WO2022168754A1 - Compound - Google Patents

Abstract

A compound having an anion represented by formula (I) [wherein ring W1 represents an optionally substituted ring; ring W2 represents a ring having at least one double bond as a ring-constituent element and the ring W2 may have a substituent; R1 and R2 each independently represent a hydrogen atom or a monovalent substituent and R1 and/or R2 has a monovalent substituent; R3, R4, R5, and R6 each independently represent a hydrogen atom or a monovalent substituent; R1 and R4 may be bonded to each other to form a ring; R3 and R4 may be bonded to each other to form a ring; R2 and R6 may be bonded to each other to form a ring; and R5 and R6 may be bonded to each other to form a ring].

Description

Compound

The present invention relates to compounds.

Dye compounds that absorb visible light are used in textiles, inks, paints, containers, packaging materials, printed matter, optical goods, eyeglasses, display devices, etc., for the purpose of coloring objects and transmitting or absorbing light of specific wavelengths. Used for a wide range of purposes. Important properties of dye compounds include selective absorption (sharpness of absorption spectrum) and durability (especially lightfastness). Among dye compounds, cyanine dyes can control a wide range of wavelengths exhibiting maximum absorption from the ultraviolet region with a wavelength of 380 nm or less to the near-infrared region with a wavelength of 780 nm or more by controlling the number of methine carbon atoms in the polymethine skeleton. Many of the cyanine dyes have been widely used because they exhibit relatively high selective absorption (for example, US Pat. No. 6,004,536 (Patent Document 1)).

U.S. Pat. No. 6,004,536

However, although cyanine dyes have high selective absorption, many of them are inferior in durability (especially light resistance), and there has been a demand for a compound that has both high selective absorption and durability.

The present invention includes the following inventions.
[1] A compound having an anion represented by the following formula (I).

[In formula (I), ring W ¹ represents a ring optionally having a substituent.
Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
R ¹ and R ⁴ may be linked together to form a ring.
R ³ and R ⁴ may be linked together to form a ring.
R ² and R ⁶ may be linked together to form a ring.
^R5 and ^R6 may be linked together to form a ring. ]
[2] The compound according to [1], wherein at least one selected from R ¹ and R ² is an electron-withdrawing group.
[3] at least one selected from R ¹ and R ² is a cyano group, a nitro group, a halogenated alkyl group, a halogenated aryl group, -CO-R ₁ , -CO-OR ₂ , -CO-NR ₃ R _3z , —CO—S—R ₄ , —CS—R ₅ , —CS—OR ₆ , —CS—S—R ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent an optionally substituted hydrocarbon group or halogen atom.) , -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₂ H or -SO ₃ H.
[4] The compound according to any one of [1] to [3], wherein at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is an electron-withdrawing group.
[5] The compound according to any one of [1] to [4], wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an electron-withdrawing group.
[6] at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is a cyano group, a nitro group, a halogenated alkyl group, a halogenated aryl group, —CO—R ₁ , —CO—OR ₂ , —CO—NR ₃ R _3z , —CO—SR ₄ , —CS—R ₅ , —CS—OR ₆ , —CS—SR ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently a hydrocarbon group optionally having a substituent or represents a halogen atom.), -OCF _{3 , -SCF 3 ,} -SF ₅ , -SF ₃ , -SO ₂ H or -SO ₃ H.
[7] The compound according to any one of [1] to [6], which exhibits a maximum absorption between wavelengths of 400 nm and 700 nm.
[8] The compound according to any one of [1] to [7], which has a gram extinction coefficient of 50 [L/(g·cm)] or more at the maximum absorption wavelength.
[9] A resin composition comprising the compound according to any one of [1] to [8] and a resin.
[10] A composition comprising the compound according to any one of [1] to [8] and a polymerizable monomer.
[11] A molded article molded from the resin composition described in [9] or the composition described in [10].
[12] An optical layer comprising the resin composition described in [9] or the composition described in [10].
[13] An optical laminate comprising the optical layer of [12].
[14] An image display device comprising the optical layered body according to [13].
[15] Formula (MA)

[In formula (MA), ring W ¹ represents a ring optionally having a substituent.
Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent.
R ¹ and R ⁴ may be linked together to form a ring.
R ³ and R ⁴ may be linked together to form a ring. ]
A compound represented by the formula (b-3)

[In formula (b-3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
X2 represents a _divalent linking group. ]
Formula (I) comprising the step of reacting with a compound represented by

[In the formula, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each have the same meaning as above. ]
A method for producing a compound having an anion represented by
[16] Furthermore, in the presence of a catalyst, formula (M)

[In the formula, ring W ¹ , ring W ² , R ¹ and R ² each have the same meaning as above. ]
A compound represented by the formula (b-2)

[In the formula, R ³ and R ⁴ each have the same meaning as above.
X ₁ represents a divalent linking group. ]
The production method according to [15], which comprises the step of obtaining a compound represented by formula (MA) by reacting with a compound represented by.
[17] Formula (M1-2)

[In formula (M1-2), R ^2′ represents a monovalent substituent, and E ₁ represents a leaving group. ]
A compound represented by and the formula (M1-3)

[In formula (M1-3), R ^1′ represents a monovalent substituent, and E ₂ represents a leaving group. ]
At least one compound selected from compounds represented by the formula (M1-1)

[In formula (M1-1), ring W ¹ represents a ring optionally having a substituent.
Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
R ³ and R ⁴ may be linked together to form a ring.
^R5 and ^R6 may be linked together to form a ring. ]
Formula (I) by reacting with a compound having an anion represented by

[In the formula, ring W ¹ , ring W ² , R ³ , R ⁴ , R ⁵ and R ⁶ each have the same meaning as above.
R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent. ]
A method for producing a compound having an anion represented by
[18] A compound represented by the formula (M).

[In formula (M), ring W ¹ represents a ring optionally having a substituent.
Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent. ]
[19] A compound represented by formula (MA).

[In formula (MA), ring W ¹ represents a ring optionally having a substituent.
Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent.
R ¹ and R ⁴ may be linked together to form a ring.
R ³ and R ⁴ may be linked together to form a ring. ]

The present invention provides a novel compound that exhibits good selective absorption of light near the maximum absorption wavelength in the visible light region (wavelength 400 nm to 750 nm, preferably wavelength 450 to 600 nm) and has good light resistance. intended to

The compound of the present invention is a compound having an anion represented by formula (I) (hereinafter sometimes referred to as compound (I)).

[In formula (I), ring W ¹ represents a ring optionally having a substituent.
Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
R ¹ and R ⁴ may be linked together to form a ring.
R ³ and R ⁴ may be linked together to form a ring.
R ² and R ⁶ may be linked together to form a ring.
^R5 and ^R6 may be linked together to form a ring. ]

<Anion>
The anions represented by formula (I) also include all resonance structures shown below.

In addition, depending on the type of monovalent substituents represented by R ³ , R ⁴ , R ⁵ and R ⁶ , there are cases where electron delocalization extends to R ³ , R ⁴ , R ⁵ and R ⁶ . do. For example, when the electron delocalization extends to the monovalent substituents represented by R ³ , R ⁴ , R ⁵ and R ⁶ as shown below, the resonance structure is also represented by the formula (I ) is included in the anion represented by

^The ring structure of ring W1 is not particularly limited. Ring W1 may be ^a monocyclic ring or a condensed ring.
Ring W ¹ may be a heterocyclic ring containing a heteroatom (e.g., an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a ring constituent, or a hydrocarbon ring consisting of a carbon atom and a hydrogen atom. good too. Ring W ¹ is preferably a hydrocarbon ring. Ring W1 may be ^a ring having no aromaticity (aliphatic ring) or may be an aromatic ring, but is preferably an aliphatic ring. A ring having no aromaticity can further enhance the selective absorption.
Ring W ¹ preferably has a 3- to 20-membered ring structure, more preferably a 3- to 12-membered ring, and preferably a 4- to 6-membered ring.
Ring W ¹ is preferably monocyclic.

Ring W2 represents a ring structure having at least one ^double bond as a ring constituent. Ring W ² has one or more double bonds as a constituent element of the ring, and the number of double bonds contained in ring W ² is usually 1 to 4, preferably 1 to 3, and 1 or 2. is more preferred, and one is even more preferred.
Ring ^W2 may be monocyclic or polycyclic. Ring W2 may be an aromatic ring or a non ^- aromatic ring (aliphatic ring), but is preferably a non-aromatic ring. A ring having no aromaticity can further enhance the selective absorption.
Ring W2 may be a heterocyclic ring containing a heteroatom ⁽ for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) or a ring composed of hydrocarbon. Ring ^W2 is preferably a hydrocarbon ring.
Ring W ² preferably has a 3- to 20-membered ring structure, more preferably a 3- to 12-membered ring, and preferably a 4- to 6-membered ring.

