JP2015168746A - Tetraazaporphyrin dimer compound, manufacturing method thereof, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tetraazaporphyrin dimer compound having strong absorption at 570-630 nm, being superior in antiglare, having extremely high durability such as light resistance and heat resistance, and being superior in solubility.SOLUTION: A tetraazaporphyrin dimer compound is shown in formula (1). [Each of R-Ris H or a substituent; each of Xand Xis such as O; Aand Aare such as alkylene groups; Y is such as O; each of n and p is an integer of 0 or 1; and M is such as two H or metal atoms.]

Description

The present invention relates to a novel tetraazaporphyrin dimer compound, a production method thereof, a resin composition containing the compound, and a molded body thereof. More specifically, the present invention relates to a resin composition having a high effect of cutting a wavelength that causes glare of external light or a light source, and a molded body formed by molding the resin composition, particularly a spectacle lens, an interlayer film for laminated glass, and the use thereof. The present invention relates to a novel tetraazaporphyrin dimer compound and a method for producing the same.

So-called anti-glare function, for example, for spectacle lenses and interlayer film of laminated glass for automobiles, etc. to reduce glare such as sun rays and automobile headlights and related discomfort and blurring of contrast and visual fatigue It is known to give This is intended to selectively cut as much as possible a wavelength band in which glare is easily felt. For example, Patent Document 1 discloses a technique in which a rare earth metal compound such as a neodymium compound is contained in a spectacle lens. The neodymium compound has a sharp absorption in the vicinity of 570 to 590 nm, and has a feature that it can selectively absorb light of 550 to 610 nm with high human visibility and easy to feel dazzling.
However, inorganic rare earth metal compounds such as neodymium compounds are easily compounded into glass lenses, but in recent years, plastics are mainly used as a material for eyeglass lenses, and inorganic rare earth metal compounds are uniformly transparent resins. There is a problem that dispersive mixing is not possible.

Patent Documents 2 to 4 disclose a technique in which a tetraazaporphyrin compound is contained in a plastic spectacle lens instead of a neodymium compound, and light near 580 to 590 nm is cut to provide antiglare property and visibility.
Patent Document 5 discloses a technique in which a tetraazaporphyrin compound is contained in an interlayer film for laminated glass to cut light in the vicinity of 560 to 635 nm to improve antiglare property and visibility.
However, these antiglare articles using a tetraazaporphyrin compound are not durable enough, especially because they are used for a long time against strong light such as sunlight, so that light resistance, heat resistance, etc. There is a need for improved durability.
Patent Document 6 discloses a porphyrin linked body linked by an acetylene bond, and Patent Document 7 discloses an axially asymmetric phthalocyanine compound dimer. The basic compound and the characteristic are completely different from the monomer compound.

JP 2000-75128 A JP 2008-134618 A JP 2011-145341 A JP 2001-175176 A JP 2010-138028 A JP 2004-168690 A No. 2011-241157

An object of the present invention is to provide a resin composition having excellent antiglare performance and high durability, a molded product thereof, a tetraazaporphyrin dimer compound suitable for the purpose, and a method for producing the same. More specifically, a resin composition having high durability such as light resistance and heat resistance, which efficiently cuts light with high human visibility near 560 to 630 nm, prevents glare and glare, increases contrast, and has high durability such as light resistance and heat resistance, and glasses. It is to provide a molded article used for an antiglare optical article such as a lens and an interlayer film for laminated glass, a tetraazaporphyrin dimer compound suitable for the purpose, and a method for producing the same.

  As a result of diligent study on the problems in the previous period, the present inventors have found that the tetraazaporphyrin dimer compound having a specific structure has strong absorption in the vicinity of 560 to 630 nm and extremely high durability, and thus is very useful for the above-described purpose. As a result, the present invention has been completed.

That is, the present invention
(I) a tetraazaporphyrin dimer compound represented by the general formula (1),

[In the formula (1), R _{1 to} R ₁₄ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, alkylthio group, substituted or An unsubstituted aryl group, a substituted or unsubstituted aryloxy group or a substituted or unsubstituted arylthio group, X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom, and A ₁ and A ₂ are An alkylene group, a substituted or unsubstituted arylene group, Y represents an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group, a sulfonyl group, a carbonyl group, or an alkylene group, and n and p are each independently 0 Or an integer of 1 is shown. M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. ]
(Ii) The tetraazaporphyrin dimer of (i), wherein M is Cu, Zn, Fe, Co, Ni, Pt, Pd, Mn, Mg, Mn (OH), Mn (OH) ₂ , VO, or TiO Body compounds,

(Iii) R _{1 to} R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenoalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, or a carbon number. 2-16 halogenoalkoxyalkyl group, substituted or unsubstituted aralkyl group having 7-20 carbon atoms, alkoxy group having 1-12 carbon atoms, halogenoalkoxy group having 1-12 carbon atoms, alkoxyalkoxy having 2-16 carbon atoms Group, an alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or a substituted or unsubstituted group having 6 to 18 carbon atoms A ₁ and A ₂ are an alkylene group having 1 to 16 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 24 carbon atoms Y is an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group having 0 to 12 carbon atoms, a sulfonyl group, a carbonyl group, or an alkylene group having 1 to 16 carbon atoms. Azaporphyrin dimer compound,

(Iv) R _{1 to} R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, an unsubstituted aralkyl group having 7 to 12 carbon atoms, C1-C8 alkoxy group, C1-C8 halogenoalkoxy group, C1-C8 alkylthio group, C2-C12 alkoxyalkoxy group, C6-C12 unsubstituted or substituted halogen atom An aryl group having 6 to 12 carbon atoms, or an arylthio group having 6 to 12 carbon atoms, and A ₁ and A ₂ are each independently an alkylene group having 1 to 12 carbon atoms or 6 carbon atoms. To an arylene group having an alkyl group, an alkenyl group, a halogen atom, a cyano group or an acyl group as an unsubstituted or substituted group of ˜18, and Y is an oxygen atom, a sulfur atom, a carbon atom Any one of (i) to (iii), which is an unsubstituted or substituted imino group having 0 to 12 alkyl groups or aryl groups, a sulfonyl group, a carbonyl group, or an alkylene group having 1 to 12 carbon atoms. Tetraazaporphyrin dimer compounds

(V) R _{1 to} R ₁₄ are each independently a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms, and R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ , R ₉ And R ₁₀ , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , one is a hydrogen atom and the other is a branched alkyl group having 1 to 8 carbon atoms, and X ₁ and X ₂ are oxygen atoms , A ₁ and A ₂ are phenylene groups, Y is an alkylene group having 1 to 8 carbon atoms, n is 0 or 1, p is 1 and M is Cu, (i) to ( iv) any tetraazaporphyrin dimer compound,

(Vi) The tetraazaporphyrin compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted in the presence of a base, (i) to (v) ) Method for producing any tetraazaporphyrin dimer compound,

[In the formula (2), R _{15 to} R ₂₁ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. An alkylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted arylthio group; Z represents a halogen atom; M represents two hydrogen atoms; A valent metal atom, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom is shown. ]

[In Formula (3), X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom, A ₁ and A ₂ represent an alkylene group, or a substituted or unsubstituted arylene group, and Y represents an oxygen atom. , A sulfur atom, a substituted or unsubstituted imino group, a sulfonyl group, a carbonyl group, or an alkylene group, and n and p each independently represent an integer of 0 or 1. ]

(vii) A resin composition comprising at least the tetraazaporphyrin dimer compound of any one of (i) to (v) and a thermoplastic resin or a thermosetting resin,
(Viii) The thermoplastic resin is at least one selected from polycarbonate resin, polyamide resin, acrylic resin, polyester resin and polyvinyl acetal resin, and the thermosetting resin is from polyurethane resin, polythiourethane resin and allyl diglycol carbonate resin. (Vii) resin composition which is at least one selected

(Ix) Further, at least one selected from an azo compound represented by the general formula (4), a quinophthalone compound represented by the general formula (5), and an anthraquinone compound represented by the general formula (6) is contained. (Vii) or (viii) resin composition,
[In the formula (4), R _{22 to} R ₃₂ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, a halogenoalkyl group, an alkoxy group, or a halogenoalkoxy group. Alkylthio group, alkoxyalkyl group, alkoxyalkoxyalkyl group, halogenoalkoxyalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, Substituted or unsubstituted acyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkyloxyalkyl group, alkyloxycarbonyl group , Replacement or Substituted aryloxycarbonyl group or a substituted or unsubstituted arylthio group. ]

[In the formula (5), R _{33 to} R ₄₁ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, a halogenoalkyl group, an alkoxy group, or a halogenoalkoxy group. Alkylthio group, alkoxyalkyl group, alkoxyalkoxyalkyl group, halogenoalkoxyalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, Substituted or unsubstituted acyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkyloxyalkyl group, alkyloxycarbonyl group Substituted or unsubstituted Shows the aryloxy carbonyl group, or a substituted or unsubstituted arylthio group, groups adjacent to each other selected from R ₃₈ to R _41, taken together, together with the carbon atom substituted, substituted or unsubstituted 5-membered ring The above rings may be formed. ]

[In the formula (6), R _{42 to} R ₄₉ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group, an alkoxy group, an alkylthio group, an alkoxyalkyl group, a substituted or unsubstituted aryl group, a substituted or An unsubstituted aralkyl group or a substituted or unsubstituted arylthio group is shown. However, at least one of R _{42 to} R ₄₉ is necessarily a substituted or unsubstituted arylthio group. ]

(X) (vii) to (ix) a molded article obtained by molding any resin composition,
(Xi) The molded article of (x), which is an optical article for antiglare,
(Xii) a molded article of (x) or (xi) which is a spectacle lens;
(Xiii) a molded body of (x) or (xi), which is an interlayer film for laminated glass,
About.

According to the present invention, a novel tetraazaporphyrin dimer compound having strong absorption in the vicinity of 560 to 630 nm, extremely high durability such as light resistance and heat resistance, and excellent solubility in organic solvents and resins and its It has become possible to provide a manufacturing method.
Further, by using the tetraazaporphyrin dimer compound of the present invention, a resin composition and its molded body that can prevent glare and glare, increase contrast, have high durability and maintain its effect for a long time. It has become possible to provide certain antiglare optical articles.

2 is an absorption spectrum diagram of compound (1) -5 produced in Example 1. FIG. 2 is an infrared absorption spectrum diagram of the compound (1) -5 produced in Example 1. FIG. 2 is an absorption spectrum diagram of compound (1) -6 produced in Example 2. FIG. 2 is an infrared absorption spectrum diagram of the compound (1) -6 produced in Example 2. FIG.

Hereinafter, the present invention will be described in detail.
[Tetraazaporphyrin dimer compound]
The tetraazaporphyrin dimer compound of the present invention is represented by the general formula (1).

[In the formula (1), R _{1 to} R ₁₄ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, alkylthio group, substituted or An unsubstituted aryl group, a substituted or unsubstituted aryloxy group or a substituted or unsubstituted arylthio group, X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom, and A ₁ and A ₂ are An alkylene group, a substituted or unsubstituted arylene group, Y represents an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group, a sulfonyl group, a carbonyl group, or an alkylene group, and n and p are each independently 0 Or an integer of 1 is shown. M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. ]

In the general formula (1), R _{1 to} R ₁₄ are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenoalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, carbon A halogenoalkoxyalkyl group having 2 to 16 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenoalkoxy group having 1 to 12 carbon atoms, an alkoxy having 2 to 16 carbon atoms An alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or a substituted or non-substituted group having 6 to 18 carbon atoms. A substituted arylthio group.
R _{1 to} R ₁₄ are more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, an unsubstituted aralkyl group having 7 to 12 carbon atoms, or 1 carbon atom. An alkoxy group having 1 to 8 carbon atoms, a halogenoalkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an aryl having a halogen atom as an unsubstituted or substituted group having 6 to 12 carbon atoms Group, an aryloxy group having 6 to 12 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.
R _{1 to} R ₁₄ are most preferably a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms, and R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ , R ₉ and R _10. , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , one is a hydrogen atom and the other is a branched alkyl group having 1 to 8 carbon atoms.

Specific examples of R _{1 to} R ₁₄ are shown below.
Examples of R _{1 to} R ₁₄ being a halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. A bromine atom and a fluorine atom are preferable, and a fluorine atom is more preferable.
As R < ₁ > -R < ₁₄ > which is an alkyl group, any linear, branched or cyclic alkyl group may be sufficient. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert -Pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methylpentyl group, 4-methyl-2 -Pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, 3 -Methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, cyclohexylmethyl group, n-octyl group, tert- Cutyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylhexyl group, n-nonyl group, 2,2-dimethylheptyl group 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 4-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, 1, 3,5,7-tetramethyloctyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group Group, n-tricosyl group, n-tetracosyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butyl group Rohekishiru group, cycloheptyl group, cyclooctyl group and the like. In particular, an iso-alkyl group having 3 to 8 carbon atoms, a sec-alkyl group having 4 to 8 carbon atoms, a tert-alkyl group having 4 to 8 carbon atoms, a cyclopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group is more preferable.

As R _{1 to} R ₁₄ being a substituted alkyl group, those having a halogen atom, an alkoxy group, a halogenoalkoxy group or an aryl group as a substituent are preferred, and those having a halogen atom or an aryl group as a substituent are more preferred. .
When R _{1 to} R ₁₄ are halogenoalkyl groups, the alkyl moiety may be linear, branched or cyclic.
Examples of halogenoalkyl groups include fluoromethyl, 3-fluoropropyl, 6-fluorohexyl, 8-fluorooctyl, trifluoromethyl, 1,1-dihydro-perfluoroethyl, 1,1-dihydro -Perfluoro-n-propyl group, 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group 1,1-dihydro-perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro- n-octyl group, 1,1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1 1-dihydro-perfluoro-n-tetradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro- n-hexyl group, 2,2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group , 2,2,2-trichloroethyl groups and the like, straight-chain, branched or cyclic halogenoalkyl groups. In particular, a perfluoroalkyl group is preferable, and a trifluoromethyl group is more preferable.
As R ₁ to R ₁₄ is an alkoxyalkyl group, the alkyl in the alkoxy moiety and / or alkyl moiety, it may be straight-chain, branched or cyclic.

Examples of alkoxyalkyl groups include methoxymethyl, ethoxymethyl, n-butoxymethyl, n-pentyloxymethyl, n-hexyloxymethyl, (2-ethylbutyloxy) methyl, n-heptyloxymethyl. Group, n-octyloxymethyl group, n-decyloxymethyl group, n-dodecyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group, 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2- n-octyloxyethyl group, 2- (2′-ethylhexyloxy) ethyl group, 2-n-decyloxyethyl group, 2-n Dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexyloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3- Isopropoxypropyl group, 3-n-butoxypropyl group, 3-n-pentyloxypropyl group, 3-n-hexyloxypropyl group, 3- (2′-ethylbutoxy) propyl group, 3-n-octyloxypropyl group Group, 3- (2′-ethylhexyloxy) propyl group, 3-n-decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, 3-cyclohexyloxypropyl group, 4 -Methoxybutyl group, 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropo Sibutyl group, 4-n-butoxybutyl group, 4-n-hexyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxy Pentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl group, 5-n-pentyloxypentyl group, 6-methoxyhexyl group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxy Hexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-methoxyheptyl group, 7-ethoxyheptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group Group, 8-ethoxyoctyl group, 9-methoxynonyl group, 9-ethoxynonyl group, 10-methoxyde Group, 10-ethoxydecyl group, 10-n-butoxydecyl group, 11-methoxyundecyl group, 11-ethoxyundecyl group, 12-methoxydodecyl group, 12-ethoxydodecyl group, 12-isopropoxide decyl group, A 14-methoxytetradecyl group, a tetrahydrofurfuryl group, etc. can be mentioned. In particular, an alkoxyalkyl group having 2 to 8 carbon atoms is preferable, and an alkoxyalkyl group having 2 to 4 carbon atoms is more preferable.
As R ₁ to R ₁₄ is a halogenoalkoxy group, the alkyl in the alkoxy moiety and / or alkyl moiety, it may be straight-chain, branched or cyclic.

