１５］に記載の成形体。
［１９］ ガラスを含んでなる、［１６］に記載の成形体。
［２０］ ［１４］〜［１９］のいずれかに記載の成形体からなる光学材料。
［２１］ 下記一般式（７）で表される化合物。

（一般式（７）中、Ｒ_９は水素原子、炭素数１〜４のアルキル基、またはフェニル基を表す。ｐおよびｑはそれぞれ独立して０〜１０の整数を表す。）
なお本発明における「ブルーライト」とは、波長３８０〜５００ｎｍにおける光線を意味する。 As a result of searching for a compound that efficiently absorbs blue light having a wavelength of 380 to 500 nm which is harmful to eyes, the present inventors have found that a trithiocarbonate group is excellent in blue light absorption effect. That is, the present inventors have found that a compound having a trithiocarbonate group can solve the above problems, and have reached the present invention.
That is, the present invention is as follows.
[1] A blue light absorbing compound having one or more trithiocarbonate groups in the molecule.
[2] The blue light-absorbing compound according to [1], which is represented by the following general formula (1).

(In the general formula (1), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and is a hydrogen atom. The moiety may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₃ and R ₄ are each independently a divalent organic residue having 1 to 20 carbon atoms. The divalent organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. A plurality of R ₃ may be the same or different, and a plurality of R ₄ may be the same or different, m represents an integer of 0 to _3. R ₁ and R ₃ are a bond To form a ring Well, when R ₂ and R ₄ may optionally combine to form a ring .m is 0, R ₁ and R ₂ may form a ring.)
[3] The blue light-absorbing compound according to [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2) or the following general formula (3).

(In the general formula (2), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and may be a hydrogen atom. The portion may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₁ and R ₂ may combine to form a ring.)

(In General Formula (3), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and may be a hydrogen atom. The moiety may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₃ and R ₄ are each independently a divalent organic residue having 1 to 20 carbon atoms. The divalent organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. R ₁ and R ₃ may be bonded to form a ring, and R ₂ and R ₄ may be bonded to form a ring.)
[4] The blue light absorbing compound according to [3], wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(In General Formula (4), R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a cyano group, or an organic residue having 1 to 20 carbon atoms. _May contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₅ and R ₆ are bonded to each other. A ring may be formed.)
[5] The blue light absorbing compound according to [3], wherein the compound represented by the general formula (2) is a compound represented by the following general formula (5).

(In General Formula (5), R ₇ and R ₈ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a cyano group, or an organic residue having 1 to 20 carbon atoms. May contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₇ and R ₈ are bonded to each other. A ring may be formed.)
[6] The blue light-absorbing compound according to [5], wherein the compound represented by the general formula (5) is a compound represented by the following general formula (6).

(In General Formula (6), Q represents a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.)
[7] The blue light-absorbing compound according to [3], wherein the compound represented by the general formula (3) is a compound represented by the following general formula (7).

(In General Formula (7), R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. P and q each independently represent an integer of 0 to 10)
[8] The blue light absorbing compound according to [1], which is represented by the following general formula (8).

(In General Formula (8), M represents a metal atom selected from nickel, palladium, platinum, zinc, copper, silver, and gold. A represents a nitrogen atom or a phosphorus atom. Y ₁ to Y ₄ represent And each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 3 to 10 carbon atoms, r represents 1 or 2.)
[9] A blue light absorbent comprising the blue light absorbent compound according to any one of [1] to [8].
[10] A composition for an optical material comprising the blue light absorbing compound according to any one of [1] to [8] and a resin or a polymerizable compound.
[11] The composition for optical materials according to [10], comprising the blue light absorbing compound in a range of 30% by weight or less.
[12] The polymerizable compound is a polyiso (thio) cyanate compound, (thio) epoxy compound, oxetanyl compound, thietanyl compound, (meth) acryloyl compound, (meth) allyl compound, allyl carbonate compound, alkene compound, alkyne compound, The composition for optical materials according to [10] or [11], which is at least one selected from bifunctional or higher active hydrogen compounds, acid anhydrides, alkoxysilane compounds and hydrolysates thereof.
[13] The optical according to [10] or [11], wherein the resin is at least one selected from the group consisting of a polyester resin, a polycarbonate resin, a polyolefin resin, a poly (meth) acrylate resin, and a polysiloxane resin. Composition for materials.
[14] A molded article obtained by curing the composition for optical materials according to any one of [10] to [13].
[15] The molded article according to [14], containing the blue light absorbing compound in a range of 30% by weight or less.
[16] A molded article comprising the blue light absorbing compound according to any one of [1] to [8] in a range of 30% by weight or less.
[17] The molded article according to any one of [14] to [16], wherein any wavelength of blue light in the range of 380 to 500 nm is cut by 5% or more at a thickness of 1.6 mm.
[18] At least selected from the group consisting of poly (thio) urethane resin, poly (meth) acrylate resin, polyallyl carbonate resin, poly (thio) ether resin, polyester resin, polycarbonate resin, polyolefin resin, and polysiloxane resin The molded article according to [14] or [15], comprising one kind.
[19] The molded article according to [16], comprising glass.
[20] An optical material comprising the molded article according to any one of [14] to [19].
[21] A compound represented by the following general formula (7).

(In General Formula (7), R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. P and q each independently represent an integer of 0 to 10)
The “blue light” in the present invention means a light beam having a wavelength of 380 to 500 nm.

  According to the present invention, it is possible to provide a blue light absorbing compound having a high blocking effect on harmful blue light having a wavelength of 380 to 500 nm, a blue light absorber or a composition for optical materials containing the compound, and the composition. The molded body and optical material obtained from the above can be provided. In particular, the optical material of the present invention can be suitably used as a plastic spectacle lens because the influence of harmful light on the eye is reduced and eye strain and stress can be suppressed.

2 is a chart showing transmittance spectra of ultraviolet light to visible light of lenses manufactured in Example 1 and Comparative Example 1. FIG. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the chloroform solution of the blue light absorption compound prepared in Example 2. FIG. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the chloroform solution of the blue light absorption compound prepared in Example 3, 4 and the comparative example 2. FIG. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the chloroform solution of the blue light absorption compound prepared in Example 5, 6 and the comparative example 3. FIG. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the chloroform solution of the blue light absorption compound prepared in Example 7, 8 and the comparative example 4. FIG. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the chloroform solution in which the blue light absorption compound density | concentration synthesize | combined in Example 10 measured in Example 12 differs. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the chloroform solution of the blue light absorption compound synthesize | combined in Example 11 measured in Example 13. FIG. It is a chart which shows the transmittance | permeability spectrum of the ultraviolet light-visible light of the lens produced in Example 14, 15, 16 and the comparative example 5. FIG.

Hereinafter, embodiments of the present invention will be specifically described.
[Blue Light Absorbing Compound]
The blue light absorbing compound of this embodiment is a trithiocarbonate compound having one or more trithiocarbonate groups in the molecule. In the present specification, the “trithiocarbonate compound” includes a trithiocarbonate compound and a structure (complex) in which the trithiocarbonate compound is coordinated to a metal atom.
A structure (complex) in which a trithiocarbonate compound is coordinated to a metal atom tends to effectively absorb light having a longer wavelength of 380 to 500 nm of blue light.

  By having one or more trithiocarbonate groups, harmful blue light in the wavelength range of 380 to 500 nm can be efficiently absorbed. In this embodiment, the trithiocarbonate compound can have preferably 1 to 4, more preferably 1 to 3, particularly preferably 1 to 2 trithiocarbonate groups in the molecule.

  As a trithiocarbonate compound which is a blue light absorption compound of this embodiment, the compound represented by following General formula (1) can be mentioned.

In General Formula (1), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.

Examples of the organic residue having 1 to 20 carbon atoms include a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, and a substituted or unsubstituted carbon number. Examples thereof include an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 3 to 20 carbon atoms, and a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms.
Examples of the substituent of the above group include at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.
Examples of the hetero atom include a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, and a phosphorus atom.

R ₃ and R ₄ each independently represents a divalent organic residue having 1 to 20 carbon atoms. The divalent organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. A plurality of R ₃ may be the same or different, and a plurality of R ₄ may be the same or different.
m represents an integer of 0 to 3, and is preferably 0 or 1.
R ₁ and R ₃ may be bonded to form a ring, and R ₂ and R ₄ may be bonded to form a ring. When m is 0, R ₁ and R ₂ may be bonded to form a ring.

Examples of the divalent organic residue having 1 to 20 carbon atoms include a substituted or unsubstituted divalent aliphatic group having 1 to 20 carbon atoms and a substituted or unsubstituted divalent alicyclic group having 3 to 20 carbon atoms. Group, substituted or unsubstituted divalent alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted divalent aryl group having 3 to 20 carbon atoms, substituted or unsubstituted divalent group having 3 to 20 carbon atoms A heterocyclic group etc. can be mentioned.
Examples of the substituent of the above group include at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.
Examples of the hetero atom include a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, and a phosphorus atom.

A ring formed by combining R ₁ and R _3, a ring formed by combining R ₂ and R _4, and a ring formed by combining R ₁ and R ₂ when m is 0, It is formed including a carbon atom to which two sulfur atoms are bonded, and may be the same or different. Examples of the ring structure include a substituted or unsubstituted 5-membered ring to 8-membered ring, a substituted or unsubstituted condensed ring, and the like. Specifically, the optionally substituted 1,3-dithiane, 1 , 3-dithiolane, 1,3,5-trithiane, lenthionine, ring structures represented by the following formulas (i) to (iii), and the like.