Ring ^W1 and ring W2 form ^a condensed ring. The condensed ring formed by ring W ¹ and ring W ² is preferably a condensed ring of aliphatic hydrocarbon, more preferably a condensed ring of aliphatic hydrocarbon having 6 to 40 carbon atoms.
Examples of the condensed ring formed by ring W ¹ and ring W ² include rings represented by formulas (W ¹ -1) to (W ¹ -19) described below. ^In addition, the condensed ring formed by ring W1 and ring W2 includes ^all of the above structures in which the anionic charge is delocalized.

Ring W ¹ and ring W ² may each independently have a substituent. The substituents include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; methyl, ethyl, propyl, normal butyl, isobutyl, tertiary butyl, pentyl, hexyl and heptyl. group, octyl group, nonyl group, decyl group, 2-ethylhexyl group, 4-butyloctyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, ethynyl group, propynyl group, allyl group, cyclohexenyl group, butadienyl aliphatic hydrocarbon groups having 1 to 25 carbon atoms (preferably alkyl groups having 1 to 12 carbon atoms) such as groups; fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2- Carbon such as difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, nonafluorobutyl group Halogenated alkyl groups of numbers 1 to 25; methoxy, ethoxy, propoxy, isopropoxy, butoxy, tertiary butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, 4-butyloctyloxy alkoxy groups having 1 to 25 carbon atoms such as groups; alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, propylthio, butylthio, pentylthio, and hexylthio groups; fluorinated alkoxy groups having 1 to 12 carbon atoms such as fluoromethoxy group, 2-fluoroethoxy group, 1,1,2,2,2-pentafluoroethoxy group and hexafluoroisopropoxy group; trifluoromethanethioalkoxy group and the like; fluorinated alkoxy group having 1 to 12 carbon atoms; amino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, diphenylamino group, piperidino group, pyrrolidino group, methylethylamino group, etc. or Amino group optionally substituted with two hydrocarbon groups having 1 to 25 carbon atoms; alkyl having 1 to 6 carbon atoms at N-position such as carbamoyl group, N-methylcarbamoyl group, N,N-dimethylcarbamoyl group a carbamoyl group optionally substituted with a group; an alkylcarbonyloxy group having 2 to 12 carbon atoms such as a methylcarbonyloxy group and an ethylcarbonyloxy group; an alkylsulfonyl group having 1 to 12 carbon atoms such as a methylsulfonyl group and an ethylsulfonyl group Group; carbon such as phenyl group, naphthyl group, biphenyl group, anthracenyl group Aromatic hydrocarbon groups having a prime number of 6 to 25 (preferably aryl groups having 6 to 18 hydrocarbons); Arylsulfonyl groups having a carbon number of 6 to 12 such as a phenylsulfonyl group; C1 groups such as a methoxysulfonyl group and an ethoxysulfonyl group Alkoxysulfonyl groups of ~12; fluoroalkylsulfonyl groups having 1 to 12 carbon atoms such as trifluoromethylsulfonyl group, pentafluoroethylsulfonyl group and trifluoroethylsulfonyl group; 2 to 12 carbon atoms such as acetyl group and ethylcarbonyl group Acyl group; aldehyde group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, alkoxycarbonyl group having 2 to 12 carbon atoms such as butyloxycarbonyl group; methoxythiocarbonyl group, 2 to 2 carbon atoms such as ethoxythiocarbonyl group nitro group; hydroxyl group; thiol group; _sulfo group; _carbamoyl group; carboxyl group;
^The condensed ring formed from ring W1 and ring W2 may also have ^a substituent, and examples of the substituent include the substituent that ring ^W1 or ring ^W2 may have.

R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one selected from R ¹ and R ² is a monovalent substituent.
The monovalent substituents represented by R ¹ and R ² are not particularly limited as long as they are not hydrogen atoms, and examples include monovalent aliphatic hydrocarbon groups, monovalent aromatic hydrocarbon groups, electron-withdrawing group, an electron-donating group, a heterocyclic group, a group having a polyoxyalkylene group, and the like.

The monovalent aliphatic hydrocarbon groups represented by R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, n -pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, undecyl group, Linear or branched alkyl groups having 1 to 25 carbon atoms such as lauryl group, myristyl group, cetyl group, stearyl group, 2-ethylhexyl group, 4-butyloctyl group: cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl cycloalkyl groups having 3 to 25 carbon atoms such as groups; cycloalkylalkyl groups having 4 to 25 carbon atoms such as cyclohexylmethyl groups; alkylcycloalkyl groups having 4 to 25 carbon atoms such as isobornyl groups; butenyl group, pentenyl group, ethynyl group, propynyl group, allyl group, cyclohexenyl group, butadienyl group, and other unsaturated aliphatic hydrocarbon groups. A linear or branched alkyl group having 1 to 12 carbon atoms is preferred.

Examples of monovalent aromatic hydrocarbon groups represented by R ¹ and R ² include phenyl, naphthyl, anthracenyl, tetracenyl, pentacenyl, phenanthryl, chrysenyl, triphenylenyl, tetraphenyl, and pyrenyl groups. , a perylenyl group, a coronenyl group, an aryl group having 6 to 18 carbon atoms such as a biphenyl group; an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, a phenylethyl group and a naphthylmethyl group; Examples thereof include arylalkoxy groups of polyalkylene glycol groups, and the like, preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group or a benzyl group.

Electron donating groups represented by R ¹ and R ² include hydroxyl group; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group; an alkoxy group having 1 to 25 carbon atoms such as a 4-butyloctyloxy group; an alkylthio group having 1 to 12 carbon atoms such as a methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group and hexylthio group; Examples include amino groups optionally substituted with one or two alkyl groups having 1 to 6 carbon atoms such as monomethylamino group, monoethylamino group, dimethylamino group, diethylamino group and methylethylamino group.

Examples of the heterocyclic group represented by R ¹ and R ² include a pyrrolidine ring group, a piperidine ring group, a pyrroline ring group, an imidazolidine ring group, an imidazoline ring group, an oxazoline ring group, a thiazoline ring group, a piperidine ring group, and a morpholine ring. C4-C20 aliphatic heterocycles such as group, piperazine ring group, indole ring group, isoindole ring group, quinoline ring group, thiophene ring group, pyrrole ring group, thiazoline ring group, furan ring group, tetrahydrofuran ring group, etc. groups, aromatic heterocyclic groups having 3 to 20 carbon atoms, and the like.

Groups having a polyoxyalkylene group represented by R ¹ and R ² include groups having an oxyethylene group (--CH ₂ CH ₂ O--), an oxypropyl group (--CH ₂ CH ₂ CH ₂ O--), and the like. is. More specifically, a group represented by —(X ¹¹ O)m—R ¹¹ (X ¹¹ represents an alkylene group having 1 to 6 carbon atoms, R ¹¹ may have a represents an alkyl group of 1 to 6, and m represents an integer of 1 to 6.) and the like.

Electron-withdrawing groups represented by R ¹ and R ² include, for example, a halogen atom, a nitro group, a cyano group, a carboxy group, a halogenated alkyl group, a halogenated aryl group, -OCF ₃ , -SCF ₃ , - Examples include SF ₅ , —SF ₃ , —SO ₃ H, —SO ₂ H, and groups represented by formula (z-1).

[In the formula (z-1), R ²²² represents a group having a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, or a polyoxyalkylene group.
X ¹ represents -CO-, -COO-, -OCO-, -CS-, -CSS-, -COS-, -CSO-, -SO ₂ -, -NR ²²³ CO- or -CONR ²²⁴ -.
R ²²³ and R ²²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
* represents a bond. ]

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Halogenated alkyl groups include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, and dichloromethyl. halogenated alkyl groups having 1 to 25 carbon atoms such as groups, bromomethyl groups and iodomethyl groups. A halogenated alkyl group having 1 to 12 carbon atoms is preferred, a fluoroalkyl group having 1 to 12 carbon atoms is more preferred, and a perfluoroalkyl group having 1 to 12 carbon atoms is even more preferred.
Examples of the halogenated aryl group include halogenated aryl groups having 6 to 18 carbon atoms such as a fluorophenyl group, a chlorophenyl group, and a bromophenyl group. It is more preferably a perfluoroaryl group of 6 to 12, more preferably a pentafluorophenyl group.

X ¹ is preferably -CO-, -COO- or -SO ₂ -.
Halogen atoms represented by R ²²² include fluorine, chlorine, bromine and iodine atoms.
The hydrocarbon group represented by R ²²² includes an aliphatic hydrocarbon group having 1 to 25 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms.
Examples of aliphatic hydrocarbon groups having 1 to 25 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, n- Hexyl group, 1-methylbutyl group, 3-methylbutyl group, n-octyl group, n-decyl, 2-hexyloctyl group, 4-butyloctyl group, cyclohexyl group, etc. Straight chain, branched chain, cyclic carbon number 1 to 25 alkyl groups; unsaturated aliphatic hydrocarbon groups such as ethenyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, allyl, cyclohexenyl, and butadienyl groups; An alkyl group having 1 to 12 carbon atoms is preferred.
Aromatic hydrocarbon groups having 6 to 18 carbon atoms include aryl groups having 6 to 18 carbon atoms such as phenyl group, naphthyl group, anthracenyl group and biphenyl group; 7 to 18 aralkyl groups and the like.
Substituents which the hydrocarbon group represented by R ²²² may have include halogen atoms, hydroxy groups, alkoxy groups, thioalkyl groups, dialkylamino groups and the like.
The group having a polyoxyalkylene group represented by R ²²² includes the same groups as those having a polyoxyalkylene group represented by R ¹ .