Examples of the halogenoalkoxyalkyl group include a fluoromethyloxymethyl group, a trifluoromethyloxymethyl group, a 2-fluoroethyloxymethyl group, a perfluoroethyloxymethyl group, a 3-fluoro-n-propyloxymethyl group, 1, 1-dihydro-perfluoroethyloxymethyl group, 1,1-dihydro-perfluoro-n-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1-dihydro-per Fluoro-n-tetradecyloxymethyl group, fluoromethyloxyethyl group, trifluoromethyloxyethyl group, 2-fluoroethyloxyethyl group, perfluoroethyloxyethyl group, 2- (8-fluoro-n-octyloxy) Ethyl group, 2- (6-fluoro-n-hexylo) Ii) ethyl group, fluoromethyloxypropyl group, trifluoromethyloxypropyl group, 2-fluoroethyloxypropyl group, perfluoroethyloxypropyl group, 3- (1,1-dihydro-perfluoroethyloxy) propyl group, 4- (perfluoro-n-hexyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group and the like can be mentioned. Fluoromethyloxymethyl group, trifluoromethyloxymethyl group, 2-fluoroethyloxymethyl group Perfluoroethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, fluoromethyl Oxyethyl group, trifluoromethyloxyethyl Group, 2-fluoroethyloxyethyl group, perfluoroethyloxyethyl group, 2- (6-fluoro-n-hexyloxy) ethyl group, fluoromethyloxypropyl group, trifluoromethyloxypropyl group, 2-fluoroethyloxy Examples thereof include a propyl group, a perfluoroethyloxypropyl group, a 4- (perfluoro-n-hexyloxy) butyl group, and a 6- (2-chloroethyloxy) hexyl group.
In particular, a halogenoalkoxyalkyl group having 1 to 8 carbon atoms is preferable, and a halogenoalkoxyalkyl group having 1 to 4 carbon atoms is more preferable.

As for R _{1 to} R ₁₄ being a substituted or unsubstituted aralkyl group, the alkyl in the alkyl group moiety may be linear, branched or cyclic. As the substituted aralkyl group, those having an alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, hydroxyl group or halogen atom as a substituent are preferable, and those having an alkyl group or alkoxy group as a substituent are more preferable. preferable.
Examples of the substituted or unsubstituted aralkyl group include benzyl group, α-methylbenzyl group, phenethyl group, α-methylphenethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenethyl group, 4-methylphenethyl group. Group, 4-methylbenzyl group, 4-isopropylbenzyl group, 4-benzylbenzyl group, 4-phenethylbenzyl group, 4-phenylbenzyl group, 4-methoxybenzyl group, 4-n-tetradecyloxybenzyl group, 4- n-heptadecyloxybenzyl group, 3,4-dimethoxybenzyl group, 4-methoxymethylbenzyl group, 4-vinyloxymethylbenzyl group, 4-benzyloxybenzyl group, 4-phenethyloxybenzyl group, 4-hydroxybenzyl group 4-hydroxy-3-methoxybenzyl group, 4-fluorobenzyl group, 3- Rorobenjiru group, 3,4-dichlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group. In particular, an aralkyl group having an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferable, and a benzyl group having a methyl group or a methoxy group is more preferable.
As for R _{1 to} R ₁₄ being a substituted or unsubstituted alkoxy group, the alkyl moiety may be linear, branched or cyclic. As the substituted alkoxy group, those having a halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group or dialkylamino group as a substituent are preferable, and those having a halogen atom or alkoxy group as a substituent are more preferable.

Examples of unsubstituted alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, n-pentyloxy, neopentyloxy, cyclopentyl Oxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy Group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n- Heptadecyloxy group, n-octadecyloxy group, n-eicosyloxy group, n-trikoshi Group, n- etc. tetracosyl group and the like. In particular, an alkoxy group having 1 to 12 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable.
Examples of halogenoalkoxy groups include fluoromethyloxy group, 3-fluoropropyloxy group, 6-fluorohexyloxy group, 8-fluorooctyloxy group, trifluoromethyloxy group, 1,1-dihydro-perfluoroethyloxy Group, 1,1-dihydro-perfluoro-n-propyloxy group, 1,1,3-trihydro-perfluoro-n-propyloxy group, 2-hydro-perfluoro-2-propyloxy group, 1,1 -Dihydro-perfluoro-n-butyloxy group, 1,1-dihydro-perfluoro-n-pentyloxy group, 1,1-dihydro-perfluoro-n-hexyloxy group, 6-fluorohexyloxy group, 4- Fluorocyclohexyloxy group, 1,1-dihydro-perfluoro-n-octyloxy group, 1 1-dihydro-perfluoro-n-decyloxy group, 1,1-dihydro-perfluoro-n-dodecyloxy group, 1,1-dihydro-perfluoro-n-tetradecyloxy group, 1,1-dihydro-per Fluoro-n-hexadecyloxy group, perfluoroethyloxy group, perfluoro-n-propyloxy group, perfluoro-n-pentyloxy group, perfluoro-n-hexyloxy group, 2,2-bis (trifluoro Methyl) propyloxy group, dichloromethyloxy group, 2-chloroethyloxy group, 3-chloropropyloxy group, 4-chlorocyclohexyloxy group, 7-chloroheptyloxy group, 8-chlorooctyloxy group, 2,2, Examples include 2-trichloroethyloxy group. In particular, a halogenoalkoxy group having 1 to 8 carbon atoms is preferable, and a perfluoroalkoxy group having 1 to 8 carbon atoms is more preferable.

Examples of alkoxyalkoxy groups include methoxymethoxy, ethoxymethoxy, n-propyloxymethoxy, n-butyloxymethoxy, isobutyloxymethoxy, tert-butyloxymethoxy, n-pentyloxymethoxy, 2 -Methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propyloxyethoxy group, 2-isopropyloxyethoxy group, 2-n-butyloxyethoxy group, 2-isobutyloxyethoxy group, 2-tert-butyloxyethoxy group Group, 2-sec-butyloxyethoxy group, 2-n-pentyloxyethoxy group, 2-isopentyloxyethoxy group, 2-tert-pentyloxyethoxy group, 2-sec-pentyloxyethoxy group, 2-cyclopentyloxy Ethoxy group, 2-n-hexyloxyethoxy Group, 2- (4-ethylcyclohexyloxy) ethoxy group, 2-n-nonyloxyethoxy group, 2- (3,5,5-trimethylhexyloxy) ethoxy group, 2-n-decyloxyethoxy group, 2- n-dodecyloxyethoxy group, 3-methoxypropyloxy group, 3-ethoxypropyloxy group, 3- (n-propyloxy) propyloxy group, 2-isopentyloxypropyloxy group, 2-methoxybutyloxy group, 4 -Alkoxyalkoxy such as ethoxybutyloxy group, 4- (n-propyloxy) butyloxy group, 4-isopropyloxybutyloxy group, 5-methoxypentyloxy group, 5-ethoxymethoxy group, 6-n-propylhexyloxy group Groups. In particular, an alkoxyalkoxy group having 2 to 8 carbon atoms is preferable, and an alkoxyalkoxy group having 2 to 4 carbon atoms is more preferable.
When R _{1 to} R ₁₄ are alkylthio groups, the alkyl moiety may be linear, branched or cyclic. As the substituted alkylthio group, those having a halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group or dialkylamino group as a substituent are preferable, and those having a halogen atom or alkoxy group as a substituent are more preferable.

Examples of unsubstituted alkylthio groups include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, n-pentylthio group, cyclopentylthio group, n-hexylthio group, 3, 3-dimethylbutylthio group, 2-ethylbutylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-undecylthio group, n-dodecylthio group, n -Tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group, n-tricosylthio group, n-tetracosylthio group, etc. Methylthio group, ethylthio group, n-propylthio group, isopropyl O group, n-butylthio group, sec-butylthio group, n-pentylthio group, n-hexylthio group, 3,3-dimethylbutylthio group, 2-ethylbutylthio group, cyclohexylthio group, n-heptylthio group, n- Octylthio group, 2-ethylhexylthio group and n-dodecylthio group are preferable, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, n-pentylthio group, n-hexylthio group 2-ethylbutylthio group, cyclohexylthio group, n-heptylthio group, and n-octylthio group are more preferable.

Examples of alkoxyalkylthio groups include methoxymethylthio, ethoxymethylthio, n-propyloxymethylthio, n-butyloxymethylthio, isobutyloxymethylthio, tert-butyloxymethylthio, n-pentyloxymethylthio, 2- Methoxyethylthio group, 2-ethoxyethylthio group, 2-n-propyloxyethylthio group, 2-isopropyloxyethylthio group, 2-n-butyloxyethylthio group, 2-isobutyloxyethylthio group, 2- tert-butyloxyethylthio group, 2-sec-butyloxyethylthio group, 2-n-pentyloxyethylthio group, 2-isopentyloxyethylthio group, 2-sec-pentyloxyethylthio group, 2-n -Hexyloxyethylthio group, 2- (4-ethylcyclohexyl) Ruoxy) ethylthio group, 2-n-nonyloxyethylthio group, 2- (3,5,5-trimethylhexyloxy) ethylthio group, 2-n-decyloxyethylthio group, 2-n-dodecyloxyethylthio group 3-methoxypropylthio group, 3-ethoxypropylthio group, 3- (n-propylthio) propylthio group, 2-isopentyloxypropylthio group, 2-methoxybutylthio group, 4-ethoxybutylthio group, 4- (N-propyloxy) butylthio group, 5-methoxypentylthio group, 5-ethoxypentylthio group, 6-n-propyloxyhexylthio group and the like can be mentioned. In particular, an alkoxyalkylthio group having 2 to 8 carbon atoms is preferable, and an alkoxyalkylthio group having 2 to 4 carbon atoms is more preferable.
Examples of the halogenoalkylthio group include a fluoromethylthio group, a 3-fluoropropylthio group, a 6-fluorohexylthio group, an 8-fluorooctylthio group, a trifluoromethylthio group, a 1,1-dihydro-perfluoroethylthio group, 1,1-dihydro-perfluoro-n-propylthio group, 1,1,3-trihydro-perfluoro-n-propylthio group, 2-hydro-perfluoro-2-propylthio group, 1,1-dihydro-perfluoro -N-butylthio group, 1,1-dihydro-perfluoro-n-pentylthio group, 1,1-dihydro-perfluoro-n-hexylthio group, 6-fluorohexylthio group, 4-fluorocyclohexylthio group, 1, 1-dihydro-perfluoro-n-octylthio group, 1,1-dihydro-perfluoro n-decylthio group, 1,1-dihydro-perfluoro-n-dodecylthio group, 1,1-dihydro-perfluoro-n-tetradecylthio group, 1,1-dihydro-perfluoro-n-hexadecylthio group, per Fluoroethylthio group, perfluoro-n-propylthio group, perfluoro-n-pentylthio group, perfluoro-n-hexylthio group, 2,2-bis (trifluoromethyl) propylthio group, dichloromethylthio group, 2-chloroethyl A thio group, a 3-chloropropylthio group, a 4-chlorocyclohexylthio group, a 7-chloroheptylthio group, an 8-chlorooctylthio group, a 2,2,2-trichloroethylthio group, and the like can be given. In particular, a halogenoalkylthio group having 1 to 8 carbon atoms is preferable, and a perfluoroalkylthio group having 1 to 8 carbon atoms is more preferable.

As R < ₁ > -R < ₁₄ > is a substituted or unsubstituted aryl group, a heteroaryl group is included. As the substituted aryl group, those having a halogen atom, alkyl group, alkoxy group, aryl group or amino group as a substituent are preferred, and those having a halogen atom as a substituent are more preferred.
Examples of substituted or unsubstituted aryl groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-ethylphenyl, 4-ethylphenyl, 4-n-propyl. Phenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert- Pentylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group, 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexa Silphenyl group, 4-n-octadecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group 3,5-dimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,5,6-tetramethylphenyl group, 5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl Group, 1,2,3,4-tetrahydro-6-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n -Propoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 4-n-pentyloxypheny Group, 4-n-hexyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxyphenyl group, 4-n-nonyloxyphenyl group, 4-n-decyl Oxyphenyl group, 4-n-undecyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl Group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group 2-methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 3-methoxy-4-methyl Phenyl group, 2-methyl-4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 3,5-ditrifluoromethylphenyl group, 2, 4-difluorophenyl group, 3,5-difluorophenyl group, 2,4-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-methyl-4-chlorophenyl group, 2-chloro-4- Methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4-methoxyphenyl 3-methoxy-4-fluorophenyl group, 3-methoxy-4-chlorophenyl group, 3-fluoro-4-methoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) phenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4 -Ethoxy-1-naphthyl group, 6-n-butyl-2-naphthyl group, 6-methoxy-2-naphthyl group, 7-ethoxy-2-naphthyl group, 2-furyl group, 2-thienyl group, 3-thienyl Group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-aminophenyl group, 3-aminophenyl group, 2-aminophenyl group, 4- (N-methylamino) phen Group, 3- (N-methylamino) phenyl group, 4- (N-ethylamino) phenyl group, 2- (N-isopropylamino) phenyl group, 4- (Nn-butylamino) phenyl group, 2 -(Nn-butylamino) phenyl group, 4- (Nn-octylamino) phenyl group, 4- (Nn-dodecylamino) phenyl group, 4-N-benzylaminophenyl group, 4-N A phenylaminophenyl group,

2-N-phenylaminophenyl group, 4- (N, N-dimethylamino) phenyl group, 3- (N, N-dimethylamino) phenyl group, 2- (N, N-dimethylamino) phenyl group, 4- (N, N-diethylamino) phenyl group, 2- (N, N-diethylamino) phenyl group, 4- (N, N-di-n-butylamino) phenyl group, 4- (N, N-di-n- Hexylamino) phenyl group, 4- (N-cyclohexyl-N-methylamino) phenyl group, 4- (N, N-diethylamino) -1-naphthyl group, 4-pyrrolidinophenyl group, 4-piperidinophenyl group 4-morpholinophenyl group, 4-pyrrolidino-1-naphthyl group, 4- (N-benzyl-N-methylamino) phenyl group, 4- (N-benzyl-N-phenylamino) phenyl group, 4- ( -Methyl-N-phenylamino) phenyl group, 4- (N-ethyl-N-phenylamino) phenyl group, 4- (Nn-butyl-N-phenylamino) phenyl group, 4- (N, N- Diphenylamino) phenyl group, 2- (N, N-diphenylamino) phenyl group, 4- [N, N-di (4′-methylphenyl) amino] phenyl group, 4- [N, N-di (3 ′) -Methylphenyl) amino] phenyl group, 4- [N, N-di (4'-ethylphenyl) amino] phenyl group, 4- [N, N-di (4'-tert-butylphenyl) amino] phenyl group 4- [N, N-di (4′-n-hexylphenyl) amino] phenyl group, 4- [N, N-di (4′-methoxyphenyl) amino] phenyl group, 4- [N, N- Di (4′-ethoxyphenyl) amino] fur Nyl group, 4- [N, N-di (4′-n-butoxyphenyl) amino] phenyl group, 4- [N, N-di (4′-n-hexyloxyphenyl) amino] phenyl group, 4- [N, N-di (1′-naphthyl) amino] phenyl group, 4- [N, N-di (2′-naphthyl) amino] phenyl group, 4- [N-phenyl-N- (3′-methyl) Phenyl) amino] phenyl group, 4- [N-phenyl-N- (4′-methylphenyl) amino] phenyl group, 4- [N-phenyl-N- (4′-octylphenyl) amino] phenyl group, 4 -[N-phenyl-N- (4'-methoxyphenyl) amino] phenyl group, 4- [N-phenyl-N- (4'-ethoxyphenyl) amino] phenyl group, 4- [N-phenyl-N- (4'-n-hexyloxyphenyl) amino ] Phenyl group, 4- [N-phenyl-N- (4'-fluorophenyl) amino] phenyl group, 4- [N-phenyl-N- (1'-naphthyl) amino] phenyl group, 4- [N- Phenyl-N- (2′-naphthyl) amino] phenyl group, 4- [N-phenyl-N- (4′-phenylphenyl) amino] phenyl group, 4- (N, N-diphenylamino) -1-naphthyl Group, 6- (N, N-diphenylamino) -2-naphthyl group, 4- (N-carbazolyl) phenyl group, 4- (N-phenoxadiyl) phenyl group and the like. In particular, a phenyl group, an alkyl-substituted phenyl group, and a halogen-substituted phenyl group are preferable. More preferred.