  Examples of the substituent of the ring represented by the following formula (i) or formula (ii) include a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms and a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms. Group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms, substituted or unsubstituted An alkylcarbonyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 20 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon number 3 To 20 arylthio groups, substituted or unsubstituted arylamino groups having 3 to 20 carbon atoms, substituted or unsubstituted benzoylthio groups, substituted or unsubstituted aryl groups having 3 to 20 carbon atoms, substituted It may be mentioned heterocyclic group unsubstituted C3-20.

Preferred examples of the compound represented by the general formula (1) include compounds represented by the following general formula (2) or the following general formula (3).
First, the compound represented by the following general formula (2) will be described.

In general formula (2), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. R ₁ and R ₂ may be bonded to form a ring.

R ₁ and R ₂ have the same meaning as in the general formula (1). The ring formed by combining R ₁ and R ₂ is a ring formed including a carbon atom to which two sulfur atoms are bonded, and is a substituted or unsubstituted 5-membered ring to 8-membered ring. , Substituted or unsubstituted condensed rings, and the like. Specific examples of the ring structure include optionally substituted 1,3-dithiane, 1,3-dithiolane, 1,3,5-trithiane. , Lenthionine, ring structures represented by the above formulas (i) to (iii), and the like. The ring substituents represented by formula (i) or formula (ii) are the same as described above.

  Examples of the compound represented by the general formula (2) include trithiocarbonic acid-S, S-diethyl ester, trithiocarbonic acid-S, S-diphenyl ester, and trithiocarbonic acid-S, S-dibenzyl. Esters, trithiocarbonic acid-S, S-dinaphthyl ester, trithiocarbonic acid-S, S-bis (2-hydroxyethyl) ester, trithiocarbonic acid-S, S-bis (2-mercaptoethyl) ester , Compounds represented by the following general formula (4), compounds represented by the following general formula (5), and their metal coordination compounds.

In General Formula (4), R ₅ and R ₆ each independently represent a halogen atom, a hydroxyl group, a mercapto group, a cyano group, or an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. R ₅ and R ₆ may combine to form a ring.
Examples of the hetero atom include a sulfur atom, an oxygen atom, a halogen atom, a nitrogen atom, and a phosphorus atom.

Examples of the organic residue having 1 to 20 carbon atoms include a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, and a substituted or unsubstituted carbon number. 1-20 alkoxy group, substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms Group, substituted or unsubstituted aryloxy group having 3 to 20 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 3 to 20 carbon atoms, substituted or unsubstituted arylthio group having 3 to 20 carbon atoms, substituted or unsubstituted A substituted arylamino group having 3 to 20 carbon atoms, a substituted or unsubstituted benzoylthio group, a substituted or unsubstituted aryl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbon number of 3 Heterocyclic group 0 can be mentioned.
Examples of the substituent of the above group include at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.

The ring formed by combining R ₅ and R ₆ includes a carbon atom to which R ₅ is bonded and a carbon atom to which R ₆ is bonded, and is a substituted or unsubstituted five-membered ring to eight Examples thereof include a member ring, a substituted or unsubstituted condensed ring, and the like. Specific examples of the ring structure include cyclopentane, cyclohexane, benzene, furan, 1,3-dithiane, 1,3-dithiolane, thiophene, thiazole, pyridine, naphthalene, quinoline, the following formula (iv) or formula (v) The ring structure etc. which are represented by these can be mentioned.

  Examples of the substituent of the ring represented by formula (iv) include the substituent of the ring represented by formula (i) or formula (ii).

  Examples of the compound represented by the general formula (4) include 1,3-dithiol-2-thione, 4-methyl-1,3-dithiol-2-thione, 4,5-bis (methylthio) -1, 3-dithiol-2-thione, 4,5-bis (benzylthio) -1,3-dithiol-2-thione, 4,5-bis (benzoylthio) -1,3-dithiol-2-thione, 4,5 -Bis (2-cyanoethylthio) -1,3-dithiol-2-thione, dimethyl-1,3-dithiol-2-thione-4,5-dicarboxylate, 4,5-methylenedithio-1,3- Dithiol-2-thione, 4,5-ethylenedithio-1,3-dithiol-2-thione, 5-propyl-1,3-dithiolo [4,5-d] [1,3] dithiol-2-thione, 5-hexyl-1,3-dithio [4,5-d] [1,3] dithiol-2-thione, can be exemplified 1,3,4,6 tetrathiapentalene-2,5-dithione like.

  Examples of the structure (complex) in which the compound represented by the general formula (4) is coordinated to a metal atom include a compound represented by the following general formula (8).

In General Formula (8), M represents a metal atom selected from nickel, palladium, platinum, zinc, copper, silver, and gold, and palladium and zinc are preferable.
A represents a nitrogen atom or a phosphorus atom. Y _{1 to} Y ₄ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 3 to 10 carbon atoms. r represents 1 or 2;

  Examples of the compound represented by the general formula (8) include tetrabutylammonium bis (1,3-dithiol-2-thione-4,5-dithiolate) nickel (III) complex, bis (tetrabutylammonium) bis ( 1,3-dithiol-2-thione-4,5-dithiolate) palladium (II) complex, bis (tetrabutylammonium) bis (1,3-dithiol-2-thione-4,5-dithiolate) zinc complex, tetra Butylphosphonium bis (1,3-dithiol-2-thione-4,5-dithiolate) nickel (III) complex, bis (tetrabutylphosphonium) bis (1,3-dithiol-2-thione-4,5-dithiolate) Palladium (II) complex, bis (tetrabutylphosphonium) bis (1,3-dithiol-2-thione-4,5-dithio Rate) zinc complex, dioctadecyldimethylammonium bis (1,3-dithiol-2-thione-4,5-dithiolate) gold complex, and the like.

In General Formula (5), R ₇ and R ₈ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a cyano group, or an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. R ₇ and R ₈ may combine to form a ring.
R ₇ and R ₈ are synonymous with R ₅ and R _{6 in} the general formula (4), and the ring formed is also synonymous.

  Examples of the compound represented by the general formula (5) include ethylene trithiocarbonate, 4-methyl-ethylene trithiocarbonate, 4-ethyl-ethylene trithiocarbonate, 4-hydroxy-ethylene trithiocarbonate, 4-benzyl. Oxy-ethylene trithiocarbonate, 4-phenyloxy-ethylene trithiocarbonate, 4-naphthoxy-ethylene trithiocarbonate, 4-nonadecyloxy-ethylene trithiocarbonate, 4-acetoxy-ethylene trithiocarbonate, ethylene trithiocarbonate-4 -Benzoate, ethylene trithiocarbonate-4-naphthoate, ethylene trithiocarbonate-4-anthracene carboxylate, 4-anthraquinonylamino-ethylene trithiocarbonate, - mercapto - ethylene trithiocarbonate, 4-methylthio - ethylene trithiocarbonate, 4-benzylthio - ethylene trithiocarbonate compounds represented by the following general formula (6) thereof, and the like metal coordination compounds.

In general formula (6), Q represents a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.
Examples of the compound represented by the general formula (6) include 4-fluoromethyl-ethylene trithiocarbonate, 4-chloromethyl-ethylene trithiocarbonate, 4-bromomethyl-ethylene trithiocarbonate, 4-iodomethyl-ethylene tri Examples thereof include thiocarbonate, 4-hydroxymethyl-ethylene trithiocarbonate, 4-mercaptomethyl-ethylene trithiocarbonate, and metal coordination compounds thereof.

In the general formula _(3), R 1 to R ₄ are the same as _R 1 to R ₄ in the general formula (1), the ring formed is also synonymous.

  Examples of the compound represented by the general formula (3) include propylene-1,3-trithiocarbonate, butylene-1,4-trithiocarbonate, and a compound represented by the following general formula (7) which is a novel compound. And their metal coordination compounds.

In General Formula (7), R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. p and q each independently represents an integer of 0 to 10.

R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is relatively preferable from the viewpoint of solubility with a resin or a polymerizable compound, Most preferred is a hydrogen atom. p and q each independently represent an integer of 0 to 10, preferably in the range of integers of 0 to 5, more preferably in the range of integers of 0 to 3, and most preferably in the range of integers of 0 to 2.

  Examples of the compound represented by the general formula (7) include bis (1,3-dithiolane-2-thione-4-methyl) sulfide and bis (1,3-dithiolane-2-thione-4-methyl) disulfide. Bis (1,3-dithiolane-2-thione-4-methyl) trisulfide, bis (1,3-dithiolane-2-thione-4-methyl) disulfide, bis (1,3-dithiolane-2-thione- 4-methyl) tetrasulfide, bis (1,3-dithiolane-2-thione-4-methyl) pentasulfide, bis (1,3-dithiolane-2-thione-4-methyl) -1,3-dithiapropane, bis (1,3-dithiolane-2-thione-4-methyl) -2-methyl-1,3-dithiapropane, bis (1,3-dithiolane-2-thione-4-methyl) -2-ethyl- , 3-dithiapropane, bis (1,3-dithiolane-2-thione-4-methyl) -2-propyl-1,3-dithiapropane, bis (1,3-dithiolane-2-thione-4-methyl) -2 -Butyl-1,3-dithiapropane, bis (1,3-dithiolane-2-thione-4-methyl) -2-phenyl-1,3-dithiapropane, bis (1,3-dithiolane-2-thione-4- Methyl) -1,3,5-trithiapentane, bis (1,3-dithiolane-2-thione-4-methyl) -1,3,5,7-tetrathiaheptane, bis (1,3-dithiolane- 2-thione-4-methyl) -1,3,5,7,9-pentathiononane, bis (1,3-dithiolane-2-thione-4-methyl) -1,4-dithiabutane, bis (1,3- Dithiolane-2-thione-4 Methyl) -1,4,7-trithiaundecane heptane, and the like their metal coordination compounds.