Examples of alkyl groups having 1 to 6 carbon atoms represented by R ²²³ and R ²²⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, sec-butyl group, n linear or branched alkyl groups having 1 to 6 carbon atoms such as -pentyl group, n-hexyl group and 1-methylbutyl group.

The group represented by formula (z-1) includes -CO-R ₁ , -CO-OR ₂ , -CO-NR ₃ R _3z , -CO-S-R ₄ , -CS-R ₅ , - CS—O—R ₆ , —CS—S—R ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent an optionally substituted hydrocarbon group or halogen atom.) is preferably
-CO-R ₁ , -CO-OR ₂ , -SO ₂ -R ₉ are more preferred,
more preferably —SO ₂ —R ₉ ,
—SO ₂ —R ₁₀ (R ₁₀ is an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms), —SO ₂ CF ₃ , —SO ₂ CHF ₂ , —SO ₂ CH ₂ F is even more preferred.

At least one selected from R ¹ and R ² is preferably an electron-withdrawing group such as a cyano group, a nitro group, a halogenated alkyl group, a halogenated aryl group, -SCF ₃ , -SF ₅ , -SF. ₃ , —SO ₃ H, —SO ₂ H, —CO—R ₁ , —CO—OR ₂ , —CO—NR ₃ R _3z , —CO—SR ₄ , —CS—R ₅ , —CS —OR ₆ , —CS—SR ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent an optionally substituted hydrocarbon group or a halogen atom.), -OCF ₃ or -SCF ₃ are more preferred,
cyano group, nitro group, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , -SO ₂ - more preferably R ₉ ,
more preferably a cyano group, a nitro group, -OCF ₃ , -SCF ₃ , -SF ₅ , -SO ₂ CF ₃ , -SO ₂ -R ₁₀ ,
A cyano group or a nitro group is more particularly preferred.

The monovalent substituents represented by R ³ , R ⁴ , R ⁵ and R ⁶ are the same as the monovalent substituents represented by R ¹ .
At least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an electron-withdrawing group,
cyano group, nitro group, halogenated alkyl group, halogenated aryl group, -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , —CO—NR ₃ R _3z , —CO—S—R ₄ , —CS—R ₅ , —CS—OR ₆ , —CS—S—R ₇ , —SO—R ₈ , —SO ₂ — R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently an optionally substituted hydrocarbon group or represents a halogen atom.), -OCF ₃ or -SCF ₃ is more preferred,
cyano group, nitro group, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , -SO ₂ - more preferably R ₉ ,
more preferably a cyano group, a nitro group, -OCF ₃ , -SCF ₃ , -SF ₅ , -SO ₂ CF ₃ , -SO ₂ -R ₁₀ ,
A cyano group or a nitro group is more particularly preferred.

Preferably, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an electron-withdrawing group.
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a cyano group, a nitro group, a halogenated alkyl group, a halogenated aryl group, -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H , —SO ₂ H, —CO—R ₁ , —CO—OR ₂ , —CO—NR ₃ R _3z , —CO—S—R ₄ , —CS—R ₅ , —CS—OR ₆ , —CS—S—R ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represents an optionally substituted hydrocarbon group or halogen atom.), -OCF ₃ or -SCF ₃ is more preferred,
cyano group, nitro group, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , -SO ₂ - more preferably R ₉ ,
more preferably a cyano group, a nitro group, -OCF ₃ , -SCF ₃ , -SF ₅ , -SO ₂ CF ₃ , -SO ₂ -R ₁₀ ,
A cyano group or a nitro group is more particularly preferred.

R ¹ and R ⁴ may be linked together to form a ring. The ring formed by connecting R ¹ and R ⁴ together forms at least three or more condensed rings with the ring formed by connecting R ¹ and R ⁴ together, ring W ¹ and ring W ² . The anion represented by the formula (I) having a ring formed by connecting R ¹ and R ⁴ together and a condensed ring formed by ring W ¹ and ring W ² are, for example, the anions described below. mentioned.

The anion represented by formula (I) having a ring formed by connecting R ¹ and R ⁴ together and a condensed ring formed by ring W ¹ and ring W ² is represented by formula (I-W2), formula It is preferably an anion represented by (I-W3), formula (I-W4), formula (I-W5), formula (I-W6), formula (I-W7) or formula (I-W14). .
The ring formed by combining R ¹ and R ⁴ may have a substituent. Examples of the substituent include the same substituents as the substituents ring W ¹ and ring W ² may have.

R ² and R ⁶ may be linked together to form a ring. The ring formed by connecting R ² and R ⁶ to each other forms at least 3 or more condensed rings with ring W ¹ and ring W ² formed by connecting R ² and R ⁶ to each other. The anion represented by formula (1) having a ring formed by connecting R ² and R ⁶ together and a condensed ring formed by ring W ¹ and ring W ² are, for example, the anions described below. mentioned.

The anion represented by formula (I) having a ring formed by connecting R ² and R ⁶ together and a condensed ring formed by ring W ¹ and ring W ² is represented by formula (I-w2), formula It is preferably an anion represented by (I-w3), formula (I-w4), formula (I-w5), formula (I-w6), formula (I-w7) or formula (I-w14). .
The ring formed by combining R ² and R ⁶ may have a substituent. Examples of the substituent include the same substituents as the substituents ring W ¹ and ring W ² may have.

R ³ and R ⁴ may be linked together to form a ring. The ring formed by combining R ³ and R ⁴ may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. The ring formed by combining R ³ and ⁴² may contain a heteroatom (nitrogen atom, oxygen atom, sulfur atom) or the like as a ring constituent.
The ring formed by combining R ³ and R ⁴ is usually a 3- to 10-membered ring, preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring.

Examples of the ring formed by combining R ³ and R ⁴ include the rings described below. * in the rings described below represents ^a bond with ring W1.

The ring formed by combining R ³ and R ⁴ is represented by formula (w-1), formula (w-4), formula (w-5), formula (w-6), and formula (w-8). , formula (w-9), formula (w-10), formula (w-11), formula (w-13), formula (w-31), formula (w-32), formula (w-35), A ring represented by formula (w-36), formula (w-37), formula (w-45), formula (w-47) or formula (w-48) is preferred.

Examples of the ring formed by connecting R ⁵ and R ⁶ to each other include the same rings as the ring formed by connecting R ³ and R ⁴ to each other. The ring formed by connecting R ⁵ and R ⁶ together is represented by formula (w-1), formula (w-4), formula (w-5), formula (w-6), and formula (w-8). , formula (w-9), formula (w-10), formula (w-11), formula (w-13), formula (w-31), formula (w-32), formula (w-35), A ring represented by formula (w-36), formula (w-37), formula (w-45), formula (w-47) or formula (w-48) is preferred.

More preferably, the anion represented by formula (I) is an anion represented by formula (IA).

[In formula (IA), R ¹ to R ⁶ each independently have the same meaning as above. ]

The anions represented by formula (I) include, for example, the anions described below. Me in the formula represents a methyl group.

<Cation>
The compound of the present invention is composed of an anion represented by formula (I) and a cation that forms a pair. In the compound of the present invention, the combination of the anion and cation represented by formula (I) is not limited.
The cation may be an organic cation or an inorganic cation.

Organic cations include N-methylpyridinium, N-ethylpyridinium, N-propylpyridinium, N-ethyl-2-methylpyridinium, N-ethyl-3-methylpyridinium, 1-ethyl-3-(hydroxymethyl)pyridinium, N-butylpyridinium, N-butyl-4-methylpyridinium, N-butyl-3-methylpyridinium, N-hexylpyridinium, N-octylpyridinium, N-octyl-4-methylpyridinium, 1,1′-dimethyl-4 ,4′-bipyridinium, 1,1′-dibenzyl-4,4′-bipyridinium and the like pyridinium cations;
piperidinium cations such as 1-butyl-1-methylpiperidinium, 1-methyl-1-propylpiperidinium;
1-allyl-1-methylpyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-(2-methoxy pyrrolidinium cations such as ethyl)-1-methylpyrrolidinium, 1-methyl-1-n-octylpyrrolidinium, 1-methyl-1-pentylpyrrolidinium;
Cations having a pyrroline skeleton such as 2-methyl-1-pyrrolinium;
1-butyl-2,3-dimethylimidazolium, 3,3′-(butane-1,4-diyl)bis(1-vinyl-3-imidazolium), 1-benzyl-3-methylimidazolium, 1, 3-dimethylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 3-ethyl-1-vinylimidazolium, 3-ethyl-1-vinylimidazolium, 1-methyl-3-(4-sulfobutyl)imidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3- imidazolium cations such as methylimidazolium;
amyltriethylammonium, butyltrimethylammonium, benzyl(ethyl)dimethylammonium, cyclohexyltrimethylammonium, diethyl(methyl)propylammonium, diethyl(2-methoxyethyl)methylammonium, ethyl(2-methoxyethyl)dimethylammonium, ethyl(dimethyl) ammonium cations such as (2-phenylethyl)ammonium, methyltri-n-octylammonium, tetrabutylammonium, tetrahexylammonium, tetrapentylammonium, tetra-n-octylammonium, tetraheptylammonium, tetrapropylammonium;
trialkylsulfonium cations such as trimethylsulfonium, tributylsulfonium, triethylsulfonium;
tributylhexadecylphosphonium, tributylmethylphosphonium, tributyl-n-octylphosphonium, tributyl-n-octylphosphonium, tetra-n-octylphosphonium, tributyl(2-methoxyethyl)phosphonium, tributylmethylphosphonium, trihexyl(tetradecyl)phosphonium, trihexyl Phosphonium cations such as (tetradecyl)phosphonium;
morpholinium cations such as 4-ethyl-4-methylmorpholinium;
and triarylmethane cations such as triphenylmethylium.