As R ₁ to R ₁₄ is a substituted or unsubstituted aryloxy group, a hetero aryloxy group. The substituted aryloxy group preferably has a halogen atom, alkyl group, alkoxy group, aryl group or amino group as a substituent, and more preferably has a halogen atom, alkyl group or alkoxy group as a substituent.

Examples of substituted or unsubstituted aryloxy groups include phenyloxy group, 2-methylphenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, 4-isopropylphenyloxy group, 4-isobutylphenyloxy. Group, 4-n-pentylphenyloxy group, 4-tert-pentylphenyloxy group, 4-cyclohexylphenyloxy group, 4-n-octylphenyloxy group, 4-n-decylphenyloxy group, 4-n-dodecyl Phenyloxy group, 4-n-hexadecylphenyloxy group, 2,3-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,4,5-trimethylphenyloxy Group, 5-indanyloxy group, 1,2,3,4-tetrahydro-6- Futyloxy group, 3-methoxyphenyloxy group, 3-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4-n-pentyloxyphenyloxy group, 4-cyclohexyloxyphenyl Oxy group, 4-n-octyloxyphenyloxy group, 4-n-decyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n-hexadecyloxyphenyloxy group, 2,3-dimethoxyphenyl Oxy group, 2,5-dimethoxyphenyloxy group, 3,5-dimethoxyphenyloxy group, 2-methoxy-4-methylphenyloxy group, 3-methoxy-4-methylphenyloxy group, 3-methyl-4-methoxy Phenyloxy group, 2-fluorophenyloxy group, 4-fluoro Phenyloxy group, 3-chlorophenyloxy group, 4-bromophenyloxy group, 3-trifluoromethylphenyloxy group, 3,5-difluorophenyloxy group, 3,4-dichlorophenyloxy group, 2-methyl-4-chlorophenyl Oxy group, 3-chloro-4-methylphenyloxy group, 3-methoxy-4-fluorophenyloxy group, 3-fluoro-4-methoxyphenyloxy group, 4-phenylphenyloxy group, 3-phenylphenyloxy group, 4- (4′-methylphenyl) phenyloxy group, 4- (4′-methoxyphenyl) phenyloxy group, 1-naphthyloxy group, 4-methyl-1-naphthyloxy group, 6-n-butyl-2- Naphtyloxy group, 7-ethoxy-2-naphthyloxy group, 2-thienyloxy group, 2-pyridyl Alkoxy groups, such as 4-pyridyloxy group. Particularly 2-chlorophenyloxy group, 4-chlorophenyloxy group, 2-bromophenyloxy group, 4-bromophenyloxy group, 2-fluorophenyloxy group, 4-fluorophenyloxy group, 4-methylphenyl group, 2,4 A dimethylphenyl group, a 4-methoxyphenyl group, and a 4-butoxyphenyl group are preferable, and a 2-fluorophenyloxy group, a 4-fluorophenyloxy group, a 4-methylphenyl group, and a 4-methoxyphenyl group are more preferable.

As R _{1 to} R ₁₄ are substituted or unsubstituted arylthio groups, heteroarylthio groups are also included, including phenylthio groups, 2-methylphenylthio groups, 4-methylphenylthio groups, and 3-ethylphenylthio groups. 4-n-propylphenylthio group, 4-n-butylphenylthio group, 4-isobutylphenylthio group, 4-tert-butylphenylthio group, 4-n-pentylphenylthio group, 4-n-hexylphenyl Thio group, 4-cyclohexylphenylthio group, 4-n-octylphenylthio group, 4-n-dodecylphenylthio group, 4-n-octadecylphenylthio group, 2,5-dimethylphenylthio group, 3,4- Dimethylphenylthio group, 5-indanylthio group, 1,2,3,4-tetrahydro-6-naphthylthio group, 2-methoxy Phenylthio group, 3-methoxyphenylthio group, 4-ethoxyphenylthio group, 4-n-propoxyphenylthio group, 2,4-dimethoxyphenylthio group, 3,5-diethoxyphenylthio group, 2-methoxy-4 -Methylphenylthio group, 2-methyl-4-methoxyphenylthio group, 2-fluorophenylthio group, 4-fluorophenylthio group, 2-chlorophenylthio group, 4-bromophenylthio group, 4-trifluoromethylphenyl Thio group, 3-trifluoromethylphenylthio group, 2,4-difluorophenylthio group, 2,4-dichlorophenylthio group, 2-chloro-4-methoxyphenylthio group, 2-naphthylthio group, 4-methyl-1 -Naphtylthio group, 4-ethoxy-1-naphthylthio group, 2-pyridylthio group, 4-aminopheny Thio group, 4- (N, N-dimethylamino) phenylthio group, 4- (N, N-diethylamino) -1-naphthylthio group, 4- [N, N-di (4′-methylphenyl) amino] phenylthio group 4- (N-phenoxadiyl) phenylthio group, etc., including phenylthio group, 2-methylphenylthio group, 4-methylphenylthio group, 3-ethylphenylthio group, 4-n-propylphenylthio group, 4-n-butylphenylthio group, 2,5-dimethylphenylthio group, 3,4-dimethylphenylthio group, 1,2,3,4-tetrahydro-6-naphthylthio group, 2-methoxyphenylthio group, 4 -Ethoxyphenylthio group, 2,4-dimethoxyphenylthio group,

3,5-diethoxyphenylthio group, 2-methoxy-4-methylphenylthio group, 2-fluorophenylthio group, 2-chlorophenylthio group, 4-trifluoromethylphenylthio group, 2,4-difluorophenylthio Group, 2,4-dichlorophenylthio group, 2-chloro-4-methoxyphenylthio group, 2-naphthylthio group, 4-methyl-1-naphthylthio group, 2-pyridylthio group, 4- (N, N-dimethylamino) A phenylthio group and a 4- (N, N-diethylamino) -1-naphthylthio group are preferable, and a phenylthio group, a 2-methylphenylthio group, a 4-methylphenylthio group, a 3-ethylphenylthio group, and 2,5-dimethylphenyl. Thio group, 3,4-dimethylphenylthio group, 2-methoxyphenylthio group, 4-ethoxyphenylthio group, , 4-Dimethoxyphenylthio group, 2-methoxy-4-methylphenylthio group, 2-chlorophenylthio group, 4-trifluoromethylphenylthio group, 2,4-dichlorophenylthio group, 2-chloro-4-methoxyphenyl A thio group and a 2-naphthylthio group are more preferable.

In the general formula (1), X ₁ and X ₂ are an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.
In the general formula (1), A ₁ and A ₂ are preferably an alkylene group having 1 to 16 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 24 carbon atoms. A ₁ and A ₂ are more preferably an alkylene group having 1 to 12 carbon atoms, or an arylene group having an alkyl group, an alkenyl group, a halogen atom, a cyano group or an acyl group as an unsubstituted or substituted group having 6 to 18 carbon atoms. It is.
As A ₁ and A ₂ being an alkylene group, any linear, branched or cyclic alkylene group may be used.

Examples of alkylene groups include methylene, ethylene, propane-1,3-diyl, propane-1.2-diyl, propane-1,1-diyl, propane-2,2-diyl, butane -1,4-diyl group, butane-2,3-diyl group, 1,1,2,2-tetramethylethane-1,2-diyl group, butane-1,2-diyl group, pentane-1,5 -Diyl group, pentane-1,2-diyl group, 2,4-diethylpentane-1,5-diyl group, 3-methylpentane-1,5-diyl group, cicyclopentane-1,3-diyl group, Hexane-1,6-diyl group, hexane-1,4-diyl group, hexane-2,4-diyl group, cyclohexane-1,4-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,2 -Diyl group, 2,2,3,3,4 4,5,5-octafluorohexane-1,6-diyl group, heptane-1,7-diyl group, adamantane-1,3-diyl group, octane-1,8-diyl group, nonane-1,9- A diyl group, a decane-1,10-diyl group, 1H, 1H, 10H, 10H-hexadecafluorodecane-1,10-diyl group is mentioned. An alkylene group having 1 to 12 carbon atoms is particularly preferable, and an alkylene group having 1 to 4 carbon atoms is more preferable.
A ₁ or A ₂ is a substituted or unsubstituted arylene group, including a heteroarylene group. The substituted arylene group preferably has an alkyl group, alkenyl group, halogen atom, cyano group or acyl group as a substituent, and more preferably has an alkyl group as a substituent.

Examples of substituted or unsubstituted arylene groups include benzene-1,4-diyl group, benzene-1,3-diyl group, benzene-1,2-diyl group, 2-methylbenzene-1,4-diyl group 3-methylbenzene-1,4-diyl group, 2,6-dimethylbenzene-1,4-diyl group, 2,3,5,6-tetramethylbenzene-1,4-diyl group, 2-allylbenzene -1,4-diyl group, 2-isopropylbenzene-1,4-diyl group, 2,3-dipropylbenzene-1,4-diyl group, 2-t-butylbenzene-1,4-diyl group, 3 -T-butylbenzene-1,4-diyl group, 2-t-butyl-5-methylbenzene-1,4-diyl group, 2,5-di-t-butylbenzene-1,4-diyl group, 2 -Cyclohexylbenzene-1,4-diyl group, 3- Cyclohexylbenzene-1,4-diyl group, 2-phenylbenzene-1,4-diyl group, 3-phenylbenzene-1,4-diyl group, 2-methoxybenzene-1,4-diyl group, 3-methoxybenzene -1,4-diyl group, 2-chlorobenzene-1,4-diyl group, 3-chlorobenzene-1,4-diyl group, 2-fluorobenzene-1,4-diyl group, 3-fluorobenzene-1,4 -Diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, 2,3-dicyanobenzene-1,4-diyl group, 2-acylbenzene-1,4-diyl group, naphthalene Examples include -1,5-diyl group, anthraquinone-2,6-diyl group, and benzonorbornene-3,6-diyl group. In particular, benzene-1,4-diyl group, benzene-1,3-diyl group, benzene-1,2-diyl group, 2-methylbenzene-1,4-diyl group, 3-methylbenzene-1,4-yl Group, 2,6-dimethylbenzene-1,4-diyl group, 2-chlorobenzene-1,4-diyl group, 3-chlorobenzene-1,4-diyl group, 2-fluorobenzene-1,4-diyl group, 3-fluorobenzene-1,4-diyl group and 2,3,5,6-tetrafluorobenzene-1,4-diyl group are preferable, benzene-1,4-diyl group, 2-methylbenzene-1, 4-diyl group, 3-methylbenzene-1,4-yl group, 2-fluorobenzene-1,4-diyl group and 3-fluorobenzene-1,4-diyl group are more preferable.

In general formula (1), Y is preferably an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group having 0 to 12 carbon atoms, a sulfonyl group, a carbonyl group, or an alkylene group having 1 to 16 carbon atoms. Y is more preferably an oxygen atom, a sulfur atom, an unsubstituted or substituted imino group having 0 to 12 carbon atoms, an sulfonyl group, a carbonyl group, or an alkylene group having 1 to 12 carbon atoms. is there.
Among those in which Y is a substituted or unsubstituted imino group, the substituted imino group preferably has an alkyl group or an aryl group as a substituent, and has an alkyl group having 1 to 4 carbon atoms or a phenyl group as a substituent. More preferred.
Examples of the alkyl-substituted imino group include a methylimino group, an ethylimino group, an n-propylimino group, an isopropylimino group, an n-butylimino group, an isobutylimino group, and a sec-butylimino group. Examples of the aryl-substituted imino group include a phenylimino group and a tolulimino group. In particular, a methylimino group, an ethylimino group, an n-propylimino group, an isopropylimino group, and a phenylimino group are preferable, and an ethylimino group and a phenylimino group are more preferable.
The group in which Y is an alkylene group may be any linear, branched or cyclic alkylene group.

Examples of alkylene groups are methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, propane-2,2-diyl, butane- 1,4-diyl group, butane-2,3-diyl group, 1,1,2,2-tetramethylethane-1,2-diyl group, butane-1,2-diyl group, pentane-1,5- Diyl group, 2-methylpentane-4,4-diyl group, 2,4-dimethylpentane-1,5-diyl group, cyclopentane-1,3-diyl group, hexane-2,2-diyl group, hexane- Examples include 3,4-diyl group, cyclohexane-1,1-diyl group, and cyclohexane-1,4-diyl group. In particular, a methylene group, an ethylene group, and a propane-2,2-diyl group are preferable, and a methylene group and an ethylene group are more preferable.
In the general formula (1), n is 0 or 1, and p is preferably 1.
In the general formula (1), M is preferably Cu, Zn, Fe, Co, Ni, Pt, Pd, Mn, Mg, Mn (OH), Mn (OH) ₂ , VO, or TiO, and Cu, Pd, and VO are More preferred.
Although the specific example of the tetraazaporphyrin dimer compound represented by General formula (1) of this invention is shown in following Table 1, it is not limited to these.

[Method for producing tetraazaporphyrin dimer compound]
A method for producing the tetraazaporphyrin dimer compound of the general formula (1) will be described below.
The tetraazaporphyrin dimer compound represented by the general formula (1) comprises a tetraazaporphyrin compound represented by the general formula (2) and a compound represented by the general formula (3) in the presence of a base. It can manufacture by making it react.

[In the formula (2), R _{15 to} R ₂₁ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted. An alkylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted arylthio group; Z represents a halogen atom; M represents two hydrogen atoms; A valent metal atom, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom is shown. ]
[In Formula (3), X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom, A ₁ and A ₂ represent an alkylene group, or a substituted or unsubstituted arylene group, and Y represents an oxygen atom. , A sulfur atom, a substituted or unsubstituted imino group, a sulfonyl group, a carbonyl group, or an alkylene group, and n and p each independently represent an integer of 0 or 1. ]
The amount of the compound of the general formula (3) used is 0.2 to 0.7 times mol, preferably 0.3 to 0.5 times mol for 1 mol of the tetraazaporphyrin compound of the general formula (2).
As the base, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, t-butoxy potassium, sodium acetate, potassium acetate and the like can be used, and potassium carbonate is preferable.
The usage-amount of a base is 1-10 times mole with respect to 1 mol of tetraazaporphyrin compounds of General formula (2), Preferably it is 2-5 times mole.