  The compound represented by the general formula (7) can be produced by a known production method. For example, typical compounds represented by the following general formulas (d) to (f) selected from the compounds represented by the general formula (7) are taken as an example, and the main production route is as follows. It is shown in the reaction formula.

First, the manufacturing route performed in order of a process (A)-> process (D) is demonstrated.
In the following, the symbol of the compound corresponds to the symbol of the compound in the above reaction formula. X represents a halogen atom, and a plurality of X present in the compound (a) may be the same or different.

Step (A):
2,3-dihalogeno-1-propanol (a) is reacted with an alkali metal trithiocarbonate. The raw material alkali metal trithiocarbonate can be obtained by a known production method such as reacting alkali metal sulfide such as sodium sulfide nonahydrate with carbon disulfide. This alkali metal trithiocarbonate is added in an amount of 1 to 10 times mol, preferably 2 to 5 times mol, more preferably 3 to 4 times mol, of 2,3-dihalogeno-1-propanol (a), The reaction is carried out in the range of 0 to 200 ° C., preferably room temperature to 150 ° C., more preferably 30 to 120 ° C. for 1 to 36 hours. By this step, a reaction mixture containing compound (b) is obtained.

  For the purpose of improving the speed of this reaction, quaternary ammonium salts such as tetrabutylammonium bromide and trioctylmethylammonium chloride, quaternary phosphine salts such as tetrabutylphosphine bromide and tetraphenylphosphine bromide, and alkyl sulfates such as sodium octyl sulfate. Known surfactants such as salts and aryl sulfonates such as potassium octylphenylsulfonate may be added. The addition amount of these surfactants is preferably 0.01 to 30 mol%, preferably 0.1 to 10 mol%, more preferably 0.3 to 3 mol%, relative to the alkali metal trithiocarbonate. It is a range.

  If the other raw material is not the 2,3-dihalogen-1-propanol (a) described above, but the isomer 1,3-dihalogen-2-propanol, the target compound ( b) is obtained. Examples of the halogeno group constituting these dihalogenopropanols include a chloro group, a bromo group, and an iodo group. Among them, a chloro group and a bromo group are preferable, and a bromo group is most preferable.

  Finally, the reaction mixture obtained above is purified by a known purification method (for example, water washing → concentration → column chromatography → concentration, water wash → concentration → distillation, etc.) to obtain compound (b) as an intermediate. obtain.

Step (D):
In the compound (b) obtained in the step (A), sulfur, oxygen, hydrogen peroxide, peracetic acid, chlorine, bromine, iodine, sodium hypochlorite, calcium hypochlorite (salach powder, salash liquid), etc. The mercapto group is oxidized by adding one or more selected from known oxidizing agents.
Among these oxidizing agents, sulfur, bromine, and iodine, which are excellent in operability, are relatively preferable. These oxidizing agents are 0.1 to 2 times the molar amount, preferably 0.2 to 1 times the molar amount, more preferably 0.4 to 0.6 times the molar amount with respect to the mercapto group of the compound (b). The reaction is carried out at −60 ° C. to 120 ° C., preferably −40 to 80 ° C., more preferably −10 to 50 ° C. for 1 to 36 hours. By this step, a reaction mixture containing compound (d) is obtained.

  In the reaction step (D), addition of a basic compound is effective for the purpose of improving the reaction rate. Specific examples of the basic compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and other inorganic basic compounds, or triethylamine, Tributylamine, triethanolamine, pyridine, N-methylpiperazine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undecene-7, triphenyl Examples include organic basic compounds such as phosphine and tributylphosphine. The amount of the basic compound used with respect to the mercapto group of the compound (b) is in the range of 0.001 to 10 times mol, preferably 0.01 to 3 times mol, more preferably 0.1 to 1 times mol. is there.

In the reaction of step (A) → step (D), a known solvent can be used, but a raw material, an intermediate, and a solvent that does not easily react with the final object are selected, and among these solvents, the raw material, An appropriate solvent is selected according to the properties of the intermediate and the final object.
Specific examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and cyclohexane, halogens such as dichloromethane, chloroform, dichloroethane, chlorobenzene and dichlorobenzene, ethyl acetate, Esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane, anisole, nitriles such as acetonitrile, adiponitrile, cyanobenzene, N, N-dimethylformamide, Aprotic polar compounds such as N, N-dimethylacetamide and N, N-dimethylimidozolidinone, methanol, ethanol, isobropanol, butanol, hexanol, octanol, 2-methyl Butoxyethanol, 2-main-butoxyethanol, 1-alcohols methoxy-2-propanol, water, and alcohols, and the like and a mixture of water.

  Finally, the reaction mixture obtained above is subjected to a known purification method (for example, water washing → concentration → column chromatography → concentration, water wash → concentration → recrystallization → filtration → drying, etc.) to obtain the target compound (d )

  Next, the manufacturing route performed in the order of step (A) → step (E) will be described. The step (A) can be performed in the same manner as the above-described step (A). Step (E) will be described.

Step (E):
Compound (b), which is an intermediate obtained in the step (A), is converted into aldehydes such as formalin and paraformaldehyde, dihalogenomethanes such as dichloromethane and dibromomethane, or dimethoxymethane, diethoxymethane, dibutoxymethane and the like. 1 type (s) or 2 or more types selected from these dialkoxymethanes are added. Among these, formalin, paraformaldehyde, dibromomethane, dimethoxymethane, and diethoxymethane, which are excellent in reactivity and operability, are relatively preferable.

These compounds are added in an amount of 0.1 to 2 times, preferably 0.2 to 1 times, more preferably 0.4 to 0.6 times the amount of the mercapto group of the compound (b). The reaction is carried out at a molar amount of −20 ° C. to 200 ° C., preferably 0 to 150 ° C., more preferably 20 to 100 ° C. for 1 to 36 hours. By this step, a reaction mixture containing compound (e) is obtained.
In this reaction step (E), addition of an acidic or basic compound is effective for the purpose of improving the reaction rate.

  When the compound to be reacted with the intermediate compound (b) is an aldehyde or dialkoxymethane, an acidic compound is effective as a catalyst. Examples of acidic compounds include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, and Lewis acids such as zinc chloride and boron trifluoride. Is mentioned. The amount of these acidic compounds added to the mercapto group of the compound (b) is, for example, preferably from 0.01 to 30 mol%, preferably from 0.1 to 10 mol%, more preferably from 0.3 to 3 mol%. It is.

When the compound to be reacted with the intermediate (b) is a dihalogenomethane, the reaction rate is improved by adding a basic compound as a scavenger (neutralizing agent) of the hydrogen halide generated as the reaction proceeds.
Examples of the basic compound include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, triethylamine, Butylamine, triethanolamine, pyridine, N-methylpiperazine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine And organic basic compounds such as tributylphosphine. The amount of the basic compound used relative to the mercapto group of the compound (b) is 0.1 to 5 times mol, preferably 0.2 to 3 times mol, more preferably 0.4 to 1.5 times mol. It is a range.

When a solvent is used in the reaction of step (E), examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and cyclohexane, dichloromethane, chloroform, dichloroethane, chlorobenzene, Halogens such as dichlorobenzene, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane and anisole, nitriles such as acetonitrile, adiponitrile and cyanobenzene, N, N-dimethylformamide, N, Aprotic polar compounds such as N-dimethylacetamide, N, N-dimethylimidozolidinone, methanol, ethanol, isobropanol, butanol, hexanol, octanol, 2-methoxyethanol, 2-mebu Butoxyethanol, alcohols such as 1-methoxy-2-propanol is preferably used relatively.
The reaction mixture thus obtained is subjected to known purification methods (for example, water washing → concentration → column chromatography → concentration, water wash → concentration → recrystallization → filtration → drying, etc.) to obtain the target compound (e). .

  In addition, when synthesizing the following compound (e-2) which is an analogous compound of the compound (e), the intermediate compound (b) and acetaldehyde, 1,1-dihalogenoethane, or 1,1-dialkoxyethane Etc. may be reacted.

  Similarly, when synthesizing the following compound (e-3), benzaldehyde or dialkoxymethylbenzene or the like may be reacted with the intermediate compound (b).

  In addition, when synthesizing the following compound (e-4), for example, the compound (b) as an intermediate is reacted with dihalogenomethanes or dialkoxymethanes and then reacted with hydrogen sulfide, and again dialkoxymethanes. It is obtained by repeating the reaction of reacting hydrogen sulfide with hydrogen sulfide, finally reacting dihalogenomethanes or dialkoxymethanes and then reacting compound (b).

In formula (e-4), q is synonymous with formula (7).
Furthermore, when synthesizing the following compound (e-5), an operation similar to that of the compound (e-4) may be performed using acetaldehyde instead of dihalogenomethanes or dialkoxymethanes.