Examples of inorganic cations include alkali metal ions such as lithium ions, sodium ions, potassium ions, rubidium ions and cesium ions; monovalent metal ions such as copper (I) ions and silver ions; beryllium ions, magnesium ions, calcium ions; Alkaline earth metal ions such as strontium ions and barium ions; Metal ions; trivalent metal ions such as cobalt (III) ions, iron (III) ions, chromium (III) ions, scandium ions, yttrium ions, ruthenium (III) ions, gallium ions; titanium ions, zirconium ions, hafnium Tetravalent metal ions such as ions, germanium (IV) ions, molybdenum (IV) ions; NH4 ⁺ and the like.

Cations include alkali metal ions, alkaline earth metal ions, copper(I) ions, copper(II) ions, nickel ions, cobalt(III) ions, iron(II) ions, iron(III) ions, palladium ions and organic Cations are preferred, potassium ions, calcium ions, barium ions, magnesium ions, copper(I) ions, copper(II) ions, nickel ions and organic cations are more preferred, potassium ions and organic cations. is more preferred.

Compound (I) is preferably a compound represented by formula (IA), although the combination of the anion and cation represented by formula (I) is not limited.

[wherein W ¹ , W ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each have the same meaning as above.
g represents an integer of 1 to 4;
G represents a monovalent cation, divalent cation, trivalent cation or tetravalent cation. ]

The molecular weight of compound (I) is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. Also, it is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

The compound (I) preferably exhibits maximum absorption at a wavelength of 450 nm to 650 nm.

The gram extinction coefficient ε at the maximum absorption wavelength (λmax) of compound (I) is preferably 50 [L/(g cm)] or more, more preferably 100 [L/(g cm)] or more, especially It is preferably 150 [L/(g·cm)] or more. Although the upper limit is not particularly limited, it is generally 100000 [L/(g·cm)] or less.
When the gram extinction coefficient ε at λmax of compound (I) is 50 [L/(g·cm)] or more, it is preferable from the viewpoint of efficiently absorbing light near the maximum absorption wavelength.

The full width at half maximum of compound (I) is preferably 45 nm or less, more preferably 40 nm, even more preferably 35 nm, and particularly preferably 30 nm or less. The full width at half maximum can be measured by the method described in Examples.

Compound (I) includes, for example, the compounds shown in Tables 1 to 6 below. Compound (1) has an anion represented by formula (I-1) and a lithium ion, and has the structure shown below.

Compound (I) includes compound (1) to compound (3), compound (6) to compound (11), compound (14) to compound (16), compound (18), compound (19), compound (21). , compound (24) to compound (30), compound (32), compound (35) to compound (38), compound (41), compound (44), compound (47), compound (50), compound (52) ~ compound (55), compound (57), compound (59), compound (61), compound (63), compound (65), compound (67), compound (70), compound (72), compound (74) , compound (76), compound (78), compound (80), compound (81), compound (83), compound (86) to compound (88), compound (95), compound (96), compound (107) , compound (108), compound (110) to compound (112), compound (114) to compound (121), compound (123) to compound (129), compound (132), compound (133), compound (135) ~ compound (138), compound (140) ~ compound (143), compound (145) ~ compound (147), compound (149) ~ compound (155), compound (158), compound (159), compound (161) ~ compound (164), compound (166) ~ compound (169), compound (171) ~ compound (173), compound (175), compound (176), compound (179) ~ compound (181), compound (184) , compound (185), compound (187) to compound (189), compound (191), compound (193) to compound (198).

<Method (1) for producing compound (I)>
Compound (I) is, for example, a compound represented by formula (M1-2) (hereinafter sometimes referred to as compound (M1-2)) and a compound represented by formula (M1-3) (hereinafter referred to as compound ( M1-3).) and a compound having an anion represented by formula (M1-1) (hereinafter sometimes referred to as compound (M1-1)). It can be obtained by reacting.

[In formula (M1-1), ring W ¹ , ring W ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as above.
In formula (M1-2), R ^2' represents a monovalent substituent, and E ₁ represents a leaving group.
In formula (M1-3), R ^1′ represents a monovalent substituent, and E ₂ represents a leaving group. ]

The monovalent substituent represented by R ^2′ includes the same monovalent substituents as those represented by R ² .
The monovalent substituent represented by R ^1′ is the same as the monovalent substituent represented by R ¹ .
The leaving groups represented by E ₁ and E ₂ each independently include a halogen atom, a succinimide group, a maleimide group, an o-sulfobenzimide group, a methylsulfonyl group, a p-methoxybenzenesulfonyl group, and p-toluene. sulfonyl group, trifluoromethylsulfonyl group, nonafluorobutanesulfonyl group and the like.

Reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) consists of compound (M1-2) and compound (M1-3) It is carried out by mixing at least one compound selected from the group with compound (M1-1).
The amount of compound (M1-2) to be used is generally 0.1-20 mol, preferably 0.5-10 mol, per 1 mol of compound (M1-1).
The amount of compound (M1-3) to be used is generally 0.1-20 mol, preferably 0.5-10 mol, per 1 mol of compound (M1-1).

The reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is preferably carried out in the presence of a base.
Examples of the base include metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium isopropoxide, sodium tertiary butoxide, potassium tertiary butoxide (preferably alkaline metal alkoxide), etc.; metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; metal hydrides such as sodium hydride, potassium hydride, lithium aluminum hydride, sodium borohydride; sodium carbonate, carbonate Metal carbonates such as sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, lithium carbonate, lithium hydrogen carbonate, and cesium carbonate; organic lithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and phenyllithium; alkyl metal halides such as methylmagnesium bromide, isopropylmagnesium bromide, n-butylmagnesium bromide, isopropylmagnesium chloride; lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidide, lithium (bistrimethylsilyl)amide , metal amide compounds such as lithium tetramethylpiperidide; pyridine, 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine, triethylamine, diisopropylethylamine, triisopropylamine, 2,2,6,6- Amine compounds such as tetramethylpiperidine, piperidine, pyrrolidine, proline, aniline, N,N-dimethylaniline and ethylenediamine; metal carboxylates such as sodium acetate, potassium acetate and sodium formate; carboxylate ammonium salts such as ammonium acetate; mentioned.
The amount of the base to be used is generally 0.001 to 20 mol, preferably 0.03 to 10 mol, more preferably 0.05 to 5 mol, per 1 mol of compound (M1-1). , more preferably 0.1 to 3 mol, particularly preferably 0.5 to 2 mol.

The reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) may be carried out in the presence of a solvent.
Examples of solvents include nitrile solvents such as acetonitrile and benzonitrile; aromatic hydrocarbon solvents such as benzene, toluene, xylene and anisole; aliphatic hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane and methylcyclohexane; Halogen-based solvents such as dichlorobenzene, meta-dichlorobenzene, para-dichlorobenzene, dichloromethane, dichloroethane, tetrachloroethane, tetrachloroethylene, and chloroform; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and n-propyl acetate; methanol, ethanol, isopropanol , hexafluoroisopropanol, n-butanol, isobutanol, tert-butanol and other alcohol solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and other ketone solvents; tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether, 4 - ether solvents such as methyltetrahydropyran, dioxane, diethyl ether, tert-butyl methyl ether, diisopropyl ether, dimethoxyethane, diethoxymethane; amide solvents such as N,N-dimethylacetamide and N,N-dimethylformamide; dimethylsulfoxide 1,3-dimethyl-2-imidazolidinone; hexamethylphosphoric acid triamide; water and the like. The solvent is preferably a nitrile solvent, an alcohol solvent, an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent, more preferably acetonitrile, tetrahydrofuran, diethyl ether, methanol, ethanol, isopropanol, 2-butanone or toluene. Acetonitrile, tetrahydrofuran, methanol, ethanol, isopropanol, 2-butanone and toluene are more preferred, and methanol, ethanol, isopropanol, acetonitrile, 2-butanone and toluene are particularly preferred.
The reaction time between at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1) is usually 0.01 to 200 hours.
The reaction temperature of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is usually -100 to 200°C.