The reaction between the tetraazaporphyrin compound represented by the general formula (2) and the compound represented by the general formula (3) is preferably performed in the presence of an organic solvent. The reaction solvent is not particularly limited as long as it does not adversely affect the reaction, and aromatic hydrocarbons such as toluene, xylene, mesitylene, pseudocumene, chlorobenzene, dichlorobenzene, hexane, heptane, cyclohexane, carbon tetrachloride, chloroform An aprotic solvent such as DMF, DMAC, DMI, or DMSO can be used, but an aprotic solvent such as DMAC, DMI, or DMSO is preferable. . The usage-amount of a solvent is 1-500 times volume with respect to the tetraazaporphyrin compound of General formula (2) used for reaction, Preferably it is 1-200 times volume, More preferably, it is 5-100 times volume.
The reaction temperature is room temperature to 200 ° C, preferably 50 to 150 ° C, more preferably 50 to 100 ° C.
The reaction time is 10 minutes to 200 hours, preferably 1 hour to 100 hours, more preferably 5 hours to 50 hours.
After the reaction, the reaction mixture is discharged into a poor solvent such as methanol and water, and the precipitate is collected by filtration and dried to obtain the desired product. If necessary, it can be purified by a known purification method such as column chromatography using silica gel to obtain a higher purity product.

[Resin composition]
The resin composition of the present invention will be described below.
The resin composition of the present invention contains at least a tetraazaporphyrin dimer compound represented by the general formula (1) and a thermoplastic resin or a thermosetting resin.
In the following description, the thermoplastic resin and / or the thermosetting resin may be simply referred to as a resin.
The compounding amount of the resin and the tetraazaporphyrin dimer compound of the general formula (1) in the resin composition of the present invention varies depending on the use and the thickness of the resin molded product, but is within the limits that the translucency and transparency are not lost. The visible light transmittance is usually adjusted to 12 to 99%, preferably 20 to 90% with respect to the thickness direction of the molded body. For example, if the spectacle lens having a thickness of 2.15 mm is mixed with the polycarbonate resin, the amount of the tetraazaporphyrin dimer compound of the general formula (1) used is 0.001% by weight to 0.1% with respect to the polycarbonate resin. %. Generally, when the thickness of the molded body is 0.1 mm to 20 mm, the amount of the tetraazaporphyrin dimer compound of the general formula (1) used is 0.0001 to 0.2% by weight with respect to the resin.
In addition to the resin and the tetraazaporphyrin dimer compound of the general formula (1), the resin composition of the present invention contains other dyes, known ultraviolet absorbers, infrared absorbers, and various resin additives as necessary. Can be blended. Various resin additives include phenolic antioxidants, mold release agents, dyes and pigments, phosphorus heat stabilizers, weather resistance improvers, antistatic agents, antifogging agents, lubricants / antiblocking agents, flame retardants, fluidity Examples include improvers, plasticizers, dispersants, antibacterial agents and the like.

The manufacturing method of the resin composition of this invention is demonstrated below.
The resin composition of the present invention is obtained by mixing a tetraazaporphyrin dimer compound of the general formula (1) and a thermoplastic resin or a thermosetting resin. The azaporphyrin dimer compound and the resin are desirably in a compatible state.
When the resin of the resin composition is a thermoplastic resin, the resin composition is obtained by mixing the tetraazaporphyrin dimer compound and the thermoplastic resin powder or pellets using various mixers such as a tumbler or a Henschel mixer. The tetraazaporphyrin dimer compound is obtained by melt kneading with a known melt kneader such as a Banbury mixer, a heating roll, a Brabender, a single screw kneading extruder, a twin screw kneading extruder, or a kneader. And a thermoplastic resin uniform resin composition can be produced.
It can also be produced by dissolving and mixing the thermoplastic resin and tetraazaporphyrin dimer compound in an organic solvent in which the thermoplastic resin and tetraazaporphyrin dimer compound can be dissolved, and then removing the organic solvent. Examples of the organic solvent used in this case include hexane, heptane, acetone, methyl ethyl ketone, benzene, toluene, dichloromethane, chloroform, etc., but are chemically inert to the resin composition and have a moderately low boiling point. If it is a thing, it will not specifically limit.

In addition, after the tetraazaporphyrin dimer compound is dissolved in a solvent, it can be produced by bringing the tetraazaporphyrin dimer compound into the resin by allowing it to contact the resin or the resin molded body, The resin composition thus obtained is also within the scope of the present invention. The organic solvent in which the tetraazaporphyrin dimer compound is dissolved is not particularly limited, but it must not decompose the tetraazaporphyrin dimer compound or alter the thermoplastic resin. Usually, liquid ketones and alcohols are often used. The concentration of the solution is arbitrary depending on the purpose, but usually about 0.01% to 30% is a good range. Diffusion conditions vary depending on the solvent, the type of thermoplastic resin, etc., but are usually 25 ° C. to 200 ° C. and several minutes to 5 hours under normal pressure or pressure.

Further, the tetraazaporphyrin dimer compound may be mixed with the raw material monomer of the thermoplastic resin by the above method, and then polymerized. This manufacturing method will be described collectively in the case where the resin of the resin composition described later is a thermosetting resin.
When the resin of the resin composition is a thermosetting resin, after the tetraazaporphyrin dimer compound is dissolved in a solvent, the resin or resin molded body is contacted to diffuse the tetraazaporphyrin dimer compound into the resin, There are a method of intruding or a method of polymerizing a tetraazaporphyrin dimer compound after mixing it with a raw material monomer of a thermosetting resin, and the latter is often used. The latter method will be described below.
In the step of mixing the tetraazaporphyrin dimer compound with the raw material monomer of the thermosetting resin, the monomer mixture after being mixed with any of the monomer groups constituting the monomer mixture depending on the mixing target of the tetraazaporphyrin dimer compound And a method of adding a catalyst after mixing with a mixture of a monomer mixture and other additives, or a method of mixing with a mixture of a monomer mixture, catalyst, and other additives.
As components other than the monomer and tetraazaporphyrin dimer compound used for polymerization and curing, there are a polymerization catalyst and other additives.

As the polymerization catalyst, an organic peroxide is known, and examples thereof include diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, and hydroperoxide.
Other additives include catalysts such as dibutyltin dichloride, UV absorbers, internal mold release agents such as acidic phosphate esters, light stabilizers, antioxidants, reaction initiators such as radical initiators, and chain extenders. , A known resin modifier, such as a hydroxy compound, a thiol compound, an epoxy compound, an episulfide compound, an organic acid and its anhydride, a (meth) acrylate compound. Olefin compounds containing etc. are mentioned.
In mixing the tetraazaporphyrin dimer compound with the raw material monomer of the thermosetting resin, the tetraazaporphyrin dimer compound may be directly mixed, or the tetraazaporphyrin dimer compound may be mixed in advance with a low boiling point. After dissolving in an organic solvent and mixing the organic solvent solution with the raw material monomer, the organic solvent may be removed by evaporation under conditions such as heating and / or reduced pressure. Examples of the organic solvent used in this case include hexane, heptane, acetone, methyl ethyl ketone, benzene, toluene, dichloromethane, chloroform, etc., but are chemically inert to the raw material monomers and have a moderately low boiling point. If it is, it will not specifically limit.
In mixing, the resin composition may be mixed so that the amount corresponding to the tetraazaporphyrin dimer compound concentration required for the resin composition is contained, and either component such as one raw material monomer. Prepare a master batch containing a tetraazaporphyrin dimer compound at a higher concentration than the target concentration, and add and dilute other components to be blended as necessary to produce a resin composition of the target concentration You may do it. In addition, when the tetraazaporphyrin dimer compound is dissolved, the tetraazaporphyrin dimer compound can be heated within a range that does not hinder the implementation in terms of deterioration of the resin composition and pot life.
The conditions for polymerization and curing will be described in the cast polymerization method for the molded article below. The conditions for polymerization and curing will be described in the cast polymerization method for the molded article below.

[Thermoplastic resin or thermosetting resin]
Next, a thermoplastic resin or a thermosetting resin will be described below.
The resin used in the resin composition of the present invention may be either a thermoplastic resin or a thermosetting resin, but is preferably a transparent resin. Two or more resins may be used in combination as long as the practicality of the antiglare optical article of the present invention is not impaired.

[Thermoplastic resin]
The thermoplastic resin is not particularly limited, but polycarbonate resin, polyamide resin, acrylic resin, polyester resin, polystyrene resin, acrylonitrile / styrene resin, norbornene resin, cellulose resin, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin. , Ethylene-acrylic copolymer resin, polyurethane resin and polyvinyl alcohol resin are preferable, and polycarbonate resin, polyamide resin, acrylic resin, polyester resin and polyvinyl acetal resin are more preferable.

Polycarbonate resin is a polymer obtained mainly by the phosgene method in which dihydroxydiaryl compounds and phosgene are reacted, or the ester exchange method in which dihydroxydiaryl compounds and carbonic esters such as diphenyl carbonate are reacted. And polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
Examples of the dihydroxydiaryl compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, bisphenol A, 2 , 2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2, 2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichloropheny ) (Hydroxyaryl) alkanes such as propane, (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4 , 4′-dihydroxydiphenyl ether, dihydroxydiaryl ethers such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′- Dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldi Such as dihydroxy diaryl sulfones such as Enirusuruhon thereof.
These are used alone or selected from two or more. Besides these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. may be used in combination. The viscosity average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 10,000 to 400,000.
Furthermore, you may use together said dihydroxyaryl compound and the trivalent or more phenolic compound as shown below. Examples of the trivalent or higher phenol include phloroglucin, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane, and the like.

The polyamide resin is a resin having a dehydration polycondensate structure of a diamine compound containing an aromatic or aliphatic group and a dicarboxylic acid compound containing an aromatic or aliphatic group. Here, the aliphatic group also includes an alicyclic aliphatic group. The resin having the structure of the dehydration polycondensate of the diamine compounds and dicarboxylic acid compounds is not necessarily limited to those obtained from the dehydration polycondensation reaction. For example, ring opening of one or more lactam compounds It can also be obtained from polymerization or the like.
Examples of the diamine compounds include hexamethylenediamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, trimethylhexamethylenediamine, and bis (aminomethyl) norbornane. Bis (aminomethyl) tetrahydrodicyclopentadiene and the like, and one or more of these diamine compounds can be selected and used.
Examples of the dicarboxylic acid compounds include adipic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, bis (hydroxycarbonylmethyl) norbornane, bis (hydroxycarbonylmethyl) tetrahydrodicyclopentadiene, and the like. 1 type or 2 types or more can be selected and used.
In particular, an amorphous polyamide resin is preferable from the viewpoint of transparency, and is generally referred to as transparent nylon. For example, Emamide's Grillamide TR-55, Grillamide TR-90, Grillamide TR-XE3805, or Hulus's Trogamide CX -7233 etc. can be illustrated.

The acrylic resin may be a polymer mainly composed of alkyl methacrylate, which may be a homopolymer of alkyl methacrylate or a copolymer using two or more kinds of alkyl methacrylate, or an alkyl methacrylate having a weight of 50 wt. % And a copolymer of 50% by weight or less of a monomer other than alkyl methacrylate may be used. As the alkyl methacrylate, those having 1 to 4 carbon atoms of the alkyl group are usually used, and among them, methyl methacrylate is preferably used.
The monomer other than alkyl methacrylate may be a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule, or two or more polymerizable carbons in the molecule. -A polyfunctional monomer having a carbon double bond may be used, but a monofunctional monomer is particularly preferably used. Examples thereof include alkyl acrylates such as methyl acrylate and ethyl acrylate, styrene monomers such as styrene and alkyl styrene, and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
As the acrylic resin, the monomer is a polymer consisting essentially only of alkyl methacrylate, or the alkyl methacrylate accounts for 70% by weight or more, preferably 90% by weight or more of the monomer composition, It is preferably a copolymer of only a monomer selected from alkyl acrylate, a styrene monomer and an unsaturated nitrile. In particular, a polymer in which the monomer is substantially composed only of alkyl methacrylate is most preferable, and a typical example is polymethyl methacrylate resin (PMMA). Polymethyl methacrylate resin is available in many commercial products such as MX150 manufactured by Soken Chemical Co., Ltd., Japan Poster Ester MA, and Sekisui Plastics Co., Ltd. MBX series.
Further, among acrylic resins, a glass transition temperature is low, for example, a glass transition temperature is less than 0 ° C., preferably a poly (meth) acrylate ester resin having a temperature of −20 ° C. or less is used as an adhesive, an adhesive, etc. For example, it is widely used for bonding each layer of an optical filter for a thin display, or for bonding an optical filter and a display screen.
To this poly (meth) acrylic ester resin adhesive, the tetraazaporphyrin dimer compound of the present invention, or an azo compound of the general formula (4), a quinophthalone compound of the general formula (5), and A resin composition containing at least one selected from the anthraquinone compounds of the general formula (6) as an organic dye is also within the scope of the present invention.
As the poly (meth) acrylic acid ester resin used as the pressure-sensitive adhesive, those using 50% by weight or more of (meth) acrylic acid ester having a C 1-14 alkyl group as a monomer are preferable.

Examples of the (meth) acrylic acid ester having an alkyl group having 1 to 14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Octyl (meth) acrylate, i-octyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and the like.
Other examples of copolymerizable monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, etc. (Meth) acrylates; styrene monomers represented by α-methylstyrene, vinyl toluene, styrene, etc .; vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid, fumaric acid Monoalkyl ester of acid, dialkyl ester of fumaric acid; maleic acid, monoalkyl ester of maleic acid, dialkyl ester of maleic acid, itaconic acid, monoalkyl ester of itaconic acid, dialkyl ester of itaconic acid, Meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl ketones, vinyl pyridine, and vinyl carbazole.
Typical examples of the polyester resin include homopolyesters such as poly C _2-4 alkylene terephthalate and poly C _2-4 alkylene naphthalate, C _2-4 alkylene arylate units (C _2-4 alkylene terephthalate and / or C _{2-2). 4-} alkylene naphthalate unit) as a main component. Polyarylate resins, aliphatic polyesters using aliphatic dicarboxylic acids such as adipic acid, and lactones such as ε-caprolactone, alone or in combination Mergers are also included.
The copolyesters, poly _{C 2-4} among constituent units of alkylene _{arylate, C 2-4} part of the alkylene glycol, polyoxy _{C 2-4} alkylene _{glycols, C 6-10} alkylene glycol, alicyclic diols (cyclohexane Dimethanol, hydrogenated bisphenol A and the like, diols having aromatic rings (9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene having a fluorenone side chain, bisphenol A, bisphenol A-alkylene oxide adducts, etc. ) Substituted copolyesters, copolyesters partially substituted with asymmetric aromatic dicarboxylic acids such as phthalic acid and isophthalic acid, and aliphatic C _6-12 dicarboxylic acids such as adipic acid It is.

As the polyester resin, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like are preferable in terms of high transparency. Amorphous copolyesters such as C _2-4 alkylene arylate copolyesters are also preferred because of their excellent processability. In particular, PET is preferable because it is produced in large quantities and is excellent in heat resistance and strength.
The polyvinyl acetal resin can be produced by, for example, reacting polyvinyl alcohol (PVA) and acetaldehyde to acetal, but a polyvinyl formal resin obtained by reacting PVA and formaldehyde, PVA and n-butyraldehyde. Polyvinyl butyral resin (PVB) obtained by reacting is also included.
PVA used for the synthesis | combination of a polyvinyl acetal type resin is obtained by saponifying a polyvinyl acetate, for example. The saponification degree of the PVA is generally preferably in the range of 80 to 99.8 mol%. Furthermore, the thing with an average degree of polymerization of PVA of 200-5000 is preferable, More preferably, it is 500-2,500. If the degree of polymerization is too low, the strength becomes too weak, and if the degree of polymerization is too high, there may be a problem when the resulting polyvinyl acetal resin is formed.
In general, the aldehyde used for the synthesis of the polyvinyl acetal resin is preferably an aldehyde having 1 to 10 carbon atoms, more preferably propionaldehyde, n-butyraldehyde or isobutyraldehyde. In addition, these aldehydes may be used independently and 2 or more types may be used together.
The polyvinyl acetal resin preferably has a hydroxyl group content of 15 to 40 mol%, more preferably 18 to 35 mol%.
The degree of acetylation is preferably in the range of 0.1 to 30 mol%, more preferably in the range of 0.5 to 20 mol%.
About acetalization degree, it is preferable to exist in the range of 60-85 mol%, More preferably, it exists in the range of 65-75 mol%.
A conventionally known plasticizer can be used as a plasticizer used for plasticizing the polyvinyl acetal resin. These plasticizers may be used independently and 2 or more types may be used together.