In formula (e-5), q is synonymous with formula (7).
Next, the manufacturing route performed in order of a process (A)-> process (C)-> process (F) is demonstrated. The step (A) can be performed in the same manner as the above-described step (A). First, the step (C) will be described.

Step (C):
A chlorinating agent such as sulfuryl halide or N-halogenosuccinimide is added to the intermediate compound (b), and then a phosphorus organic base compound such as triphenylphosphine or triphenylphosphite is added. The addition amount of the chlorinating agent and the phosphorus basic compound is 0.3 to 3 times the molar amount, preferably 0.5 to 2 times the molar amount, more preferably the mercapto group of the compound (b). The molar amount is 0.9 to 1.2 times, and in each case, the reaction is performed in the range of −60 to 100 ° C., preferably −40 to 50 ° C., more preferably −25 to 30 ° C. for 1 to 72 hours. By this step, a reaction mixture containing compound (c) is obtained.

When a solvent is used in the reaction of step (C), examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and cyclohexane, dichloromethane, chloroform, dichloroethane, chlorobenzene, Halogens such as dichlorobenzene, esters such as ethyl acetate and butyl acetate, ethers such as diethyl ether, tetrahydrofuran, dioxane and anisole, nitriles such as acetonitrile, adiponitrile and cyanobenzene, N, N-dimethylformamide, N, Aprotic polar compounds such as N-dimethylacetamide and N, N-dimethylimidozolidinone are relatively preferably used.
The reaction mixture thus obtained is subjected to known purification methods (for example, water washing → concentration → column chromatography → concentration, water wash → concentration → recrystallization → filtration → drying, etc.) to obtain the desired compound (c).

Step (F):
The compound (c) obtained in the step (C) is added to the intermediate compound (b). The amount of compound (c) added to compound (b) is 0.3 to 3 times the molar amount, preferably 0.5 to 2 times the molar amount, more preferably 0.8 to 1.2 times the molar amount, The reaction is carried out in the range of 10 to 200 ° C., preferably 0 to 150 ° C., more preferably 20 to 100 ° C. for 1 to 72 hours. By this step, a reaction mixture containing compound (f) is obtained.

  In the above reaction, a basic compound is preferably used for the purpose of improving the reaction rate. Examples of the basic compound include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, or triethylamine, tributylamine. , Triethanolamine, pyridine, N-methylpiperazine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undecene-7, triphenylphosphine, Examples include organic basic compounds such as tributylphosphine. The basic compound is used in an amount of 0.1 to 5 times, preferably 0.2 to 3 times, more preferably 0.4 to 1.5 times the amount of the mercapto group of the compound (b). A range of molar amounts.

When a solvent is used in the step (F), examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dioxane and anisole. Nitriles such as ethers, acetonitrile, adiponitrile, cyanobenzene, aprotic polar compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidozolidinone, methanol, ethanol, isobromine Alcohols such as panol, butanol, hexanol, octanol, 2-methoxyethanol, 2-mebutoxyethanol, 1-methoxy-2-propanol, water, and a mixture of alcohols and water are relatively preferable. It is needed.
The reaction mixture thus obtained is subjected to known purification methods (for example, washing with water → concentration → column chromatography → concentration, washing with water → concentration → recrystallization → filtration → drying, etc.) to obtain the desired compound (f). Can do.

  The trithiocarbonate compound of the present embodiment is preferably a compound represented by the general formula (1) and its metal coordination compound (complex), more preferably a compound represented by the general formulas (2) to (3). And a metal coordination compound (complex) thereof, more preferably a compound represented by the general formulas (4) to (7) and a compound represented by the metal coordination compound (complex) or the general formula (8). And most preferred is a compound represented by formula (8).

  The central metal for the metal complex is not particularly limited, but relatively preferably used metals include 8A group metals such as nickel, palladium and platinum, 2B group metals such as zinc, copper, 1B group metals, such as silver and gold, are mentioned, More preferably, 8A group metals and 2B group metals are mentioned.

  When the metal coordination compound (complex) of the above-mentioned trithiocarbonate compound and a metal compound is used as the blue light-absorbing compound of this embodiment, the coordination molar ratio is usually 6: trithiocarbonate compound: metal compound. The range is from 1: 1 to 3: 3, preferably from 4: 1 to 1: 2, and more preferably from 3: 1 to 1: 1.

[Blue Light Absorber]
The blue light absorbent of this embodiment comprises a blue light absorbent compound that is the trithiocarbonate compound. The blue light absorbent may be composed only of the trithiocarbonate compound or may be a mixture with other components other than the trithiocarbonate compound.

  Examples of other components include compounds other than the trithiocarbonate compound according to the present embodiment, such as raw materials, intermediates, solvents, additives, and polymerization reactive monomers and polymers thereof.

  The mixing ratio of the trithiocarbonate compound and other components according to this embodiment is 0.001 to 100 wt%: 99.999 to 0 wt%, preferably expressed as the weight mixing ratio of the trithiocarbonate compound to other components. 0.1-100 wt%: 99.9-0 wt%, more preferably 1-100 wt%: 99-0 wt%, more preferably 10-100 wt%: 90-0 wt%, most preferably 30-100 wt%: 70 It is in the range of ˜0 wt%.

The blue light absorbent comprising the trithiocarbonate compound of this embodiment can be added to various materials in order to cut harmful blue light in the wavelength range of 380 to 500 nm.
In order to protect the eyes from this harmful blue light, it is desirable to cut at least 5% on average blue light in the range of 380 to 500 nm (decrease by 5% or more in transmittance), and average 10%. The above cut rate (decrease of 10% or more in transmittance) is preferable, 40% or more on average (decrease of 40% or more in transmittance) is more preferable, 60% or more (decrease in transmittance of 60% or more) is further preferable, 80% or more (80% or more decrease in transmittance) is most preferable. By using the blue light absorbent comprising the trithiocarbonate compound of the present embodiment, the above cut rate can be realized.

  Among this harmful blue light, a specific blue light region having a particularly high energy in the short wavelength range of 380 to 420 nm is a benzotriazole-based compound used as a general ultraviolet absorber (for example, tinuvin 326, Eversorb 109, etc.) Although it is being solved by adding a large amount, it is in a situation where it cannot absorb up to a long wavelength region of 420 to 500 nm. Therefore, it is preferable to cut at least 5% on average for the specific blue light light in the range of 420 to 500 nm that cannot be handled by a general ultraviolet absorber according to the present embodiment, and more preferably 10% or more. % Or more is more preferable, and 50% or more is most preferable.

  The blue light absorber having the trithiocarbonate group of the present embodiment added to cut harmful blue light has a target wavelength cut region determined by its type and structure, etc. Tend to be controlled by.

  For example, among the blue light absorbents having a trithiocarbonate group of the present embodiment, when it is desired to cut a relatively long wavelength region (420 to 500 nm), the compound represented by the general formula (4) or the general formula (8) It is preferable to use a metal coordination compound (complex) represented by: When it is desired to cut a particularly harmful short wavelength region (380 to 420 nm), it is preferable to use the compounds represented by the general formulas (5) to (7) and their metal coordination compounds (complexes).

[Composition for optical materials]
The composition for optical materials of this embodiment contains a blue light absorbing compound (or blue light absorber) and a resin or a polymerizable compound.

  The resin is at least one selected from the group consisting of polyester resins, polycarbonate resins, polyolefin resins, poly (meth) acrylate resins, and polysiloxane resins.

  The polymerizable compound is a polyiso (thio) cyanate compound, (thio) epoxy compound, oxetanyl compound, thietanyl compound, (meth) acryloyl compound, (meth) allyl compound, allyl carbonate compound, alkene compound, alkyne compound, bifunctional or more Active hydrogen compounds, acid anhydrides, alkoxysilane compounds and hydrolysates thereof.

  The polyiso (thio) cyanate compound is a compound having two or more isocyanate groups or isothiocyanate groups. For example, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanate methyl) cyclohexane, bis (isocyanate). Natomethyl) norbornane, bis (isocyanatocyclohexyl) methane, bis (isocyanatomethylthio) methane, bis (isocyanatomethyl) disulfide, dithiolane diisocyanate, isophorone diisothiocyanate, bis (isothiocyanatomethyl) cyclohexane, bis (isothiocyanana) Tomethyl) norbornane, bis (isothiocyanatocyclohexyl) methane, tris (isocyanatopentyl) isocyanurate, Scan (isocyanatomethyl-hexyl) isocyanurate and the like can be given.

Examples of (thio) epoxy compounds include bisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane diglycidyl. Ether, hexahydrophthalic anhydride diglycidyl ester, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, diglycidyl ether, diglycidyl sulfide, diglycidyl disulfide, dithioglucidyl sulfide, dithioglycidyl disulfide (Thio) epoxy compounds such as
Oxetanyl compounds such as 3-ethyl-3-hydroxyethyloxetane, 1,4-bis {(3-ethyl-3-oxetanylmethoxy) methyl} benzene,
Examples include thietanyl compounds such as dithietanyl sulfide and dithietanyl disulfide.

  Examples of the oxetanyl compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (phenoxy Examples include methyl) oxetane, di [1-ethyl- (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and phenol novolac oxetane.