Examples of the compound (M1-1) include compounds described below.

Commercially available products may be used as the compound (M1-2) and the compound (M1-3). For example, chlorocyanate, bromocyanide, p-toluenesulfonyl cyanide, trifluoromethanesulfonyl cyanide, benzyl thiocyanate, tert-butyl isocyanide, copper(I) cyanide, potassium cyanide, 1-cyano-4-(dimethylamino)pyridinium tetrafluoro Borate, p-toluenesulfonylmethyl isocyanide, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Select Floor from Air Products and Chemicals (registered trademark)), benzoyl(phenyliodonio)(trifluoromethanesulfonyl)methanide, 2,8-difluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium trifluoromethane sulfonate, 1-fluoro-3,3-dimethyl-1,2-benzoiodoxol, N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, tetramethylammonium tribromide, fluorine (F ₂ ), Bromine (Br ₂ ), chlorine (Cl ₂ ), iodine (I ₂ ), N-bromophthalimide, N-chlorophthalimide, N-iodophthalimide, N-bromosaccharin, N-(trifluoromethylthio)saccharin, N-( trifluoromethylthio)saccharin, N-(trifluoromethylthio)aniline, N-methyl-N-[(trifluoromethyl)thio]-p-toluenesulfonamide, 1-trifluoromethyl-3,3-dimethyl-1,2 -benzoiodoxol, 1-trifluoromethyl-1,2-benzoiodoxol-3(1H)-one, nitric acid, iodomethane, dimethyl sulfate, methyl triflate, ethyl triflate, normal butyl triflate, acetyl chloride and the like. be done.
Note that when R ^1′ and R ^2′ are the same group and E ₁ and E ₂ are the same group, the compound (M1-2) and the compound (M1-3) are the same compound. be.

When the compound (M1-1) is reacted with at least one compound selected from the group consisting of the compound (M1-2) and the compound (M1-3), the cation derived from the compound (M1-1) and the formula (I) A compound (I) having an anion represented by can be obtained.
When the cation of compound (I) is to be exchanged for a desired cation, ion exchange can be carried out by mixing compound (I) with a salt having the desired cation. The ion exchange may be performed in the presence of a solvent. The salt having the desired cation is, for example, a chloride salt consisting of the desired cation and a chloride ion, a bromide salt consisting of the desired cation and a bromide ion, an iodide salt consisting of the desired cation and an iodide ion, Fluoride salts consisting of desired cations and fluoride ions, nitrates consisting of desired cations and nitrate ions, sulfates consisting of desired cations and sulfate ions, perchlorates consisting of desired cations and perchlorate ions a sulfonate consisting of a desired cation and a sulfonate ion; a carboxylate consisting of a desired cation and a carboxylate ion; a hypochlorite consisting of a desired cation and a hypochlorite ion; and a hexafluorophosphate salt consisting of a cation and hexafluorophosphate, an imide salt consisting of a desired cation and an imide, and the like.

The compound (I) having a divalent or higher cation can be obtained by obtaining the compound (I) having a monovalent cation and then performing ion exchange. Further, when the compound (M1-1) is reacted with at least one compound selected from the group consisting of the compound (M1-2) and the compound (M1-3), the compound (M1-1 ) can also be obtained by using

The anion moiety in the compound (M1-1) includes the compound represented by the formula (M1-4) (hereinafter sometimes referred to as the compound (M1-4)), the compound represented by the formula (b-2) ( hereinafter sometimes referred to as compound (b-2)) and a compound represented by formula (b-3) (hereinafter sometimes referred to as compound (b-3)). can.

[In formula (M1-4), ring W ¹ and ring W ² have the same meanings as above.
In formula (b-2), R ³ and R ⁴ have the same meanings as above, and X ₁ represents a divalent linking group.
In formula (b-3), R ⁵ and R ⁶ have the same meanings as above, and X ₂ represents a divalent linking group. ]

The reaction of compound (M1-4), compound (b-2) and compound (b-3) involves mixing compound (M1-4), compound (b-2) and compound (b-3). carried out by
The reaction of compound (M1-4), compound (b-2) and compound (b-3) is preferably carried out in the presence of a base, and compound (M1-4) and compound (b-2) are is preferably mixed with the compound (b-3) and a base.
Mixing the compound (M1-4), the compound (b-2), the compound (b-3) and the base with the compound (b-2) in the mixture (1) of the compound (M1-4) and part of the base ) to obtain a mixture (2), and to the resulting mixture (2) is added a mixture (3) of compound (b-3) and the rest of the base.

The reaction of compound (M1-4), compound (b-2), compound (b-3) and a base may be carried out in the presence of a solvent. Examples of the solvent include the same solvents that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3). Acetonitrile, ethanol, methanol, 2-butanone, toluene, 2-butanone, tetrahydrofuran and dioxane are preferred.
Also, the solvent is preferably a dehydrated solvent.

The reaction time of compound (M1-4), compound (b-2), compound (b-3) and a base is usually 0.05 to 100 hours.
The reaction temperature of compound (M1-4), compound (b-2), compound (b-3) and a base is usually -100 to 200°C.
The amount of compound (b-2) to be used is generally 0.01-10 mol per 1 mol of compound (M1-4).
The amount of compound (b-3) to be used is generally 0.01-10 mol per 1 mol of compound (M1-4).
The amount of the base to be used is generally 0.01-10 mol per 1 mol of compound (M1-4).

As the compound (M1-4), a commercial product may be used, including 7-hydroxy-2,3,4,4a,5,6-hexahydronaphthalen-2-one.

Compound (b-2) and compound (b-3) may each independently be a commercially available product, such as malononitrile, 2-cyanoacetamide, cyanoacetic acid, methyl cyanoacetate, ethyl cyanoacetate, cyanoacetic acid. Propyl, isopropyl cyanoacetate, butyl cyanoacetate, tert-butyl cyanoacetate, 2-ethylhexyl cyanoacetate, 2-ethoxyethyl cyanoacetate, 2-cyano-N,N-dimethylacetamide, pivaloylacetonitrile, cyanoacetylurea, benzoyl Acetonitrile, 2-cyanoacetanilide, 3-oxo-3-(2-thienyl)propanenitrile, methyl acetoacetate, dimedone, 1,3-cyclopropanedione, tetronic acid, acetylacetone, malonamide, malonic acid, 1,3-cyclohexane dione, 2,4-piperidinedione, 1,3-cycloheptanedione, barbituric acid, 3,5-heptanedione, dimethyl malonate, Meldrum's acid, 1,3-indanedione, trifluoroacetylacetone, 1,3- dimethylbarbituric acid, 1,3-dicyclohexylbarbituric acid, 2-thiobarbituric acid, 1,3-diethyl-2-thiobarbituric acid and the like.
When X ₁ and X ₂ are the same group, R ³ and R ⁴ are the same group, and R ⁵ and R ⁶ are the same group, compound (b-2) and compound ( b-3) is the same compound.

The base is the same base that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3). mentioned.
Compound (M1-1) usually has a cation derived from a base. For example, if the cation derived from the base is monovalent, a compound consisting of the monovalent cation and one anion represented by formula (M1-1) can be obtained. If the cation derived from the base is divalent, a compound consisting of the divalent cation and two anions represented by formula (M1-1) can be obtained.

<Method (2) for producing compound (I)>
The anion moiety of compound (I) can be produced by reacting a compound represented by formula (MA) (hereinafter sometimes referred to as compound (MA)) and compound (b-3). can also

[wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X ₂ , W ¹ and W ² each have the same meaning as above. ]

The reaction between compound (MA) and compound (b-3) is preferably carried out in the presence of a catalyst.
Carboxylic acids such as formic acid, acetic acid, trifluoroacetic acid; ammonium chloride; titanium tetrachloride, aluminum chloride, aluminum isopropoxide, boron tribromide, boron trifluoride, iron chloride, gallium chloride, tin tetrachloride , Lewis acids such as lanthanoid triflate; sulfonic anhydrides such as methanesulfonic anhydride, paratoluenesulfonic anhydride, trifluoromethanesulfonic anhydride, and nonafluorobutanesulfonic anhydride; paratoluenesulfonic acid, trifluoromethanesulfone Acids, sulfonic acids such as fluorosulfuric acid; electrophilic alkylating agents such as dimethylsulfuric acid, methyltriflate (methyl trifluoromethanesulfonate), iodomethane, trimethyloxonium tetrafluoroborate, dimethyl fluorosulfate; paratoluenesulfonyl chloride, trifluoromethane and sulfonic acid halides such as sulfonyl chloride. Preferred are electrophilic alkylating agents, sulfonic anhydrides, or sulfonic acid halides, more preferably dimethyl sulfate, methyl triflate, para-toluenesulfonic anhydride, or trifluoromethanesulfonic anhydride, para-toluene. Sulfonyl chloride and trifluoromethanesulfonyl chloride, more preferably methyl triflate or trifluoromethanesulfonic anhydride.