[Thermosetting resin]
Examples of thermosetting resins include allyl diglycol carbonate monomers, diallyl phthalate monomers, mixtures of isocyanate compounds and polyols and polythiols, and cured products of monomers used in the manufacture of correction lenses such as acrylic monomers. It is selected from polyurethane resin obtained by polymerization reaction of isocyanate compound and polyol, polythiourethane resin obtained by polymerization of isocyanate compound and polythiol compound, and allyl diglycol carbonate resin which is curing of allyl diglycol carbonate monomer At least one is preferable.
The polyurethane resin is mainly composed of a block type polyisocyanate and a polyol. Examples of the block type polyisocyanate include hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, Examples include adducts in which several molecules of isophorone diisocyanate and hydrogenated xylylene diisocyanate are bonded, isocyanurates and allophanates blocked with acetoacetic acid and malonic acid, etc. Examples include ether, polycarbonate, polyacrylate, polycaptolactone, and the like.
A typical example of the polythiourethane resin is a polythiourethane resin produced from metaxylylene diisocyanate and pentaerythritol tetrakis (3-mercaptopropionate).
As the allyl diglycol carbonate resin, polydiethylene glycol bisallyl carbonate is preferable, and examples thereof include CR-39 resin (also referred to as ADC resin).

[Other pigments]
In the resin composition of the present invention, other dyes can be used in combination for the purpose of cutting unnecessary light, toning, and decolorization, as long as the effects of the present invention are not hindered.
For example, by using together a dye having a maximum absorption in the wavelength range of 380 to 470 nm, it simultaneously cuts short wavelength light that causes glare and is harmful to the eyes, and reduces coloring of the resin composition. be able to.
Examples of such a dye include azo compounds represented by the following general formula (4),

A quinophthalone compound represented by the general formula (5) and an anthraquinone compound represented by the following general formula (6) are preferred. Any one of these pigments may be used, or two or more thereof may be used in combination.

[In the formula (4), R _{22 to} R ₃₂ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, a halogenoalkyl group, an alkoxy group, or a halogenoalkoxy group. Alkylthio group, alkoxyalkyl group, alkoxyalkoxyalkyl group, halogenoalkoxyalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, Substituted or unsubstituted acyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkyloxyalkyl group, alkyloxycarbonyl group , Replacement or Substituted aryloxycarbonyl group or a substituted or unsubstituted arylthio group. ]

[In the formula (5), R _{33 to} R ₄₁ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, a halogenoalkyl group, an alkoxy group, or a halogenoalkoxy group. Alkylthio group, alkoxyalkyl group, alkoxyalkoxyalkyl group, halogenoalkoxyalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, Substituted or unsubstituted acyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkyloxyalkyl group, alkyloxycarbonyl group , Substituted or unsubstituted Of the aryloxycarbonyl group, or a substituted or unsubstituted arylthio group, and adjacent groups selected from R _{38 to} R ₄₁ are bonded to each other, and together with the substituted carbon atom, a substituted or unsubstituted 5-membered member You may form the ring more than a ring. ]

[In the formula (6), R _{42 to} R ₄₉ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group, an alkoxy group, an alkylthio group, an alkoxyalkyl group, a substituted or unsubstituted aryl group, a substituted or An unsubstituted aralkyl group or a substituted or unsubstituted arylthio group is shown. However, at least one of R _{42 to} R ₄₉ is necessarily a substituted or unsubstituted arylthio group. ]

In the azo compound of the general formula (4), R _{22 to} R ₃₂ are substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted aryloxyalkyls. In the case of a group, a substituted or unsubstituted aralkyloxy group, a substituted or unsubstituted aralkyloxyalkyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted arylthio group, , Cyano group, nitro group, hydroxyl group, alkylthio group, carboxyl group, alkyl group, alkenyl group, halogenoalkyl group, alkoxy group, halogenoalkoxy group, alkylthio group, alkoxyalkyl group, amino group, alkylamino group, dialkylamino group Can be mentioned.
When R _{22 to} R ₃₂ are a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, or a substituted or unsubstituted acyl group is substituted, the substituent is an alkyl group, substituted or unsubstituted aryl, respectively. Group, substituted or unsubstituted aralkyl group.

In the general formula (4), R _{22 to} R ₃₂ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. Halogenoalkyl group, alkoxy group having 1 to 12 carbon atoms, halogenoalkoxy group having 1 to 12 carbon atoms, alkylthio group having 1 to 12 carbon atoms, alkoxyalkyl group having 2 to 16 carbon atoms, alkoxyalkoxy having 3 to 20 carbon atoms Alkyl group, substituted or unsubstituted aryl group having 6 to 18 carbon atoms, substituted or unsubstituted amino group having 1 to 18 carbon atoms, substituted or unsubstituted amide group having 1 to 18 carbon atoms, 7 to 20 carbon atoms Substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, substituted or unsubstituted aryloxy group having 7 to 20 carbon atoms Group, an alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group having 7 to 19 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms 2 to 13 carbon atoms.
More preferably, R _{22 to} R ₃₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or 1 to 8 carbon atoms. Alkoxy group having 1 to 8 carbon atoms, alkylthio group having 1 to 8 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms, halogenoalkoxyalkyl group having 2 to 12 carbon atoms, 6 to 14 carbon atoms Substituted or unsubstituted aryl group, substituted or unsubstituted amino group having 1 to 14 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 14 carbon atoms , A substituted or unsubstituted arylthio group having 6 to 14 carbon atoms.

Specific examples of R _{22 to} R ₃₂ will be described below.
R _{22 to} R ₃₂ are a halogen atom, an alkyl group, a halogenoalkyl group, an alkoxyalkyl group, a halogenoalkoxyalkyl group, a substituted or unsubstituted aralkyl group, an alkoxy group, a halogenoalkoxy group, an alkylthio group, a substituted or unsubstituted aryl group. , A substituted or unsubstituted aryloxy group, or a specific example or a preferred example in which it is a substituted or unsubstituted arylthio group, R _{1 to} R ₁₄ of the tetraazaporphyrin-based compound of the general formula (1) are respectively Examples similar to those given for these substituents are given.

Examples of the group in which R _{22 to} R ₃₂ are alkenyl groups include vinyl group, propenyl group, 1-butenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 1-hexenyl. A vinyl group, a propenyl group, and a 1-butenyl group are preferable, and a vinyl group and a propenyl group are more preferable.

Examples of the group in which R _{22 to} R ₃₂ are alkoxyalkoxyalkyl groups include (2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (3-methoxy Propyloxy) methyl group, (3-ethoxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (6-methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2 -(2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (3-ethoxypropyloxy) ethyl group, 2- (4-ethoxybutyloxy) ethyl group, 2- (4- Butyloxybutyloxy) ethyl group, 2- (5-methyloxypentyloxy) ethyl group, 3- (1-methoxyeth) Ii) propyl group, 3- (2-ethoxyethoxy) propyl group, 3- (3-methoxypropyloxy) propyl group, 3- (3-propyloxypropyloxy) propyl group, 3- (4-ethoxybutyloxy) Propyl group, 3- (4-butyloxybutyloxy) propyl group, 3- (5-methyloxypentyloxy) propyl group, 4- (2-methoxyethoxy) butyl group, 4- (2-ethoxyethoxy) butyl group 4- (3-ethoxypropyloxy) butyl group, 4- (4-ethoxybutyloxy) butyl group, 4- (4-butyloxybutyloxy) butyl group, 2- (5-methyloxypentyloxy) butyl group , 5- (2-methoxyethoxy) pentyl group, 5- (2-ethoxyethoxy) pentyl group, 5- (3-ethoxypropyloxy) pentyl Group, 5- (4-ethoxybutyloxy) pentyl group, 5- (4-butyloxybutyloxy) pentyl group, 5- (5-pentyloxypentyloxy) pentyl group, 6- (2-methoxyethoxy) hexyl Group, 6- (2-ethoxyethoxy) hexyl group, 6- (6-cybutyloxysibutyloxy) hexyl group, 8- (2-ethoxyethoxy) octyl group and the like, and (2-methoxyethoxy) methyl Group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (3-methoxypropyloxy) methyl group, (3-ethoxypropyloxy) methyl group, 2- (2-methoxyethoxy) ) Ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (3-ethoxypropyloxy) ethyl group, 2- (4-ethoxybutyloxy) ) Ethyl group, 2- (4-butyloxybutyloxy) ethyl group, 2- (5-methyloxypentyloxy) ethyl group, 3- (1-methoxyethoxy) propyl group, 3- (2-ethoxyethoxy) propyl Group, 3- (3-methoxypropyloxy) propyl group, 3- (3-propyloxypropyloxy) propyl group, 3- (4-ethoxybutyloxy) propyl group, 4- (2-methoxyethoxy) butyl group, 4- (2-ethoxyethoxy) butyl group, 4- (3-ethoxypropyloxy) butyl group, 4- (4-butyloxybutyloxy) butyl group, 5- (2-methoxyethoxy) pentyl group, 5- ( 2-ethoxyethoxy) pentyl group, 5- (3-ethoxypropyloxy) pentyl group, 5- (4-butyloxybutyloxy) pentyl group 6- (2-methoxyethoxy) hexyl group, 6- (2-ethoxyethoxy) hexyl group and 8- (2-ethoxyethoxy) octyl group are preferable, (2-methoxyethoxy) methyl group, (2-ethoxyethoxy) Methyl group, (3-methoxypropyloxy) methyl group, (3-ethoxypropyloxy) methyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (3- Ethoxypropyloxy) ethyl group, 2- (4-ethoxybutyloxy) ethyl group, 3- (1-methoxyethoxy) propyl group, 3- (2-ethoxyethoxy) propyl group, 3- (3-methoxypropyloxy) Propyl, 3- (3-propyloxypropyloxy) propyl, 4- (2-methoxyethoxy) butyl, 4- (2-eth Shietokishi) butyl group, 4- (3-ethoxy-propyloxy) butyl group, 5- (2-ethoxyethoxy) pentyl group, 5- (3-ethoxy-propyl) pentyl group is more preferable.

R _{22 to} R ₃₂ are substituted or unsubstituted amino groups such as amino group, N-methylamino group, N-ethylamino group, Nn-propylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group, N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (2-naphthyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-di- n-propylamino group, N, N-di-n-butylamino group, N, N-di-n-octylamino group, N, N-di-n-decylamino group, N-methyl-N-ethylamino group , N-Echi -Nn-butylamino group, N-methyl-N-phenylamino group, Nn-butyl-N-phenylamino group, N-benzyl-N-phenylamino group, N, N-diphenylamino group, N , N-di (3-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4 -Methoxyphenyl) amino group, N, N-di (4-ethoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (2-naphthyl) amino group N-phenyl-N- (4-methylphenyl) amino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-n-hexyloxyphenyl) amino group, N -Phenyl-N- (1-naphthyl) ) Amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (4-phenylphenyl) amino group, N-phenoxadiyl group, N-phenothiadiyl group and the like. Group, N-methylamino group, N-ethylamino group, Nn-propylamino group, Nn-butylamino group, Nn-octylamino group, N-benzylamino group, N-phenylamino group, N- (4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N, N-dimethylamino group, N, N-diethylamino group, N, N -Di-n-propylamino group, N, N-di-n-butylamino group, N, N-di-n-octylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn -Butylami Group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N- Phenyl-N- (4-methylphenyl) amino group is preferable, and amino group, N-methylamino group, N-ethylamino group, Nn-propylamino group, Nn-butylamino group, Nn- Octylamino group, N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-di-n-butylamino group, N N-di-n-octylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group N, N-di (3-methylphenol Yl) amino group, N, N-di (4-methoxyphenyl) amino group are more preferable.

Examples of R _{22 to} R _{32 that} are substituted or unsubstituted amide groups include amide groups, N-methylamide groups, N-ethylamide groups, Nn-propylamide groups, Nn-butylamide groups, N-cyclohexyl groups. Amide group, Nn-octylamide group, N-benzylamide group, N-phenylamide group, N- (3-methylphenyl) amide group, N- (4-methoxyphenyl) amide group, N- (3- Fluorophenyl) amide group, N- (4-chlorophenyl) amide group, N- (2-naphthyl) amide group, N, N-dimethylamide group, N, N-diethylamide group, N, N-di-n-propyl Amide group, N, N-di-n-butylamide group, N, N-di-n-octylamide group, N, N-di-n-decylamide group, N-methyl-N-ethylamide group, N-ethyl -N-n-butylamide group, N-methyl-N-phenylamide group, Nn-butyl-N-phenylamide group, N-benzyl-N-phenylamide group, N, N-diphenylamide group, N, N-di (3-methylphenyl) amide group, N, N-di (4-ethylphenyl) amide group, N, N-di (4-tert-butylphenyl) amide group, N, N-di (4- Methoxyphenyl) amide group, N, N-di (4-ethoxyphenyl) amide group, N, N-di (4-n-hexyloxyphenyl) amide group, N, N-di (2-naphthyl) amide group, N-phenyl-N- (4-methylphenyl) amide group, N-phenyl-N- (4-methoxyphenyl) amide group, N-phenyl-N- (4-n-hexyloxyphenyl) amide group, N- Phenyl-N- (1-naphthyl) a Amide group, N-phenyl-N- (2-naphthyl) amide group, N-phenyl-N- (4-phenylphenyl) amide group, and the like. Amide group, N-methylamide group, N-ethylamide group, N -N-propylamide group, Nn-butylamide group, Nn-octylamide group, N-benzylamide group, N-phenylamide group, N- (4-methoxyphenyl) amide group, N- (3- Fluorophenyl) amide group, N- (4-chlorophenyl) amide group, N, N-dimethylamide group, N, N-diethylamide group, N, N-di-n-propylamide group, N, N-di-n -Butylamide group, N, N-di-n-octylamide group, N-methyl-N-ethylamide group, N-ethyl-Nn-butyramide group, N-methyl-N-phenylamide group, N, N- Giffeni Amide group, N, N-di (3-methylphenyl) amide group, N, N-di (4-methoxyphenyl) amide group, N-phenyl-N- (4-methylphenyl) amide group are preferable, and amide group N-methylamide group, N-ethylamide group, Nn-propylamide group, Nn-butylamide group, Nn-octylamide group, N-phenylamide group, N, N-dimethylamide group, N, N-diethylamide group, N, N-di-n-propylamide group, N, N-di-n-butylamide group, N, N-di-n-octylamide group, N-methyl-N-ethylamide group, N -Ethyl-Nn-butyramide group, N-methyl-N-phenylamide group, N, N-diphenylamide group, N, N-di (3-methylphenyl) amide group, N, N-di (4- Methoxyphenyl) amide It is more preferable.

Examples of R _{22 to} R _{32 that} are substituted or unsubstituted acyl groups include formyl group, acetyl group, propanoyl group, n-propylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, tert-butylcarbonyl group, n-pentylcarbonyl group, isopentylcarbonyl group, 2-methylbutylcarbonyl group, propenoyl group, benzoyl group, 4-methylbenzoyl group, 2,4-dimethylbenzoyl group, 3-chlorobenzoyl group, 4-dimethylaminobenzoyl group , 2-methoxybenzoyl group, 3-butoxy-2-naphthoyl group, cinnamoyl group, and the like. Formyl group, acetyl group, propanoyl group, n-propylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, n- Pentylcarbonyl group, isopen Preferred are a tilcarbonyl group, propenoyl group, benzoyl group, 4-methylbenzoyl group, 2,4-dimethylbenzoyl group, 3-chlorobenzoyl group, 4-dimethylaminobenzoyl group, 2-methoxybenzoyl group, cinnamoyl group, and formyl group Acetyl group, propanoyl group, n-propylcarbonyl group, benzoyl group, 4-methylbenzoyl group, 2,4-dimethylbenzoyl group, 3-chlorobenzoyl group, 4-dimethylaminobenzoyl group, and cinnamoyl group are more preferable.