  Examples of the thietanyl compound include 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio). -2,4,6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl- 2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5-mercapto-2,4-dithiapentylthio] -1,3-dithiane, 3- { 2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3- Dithietanyl) Methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl) )} Methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- ( 1,3-dithietanyl)} methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto -2-thiapropylthio] -1,3-dithiolane, 4- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (Mercaptomethylthio -4-mercapto-3-thiabutylthio} -1,3-dithiolane, 4- {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio} -5- [1- {2- (1,3-dithietanyl) )}-3-mercapto-2-thiapropylthio] -1,3-dithiolane and the like.

Examples of the (meth) acryloyl compound include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl ( (Meth) acrylate, hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, N- (meth) acryloylpyrrolidone, N- ( Monofunctional (meth) acryloyl compounds such as (meth) acryloylimidazole and N- (meth) acryloylcaprolactone;
For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and urethane (meth) acrylate reacted with hydroxybutyl (meth) acrylate and phenyl isocyanate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and Urethane (meth) acrylate reacted with hydroxybutyl (meth) acrylate and benzyl isocyanate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and urethane (meth) acrylate reacted with hydroxybutyl (meth) acrylate and cyclohexyl isocyanate Monofunctional urethane (meth) acryloyl compounds such as
For example, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cyclohexanedimethanol di (Meth) acrylate, alkoxylated hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, caprolactone modified neopentyl glycol hydroxypivalate di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 4,4′-bis (4- (meth) acryloylio Si-3-hydroxy-1-oxabutyl) bisphenol A, 4,4′-bis (4- (meth) acryloyloxy-3-hydroxy-1-oxabutyl) -dicyclohexyl-2,2-propane, hydroxypivalaldehyde modified tri Methylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecandi Methanol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate,
Glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, N, N'- Di (meth) acryloylethyleneurea, N, N ′, N′-tri (meth) acryloyl isocyanurate, 1,2-bis {(meth) acryloylthio} ethane, 1,5-bis (Meth) acryloylthio} -3- difunctional or more poly (meth) such as Chiapentan acryloyl compound;
For example, urethane (meth) acrylate reacted with 2-hydroxyethyl (meth) acrylate and the polyiso (thio) cyanate compound, urethane (meth) reacted with 2-hydroxypropyl (meth) acrylate and the polyiso (thio) cyanate compound Acrylate, urethane (meth) acrylate reacted with 3-hydroxypropyl (meth) acrylate and the polyiso (thio) cyanate compound, urethane (meth) reacted with 4-hydroxybutyl (meth) acrylate and the polyiso (thio) cyanate compound Urethane (meth) acrylate, pentaerythritol tri (meth) acrylate and polyiso (thio) cyanate compound reacted with acrylate, glycerin-2-hydroxy-1,3-di (meth) acrylate and the polyiso (thio) cyanate compound Reacted Examples thereof include urethane (meth) acrylate compounds such as urethane (meth) acrylate, dipentaerythritol penta (meth) acrylate and urethane (meth) acrylate reacted with the polyiso (thio) cyanate compound.

  Examples of (meth) allyl compounds include (meth) allyl alcohol, (meth) allyl chloride, (meth) allylcyclohexane, (meth) allylbenzene, (meth) allylnaphthalene, bis {(meth) allyl} ether, bis (Meth) allyl compounds such as {(meth) allyl} sulfide, bis {(meth) allyl} disulfide, bis {(meth) allyl} benzene and the like.

  Examples of the allyl carbonate compound include ethylene glycol diallyl carbonate, diethylene glycol diallyl carbonate, triethylene glycol diallyl carbonate, tetraethylene glycol diallyl carbonate, propylene glycol diallyl carbonate, dipropylene glycol diallyl carbonate, butylene glycol diallyl carbonate, and xylylenediol diallyl carbonate. Etc.

  Examples of the alkene compound include polyethylene, polypropylene, polyisobutylene, diethylene glycol bis (allyl carbonate), divinylbenzene, and the like.

Examples of the alkyne compound include 2-butyne, 2-pentyne, 2-hexyne, 3-hexyne, 2-heptin, 3-heptin, 2-octyne, 3-octyne, 4-octyne, diisopropylacetylene, 2-nonine, 3-nonine, 4-nonine, 5-nonine, 2-decyne, 3-decyne, 4-decyne, 5-decyne, di-tert-butylacetylene, diphenylacetylene, dibenzylacetylene, methyl-iso-propylacetylene, methyl -Tert-butylacetylene, ethyl-iso-propylacetylene, ethyl-tert-butylacetylene, n-propyl-iso-propylacetylene, n-propyl-tert-butylacetylene, phenylmethylacetylene, phenylethylacetylene, phenyl-n- Propylacetylene Phenyl -iso- propyl acetylene, phenyl -n- butyl acetylene, hydrocarbon alkynes such as phenyl -tert- butyl acetylene;
Alkynyl alcohols such as acetylenic diol, propyneol, butyneol, pentyneol, hexyneol, hexynediol, heptinol, heptindiol, octyneol, octynediol, and a part or all of the OH groups of the above alkynyl alcohols And alkynylamines substituted with NH ₂ group.

The bifunctional or higher functional hydrogen compound is a compound having two or more functional groups selected from a hydroxy group, a mercapto group, and an amino group. For example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, poly Bifunctional or more active hydrogen compounds having a hydroxy group such as glycerin and thioglycerin,
Trithioglycerin, pentaerythritol tetrakis (thioglycolate), trimethylolpropane (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), Bis (2-mercaptoethyl) sulfide, 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, 4,8-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11- Dithiol, 4,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1, 11-dithiol, 1,1,3,3-tetrakis (mercaptomethi Bifunctional or higher functional hydrogen compounds having a mercapto group such as 2-thiapropane, 1,4-dithian-2,5-dithiol, 2,5-bis (mercaptomethyl) -1,4-dithiane, xylylenedithiol ,
Cyclohexylamine, benzylamine, xylylenediamine, α, α, α ′, α′-tetramethyl-xylylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, diaminopolypropylene, diaminopolyethylene, isophoronediamine, Bifunctional or higher functional hydrogen compounds having an amino group such as bis (aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornane, and the like can be given.

  The acid anhydride can be used as a curing agent, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

  The alkoxysilane compound is a compound having one or more alkoxysilyl groups, such as tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, glycidyltrimethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane. , Isocyanatopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and the like. Examples of the hydrolyzate include compounds in which part or all of the alkoxysilyl groups of the alkoxysilane compound are hydrolyzed to change into hydroxyl groups.

  The composition for optical materials of the present embodiment can contain a catalyst, an ultraviolet polymerization initiator, a thermal polymerization initiator, an ultraviolet polymerization initiator, an internal mold release agent, a curing agent, and the like as necessary. Furthermore, various other components such as an ultraviolet absorber, an antioxidant, a photochromic agent, a thermochromic agent, a dye, a dye, a pigment, a leveling agent, a surfactant, and a plasticizer can be further included. The content of other components is usually in the range of 50 wt% or less, preferably 20 wt% or less, more preferably 10 wt% or less, and most preferably 5 wt% or less.

  In addition, when the molded object of this embodiment is comprised from glass, the composition for optical materials is a blue light absorption compound and tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane contained in said alkoxysilane compound, A tetraalkoxysilane compound such as tetrabutoxysilane and a silane compound converted to a hydroxyl group such as tetrahydroxysilane obtained by hydrolyzing them.

  The blue light absorber of this embodiment is usually 30 wt% or less, preferably in the range of 0.0001 to 30 wt%, more preferably 0.001 to 10 wt% in the composition for optical materials as a bluelight absorbing compound. It is included in the range, more preferably in the range of 0.001 to 3 wt%, and most preferably in the range of 0.01 to 2 wt%. Thereby, harmful blue light (380 to 500 nm) can be effectively cut.

[Molded body]
The molded product of the present embodiment can be obtained by curing the composition for optical materials.
The molded body is made of glass; or poly (thio) urethane resin, poly (meth) acrylate resin, polyallyl carbonate resin, poly (thio) ether resin, polyester resin, polycarbonate resin, polyolefin resin, polysiloxane resin, etc. At least one resin selected.

  Among these materials, poly (thio) urethane resins, poly (meth) acrylate resins, polyallyl carbonate resins, poly (thio) ether resins, polyester resins, and polycarbonate resins, which are highly soluble and excellent in transparency, are preferable. A poly (thio) urethane resin that can be easily produced as a molded product by mixing and dissolving the blue light-absorbing compound having a trithiocarbonate group of the present embodiment into a polymerizable compound mainly in a low-viscosity and monomer state, and performing cast polymerization. Poly (meth) acrylate resins, polyallyl carbonate resins, and poly (thio) ether resins are more preferred.

  The poly (thio) urethane resin molded article containing the trithiocarbonate compound of the present embodiment was obtained by mixing and dissolving the polyiso (thio) cyanate compound, the bifunctional or higher active hydrogen compound, and the trithiocarbonate compound. It is obtained by polymerizing and curing a polymerizable compound with heat.

  If necessary, a urethane catalyst and an internal release agent may be added to the polymerizable compound. Examples of urethane catalysts include dimethyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dimethyltin dichloride, dibutyltin dichloride, dioctyltin dichloride, organometallic compounds such as bis (2-ethylhexanoate) zinc, triethylamine, Examples thereof include tertiary amine compounds such as butylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine and pyridine, and phosphine compounds such as triphenylphosphine and tributylphosphine.