The reaction between compound (MA) and compound (b-3) is preferably carried out in the presence of a base.
Examples of the base include the same bases that can be used for the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3).
The reaction between compound (MA) and compound (b-3) may be carried out in the presence of a solvent. Examples of the solvent include the same solvents that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3).
Also, the solvent is preferably a dehydrated solvent.

The reaction of compound (MA) and compound (b-3) is preferably carried out by mixing the catalyst, compound (MA) and compound (b-3), and It is more preferably carried out by mixing compound (MA) and compound (b-3).
The reaction between compound (MA) and compound (b-3) is preferably carried out under a deoxygenating atmosphere (for example, under a nitrogen atmosphere).

The amount of compound (b-3) to be used is generally 0.01-20 mol, preferably 0.1-10 mol, per 1 mol of compound (MA).
The amount of the catalyst to be used is generally 0.001-20 mol, preferably 0.1-10 mol, per 1 mol of compound (MA).
The amount of the base to be used is generally 0.001-20 mol, preferably 0.1-10 mol, per 1 mol of compound (MA).
The reaction time of compound (MA) and compound (b-3) is generally 0.01 to 200 hours.
The reaction temperature of compound (MA) and compound (b-3) is usually -100 to 200°C.

Compound (MA) includes, for example, compounds described below.

By reacting compound (MA) and compound (b-3) in the presence of a base, compound (I) having a cation derived from the base and an anion represented by formula (I) can be obtained. .
When the cation of compound (I) is to be exchanged for a desired cation, ion exchange can be carried out by mixing compound (I) with a salt having the desired cation. The ion exchange may be performed in the presence of a solvent. The salt having the desired cation is, for example, a chloride salt consisting of the desired cation and a chloride ion, a bromide salt consisting of the desired cation and a bromide ion, an iodide salt consisting of the desired cation and an iodide ion, Fluoride salt composed of desired cation and fluoride ion, Nitrate composed of desired cation and nitrate ion, Sulfate composed of desired cation and sulfate ion, Perchlorate composed of desired cation and perchlorate ion a sulfonate consisting of a desired cation and a sulfonate ion; a carboxylate consisting of a desired cation and a carboxylate ion; a hypochlorite consisting of a desired cation and a hypochlorite ion; and a hexafluorophosphate salt consisting of a cation and hexafluorophosphate, an imide salt consisting of a desired cation and an imide, and the like.

Compound (MA) is produced by reacting a compound represented by formula (M) (hereinafter sometimes referred to as compound (M)) with compound (b-2) in the presence of a catalyst. be able to.

[In the formula, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , R ⁴ and X ₁ each have the same meaning as above. ]

Examples of the catalyst include the same catalysts that can be used in the reaction between compound (MA) and compound (b-3). Preferred are electrophilic alkylating agents, sulfonic anhydrides or sulfonic acid halides, more preferably dimethyl sulfate, methyl triflate, para-toluenesulfonic anhydride or trifluoromethanesulfonic anhydride, para-toluenesulfonyl chloride, trifluoromethanesulfonyl chloride, more preferably methyl triflate or trifluoromethanesulfonic anhydride.

The reaction between compound (M) and compound (b-2) is preferably further carried out in the presence of a base.
The base is the same base that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3). metal alkoxides, metal hydroxides, metal hydrides, metal carbonates, organic lithium, metal amide compounds, amine compounds or metal carboxylates, and potassium ethoxide, sodium tertiary butoxide, potassium tertiary Libutoxide, sodium hydroxide, potassium hydroxide, sodium hydride, lithium aluminum hydride, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, methyl lithium, normal butyl lithium, tertiary butyl lithium, lithium diisopropylamide, Lithium 2,2,6,6-tetramethylpiperidide, lithium (bistrimethylsilyl)amide, lithium tetramethylpiperidide, pyridine, 2,6-dimethylpyridine, 2,6-ditertiarybutylpyridine, triethylamine, diisopropyl More preferred are ethylamine, triisopropylamine, 2,2,6,6-tetramethylpiperidine, piperidine, pyrrolidine, proline, aniline, N,N-dimethylaniline, sodium acetate, sodium formate and ammonium acetate.

The reaction between compound (M) and compound (b-2) may be carried out in the presence of a solvent. The solvent is the same solvent that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3). mentioned. Preferably the solvent is acetonitrile, methanol, ethanol, toluene, 2-butanone, dioxane, tetrahydrofuran, dimethylsulfoxide, dimethylformamide or dimethylacetamide.
Also, the solvent is preferably a dehydrated solvent.

The reaction of the compound (M) and the compound (b-2) is carried out by mixing the catalyst, the compound (M) and the compound (b-2), the catalyst, the base, the compound (M) and the compound (b -2) is preferably carried out by mixing.
The reaction between compound (M) and compound (b-2) is preferably carried out under a deoxygenated atmosphere (for example, under a nitrogen atmosphere).

The amount of compound (b-2) to be used is generally 0.01-20 mol, preferably 0.1-10 mol, per 1 mol of compound (M).
The amount of the catalyst to be used is generally 0.001-20 mol, preferably 0.1-10 mol, per 1 mol of compound (M).
The amount of the base to be used is generally 0.001-20 mol, preferably 0.1-10 mol, per 1 mol of compound (M).
The reaction time of compound (M) and compound (b-2) is generally 0.1 to 200 hours.
The reaction temperature of compound (M) and compound (b-2) is usually -100 to 200°C.

<Compound (M)>
Compound (M) is a novel compound having a structure represented by the following formula, and a synthetic intermediate of compound (I).

[In the formula, ring W ¹ , ring W ² , R ¹ and R ² have the same meanings as above. ]

Examples of the compound (M) include the compounds described below.

<Method for producing compound (M)>
Compound (M) is a compound represented by formula (M1-4) (hereinafter sometimes referred to as compound (M1-4)), a group consisting of compound (M1-2) and formula (M1-3) It can be produced by reacting with at least one compound selected from

[In the formula, ring W ¹ , ring W ² , R ¹ , R ² , R ^1′ , R ^2′ , E ₁ and E ₂ have the same meanings as above. ]
_The leaving group represented by _E2 includes the same leaving groups as those represented by E1.

The reaction of compound (M1-4) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is preferably carried out in the presence of a base.
The base is the same base that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3). metal alkoxides, metal hydroxides, metal hydrides, metal carbonates, organic lithium, metal amide compounds, amine compounds or metal carboxylates, and potassium ethoxide, sodium tertiary butoxide, potassium tertiary Libutoxide, sodium hydroxide, potassium hydroxide, sodium hydride, lithium aluminum hydride, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, methyl lithium, normal butyl lithium, tertiary butyl lithium, lithium diisopropylamide, Lithium 2,2,6,6-tetramethylpiperidide, lithium (bistrimethylsilyl)amide, lithium tetramethylpiperidide, pyridine, 2,6-dimethylpyridine, 2,6-ditertiarybutylpyridine, triethylamine, diisopropyl More preferred are ethylamine, triisopropylamine, 2,2,6,6-tetramethylpiperidine, piperidine, pyrrolidine, proline, aniline, N,N-dimethylaniline, sodium acetate, sodium formate and ammonium acetate.
The amount of the base to be used is generally 0.001-20 mol, preferably 0.1-10 mol, per 1 mol of compound (M1-4).

The reaction of compound (M1-4) and at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) may be carried out in the presence of a solvent. The solvent is the same solvent that can be used in the reaction of compound (M1-1) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3). mentioned. Acetonitrile, methanol, ethanol, toluene, 2-butanone, dioxane, tetrahydrofuran, dimethylsulfoxide, dimethylformamide and dimethylacetamide are preferred.
Also, the solvent is preferably a dehydrated solvent.

The reaction of compound (M1-4) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) comprises: compound (M1-4) and compound (M1-2) and compound (M1-3) by mixing at least one compound selected from the group consisting of a base, compound (M1-4), compound (M1-2) and compound (M1-3) It is preferably carried out by mixing with at least one compound selected from the group consisting of
The reaction of compound (M1-4) with at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is carried out under a deoxidizing atmosphere (for example, under a nitrogen atmosphere). preferably.

The amount of compound (M1-2) to be used is generally 0.1-20 mol, preferably 0.5-10 mol, per 1 mol of compound (M1-4).
The amount of compound (M1-3) to be used is generally 0.1-20 mol, preferably 0.5-10 mol, per 1 mol of compound (M1-4).
The amount of the base to be used is generally 0.001-20 mol, preferably 0.1-10 mol, per 1 mol of compound (M1-4).
The reaction time of compound (M1-4) and at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is usually 0.1 to 200 hours.
The reaction temperature of compound (M1-4) and at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is usually -100 to 200°C.

<Composition containing compound (I)>
The present invention also includes compositions containing compound (I). A molded article molded from a composition containing compound (I) preferably has a transmittance of 50% or less, more preferably 30% or less, at the maximum absorption wavelength [nm] of compound (I) contained. It is preferably 15% or less, more preferably 10% or less.
The composition containing compound (I) is a resin composition containing compound (I) and a resin (hereinafter sometimes referred to as "resin composition") or a composition containing compound (I) and a polymerizable monomer. (hereinafter sometimes referred to as "composition (1)").