Examples of the group in which R _{22 to} R ₃₂ are a substituted or unsubstituted aryloxyalkyl group include a phenyloxymethyl group, a 4-methylphenyloxymethyl group, a 4-ethylphenyloxymethyl group, and 4-n-butylphenyl. Oxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group 4-fluorophenyloxymethyl group, 2-fluorophenyloxymethyl group, 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 2-naphthyloxymethyl group, 1 -Phenyloxyethyl group, 2- (4'- Tilphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4′-n-butoxyphenyloxy) ethyl group, 2- (4′-fluorophenyloxy) ethyl group, 2- (3′-chlorophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3 -(4'-methylphenyloxy) propyl group, 4-phenyloxybutyl group, 4- (2'-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5- (4'-tert-butylphenyloxy) ) Pentyl group, 6-phenyloxyhexyl group, 8-phenyloxyoctyl group, 10- (3′-methylphenyloxy) decyl group, etc. Phenyloxymethyl group, 4-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-decylphenyloxymethyl group 4-methoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3,4-difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-naphthyloxymethyl group, 1 -Phenyloxyethyl group, 2- (4'-methylphenyloxy) ethyl group, 2- (4'-ethylphenyloxy) ethyl group, 2- (4'-methoxyphenyloxy) ethyl group, 2- (4 ' -N-butoxyphenyloxy) ethyl group, 2- (4'-fluorophenyloxy) ethyl Group, 2- (3′-chlorophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 3-phenyloxypropyl group, 3- (4′-methylphenyloxy) propyl group, 4-phenyl An oxybutyl group, a 4-phenyloxypentyl group, a 6-phenyloxyhexyl group, and an 8-phenyloxyoctyl group are preferable, and a phenyloxymethyl group, a 4-methylphenyloxymethyl group, a 4-ethylphenyloxymethyl group, a 4- n-butylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-naphthyloxymethyl group, 1-phenyloxyethyl group, 2- (4 ′ -Methylphenyloxy) ethyl group, 2- (4'-ethylphenyloxy) ethyl group, -(4'-methoxyphenyloxy) ethyl group, 2- (3'-chlorophenyloxy) ethyl group, 2- (1'-naphthyloxy) ethyl group, 3-phenyloxypropyl group, 3- (4'-methyl) More preferred are a phenyloxy) propyl group, a 4-phenyloxybutyl group, and a 4-phenyloxypentyl group.

Examples of R _{22 to} R _{32 which} are substituted or unsubstituted aralkyloxy groups include benzyloxy group, α-methylbenzyloxy group, α-ethylbenzyloxy group, α, α-dimethylbenzyloxy group, α-phenyl Benzyloxy group, α, α-diphenylbenzyloxy group, phenethyloxy group, α-methylphenethyloxy group, β-methylphenethyloxy group, α, α-dimethylphenethyloxy group, 4-methylphenethyloxy group, 4-methyl Benzyloxy group, 2-methylbenzyloxy group, 4-ethylbenzyloxy group, 2-ethylbenzyloxy group, 4-tert-butylbenzyloxy group, 2-tert-butylbenzyloxy group, 4-n-pentylbenzyloxy Group, 4-cyclohexylbenzyloxy group, 4-n-octylbenzyl Oxy group, 4-phenylbenzyloxy group, 4- (4′-methylphenyl) benzyloxy group, 4- (4′-tert-butylphenyl) benzyloxy group, 4-methoxybenzyloxy group, 2-ethoxybenzyloxy Group, 4-n-heptyloxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-fluorobenzyloxy group, 3-chlorobenzyloxy group, 3,4-dichlorobenzyloxy group, 2-furfuryloxy group 2-naphthylmethyloxy group, benzyloxy group, α-methylbenzyloxy group, α-ethylbenzyloxy group, α, α-dimethylbenzyloxy group, phenethyloxy group, α-methylphenethyloxy group, β-methylphenethyloxy group, α, α-dimethylphenethyloxy group, 4-methylphenethylo group Si group, 4-methylbenzyloxy group, 2-methylbenzyloxy group, 4-ethylbenzyloxy group, 2-ethylbenzyloxy group, 4-tert-butylbenzyloxy group, 4-n-pentylbenzyloxy group, 2 -Ethoxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-fluorobenzyloxy group, 3-chlorobenzyloxy group, 3,4-dichlorobenzyloxy group, 2-furfuryloxy group, 2-naphthylmethyloxy Group is preferred, benzyloxy group, α-methylbenzyloxy group, α-ethylbenzyloxy group, α, α-dimethylbenzyloxy group, phenethyloxy group, α-methylphenethyloxy group, β-methylphenethyloxy group, α , Α-dimethylphenethyloxy group, 4-methylbenzyloxy group, 2-methylbenzyl Oxy group, 4-ethylbenzyloxy group, 2-ethylbenzyloxy group, 2-ethoxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 3-chlorobenzyloxy group, 3,4-dichlorobenzyloxy group, 2 -A furfuryloxy group and a 2-naphthylmethyloxy group are more preferable.

Examples of R _{22 to} R _{32 that} are substituted or unsubstituted aralkyloxyalkyl groups include benzyloxymethyl group, phenethyloxymethyl group, 4-methylbenzyloxymethyl group, 4-n-propylbenzyloxymethyl group, 4 -N-octylbenzyloxymethyl group, 4-methoxybenzyloxymethyl group, 4-n-butoxybenzyloxymethyl group, 4-fluorobenzyloxymethyl group, 3-fluorobenzyloxymethyl group, 4-chlorobenzyloxymethyl group 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (4′-fluorobenzyloxy) ethyl group, 2- (4′-chlorobenzyloxy) ) Ethyl group, 3- (4′-methoxybenzyloxy) propyl group, 4 -Benzyloxybutyl group, 4- (4'-phenylbenzyloxy) butyl group, 6-benzyloxyhexyl group and the like are exemplified, such as benzyloxymethyl group, phenethyloxymethyl group, 4-methylbenzyloxymethyl group, 4- n-propylbenzyloxymethyl group, 4-methoxybenzyloxymethyl group, 4-n-butoxybenzyloxymethyl group, 3-fluorobenzyloxymethyl group, 4-chlorobenzyloxymethyl group, 2-benzyloxyethyl group, 2 -Phenethyloxyethyl group, 3- (4'-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 4- (4'-phenylbenzyloxy) butyl group are preferable, benzyloxymethyl group, phenethyloxymethyl group 4-methylbenzyloxymethyl group, 4-methoxy Benzyloxymethyl group, 4-n-butoxybenzyloxymethyl group, 3-fluorobenzyloxymethyl group, 4-chlorobenzyloxymethyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 3- (4 ′ -Methoxybenzyloxy) propyl group and 4-benzyloxybutyl group are more preferable.

R _{22 to} R ₃₂ are alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyl. Oxycarbonyl group, cyclopentyloxycarbonyl group, n-hexyloxycarbonyl group, 3,3-dimethylbutyloxycarbonyl group, 2-ethylbutyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Carbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tridecyloxycarbonyl group, n- Tradecyloxycarbonyl group, n-pentadecyloxycarbonyl group, n-hexadecyloxycarbonyl group, n-heptadecyloxycarbonyl group, n-octadecyloxycarbonyl group, n-tricosyloxycarbonyl group, n-tetracosyl group And methoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxy Carbonyl group, 3,3-dimethylbutyloxycarbonyl group, 2-ethylbutyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethyl Xyloxycarbonyl group and n-dodecyloxycarbonyl group are preferred, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl Group, n-hexyloxycarbonyl group, 2-ethylbutyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, and n-octyloxycarbonyl group are more preferable.

R _{22 to} R ₃₂ are substituted or unsubstituted aryloxycarbonyl groups such as phenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 4-ethylphenyloxycarbonyl group, 4-isopropylphenyloxycarbonyl group, 4-isobutylphenyloxycarbonyl group, 4-n-pentylphenyloxycarbonyl group, 4-tert-pentylphenyloxycarbonyl group, 4-cyclohexylphenyloxycarbonyl group, 4-n-octylphenyl Oxycarbonyl group, 4-n-decylphenyloxycarbonyl group, 4-n-dodecylphenyloxycarbonyl group, 4-n-hexadecylphenyloxycarbonyl group, 2,3-dimethylphenyloxycarbonyl group 2,5-dimethylphenyloxycarbonyl group, 3,4-dimethylphenyloxycarbonyl group, 3,4,5-trimethylphenyloxycarbonyl group, 5-indanyloxycarbonyl group, 1,2,3,4-tetrahydro- 6-naphthyloxycarbonyl group, 3-methoxyphenyloxycarbonyl group, 3-ethoxyphenyloxycarbonyl group, 4-n-propoxyphenyloxycarbonyl group, 4-n-butoxyphenyloxycarbonyl group, 4-n-pentyloxyphenyl Oxycarbonyl group, 4-cyclohexyloxyphenyloxycarbonyl group, 4-n-octyloxyphenyloxycarbonyl group, 4-n-decyloxyphenyloxycarbonyl group, 4-n-dodecyloxyphenyloxycarbonyl group, 4-n- Heki Decyloxyphenyloxycarbonyl group, 2,3-dimethoxyphenyloxycarbonyl group, 2,5-dimethoxyphenyloxycarbonyl group, 3,5-dimethoxyphenyloxycarbonyl group, 2-methoxy-4-methylphenyloxycarbonyl group, 3 -Methoxy-4-methylphenyloxycarbonyl group, 3-methyl-4-methoxyphenyloxycarbonyl group, 2-fluorophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 4-bromophenyl Oxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3,5-difluorophenyloxycarbonyl group, 3,4-dichlorophenyloxycarbonyl group, 2-methyl-4-chlorophenyloxy Carbonyl group, 3-chloro-4-methylphenyloxycarbonyl group, 3-methoxy-4-fluorophenyloxycarbonyl group, 3-fluoro-4-methoxyphenyloxycarbonyl group, 4-phenylphenyloxycarbonyl group, 3-phenyl Phenyloxycarbonyl group, 4- (4′-methylphenyl) phenyloxycarbonyl group, 4- (4′-methoxyphenyl) phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 4-methyl-1-naphthyloxycarbonyl group , 6-n-butyl-2-naphthyloxycarbonyl group, 7-ethoxy-2-naphthyloxycarbonyl group, 2-thienyloxycarbonyl group, 2-pyridyloxycarbonyl group, 4-pyridyloxycarbonyl group, etc. Phenyloxycarbonyl group, -Methylphenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 4-ethylphenyloxycarbonyl group, 4-isopropylphenyloxycarbonyl group, 4-isobutylphenyloxycarbonyl group, 4-n-pentylphenyloxycarbonyl group, 4 -N-octylphenyloxycarbonyl group, 4-n-dodecylphenyloxycarbonyl group, 2,3-dimethylphenyloxycarbonyl group, 2,5-dimethylphenyloxycarbonyl group, 3,4,5-trimethylphenyloxycarbonyl group 1,2,3,4-tetrahydro-6-naphthyloxycarbonyl group, 3-methoxyphenyloxycarbonyl group, 3-ethoxyphenyloxycarbonyl group, 4-n-propoxyphenyloxycarbonyl group, 4-n- Toxiphenyloxycarbonyl group, 2,3-dimethoxyphenyloxycarbonyl group, 3,5-dimethoxyphenyloxycarbonyl group, 2-methoxy-4-methylphenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 3-chlorophenyloxy Carbonyl group, 4-bromophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3,4-dichlorophenyloxycarbonyl group, 3-chloro-4-methylphenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 4 -Methyl-1-naphthyloxycarbonyl group is preferable, phenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 4-ethylphenyloxycarbonyl group, 4-isopropylphenyloxycarbonyl group, 4-isobutylphenyloxycarbonyl group, 2,3-dimethylphenyloxycarbonyl group, 2,5-dimethylphenyloxycarbonyl group, 3,4,5-trimethylphenyloxycarbonyl group, 3- Methoxyphenyloxycarbonyl group, 3-ethoxyphenyloxycarbonyl group, 4-n-propoxyphenyloxycarbonyl group, 4-n-butoxyphenyloxycarbonyl group, 2,3-dimethoxyphenyloxycarbonyl group, 3,5-dimethoxyphenyl Oxycarbonyl group, 2-methoxy-4-methylphenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 4-bromophenyloxycarbonyl group, 3-trifluoro B methylphenyl oxycarbonyl group, 3,4-dichlorophenyl oxycarbonyl group, 1-naphthyloxycarbonyl group, 4-methyl-1-naphthyloxycarbonyl group is more preferable.
Specific examples of the azo compound of the general formula (4) are shown in Table 2 below, but are not limited to these ranges.

In the quinophthalone compound of the general formula (5), R _{33 to} R ₄₁ are substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted aryloxyalkyls. Adjacent to each other selected from a group, a substituted or unsubstituted aralkyloxy group, a substituted or unsubstituted aralkyloxyalkyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted arylthio group, and R _{38 to} R ₄₁ When a substituted or unsubstituted 5-membered ring or more formed with a carbon atom bonded to each other is substituted, the substituents are as follows: halogen atom, cyano group, nitro group, hydroxyl group, alkylthio Group, carboxyl group, alkyl group, alkenyl group, halogenoalkyl Group, an alkoxy group, halogenoalkoxy group, an alkylthio group, an alkoxyalkyl group, an amino group, an alkylamino group, dialkylamino group.
When R _{33 to} R ₄₁ are a substituted or unsubstituted amino group, a substituted or unsubstituted amide group, or a substituted or unsubstituted acyl group is substituted, the substituent is an alkyl group, substituted or unsubstituted aryl, respectively. Group, substituted or unsubstituted aralkyl group.

In the general formula (5), R _{33 to} R ₄₁ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. Halogenoalkyl group, alkoxy group having 1 to 12 carbon atoms, halogenoalkoxy group having 1 to 12 carbon atoms, alkylthio group having 1 to 12 carbon atoms, alkoxyalkyl group having 2 to 16 carbon atoms, alkoxyalkoxy having 3 to 20 carbon atoms Alkyl group, substituted or unsubstituted aryl group having 6 to 18 carbon atoms, substituted or unsubstituted amino group having 1 to 18 carbon atoms, substituted or unsubstituted amide group having 1 to 18 carbon atoms, 7 to 20 carbon atoms Substituted or unsubstituted aralkyl group, substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, substituted or unsubstituted aryloxy group having 7 to 20 carbon atoms Group, an alkyloxycarbonyl group having 2 to 13 carbon atoms, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms from 7 to 19 carbon atoms, or _R 38 _{to R 41,} And a group adjacent to each other selected from is bonded to each other, and is a substituted or unsubstituted benzene ring or naphthalene ring formed together with a substituted carbon atom.
More preferably, R _{33 to} R ₄₁ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or 1 to 1 carbon atom. An alkoxy group having 8 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, and a substituted or unsubstituted amino group having 1 to 14 carbon atoms Group, a substituted or unsubstituted amide group having 1 to 14 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 14 carbon atoms, 2 carbon atoms -9 alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group having 7 to 15 carbon atoms, substituted or unsubstituted arylthio group having 6 to 14 carbon atoms It is.