  Internal release agents include monobutyl phosphate, dibutyl phosphate, monohexyl phosphate, dihexyl phosphate, monooctyl phosphate, dioctyl phosphate, monoundecane phosphate, diundecane phosphate, monobutoxyethyl phosphate, dibutoxyethyl Examples thereof include phosphoric acid compounds such as phosphoric acid, monooctylphenyl phosphoric acid, and dioctylphenyl phosphoric acid.

  The poly (meth) acrylate resin molded product containing the trithiocarbonate compound of the present embodiment is obtained by mixing a polymerizable composition obtained by mixing and dissolving the trithiocarbonate compound of the present embodiment with the (meth) acryloyl compound. Alternatively, it can be obtained by polymerizing and curing with radiation.

When polymerizing the polymerizable composition using radiation such as UV, an ultraviolet polymerization initiator may be added, and when polymerizing by heat, a thermal polymerization initiator may be added.
Examples of the ultraviolet polymerization initiator include Irgacure 127 (manufactured by Ciba Specialty Chemicals), Irgacure 651 (manufactured by Ciba Specialty Chemicals), and Irgacure 184 (manufactured by Ciba Specialty Chemicals). Darocur 1173 (manufactured by Ciba Specialty Chemicals), benzophenone, 4-phenylbenzophenone, Irgacure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 2959 (manufactured by Ciba Specialty Chemicals), Irga Cure 907 (Ciba Specialty Chemicals), Irgacure 369 (Ciba Specialty Chemicals), Irgacure 1300 (Ciba Specialty Chemicals), Irgaki Are 819 (Ciba Specialty Chemicals), Irgacure 1800 (Ciba Specialty Chemicals), Darocur TPO (Ciba Specialty Chemicals), Darocur 4265 (Ciba Specialty Chemicals) ), Irgacure OXE01 (Ciba Specialty Chemicals), Irgacure OXE02 (Ciba Specialty Chemicals)), Esacure KT55 (Lamberti), Esacure ONE (Lamberti), Esacure KIP150 (Lamberti), Esacure KIP100F (Lamberti), Esacure KT37 (Lamberti), Esacure KTO46 (Lamberti), Esaki Ah 1001M (manufactured by run Bell tee Co.), Esakyua KIP / EM (manufactured by run Bell tee Co.), Esakyua DP250 (manufactured by run Bell tee Co.), Esakyua KB1 (manufactured by run Bell tee Co.), 2,4-diethyl thioxanthone, and the like.

Examples of the thermal polymerization initiator include ketone peroxides such as methyl isobutyl ketone peroxide and cyclohexanone peroxide;
Diacyl peroxides such as isobutyryl peroxide, o-chlorobenzoyl peroxide, benzoyl peroxide;
Dialkyl peroxides such as tris (t-butylperoxy) triazine, t-nutylcumyl peroxide;
Peroxyketals such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and 2,2-di (t-butylperoxy) butane;
α-cumylperoxyneodecanoate, t-butylperoxypivalate, 2,4,4-trimethylpentylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, alkyl peresters such as t-butylperoxy-3,5,5-trimethylhexanoate;
Percarbonates such as di-3-methoxybutyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, diethylene glycol bis (t-butylperoxycarbonate), etc. Can be mentioned.

In the polyallyl carbonate resin molded article containing the trithiocarbonate compound of the present embodiment, the polymerizable composition obtained by mixing and dissolving the allyl carbonate compound and the trithiocarbonate compound is polymerized and cured by heat or radiation. Obtained by.
A polymerization initiator similar to the (meth) acryloyl compound may be added to the polymerizable composition as necessary.

  The poly (thio) ether resin molded product containing the trithiocarbonate compound according to the present embodiment is obtained by mixing and dissolving the trithiocarbonate compound in the (thio) epoxy compound, the oxetanyl compound, and the thietanyl compound. It is obtained by polymerizing and curing the composition by heat or radiation.

  Polymerizable composition includes tertiary amine, quaternary amine halide, phosphine, phosphine halide, allyldiazonium salt, diallyliodonium salt, triallylsulfonium salt, silicone compound or phosphate compound as necessary. A hardener such as an internal mold release agent such as acid anhydride may be added.

  The polysiloxane resin molded article containing the trithiocarbonate compound of the present embodiment is obtained by polymerizing and curing a polymerizable composition obtained by mixing and dissolving the trithiocarbonate compound in the alkoxysilane compound.

  Filler components such as acidic catalysts such as phosphoric acid, hydrochloric acid and sulfuric acid, basic catalysts such as sodium hydroxide and ammonia, tetraalkoxy titanium, titanium oxide particles and silica particles are added to the polymerizable composition as necessary. May be.

  Examples of the method for producing the molded body of the present embodiment include casting polymerization, injection molding, RIM (reaction injection molding process) and the like. In the present embodiment, explanation will be given by cast polymerization.

  The polymerizable composition containing the trithiocarbonate compound of this embodiment is injected into a cavity formed from glass or a metal mold, and polymerized by heat or radiation to obtain a resin molded body. At that time, if a large amount of residual solvent and moisture remain in the polymerizable composition, bubbles are likely to be generated during injection and polymerization curing, and the bubbles are finally fixed (solidified) inside the molded body. Therefore, it is preferable that the composition contains as little solvent and water as possible. Accordingly, the amount of the solvent and water contained in the polymerizable composition immediately before being injected into the cavity is preferably at least 20% by weight, more preferably 5% by weight or less, and even more preferably 1% by weight or less. .3% by weight or less is most preferable.

  In the case of polymerization by heating, for the purpose of preventing polymerization inhomogeneity (stratification) due to convection, heating is usually performed by gradually raising the temperature from a low temperature over several days. As heating conditions, for example, the temperature is gradually raised from a low temperature in the range of −25 to 200 ° C. and 64 hours, similarly in the range of 5 to 160 ° C. for 40 hours, and similarly in the range of 20 to 140 ° C. for 16 hours. Etc.

  Similarly, in the case of polymerization using radiation such as UV, in order to prevent polymerization nonuniformity (striasis) due to convection, the polymerization is usually performed gradually by dividing the irradiation of radiation or reducing the illuminance. . In order to prevent more convection, after injecting a uniform polymerizable composition into the cavity, it is cooled once to form a state where convection is unlikely to occur, and then a weak radiation is irradiated to form a uniform gel state In some cases, a dual cure method or the like in which the semi-cured composition is completely cured by heating may be used.

  In the case of polymerization by radiation, energy rays having a wavelength region of 0.0001 to 800 nm are usually used as radiation. The radiation is classified into α-rays, β-rays, γ-rays, X-rays, electron beams, ultraviolet rays, visible light, and the like, and can be appropriately selected and used according to the composition of the mixture. Among these radiations, ultraviolet rays are preferable, and the output peak of ultraviolet rays is preferably in the range of 200 to 450 nm, more preferably in the range of 220 to 445 nm, still more preferably in the range of 230 to 430 nm, and particularly preferably in the range of 240 to 400 nm. When ultraviolet rays in the above output peak range are used, there are few problems such as yellowing and thermal deformation during polymerization, and the polymerization can be completed in a relatively short time even when an ultraviolet absorber is added.

  In the glass molded body containing the trithiocarbonate compound of this embodiment, the trithiocarbonate compound is added to the alkoxysilane, and then water necessary for hydrolysis and a catalyst such as sulfuric acid and hydrochloric acid are added and mixed to hydrolyze the alkoxysilane. Disassemble. The obtained mixed solution is obtained by performing solvent removal and defoaming under reduced pressure, and then cast polymerization.

  The polyester resin molded body containing the trithiocarbonate compound of the present embodiment is mainly made of PET (polyethylene terephthalate resin), and is obtained by melt mixing in the same manner as described above and then injection molding. At that time, additives such as an internal mold release agent may be added as necessary.

  The polycarbonate resin molded body containing the trithiocarbonate compound of the present embodiment is mainly made of PC (polycarbonate resin), and is obtained by melt-mixing in the same manner as described above and then injection molding. At that time, additives such as an internal mold release agent may be added as necessary.

  The polyolefin resin molded body containing the trithiocarbonate compound of the present embodiment is mainly made of PE (polyethylene resin), PP (polypropylene resin), TPX (polymethylpentene resin), etc., and melt-mixed in the same manner as described above. And then obtained by injection molding.

  A glass or resin molded body can be obtained by adding the trithiocarbonate compound of this embodiment and injection molding, but since the glass molded body has a very high melting temperature (> 400 ° C.), the added trithiocarbonate The blue light absorbent having a group may be thermally decomposed. Therefore, it is preferable to use a resin molded body.

  The molten polymer added with the trithiocarbonate compound of the present embodiment and heated and mixed is poured into a cavity formed of glass, a metal mold, or the like, and cooled to obtain a molded body. Also in this injection molding, it is preferable that the solvent and water are not contained as much as possible for the same reason as in the casting polymerization. The amount of the solvent and water contained in the molten polymer to which the blue light absorbent of this embodiment just before being injected into the cavity is added is preferably at least 20% by weight, more preferably 5% by weight or less, more preferably 1% by weight. The following is more preferable, and 0.3% by weight or less is most preferable.

  The resin molded body or glass molded body of the present embodiment can be subjected to various surface treatments such as corona treatment, plasma treatment, ultraviolet treatment, flare treatment, and itro treatment.

  In addition, on the molded body of this embodiment, a primer layer that improves adhesion, a hard coat layer that prevents scratches, an antireflection layer that suppresses reflectance and further improves transparency, and a water repellent that imparts slipperiness Various layers such as a layer or a hydrophilic layer imparting antifogging properties and a water absorbing layer can be laminated.