A composition containing compound (I) can be used for all purposes, but is particularly suitable for uses that may be exposed to sunlight or light including ultraviolet rays. Specific examples include, for example, glass substitutes and surface coating materials thereof; window glass for housing, facilities, transportation equipment, etc., coating materials for daylighting glass and light source protection glass; window films for housing, facilities, transportation equipment, etc.; Interior and exterior materials such as facilities and transportation equipment, interior and exterior paints, and coating films formed therefrom; alkyd resin lacquer paints and coating films formed therefrom; acrylic lacquer paints and coating films formed therewith; Materials for light sources that emit ultraviolet light such as fluorescent lamps and mercury lamps; Materials for shielding electromagnetic waves generated by precision machinery, electronic and electrical equipment, and various displays; For blisters, cups, special packaging, compact disc coats, agricultural and industrial sheet or film materials; anti-fading agents for printed matter, dyed matter, dyes and pigments; for polymer substrates (e.g. plastic parts such as machine and automobile parts optical light films; safety glass/windshield interlayers; electrochromic/photochromic applications; overlaminate films; Cosmetics such as conditioners and hairdressing products; Textile products and fibers for clothing such as sportswear, stockings and hats; Interior goods for home use such as curtains, carpets and wallpaper; Medical equipment such as plastic lenses, contact lenses and artificial eyes; Optical filters , backlight display films, prisms, mirrors, photographic materials, and other optical supplies; stationery such as mold films, decals, anti-graffiti films, tapes, and inks; be able to.

Shapes of molded articles formed from the composition of the present invention include flat film, powder, spherical particles, crushed particles, continuous lumps, fibrous, tubular, hollow fiber, granular, plate-like, and porous. may be any shape.

Examples of the resin used in the resin composition include thermoplastic resins and thermosetting resins conventionally used in the production of various known molded articles, sheets, films, and the like.
Examples of thermoplastic resins include polyethylene resins, polypropylene resins, olefin resins such as polycycloolefin resins, poly(meth)acrylic acid ester resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins. Resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin, polybutylene terephthalate resin, Examples include polyester resins such as liquid crystal polyester resins, polyacetal resins, polyamide resins, polycarbonate resins, polyurethane resins, polyphenylene sulfide resins, and the like. One or more of these resins may be used as a polymer blend or polymer alloy.

Examples of thermosetting resins include epoxy resins, melamine resins, unsaturated polyester resins, phenol resins, urea resins, alkyd resins, and thermosetting polyimide resins.

When the resin composition is used as an ultraviolet absorbing filter or an ultraviolet absorbing film, the resin is preferably a transparent resin.

The resin composition can be obtained by mixing compound (I) and a resin. The compound (I) may be contained in an amount necessary to impart desired performance, for example, 0.00001 to 99 parts by mass per 100 parts by mass of the resin.
The resin composition may contain other additives such as solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, etc., if necessary.

The polymerizable monomer used in the composition (1) is not particularly limited, but is preferably a radically polymerizable monomer, more preferably a radically photopolymerizable monomer, and preferably a (meth)acrylate. More preferred.
(Meth)acrylates include monofunctional (meth)acrylate monomers having one (meth)acryloyloxy group in the molecule, and bifunctional (meth)acrylate monomers having two (meth)acryloyloxy groups in the molecule. , polyfunctional (meth)acrylate monomers having 3 or more (meth)acryloyloxy groups in the molecule.
Composition (1) preferably further contains a polymerization initiator. When the polymerizable monomer is a radically polymerizable monomer, the polymerization initiator is preferably a radical polymerization initiator, more preferably a photopolymerization initiator.
Composition (1) can be obtained by mixing compound (I) and a polymerizable monomer. The compound (I) may be contained in an amount necessary for imparting desired performance, and may be contained, for example, in an amount of 0.01 to 20 parts by mass per 100 parts by mass of the polymerizable monomer.
Composition (1) may contain other additives such as solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, dyes, pigments and inorganic fillers, if necessary.

When the composition of the present invention is used for optical products such as optical films, it can be applied to, for example, image display devices. When applying the composition of the present invention to an image display device, the optical layer formed from the composition of the present invention may be applied to any of a film layer, an adhesive layer, a coat layer, and the like. It is preferably a coat layer.
When the composition of the present invention is used for an optical article, it may consist of only an optical layer formed from the composition of the present invention, or an optical layer formed from the composition of the present invention and another layer may be laminated. It may also be an optical laminate. Other layers include, for example, polarizing films, retardation films, thermoplastic resin films, and the like. If the optical laminate is a laminate in which the optical layer of the present invention, an adhesive layer, and a polarizing film are laminated in this order, the optical layer of the present invention is an optical layer (optical film) formed from the composition of the present invention. ) is preferred. If the optical laminate is a laminate in which the optical layer of the present invention, a thermoplastic resin film, an adhesive layer, and a polarizing film are laminated in this order, the optical layer of the present invention is formed from the composition of the present invention. It is preferably an optical layer (coat layer). If the optical laminate is a laminate in which the retardation film, the optical layer of the present invention, and the retardation film are laminated in this order, the optical layer of the present invention is an optical layer (adhesive layer) formed from the composition of the present invention. ) is preferred.

<Adhesive composition>
When the layer formed from the composition of the present invention is a pressure-sensitive adhesive layer, a pressure-sensitive adhesive composition (hereinafter referred to as pressure-sensitive adhesive may be referred to as composition (i)). The pressure-sensitive adhesive composition (i) further contains a radical-curing component (D), an initiator (E), and a light-absorbing compound (F) other than the compound (I) (hereinafter referred to as a light-selective absorbing compound (F) ), may contain an antistatic agent, etc., and may contain at least one selected from the group consisting of a radical curing component (D), an initiator (E) and a photoselective absorption compound (F) preferable.

The resin (A) is not particularly limited as long as it is a resin used in adhesive compositions. It is preferable that the resin (A) does not exhibit maximum absorption in the wavelength range of 300 nm to 780 nm.
Resin (A) is preferably a resin having a glass transition temperature (Tg) of 40° C. or lower. The glass transition temperature (Tg) of the resin (A) is more preferably 20° C. or lower, still more preferably 10° C. or lower, and particularly preferably 0° C. or lower. The glass transition temperature of the resin (A) is usually −80° C. or higher, preferably −70° C. or higher, more preferably −60° C. or higher, further preferably −55° C. or higher. , −50° C. or higher. When the glass transition temperature of the resin (A) is 40° C. or lower, it is advantageous for improving the adhesion of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (i) to the adherend. Further, when the glass transition temperature of the resin (A) is −80° C. or higher, it is advantageous for improving the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (i). The glass transition temperature can be measured with a differential scanning calorimeter (DSC).

Examples of the resin (A) include (meth)acrylic resins, silicone resins, rubber resins, urethane resins, etc., and (meth)acrylic resins are preferred.

The (meth)acrylic resin is preferably a polymer containing (preferably at least 50% by mass) a structural unit derived from (meth)acrylic ester as a main component. Structural units derived from (meth)acrylate esters are structural units derived from one or more monomers other than (meth)acrylate esters (e.g., units having polar functional groups such as hydroxyl groups, carboxyl groups, and amino groups). a structural unit derived from a mer).

The content of the resin (A) is usually 50% by mass to 99.9% by mass, preferably 60% by mass to 95% by mass, based on 100% by mass of the solid content of the adhesive composition (i). It is preferably 70% by mass to 90% by mass.
The content of compound (I) is usually 0.01 to 20 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass, relative to 100 parts by mass of resin (A). 10 parts by mass, particularly preferably 0.5 to 5 parts by mass.

Examples of the cross-linking agent (B) include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, and metal chelate-based cross-linking agents. An isocyanate-based cross-linking agent is preferred from the viewpoint of speed and the like.
The content of the cross-linking agent (B) is usually 0.01 to 25 parts by mass, preferably 0.1 to 15 parts by mass, more preferably 0.15 parts by mass, relative to 100 parts by mass of the resin (A). 7 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.25 to 2 parts by mass.

Examples of the silane compound (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 - glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.
The silane compound (C) may be a silicone oligomer.
The content of the silane compound (C) is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.15 parts by mass, relative to 100 parts by mass of the resin (A). 7 parts by mass, more preferably 0.2 to 5 parts by mass, and particularly preferably 0.25 to 2 parts by mass.

Examples of the radical-curable component (D) include radical-curable components such as compounds or oligomers that cure by a radical polymerization reaction.
Examples of the radically polymerizable component (D) include (meth)acrylate compounds, styrene compounds, vinyl compounds and the like.
The pressure-sensitive adhesive composition (i) may contain two or more radical-curable components (D).

The (meth)acrylate compound includes a (meth)acrylate monomer having at least one (meth)acryloyloxy group in the molecule, a (meth)acrylamide monomer, and at least two (meth)acryloyl groups in the molecule. (Meth)acryloyl group-containing compounds such as (meth)acrylic oligomers having The (meth)acrylic oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloyloxy groups in the molecule. Only one type of (meth)acrylate compound may be used alone, or two or more types may be used in combination.