Specific examples of R _{33 to} R ₄₁ will be described below.
R _{33 to} R ₄₁ are halogen atoms, alkyl groups, halogenoalkyl groups, alkoxyalkyl groups, halogenoalkoxyalkyl groups, substituted or unsubstituted aralkyl groups, alkoxy groups, halogenoalkoxy groups, alkylthio groups, substituted or unsubstituted aryl groups. , A substituted or unsubstituted aryloxy group, or a specific example or a preferred example in which it is a substituted or unsubstituted arylthio group, R _{1 to} R ₁₄ of the tetraazaporphyrin-based compound of the general formula (1) are respectively Examples similar to those given for these substituents are given.
R _{33 to} R ₄₁ are alkenyl groups, alkoxyalkoxyalkyl groups, substituted or unsubstituted amino groups, substituted or unsubstituted amide groups, substituted or unsubstituted acyl groups, substituted or unsubstituted aryloxyalkyl groups, substituted or Specific examples and preferred examples in the case of an unsubstituted aralkyloxy group, a substituted or unsubstituted aralkyloxyalkyl group, an alkyloxycarbonyl group, and a substituted or unsubstituted aryloxycarbonyl group include those of the general formula (4). Examples similar to the examples given when R _{22 to} R ₃₂ of the azo compound are each these substituents.
Specific examples of the quinophthalone compound of the general formula (5) are shown in Table 3 below, but are not limited to these ranges.

In the anthraquinone compound of the general formula (6), R _{42 to} R ₄₉ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenoalkyl group having 1 to 12 carbon atoms, a carbon atom. An alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, and at least one of R _{42 to} R ₄₉ One is necessarily a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms.
More preferably, R _{42 to} R ₄₉ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 1 to carbon atoms. An alkylthio group having 8 carbon atoms and a substituted or unsubstituted phenylthio group having 6 to 12 carbon atoms, and at least one of R _{42 to} R ₄₉ is necessarily a substituted or unsubstituted phenylthio group having 6 to 12 carbon atoms.

Specific examples of R _{42 to} R ₄₉ will be described below.
R _{42 to} R ₄₉ are a halogen atom, an alkyl group, a halogenoalkyl group, an alkoxy group, an alkylthio group, an alkoxyalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted arylthio group. Specific examples and preferred examples in the case of the above are the same examples as those given when R _{1 to} R ₁₄ of the tetraazaporphyrin-based compound of the general formula (1) are each these substituents. .

Specific examples of the quinophthalone compound of the general formula (6) are shown in Table 4 below, but are not limited to these ranges.

Moreover, in order to cut the light of 480-490 nm vicinity, it is also preferable to use together the porphyrin type compound of the following general formula (7).


[In Formula (7), R _{50 to} R ₅₇ each independently represents an ethynyl group or an ethynyl group having a C 1-12 alkyl group as a substituent, and M ′ represents two hydrogen atoms, A monovalent metal atom, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom is shown. ]
In particular, R _{50 to} R ₅₇ are preferably an ethynyl group having a tert-butyl group, that is, a 3,3-dimethyl-1-butyne group, and M ′ is preferably Ni or Cu.

A yellow pigment such as Kayaset Yellow AG or an orange pigment such as PS Orange GG may be used in combination.
For the purpose of blocking heat rays, a near infrared absorbing dye, for example, a phthalocyanine compound of the following general formula (8) or a naphthalocyanine compound of the general formula (9) may be used in combination.

[In the formula (8), R _{58 to} R ₇₃ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxyalkyl group, substituted or An unsubstituted aryl group, or a substituted or unsubstituted aryloxy group is represented. M ₁ represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. ]

In the general formula (8), R _{58 to} R ₇₃ are preferably each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. Substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxyalkyl group having 2 to 18 carbon atoms, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or substituted or unsubstituted group having 6 to 24 carbon atoms An aryloxy group.
In the general formula (8), M ₁ is preferably Cu, Fe, Co, Pt, Pd, Mn, VO or TiO.

[In the formula (9), R _{74 to} R ₉₇ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxyalkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group. M ₂ represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. ]
In the general formula (9), R _{74 to} R ₉₇ are preferably each independently a hydrogen atom, a chlorine atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. Substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxyalkyl group having 2 to 18 carbon atoms, substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or substituted or unsubstituted group having 6 to 24 carbon atoms An aryloxy group.

In the general formula (9), M ₂ is preferably Cu, Fe, Co, Pt, Pd, Mn, VO or TiO.
When these other dyes are used in combination with the tetraazaporphyrin dimer compound represented by the general formula (1), the amount used varies depending on the purpose of use and is not particularly limited, but the tetraazaporphyrin dimer compound It is preferable that the quantity of the whole pigment | dye containing is in the compounding quantity range of resin and tetraazaporphyrin dimer compound in the resin composition prescribed | regulated previously.
That is, when the thickness of the resin molded body is 0.1 mm to 20 mm, the total amount of the tetraazaporphyrin dimer compound of the general formula (1) and other dyes is 0 with respect to the thermoplastic resin or the thermosetting resin. It is preferably 0.0001 to 0.2% by weight.
When a dye having a maximum absorption in the wavelength range of 380 to 470 nm is used in combination with the tetraazaporphyrin dimer compound of the general formula (1) for the purpose of decolorization or the like, the use ratio is as follows: Tetraazaporphyrin dimer compound: The ratio of the dye having the maximum absorption in the wavelength region of 380 to 470 nm is preferably 90:10 to 30:70, and preferably 80:20 to 40:60. Is more preferable.

[Molded body]
Below, the molded object of this invention is demonstrated.
The molded body of the present invention is formed by molding the resin composition of the present invention.
The form of the molded body may be an optical article made of a resin composition, an optical article partially containing an intermediate film or a resin composition, an intermediate film, or an optical article such as a powder or a pellet, It may be an intermediate material for film production.
In this specification, an optical article partially containing a resin composition is a state in which it is contained inside various members or films of the optical article, and is coated or pasted on the surface of the member or each layer. Including the state.
Optical articles include anti-glare lenses, sun visors, shields for helmets, interlayer films for laminated glass, anti-glare coatings or anti-glare films for display devices of information equipment, various filters, lighting equipment covers and the like, as will be described later. Illustrative optical articles can be exemplified.
The molding method varies depending on the product and the type of resin used. In the case of a resin composition using a thermoplastic resin, for example, a known method such as a compression molding method, a transfer molding method, an extrusion molding method, or an injection molding method is used. In the case of a resin composition using a molded or thermosetting resin, for example, a casting polymerization method is used.

The cast polymerization method will be described below.
The resin composition is poured into the casting mold and incorporated therein, and then the casting mold is heated in a heatable apparatus such as an oven or in water for several hours to several tens of hours with a predetermined temperature program. The polymerization curing temperature and time vary depending on the composition of the mixture, the type of catalyst, the shape of the mold, and the like, but are approximately -50 to 200 ° C. for 1 to 100 hours. In general, it is common to start at a temperature in the range of 5 ° C. to 40 ° C., then gradually raise the temperature to a range of 80 ° C. to 130 ° C. and heat at that temperature for 1 to 4 hours.
After completion of the curing and molding, the target molded product can be obtained by taking out from the casting mold.

[Anti-glare optical article]
The molded body of the resin composition of the present invention is very useful as an optical article for antiglare.
Optical articles for anti-glare include eyeglass lenses, sun visors, shields for helmets, interlayer films for laminated glass, films for windshields for automobiles and airplanes, covers for automobile headlights, ski goggles, and protective equipment for information device display devices. A dazzling coat or an antiglare film, a filter for LED lighting, and the like can be mentioned, but it can be used without limitation for the purpose of preventing glare and ensuring contrast and natural color tone.
The method for producing an antiglare optical article varies depending on the form of the article and the type of resin, and the above-described method for producing a molded article can be applied.
Depending on the function required for the antiglare optical article, one or more of an antireflection function, a hard coat function (friction resistance function), an antistatic function, an antifouling function, a gas barrier function, and an ultraviolet cut function A function may be provided.

[Glasses lens]
The case where the molded body of the resin composition of the present invention is a spectacle lens will be described below.
As an aspect of the spectacle lens, a spectacle lens wafer obtained by molding a resin composition containing the tetraazaporphyrin dimer compound represented by the general formula (1), the tetraazaporphyrin dimer compound is included in the entire spectacle lens wafer. The tetraazaporphyrin dimer compound may be localized in a depth range of 500 μm or less from at least one surface of the spectacle lens wafer.
Moreover, even if the tetraazaporphyrin dimer compound is contained only in the hard coat layer or primer layer or other component layers formed on one side or both sides of the spectacle lens wafer not containing the tetraazaporphyrin dimer compound good. When there are a plurality of component layers, at least one of them may contain a tetraazaporphyrin dimer compound.
Furthermore, a tetraazaporphyrin dimer compound may be contained in both the spectacle lens wafer and the component layer.
The resin of the resin composition differs depending on the type of eyeglass lens, the manufacturing method, or the means for containing the tetraazaporphyrin dimer compound, and may be a thermoplastic resin or a thermosetting resin.

As the thermoplastic resin, polycarbonate resin, polyamide resin, and acrylic resin are preferable, and any mixture thereof may be used.
As the thermosetting resin, polyurethane resin, polythiourethane resin, and thermosetting (meth) acrylic resin are preferable.
The content of the tetraazaporphyrin dimer compound with respect to the resin varies depending on the thickness of the resin layer containing the tetraazaporphyrin dimer compound. For example, if it is mixed with a polycarbonate resin with a spectacle lens having a thickness of 2.15 mm The amount of the tetraazaporphyrin dimer compound used is 0.001% to 0.1% by weight based on the polycarbonate resin. Generally, if the thickness of the resin layer containing the tetraazaporphyrin dimer compound is 0.1 mm to 20 mm, the content of the tetraazaporphyrin dimer compound is 0.0001 to 0.2% by weight based on the resin. Preferably, it is 0.0002% by weight to 0.05% by weight.
In addition, a component layer composed of a single layer or a multilayer stack is applied to at least one surface of the spectacle lens wafer, and at least one of the layers constituting the component layer contains a tetraazaporphyrin dimer compound. In the case of this embodiment, the concentration of the tetraazaporphyrin dimer compound in the component layer is preferably in the range of 0.02 wt% to 5 wt%.

As a method for producing the spectacle lens, for example, when the lens wafer material is a thermoplastic resin, a known method such as a compression molding method, a transfer molding method, an injection molding method, or a compression injection molding method is usually employed. When the lens wafer material is a thermosetting resin, a tetraazaporphyrin dimer compound is contained in a thermosetting resin compound (such as a monomer before curing), and the resin compound is used as a lens casting mold. The polymer is supplied and polymerized to form a spectacle lens. The polymerization method is not particularly limited, but usually cast polymerization is employed.
The spectacle lens of the present invention has functional processing that is possible within the conventional technical range, such as multi-coating (antireflection layer), anti-fogging treatment, water repellent treatment, or antistatic treatment, as necessary. May be applied.

[Interlayer film for laminated glass]
The case where the molded body of the resin composition of the present invention is an interlayer film for laminated glass will be described below.
The resin composition of the present invention is very useful as an interlayer film for laminated glass used in automobiles, railway vehicles, aircraft, ships, buildings and the like.
Laminated glass is made by interposing an interlayer film for laminated glass between at least a pair of plate glasses, and these are integrated. It is safe to reduce the amount of glass fragments scattered when damaged by external impact. It improves the performance. In such a laminated glass, in order to protect human eyes located inside from strong light such as sunlight and headlights of oncoming vehicles, there is an increasing demand for providing an antiglare property to the interlayer film for laminated glass. ing.
In the interlayer film for laminated glass using the resin composition of the present invention, a thermoplastic resin is preferably used as the resin, and as the thermoplastic resin for the interlayer film, polyvinyl alcohol resin, plasticized polyvinyl acetal resin, ethylene-vinyl acetate copolymer Examples thereof include a coalesced resin, an ethylene-acrylic copolymer resin, a polyurethane resin, and a polyurethane resin containing a sulfur element. In particular, a water-soluble polymer such as polyvinyl alcohol resin is preferable.
The content of the tetraazaporphyrin dimer compound relative to 100 parts by weight of the thermoplastic resin is preferably in the range of 0.001 to 0.15 parts by weight, and in the range of 0.005 to 0.075 parts by weight. It is more preferable that it is in the range of 0.01 to 0.05 parts by weight.

In the interlayer film for laminated glass of the present invention, the above-mentioned azo compound, quinophthalone compound, porphyrin compound and the like can be used in combination as other dyes, as long as the effects of the present invention are not disturbed. It is preferable to use a phthalocyanine compound of the general formula (8) or a naphthalocyanine compound of the general formula (9) in combination.
The interlayer film for laminated glass of the present invention further includes an ultraviolet absorber, a heat ray shielding agent, an antioxidant, an anti-aging agent, a heat stabilizer, a dimensional stabilizer, and an adhesive strength adjustment as long as the effects of the present invention are not impaired. Metal salt, silicone oil for adhesive strength adjustment, silane coupling agent for adhesive strength adjustment, anti-blocking agent, pigment, dye, colorant, light diffusing agent, light diffusing particles, antistatic agent, moisture absorption by interlayer film Inorganic fine particles effective in preventing whitening, surfactants for dispersing fine particle additives, chelating agents for trapping free metal ions, and prevention of migration of low molecular weight compounds in the interlayer film Adsorbents, plasticizers, organic solvents, additives for adjusting the polarity of plasticizers and organic solvents, tackifiers, crystal nucleating agents to prevent haze rise due to crystallization of interlayer film resins, crosslinking agents, Containing flame retardant It may be.

The heat ray shielding agent means particles capable of absorbing infrared rays having a wavelength of 780 nm or more, and includes aluminum-doped tin oxide, indium-doped tin oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and aluminum. In addition to metal oxides such as doped zinc oxide (AZO), tungsten oxide, composite tungsten oxide, and the like can be given. In particular, tin-doped indium oxide (ITO) is preferable.
As the ultraviolet absorber, benzophenone compounds, benzotriazole compounds, triazine compounds, benzoate compounds, hindered amine compounds, and the like can be used. In particular, benzophenone compounds and benzotriazole compounds are preferred.
As a method for producing an interlayer film for laminated glass, for example, a thermoplastic resin and a tetraazaporphyrin dimer compound, and, if necessary, the above-mentioned other dyes and additives are blended and mixed while arbitrarily heating. It can be obtained by forming into a sheet by tempering, press molding, injection molding, calendar molding, extrusion molding, or the like.
The interlayer film for laminated glass according to the present invention has at least one of a primer function, an ultraviolet cut function, a flame retardant function, an antireflection function, an antiglare function, an antireflection antiglare function, and an antistatic function as necessary. It is good also as a multilayer structure combined with the functional transparent layer which has a function.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
[Example 1] Production of tetraazaporphyrin dimer compound (specific example compound (1) -5) 20 g of the following compound (2) -1, 2.74 g of 4,4'-biphenol and 12.21 g of potassium carbonate were added to 400 mL of DMI. The mixture was stirred at an internal temperature of 100 ° C. for 96 hours.
After cooling, the reaction mixture was discharged into 200 mL of water, the precipitate was collected by filtration, washed with water and dried.
This crude product was purified by column chromatography (silica gel / hexane) to obtain 5.1 g of a reddish purple powder (decomposition point 388 ° C.).

The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1380 (M +)
Elemental analysis values: measured values (C: 66.23%, H: 6.31%, N: 16.03%); theoretical values (C: 66.02%, H: 6.27%, N: 16 .21%)

[Example 2] Production of tetraazaporphyrin dimer compound (specific example compound (1) -6) 2,2-bis (4-hydroxyphenyl) propane instead of 4,4'-dihydroxydiphenyl in Example 1 Synthesis and purification were carried out in the same manner as in Example 1 except that 3.36 g of (bisphenol A) was used, to obtain 6.3 g of a reddish purple powder (decomposition point 401 ° C.). The obtained compound was confirmed to be the target compound from the following analysis results.
MS: (EI) m / z 1424 (M +)
Elemental analysis values: measured values (C: 66.83%, H: 6.73%, N: 15.55%); theoretical values (C: 66.60%, H: 6.51%, N: 15) .73%)

[Example 3]
1000 parts by weight of polycarbonate resin (H-3000FN manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and 0.0148 parts by weight of Example Compound (1) -5 produced in Example 1 as a tetraazaporphyrin dimer compound After mixing for 20 minutes, the mixture was melted and kneaded into pellets by a single screw extruder under conditions of a cylinder set temperature of 260 ° C. and a screw rotation speed of 56 rpm.