  Various functionalities such as dyeing treatment for fashionability, surface and edge polishing, and polarizing film inside and pasting on the surface for the purpose of imparting polarization You may perform the process etc. which provide.

  The blue light absorbent of the present embodiment is usually 30 wt% or less, preferably in the range of 0.0001 to 30 wt%, more preferably in the range of 0.001 to 10 wt% in the molded body as a bluelight absorbing compound. Preferably it is contained in the range of 0.001 to 3 wt%, most preferably in the range of 0.01 to 2 wt%. Thereby, harmful blue light (380 to 500 nm) can be effectively cut.

  By containing the blue light absorbing compound, the molded product of this embodiment cuts blue light light in the range of 380 to 500 nm on average at 5% or more at a thickness of 1.6 mm (reduced by 5% or more in transmittance). Preferably, the cut rate can be 10% or more on average (decrease of 10% or more in transmittance), and more preferably 40% or more on average (decrease of 40% or more in transmittance). More preferably, it can be 60% or more (60% or more decrease in transmittance), and most preferably 80% or more (80% or more decrease in transmittance).

  The molded body of the present embodiment can be used for various purposes aimed at blocking harmful blue light. Among them, it can be suitably used for optical materials such as eyeglass lenses, camera lenses, pickup lenses, sunglasses, goggles, panel materials, window glass, and shields such as helmets that require high transparency.

  Furthermore, among the uses of the above-mentioned optical materials, it is particularly suitable for use as a spectacle lens in which the influence of harmful blue light light on the eyes is reduced and the effects such as eye strain and stress can be directly suppressed. Can do.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The evaluation of the cured resin and the plastic lens was performed by the following method.

<Measurement of transmittance of blue light absorber>
A homogeneous solution was prepared by adding 10 ml of chloroform to the blue light absorbent and mixing and dissolving. The obtained uniform solution was filled in a SHIMADZU UV-1850 ultraviolet-visible spectrophotometer 10 mm square cell, and the transmittance from ultraviolet to visible light was measured. The initial zero point correction (reference) was performed with chloroform.

<Measurement of transmittance of resin plate>
A resin plate having a thickness of 1.6 mm was prepared, and the obtained resin plate was fixed to SHIMADZU UV-1850, and the transmittance from ultraviolet rays to visible light was measured. The first zero point correction (reference) was performed with air.

[Example 1]
(ETC 0.01wt% addition test)
0.01 parts by weight (0.01 wt%) of ethylene trithiocarbonate (hereinafter referred to as ETC) represented by the following formula as a blue light absorbent, and alkyl phosphate ester (trade name: ZelecUN) as an internal mold release agent 12 parts by weight (0.12 wt%), DBC (dibutyltin dilaurate) as a catalyst 0.13 parts by weight (0.13 wt%), Tinuvin 326 1.1 parts by weight (1.1 wt%) and Eversorb 109 5.0 parts by weight (5 wt%) and 58.9 parts by weight of H ₁₂ MDI {bis (4-isocyanatocyclohexyl) methane} were mixed and dissolved, and then FSH (4,8-bis (mercaptomethyl) -3, 6,9-trithiaundecane-1,11-dithiol, 4,7-bis (mercaptomethyl) -3,6,9-trithiaundecane 1,11-dithiol and 5,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol) (41.1 parts by weight) at a reduced pressure of 40 torr or less The mixture was dissolved and defoamed for 1 hour, and passed through a 1 μm Teflon filter to obtain a uniform polymerizable composition.
After depressurization, the obtained polymerizable composition is poured into a cavity in a mold composed of a glass mold and a tape, covered with a tape and placed in a polymerization oven. Polymerization was performed by gradually raising the temperature. After cooling to room temperature, the mold was released, and a 1.6 mm thick plastic lens (plano lens) formed in the cavity was taken out. The obtained molded body was reheated again at 130 ° C. for 2 hours and then slowly cooled to room temperature to obtain a measurement sample.
The transmittance of the obtained plastic lens (plano lens) was measured. The transmittance curve is shown in FIG. 1, and the average transmittance in each wavelength region is shown in Table 1.

[Comparative Example 1]
(ETC additive-free test)
A plastic lens (plano lens) molded body was prepared in the same manner as in Example 1 except that ETC was not added. The transmittance spectrum is shown in FIG. 1, and the average transmittance in each wavelength region is shown in Table 1.

[Example 2]
(Measurement of transmittance of blue light absorbent (solution))
The transmittance of a 0.1% (wt / vol) solution prepared by adding 10 ml of chloroform to 0.01 g of ETC (ethylene trithiocarbonate), which is the blue light absorbent used in Example 1, was mixed and measured. However, the measurement was performed with baseline correction using chloroform alone. The transmittance spectrum is shown in FIG. 2, and the average transmittance at a wavelength of 380 to 500 nm is shown in Table 2.

[Examples 3 to 4, Comparative Example 2]
The blue light absorber is 4,5-bis (methylthio) -1,3-dithiol-2-thione (hereinafter referred to as MTTC), trithiocarbonic acid-S, S-dibenzyl ester (hereinafter referred to as the following formula). , BZTC), and trithiocarbonic acid-S, S-diethyl ester (hereinafter referred to as DEDC), a 0.1% (wt / vol) solution was prepared in the same manner as in Example 2 to obtain the transmittance. Measurements were made. The transmittance spectrum is shown in FIG. 3, and the average transmittance at a wavelength of 380 to 500 nm is shown in Table 3.
From the results of transmittance measurement, it is estimated that MTTC and BZTC, which are blue light absorbers, have a high blocking effect on blue light with a wavelength of 380 to 500 nm, and the same effect can be obtained with a lens containing the blue light absorber. It was.

[Examples 5 to 6, Comparative Example 3]
The blue light absorber is 5-n-propyl-1,3-dithiolo [4,5-d] [1,3] dithiol-2-thione (hereinafter referred to as PDTTC), represented by the following formula, 5-n- Hexyl-1,3-dithiolo [4,5-d] [1,3] dithiol-2-thione (hereinafter referred to as HDTTC), 4,5-methylenedithio-1,3-dithiol-2-one (hereinafter referred to as MDTO) Except for changing to), a 0.1% (wt / vol) solution was prepared in the same manner as in Example 2, and the transmittance was measured. The transmittance spectrum is shown in FIG. 4, and the average transmittance at a wavelength of 380 to 500 nm is shown in Table 4.
From the results of transmittance measurement, it is estimated that PDTTC and HDTTC, which are blue light absorbers, have a high blocking effect on blue light with a wavelength of 380 to 500 nm, and the same effect can be obtained with a lens containing the blue light absorber. It was.

[Examples 7 to 8, Comparative Example 4]
The blue light absorber is bis (tetrabutylammonium) bis (1,3-dithiol-2-thione-4,5-dithiolate) palladium (II) complex (hereinafter referred to as BTC-Pd), bis represented by the following formula: (Tetrabutylammonium) bis (1,3-dithiol-2-thione-4,5-dithiolate) zinc complex (hereinafter referred to as BTC-Zn), 1,3,4,6-tetrathiapentalene-2,5- The transmittance was measured in the same manner as in Example 2 except that the concentration was changed to dione (hereinafter referred to as TPDO) and the concentration was changed to 0.01% (wt / vol). The transmittance spectrum is shown in FIG. 5, and the average transmittance at a wavelength of 380 to 500 nm is shown in Table 5.
From the results of transmittance measurement, BTC-Pd and BTC-Zn, which are blue light absorbers, have a high blocking effect on blue light having a wavelength of 380 to 500 nm even at a low concentration (0.01%). It was estimated that the same effect was obtained with a lens containing an absorbent.

[Example 9]
Preparation of reaction reagent sodium trithiocarbonate (Na ₂ CS ₃ ) 560 ml of water was added to 240.2 g (1.0 mol) of Na ₂ S · 9H ₂ O, mixed and dissolved, and 0.2 g of surfactant tetrabutylammonium bromide was added. After that, 91.4 g (1.2 mol) of carbon disulfide was added dropwise in the range of 20 to 40 ° C. and heated and stirred at 40 to 45 ° C. for 1.5 hours and further under reflux for 30 minutes. A part of the water was distilled off under reduced pressure using a rotary evaporator to obtain 513.9 g (1.0 mol) of sodium trithiocarbonate Na ₂ CS ₃ having a content of 30 wt%.

[Example 10]
Preparation of 4-mercaptomethyl-trithiocarbonate (MMTC, also known as: 4-mercaptomethyl-1,3-dithiolane-2-thione) Sodium trithiocarbonate Na ₂ CS ₃ (content) obtained in Example 9 in 500 ml of benzene 30 wt%) 308.3 g (0.60 mol) and 3.2 g (8 mmol) of trioctylmethylammonium chloride as a phase transfer catalyst were added, and 43.6 g (0.20 mol) of 2,3-dibromo-1-propanol with stirring. And then heated and stirred at 60 ° C. for 8 hours.
After standing, the organic layer (benzene layer) was separated, washed with water, dehydrated with anhydrous sodium sulfate, and filtered. The obtained filtrate was concentrated on a rotary evaporator.
The concentrated solution was purified by silica gel column chromatography, concentrated again by a rotary evaporator, and 108.0 g of liquid 4-mercaptomethyl-ethylene trithiocarbonate (MMTC) represented by the following formula (yield 59%). Got.