[Example 4]
Pellets were produced in the same manner as in Example 3 except that 0.0148 parts by weight of the specific example compound (1) -12 was used.

[Example 5]
Pellets were produced in the same manner as in Example 3 except that 0.0148 parts by weight of the specific example compound (1) -20 was used.

[Example 6]
Pellets were produced in the same manner as in Example 3 except that 0.0148 parts by weight of the specific example compound (1) -27 was used.

[Example 7]
Pellets were produced in the same manner as in Example 3 except that 0.0148 parts by weight of the specific example compound (1) -43 was used.

[Example 8]
Pellets were produced in the same manner as in Example 3 except that 0.0148 parts by weight of the specific example compound (1) -44 was used.

[Example 9]
1000 parts by weight of a polycarbonate resin (H-3000FN manufactured by Mitsubishi Engineering Plastics) and 0.0068 parts by weight of a specific compound (1) -5 as a tetraazaporphyrin compound and a specific compound (4) as an azo compound After mixing 0.008 parts by weight of 4 with a tumbler for 20 minutes, the mixture was melted and kneaded with a single-screw extruder at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 56 rpm to be pelletized.

[Example 10]
Example 4 is the same as Example 4 except that 0.0068 parts by weight of the specific compound (1) -6 is used as the tetraazaporphyrin compound and 0.008 parts by weight of the specific compound (4) -2 is used as the azo compound. The operation was performed to produce pellets.

[Example 11]
Specific compound (1) -5 as a tetraazaporphyrin compound is 0.0068 parts by weight, specific compound (4) -13 as an azo compound is 0.006 parts by weight, and specific compound 5-21 is used as a quinophthalone compound. Pellets were produced in the same manner as in Example 4 except that 0.002 part by weight was used.

[Example 12]
Specific compound (1) -5 as a tetraazaporphyrin compound is 0.0068 parts by weight, specific compound (4) -13 is 0.006 parts by weight as an azo compound, and specific compound 5-21 is used as a quinophthalone compound. Pellets were produced in the same manner as in Example 4 except that 0.001 part by weight and 0.001 part by weight of Example 6-1 were used as an anthraquinone compound.

[Example 13] Manufacture of spectacle lens Using the pellets manufactured in Example 3 as a raw material, melting them at 250 ° C, and molding them with an injection molding machine using a predetermined mold, a plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm Got.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 14] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained in the same manner as in Example 13 except that the pellets manufactured in Example 4 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 15] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained by performing the same operation as in Example 13 except that the pellets manufactured in Example 5 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 16] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mm and a center thickness of 2 mm was obtained by performing the same operation as in Example 13 except that the pellets manufactured in Example 6 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 17] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained in the same manner as in Example 13 except that the pellets manufactured in Example 7 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 18] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained in the same manner as in Example 13 except that the pellets manufactured in Example 8 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 19] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained by performing the same operation as in Example 13 except that the pellets manufactured in Example 9 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 20] Manufacture of spectacle lens A plastic lens having an outer diameter of 75 mm and a center thickness of 2 mm was obtained by performing the same operation as in Example 13 except that the pellets manufactured in Example 10 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 21] Manufacture of spectacle lenses A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained in the same manner as in Example 13 except that the pellets manufactured in Example 11 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Example 22] Manufacture of spectacle lenses A plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm was obtained by performing the same operation as in Example 13 except that the pellets manufactured in Example 12 were used as raw materials.
Observation through the spectacles equipped with the obtained lens rarely felt dazzling even during long-term use under fine weather.

[Comparative Example 1] Manufacture of spectacle lenses 1000 parts by weight of polycarbonate resin (H-3000FN manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and 0.01148 parts by weight of the following tetraazaporphyrin compound (Comparative Example Compound (A)) After mixing for 20 minutes, the mixture was melted and kneaded into pellets by a single screw extruder under conditions of a cylinder set temperature of 260 ° C. and a screw rotation speed of 56 rpm.
This pellet was used as a raw material, melted at 250 ° C., and molded by an injection molding machine using a predetermined mold to obtain a plastic lens having an outer diameter of 75 mmφ and a center thickness of 2 mm.
In the observation through the spectacles equipped with the obtained lens, the glare was rarely felt even when used in fine weather. However, as shown in Table 5, after 2,000 W light irradiation for 2,000 hours, anti-glare was observed. The effect was reduced.
Comparative Example Compound (A): Substituent position isomer mixture of tetraazaporphyrin compound having the following structure

[Example 23] Production of interlayer film for laminated glass and laminated glass As an organic ester plasticizer, 40 parts by weight of triethylene glycol-di-2-ethylhexanoate was mixed with a tetraazaporphyrin dimer compound (specific example (1 -5) After dissolving 0.008 part by weight, this solution was added to 100 parts by weight of polyvinyl butyral resin (trade name: BH-3, manufactured by Sekisui Chemical Co., Ltd.) and sufficiently melt-kneaded with a mixing roll. The film was extruded using an extruder to obtain an interlayer film for laminated glass having a thickness of 0.76 mm.

The intermediate film is cut into a size of 100 mm × 100 mm, sandwiched between two float plate glasses (length 100 mm × width 100 mm × thickness 2.0 mm), placed in a rubber bag, and a vacuum degree of 2.6 kPa for 20 minutes. After deaeration, it was transferred into an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum pressed. Then, it pressure-bonded for 20 minutes on the conditions of the temperature of 130 degreeC, and the pressure of 1.3 MPa in the autoclave, and the sample of the laminated glass was obtained.
[Example 24] Manufacture of interlayer film for laminated glass and laminated glass The same operation as in Example 23 was performed, except that 0.008 g part by weight of the specific example compound (1) -6 was used as the tetraazaporphyrin dimer compound. An interlayer film for laminated glass and a laminated glass were produced.

[Example 25] Manufacture of interlayer film for laminated glass and laminated glass The same operation as in Example 23 was performed, except that 0.008 g part by weight of the specific example compound (1) -12 was used as the tetraazaporphyrin dimer compound. An interlayer film for laminated glass and a laminated glass were produced.

[Example 26] Manufacture of interlayer film for laminated glass and laminated glass The same operation as in Example 23 was performed, except that 0.008 g part by weight of the specific example compound (1) -20 was used as the tetraazaporphyrin dimer compound. An interlayer film for laminated glass and a laminated glass were produced.

[Example 27] Production of interlayer film for laminated glass and laminated glass The same operation as in Example 23 was performed, except that 0.008 g by weight of the specific example compound (1) -44 was used as the tetraazaporphyrin dimer compound. An interlayer film for laminated glass and a laminated glass were produced.

[Comparative Example 2] Production of interlayer film for laminated glass and laminated glass Example of tetraazaporphyrin dimer compound in Example 13 Instead of 0.008 parts by weight, the following tetraazaporphyrin compound (Comparative Example Compound (B)) An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 13 except that 0.008 part by weight was used.
Comparative Example Compound (B): Substituent Position Isomeric Mixture of Tetraazaporphyrin Compound with the Structure below

[Comparative Example 3] (Production of interlayer film for laminated glass and laminated glass)
Specific Example Compound (1) -5 of Tetraazaporphyrin Dimer Compound in Example 13 Instead of 0.008 part by weight, 0.008 part by weight of the tetraazaporphyrin compound (Comparative Example Compound (A)) was used. An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 13 except that.

[Anti-glare and light resistance test]
Through a spectacle lens using the spectacle lens manufactured in Examples 8 to 14 and Comparative Examples 1 to 3, and a laminated glass, a monitor (20 persons) was allowed to observe a car equipped with a discharge headlight for 3 minutes. When it was determined that the monitor did not feel dazzling, the following determination was made based on the number of persons who were recognized as having anti-glare properties and having anti-glare properties.
◎: 18 or more, ○: 14-17, Δ: 10-13, ×: 9 or less Next, the xenon light resistance tester (manufactured by Toyo Seiki Co., Ltd .: After irradiating with 550 W / h light for 2000 hours using Suntest XLS +), an anti-glare test was conducted in the same manner. The results are shown in Table 5 below.

Table 6 shows the amount of change in transmittance by the light resistance test. The greater the change in transmittance, the lower the light resistance. The light resistance measurement was performed as follows.
Using a xenon weathering device (ATLAS Suntest XLS + II type), the test object is a xenon lamp at a black standard temperature of 65 ° C. and a tank temperature of 45 ° C. at an irradiance of 550 W / m ² for 100 hours and 200 hours. After irradiating for 300 hours, the minimum transmittance at 550 nm to 650 nm of each sample was measured.
The transmittance change rate is expressed by the following equation.
Transmittance change rate in n hours of light resistance test = (transmittance after n hours of light resistance test−transmittance before test) / transmittance before test

The tetraazaporphyrin dimer compound of the present invention has strong absorption at 570 to 630 nm and extremely high durability such as light resistance and heat resistance. It has become possible to provide optical articles such as highly durable spectacle lenses and interlayer films for laminated glass.
Further, the tetraazaporphyrin dimer compound of the present invention is also used in a color correction filter used in a liquid crystal display device or a lighting device using a white LED composed of a blue LED element and a yellow-emitting phosphor as a light source. It can be suitably used.

Claims (13)

A tetraazaporphyrin dimer compound represented by the general formula (1).

[In the formula (1), R _{1 to} R ₁₄ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, alkylthio group, substituted or An unsubstituted aryl group, a substituted or unsubstituted aryloxy group or a substituted or unsubstituted arylthio group, X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom, and A ₁ and A ₂ are An alkylene group, a substituted or unsubstituted arylene group, Y represents an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group, a sulfonyl group, a carbonyl group, or an alkylene group, and n and p are each independently 0 Or an integer of 1 is shown. M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. ] The tetraazaporphyrin dimer compound according to claim 1, wherein M is Cu, Zn, Fe, Co, Ni, Pt, Pd, Mn, Mg, Mn (OH), Mn (OH) ₂ , VO, or TiO. . R _{1 to} R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenoalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, or 2 to 16 carbon atoms. Halogenoalkoxyalkyl group, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogenoalkoxy group having 1 to 12 carbon atoms, alkoxyalkoxy group having 2 to 16 carbon atoms, carbon An alkylthio group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms A ₁ and A ₂ are an alkylene group having 1 to 16 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, and Y is The tetraazaporphyrin 2 according to claim 1 or 2, which is an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group having 0 to 12 carbon atoms, a sulfonyl group, a carbonyl group, or an alkylene group having 1 to 16 carbon atoms. A monomeric compound. R _{1 to} R ₁₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, an unsubstituted aralkyl group having 7 to 12 carbon atoms, or 1 carbon atom. An alkoxy group having 1 to 8 carbon atoms, a halogenoalkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an aryl having a halogen atom as an unsubstituted or substituted group having 6 to 12 carbon atoms Group, an aryloxy group having 6 to 12 carbon atoms, or an arylthio group having 6 to 12 carbon atoms, and A ₁ and A ₂ are each independently an alkylene group having 1 to 12 carbon atoms, or 6 to 18 carbon atoms. An unsubstituted or substituted arylene group having an alkyl group, an alkenyl group, a halogen atom, a cyano group, or an acyl group, and Y is an oxygen atom, a sulfur atom, or a carbon number of 0 The tetraazaporphyrin according to any one of claims 1 to 3, which is an imino group having 12 alkyl groups or an aryl group as an unsubstituted or substituted group, a sulfonyl group, a carbonyl group, or an alkylene group having 1 to 12 carbon atoms. Dimer compound. R _{1 to} R ₁₄ are each independently a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms, and R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ , R ₉ and R ₁₀ , R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , one is a hydrogen atom, the other is a branched alkyl group having 1 to 8 carbon atoms, X ₁ and X ₂ are oxygen atoms, and A ₁ , _{a 2} is a phenylene group, Y is an alkylene group having 1 to 8 carbon atoms, n is 0 or 1, p is 1, M is Cu, any of claims 1 to 4 The tetraazaporphyrin dimer compound described in 1. The tetraazaporphyrin compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted in the presence of a base, according to any one of claims 1 to 5, The manufacturing method of the tetraaza porphyrin dimer compound of description.

[In the formula (2), R _{15 to} R ₂₁ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted. An alkylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted arylthio group; Z represents a halogen atom; M represents two hydrogen atoms; A valent metal atom, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom is shown. ]

[In Formula (3), X ₁ and X ₂ each independently represents an oxygen atom or a sulfur atom, A ₁ and A ₂ represent an alkylene group, or a substituted or unsubstituted arylene group, and Y represents an oxygen atom. , A sulfur atom, a substituted or unsubstituted imino group, a sulfonyl group, a carbonyl group, or an alkylene group, and n and p each independently represent an integer of 0 or 1. ] A resin composition comprising at least the tetraazaporphyrin dimer compound according to claim 1 and a thermoplastic resin or a thermosetting resin. The thermoplastic resin is at least one selected from polycarbonate resin, polyamide resin, acrylic resin, polyester resin and polyvinyl acetal resin, and the thermosetting resin is at least selected from polyurethane resin, polythiourethane resin and allyl diglycol carbonate resin. The resin composition of Claim 7 which is 1 type. Furthermore, it contains at least one selected from an azo compound represented by the general formula (4), a quinophthalone compound represented by the general formula (5), and an anthraquinone compound represented by the general formula (6). The resin composition according to claim 7 or 8, characterized in that

[In the formula (4), R _{22 to} R ₃₂ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, a halogenoalkyl group, an alkoxy group, or a halogenoalkoxy group. Alkylthio group, alkoxyalkyl group, alkoxyalkoxyalkyl group, halogenoalkoxyalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, Substituted or unsubstituted acyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkyloxyalkyl group, alkyloxycarbonyl group , Replacement or Substituted aryloxycarbonyl group or a substituted or unsubstituted arylthio group. ]

[In the formula (5), R _{33 to} R ₄₁ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, a halogenoalkyl group, an alkoxy group, or a halogenoalkoxy group. Alkylthio group, alkoxyalkyl group, alkoxyalkoxyalkyl group, halogenoalkoxyalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted amino group, substituted or unsubstituted amide group, Substituted or unsubstituted acyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryloxyalkyl group, substituted or unsubstituted aralkyloxy group, substituted or unsubstituted aralkyloxyalkyl group, alkyloxycarbonyl group , Substituted or unsubstituted Of the aryloxycarbonyl group, or a substituted or unsubstituted arylthio group, and adjacent groups selected from R _{38 to} R ₄₁ are bonded to each other, and together with the substituted carbon atom, a substituted or unsubstituted 5-membered member You may form the ring more than a ring. ]

[In the formula (6), R _{42 to} R ₄₉ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogenoalkyl group, an alkoxy group, an alkylthio group, an alkoxyalkyl group, a substituted or unsubstituted aryl group, a substituted or An unsubstituted aralkyl group or a substituted or unsubstituted arylthio group is shown. However, at least one of R _{42 to} R ₄₉ is necessarily a substituted or unsubstituted arylthio group. ] The molded object formed by shape | molding the resin composition in any one of Claims 7-9. The molded article according to claim 10, which is an antiglare optical article. The molded article according to claim 10 or 11, which is a spectacle lens. The molded article according to claim 10 or 11, which is an interlayer film for laminated glass.