[Example 11]
Preparation of bis (ethylenetrithiocarbonate-4-methyl) disulfide (BEDS, also known as: bis (1,3-dithiolane-2-thione-4-methyl) disulfide) 4-mercaptomethyl-ethylene obtained in Example 10 A mixture of 91.2 g (0.50 mol) of trithiocarbonate with 60 ml of water, 20 ml of methanol, and 46.2 g (0.55 mol) of sodium carbonate was added to bromine 44 while controlling the internal temperature at 10 to 15 ° C. 0.0 g (0.175 mol) was dropped into the liquid and aged at 15 ° C. for 1 hour.
To the obtained reaction liquid, 100 ml of toluene and 100 ml of water were added, mixed and stirred, and allowed to stand, and then the lower aqueous layer was discarded. Next, the obtained organic layer (toluene layer) was washed with 100 ml of a 1 wt% aqueous acetic acid solution, and again washed with 100 ml of water, and the obtained organic layer (toluene layer) was concentrated by a rotary evaporator.
The concentrated solution was purified by silica gel column chromatography, and again concentrated by a rotary evaporator to obtain 68.0 g of bis (ethylenetrithiocarbonate-4-methyl) disulfide represented by the following formula having a purity of 98% (yield: 73). %).

Identification data of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ ): σ = 3.1 (2H, CH2), σ = 4.0 (1H, CH), σ = 4.2 (1H, CH), σ = 4.4 (1H, CH)

[Example 12]
The blue light absorbent was changed to 4-mercaptomethyl-ethylene trithiocarbonate obtained in Example 10, and the concentration (wt / vol) was 0.01%, 0.05%, 0.30%, 1.00. Except for the change to%, a solution was prepared in the same manner as in Example 2, and the transmittance was measured. The transmittance spectrum at each concentration is shown in FIG.
From the results of the transmittance measurement, 4-mercaptomethyl-ethylene trithiocarbonate (MMTC), which is a blue light absorber, has a high blocking effect on blue light with a wavelength of 380 to 500 nm, and the same applies to lenses containing the blue light absorber. It was estimated that the effect of.

[Example 13]
A solution was prepared in the same manner as in Example 2 except that the blue light absorbent was changed to bis (ethylenetrithiocarbonate-4-methyl) disulfide (abbreviated as BEDS) obtained in Example 11, and the transmittance was adjusted. Measurements were made. The transmittance spectrum is shown in FIG.
From the results of transmittance measurement, it was estimated that BEDS, which is a blue light absorber, has a high blocking effect on blue light having a wavelength of 380 to 500 nm, and a lens including the blue light absorber can obtain the same effect.

[Example 14]
NBDI {Bis (isocyanatomethyl) norbornane} 32.9 parts by weight DBC (dibutyltin dichloride) as a catalyst 0.023 parts by weight (0.035 wt%), alkyl phosphate ester (trade name: ZelecUN) as an internal release agent ) 0.065 parts by weight (0.10 wt%), tinuvin 326 (BASF) 0.65 parts by weight (1.0 wt%) as an ultraviolet absorber, and PDTTC 0.0065 parts by weight (0.010 wt as a blue light absorber) %) Was added and mixed and dissolved at room temperature.
Next, 15.5 parts by weight of PEMP {pentaerythritol tetrakis (3-mercaptopropionate)} and 16.6 parts by weight of GST (4-mercaptomethyl-3,6-dithiaoctyl-1,8-dithiol) were added and mixed again. After dissolution, the resulting solution was mixed and degassed for 1 hour at a reduced pressure of 40 torr or less, and passed through a 3 μm Teflon filter to obtain a uniform polymerizable composition.
After releasing the pressure, the obtained polymerizable composition is poured into a cavity in a mold composed of a glass mold and a tape, covered with a tape and placed in a polymerization oven. Polymerization was performed by gradually raising the temperature. After cooling to room temperature, the mold was released, and a plastic lens (plano lens) molded body having a thickness of 1.6 mm formed in the cavity was taken out. The obtained molded body was reheated again at 130 ° C. for 2 hours and then slowly cooled to room temperature to obtain a measurement sample.
The transmittance of the obtained plastic lens (plano lens) was measured. The transmittance curve is shown in FIG. 8, and the average transmittance in each wavelength region is shown in Table 6.

[Example 15]
The test was conducted in the same manner as in Example 14 except that tinuvin 326 (BASF) was not added and the blue light absorbent PDTTC was increased to 0.013 part by weight (0.020 wt%).
The transmittance curve is shown in FIG. 8, and the average transmittance in each wavelength region is shown in Table 6.

[Example 16]
The test was conducted in the same manner as in Example 15 except that HDTTC was used instead of PDTTC as a blue light absorbent.
The transmittance curve is shown in FIG. 8, and the average transmittance in each wavelength region is shown in Table 6.

[Comparative Example 5]
The test was conducted in the same manner as in Example 14 without adding the blue light absorbent PDTTC.
The transmittance curve is shown in FIG. 8, and the average transmittance in each wavelength region is shown in Table 6.

Claims (21)

  A blue light absorbing compound having one or more trithiocarbonate groups in a molecule. The blue light absorption compound of Claim 1 represented by following General formula (1).

(In the general formula (1), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and is a hydrogen atom. The moiety may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₃ and R ₄ are each independently a divalent organic residue having 1 to 20 carbon atoms. The divalent organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. A plurality of R ₃ may be the same or different, and a plurality of R ₄ may be the same or different, m represents an integer of 0 to _3. R ₁ and R ₃ are a bond To form a ring Well, when R ₂ and R ₄ may optionally combine to form a ring .m is 0, R ₁ and R ₂ may form a ring.) The bluelight absorbing compound according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2) or the following general formula (3).

(In the general formula (2), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and may be a hydrogen atom. The portion may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₁ and R ₂ may combine to form a ring.)

(In General Formula (3), R ₁ and R ₂ each independently represents an organic residue having 1 to 20 carbon atoms. The organic residue may contain a hetero atom, and may be a hydrogen atom. The moiety may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₃ and R ₄ are each independently a divalent organic residue having 1 to 20 carbon atoms. The divalent organic residue may contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group. R ₁ and R ₃ may be bonded to form a ring, and R ₂ and R ₄ may be bonded to form a ring.) The bluelight-absorbing compound according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(In General Formula (4), R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a cyano group, or an organic residue having 1 to 20 carbon atoms. _May contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₅ and R ₆ are bonded to each other. A ring may be formed.) The blue light absorbing compound according to claim 3, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (5).

(In General Formula (5), R ₇ and R ₈ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a cyano group, or an organic residue having 1 to 20 carbon atoms. May contain a hetero atom, and a part of the hydrogen atom may be substituted with at least one selected from a halogen atom, a hydroxyl group, a mercapto group, and a cyano group, and R ₇ and R ₈ are bonded to each other. A ring may be formed.) The blue light absorbing compound according to claim 5, wherein the compound represented by the general formula (5) is a compound represented by the following general formula (6).

(In General Formula (6), Q represents a halogen atom, a hydroxyl group, a mercapto group, and a cyano group.) The blue light absorbing compound according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (7).

(In General Formula (7), R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. P and q each independently represent an integer of 0 to 10) The blue light absorption compound of Claim 1 represented by following General formula (8).

(In General Formula (8), M represents a metal atom selected from nickel, palladium, platinum, zinc, copper, silver, and gold. A represents a nitrogen atom or a phosphorus atom. Y ₁ to Y ₄ represent And each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 3 to 10 carbon atoms, r represents 1 or 2.)   The blue light absorber containing the blue light absorption compound in any one of Claims 1-8.   The composition for optical materials containing the blue light absorption compound in any one of Claims 1-8, and resin or polymeric compound.   The composition for optical materials according to claim 10, comprising the blue light absorbing compound in a range of 30% by weight or less.   The polymerizable compound is a polyiso (thio) cyanate compound, (thio) epoxy compound, oxetanyl compound, thietanyl compound, (meth) acryloyl compound, (meth) allyl compound, allyl carbonate compound, alkene compound, alkyne compound, bifunctional or more The composition for optical materials according to claim 10 or 11, which is at least one selected from active hydrogen compounds, acid anhydrides, alkoxysilane compounds and hydrolysates thereof.   The composition for optical materials according to claim 10 or 11, wherein the resin is at least one selected from the group consisting of a polyester resin, a polycarbonate resin, a polyolefin resin, a poly (meth) acrylate resin, and a polysiloxane resin.   The molded object which hardened | cured the composition for optical materials in any one of Claims 10-13.   The molded object of Claim 14 which contains the said blue light absorption compound in 30 weight% or less.   The molded object which contains the blue light absorption compound in any one of Claims 1-8 in 30 weight% or less.   The molded product according to any one of claims 14 to 16, wherein at a thickness of 1.6 mm, any wavelength of blue light in the range of 380 to 500 nm is cut by 5% or more.   Contains at least one selected from the group consisting of poly (thio) urethane resins, poly (meth) acrylate resins, polyallyl carbonate resins, poly (thio) ether resins, polyester resins, polycarbonate resins, polyolefin resins, and polysiloxane resins The molded product according to claim 14 or 15, which comprises   The molded object according to claim 16, comprising glass.   The optical material which consists of a molded object in any one of Claims 14-19. A compound represented by the following general formula (7).

(In General Formula (7), R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. P and q each independently represent an integer of 0 to 10)

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