(Meth)acrylate monomers include monofunctional (meth)acrylate monomers having one (meth)acryloyloxy group in the molecule, and bifunctional (meth)acrylates having two (meth)acryloyloxy groups in the molecule. Examples include monomers and polyfunctional (meth)acrylate monomers having 3 or more (meth)acryloyloxy groups in the molecule.
(Meth)acrylate compounds are preferable, and polyfunctional (meth)acrylate compounds are more preferable. The polyfunctional (meth)acrylate compound is preferably trifunctional or higher.

The content of the radical curing component (D) is usually 0.5 to 100 parts by mass, preferably 1 to 70 parts by mass, and 3 to 50 parts by mass, relative to 100 parts by mass of the resin (A). is more preferably 5 to 30 parts by mass, and particularly preferably 7.5 to 25 parts by mass.

The initiator (E) is either a compound that induces a polymerization reaction by absorbing thermal energy (thermal polymerization initiator) or a compound that induces a polymerization reaction by absorbing light energy (photopolymerization initiator). good too. Here, the light is preferably visible light, ultraviolet rays, X-rays, or active energy rays such as electron beams.

Examples of thermal polymerization initiators include compounds that generate radicals by heating (thermal radical generators), compounds that generate acids by heating (thermal acid generators), and compounds that generate bases by heating (thermal base generators). ) and the like.
Photopolymerization initiators include compounds that generate radicals by absorbing light energy (photoradical generators), compounds that generate acids by absorbing light energy (photoacid generators), light energy and a compound (photobase generator) that generates a base by absorbing the .

The initiator (E) is preferably selected from those suitable for the polymerization reaction of the radical-curable component (D) described above, preferably a radical polymerization initiator, more preferably a radical photopolymerization initiator. preferable.
Examples of radical polymerization initiators include alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, phosphine compounds and the like. The radical polymerization initiator is preferably a radical photopolymerization initiator, and more preferably an oxime ester-based radical photopolymerization initiator from the viewpoint of the reactivity of the polymerization reaction. By using an oxime ester photoradical polymerization initiator, the reaction rate of the radical curing component (D) can be increased even under curing conditions with a weak illumination or light intensity.

The content of the initiator (E) is usually 0.01 to 20 parts by mass, preferably 0.3 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin (A). It is more preferably 0.75 to 4 parts by mass, particularly preferably 1 to 3 parts by mass.

The light selective absorption compound (F) is a light absorption compound other than the compound (I), for example, a compound (ultraviolet absorber) that absorbs light with a wavelength of 250 nm to 380 nm (preferably 250 nm or more and less than 360 nm). , a compound (dye) that absorbs from 380 to 780 nm, and a compound (infrared absorber) that absorbs from 780 to 1500 nm.
The structure of the ultraviolet absorber is not particularly limited as long as it is a compound that absorbs light with a wavelength of 250 nm to 380 nm. Benzotriazole compounds, benzophenone compounds, triazine compounds, salicylic acid compounds, cyanoacrylate compounds, Compounds such as benzoxazine compounds are preferred.
The content of the photoselective absorption compound (F) is usually 0.1 to 50 parts by mass, preferably 0.2 to 40 parts by mass, more preferably 0 parts by mass with respect to 100 parts by mass of the resin (A). .5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and particularly preferably 2 to 20 parts by mass.

The optical layer of the present invention and the optical layered body containing the optical layer are laminated on a display element such as an organic EL element or a liquid crystal cell to form an image display device (FPD: flat panel display) such as an organic EL display device or a liquid crystal display device. ) can be used for

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing contents or amounts used are based on mass unless otherwise specified.

(Example 1) Synthesis of compound represented by formula (1)

A 300 mL four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 7-hydroxy-2,3,4,4a,5,6-hexahydronaphthalen-2-one 7 parts, ethanol 70 parts , 2.4 parts of potassium hydroxide and 6.2 parts of malononitrile were added, and the mixture was heated under reflux with stirring at 80° C. for 3 hours. 62 parts of ethanol, 6.2 parts of malononitrile and 4.8 parts of potassium hydroxide were added to the obtained mixture, and the mixture was heated under reflux with stirring at 80° C. for 3 hours. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 6.9 parts of the compound represented by the formula (a1).

A 20 mL four-necked flask equipped with a Dimroth condenser and a thermometer was set to a nitrogen atmosphere, and 1.5 parts of the compound represented by the formula (a1), 1.0 parts of paratoluenesulfonyl cyanide, and 0.0 parts of potassium hydroxide. 3 parts and 10 parts of ethanol were charged, and the mixture was heated under reflux and stirred for 3 hours. The solvent was distilled off from the resulting mixture and the residue was purified to obtain 0.7 parts of the compound represented by formula (1).

LC-MS measurement and ¹ H-NMR analysis were performed to confirm that the compound represented by formula (1) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis).
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.21-1.40 (m, 2H), 1.84-1.99 (m, 2H), 2.33-2.76 (m, 5H), 6.38 (s, 1H)
LC-MS; [M] ⁻ =284.2

<Measurement of maximum absorption wavelength and gram extinction coefficient ε>
The resulting 2-butanone solution (0.003 g/L) of the compound represented by formula (1) was placed in a 1 cm quartz cell, and the quartz cell was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation). Then, the absorbance in the wavelength range from 300 to 800 nm was measured at every 1 nm step by the double beam method. A gram extinction coefficient for each wavelength was calculated from the obtained absorbance value, the concentration of the compound represented by the formula (1) in the solution, and the optical path length of the quartz cell.
ε(λ)=A(λ)/CL
[Wherein, ε (λ) represents the gram extinction coefficient (L/(g cm)) of the compound represented by formula (1) at the wavelength λ nm, A (λ) represents the absorbance at the wavelength λ nm, and C represents the concentration (g/L) and L represents the optical path length (m) of the quartz cell. ]
The maximum absorption wavelength of the obtained compound represented by formula (1) was 518 nm. The ε (λmax) of the obtained compound represented by formula (1) was 444 L/(g·cm).

<Measurement of full width at half maximum of compound>
The obtained 2-butanone solution (concentration: 0.003 g/L) of the compound represented by formula (1) was placed in a 1 cm quartz cell, and the quartz cell was subjected to spectrophotometer UV-2450 (manufactured by Shimadzu Corporation). , and the absorbance in the wavelength range from 300 to 800 nm was measured at every 1 nm step by the double beam method. Two wavelengths were identified at which the absorbance was half the absorbance of the maximum absorption wavelength. Of the wavelengths at the two points, the wavelength on the short wavelength side was subtracted from the wavelength on the long wavelength side to obtain the full width at half maximum. The full width at half maximum of the compound represented by formula (1) was 26 nm.

(Example 2) Synthesis of compound represented by formula (M-2)

A 500 mL-four-necked flask equipped with a Dimroth condenser and a thermometer was set to a nitrogen atmosphere, and the compound represented by the formula (M-1) (7-hydroxy-2,3,4,4a,5,6-hexa 25 parts of hydronaphthalene-2-one), 150 parts of ethanol, 10.3 parts of potassium hydroxide and 33.11 parts of p-toluenesulfonyl cyanide were added and stirred for 4 hours in an ice bath. After distilling off the solvent from the obtained mixture, the mixture was purified to obtain 17.4 parts of the compound represented by the formula (M-2).

LC-MS measurement and ¹ H-NMR analysis were performed to confirm that the compound represented by formula (M-2) was produced.
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.49-1.65 (m, 2H), 1.91-2.00 (m, 2H), 2.30-2.67 (m, 5H), 5.89 (s, 1H)
LC-MS; [M] = 188.1

(Example 3) Synthesis of compound represented by formula (M-3)

A 300 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, 5 parts of the compound represented by the formula (M-2), 100 parts of dehydrated acetonitrile, 4.4 parts of diisopropylethylamine, trifluoromethanesulfone 9 parts of an acid anhydride was added and the mixture was stirred in an ice bath for 10 minutes. 2.1 parts of malononitrile and 4.4 parts of diisopropylethylamine were added to the obtained mixture, and the mixture was further stirred for 30 minutes. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 5.4 parts of the compound represented by the formula (M-3).

LC-MS measurement and ¹ H-NMR analysis were conducted to confirm that the compound represented by formula (M-3) was produced.
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.14-1.54 (m, 2H), 1.87-1.99 (m, 2H), 2.22-2.68 (m, 5H), 6.08 (s, 1H)
LC-MS; [M] = 236.3

(Example 4) Synthesis of compound represented by formula (1)

A 100 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 2 parts of the compound represented by the formula (M-3), 20 parts of dehydrated methyl ethyl ketone, 1.2 parts of potassium carbonate, trifluoromethanesulfone. 2.8 parts of methyl acid were mixed and stirred in an ice bath for 2 hours. 0.7 parts of malononitrile and 1.4 parts of diisopropylethylamine were added to the obtained mixture, and the mixture was further stirred for 30 minutes. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 1.4 parts of the compound represented by the formula (1).

LC-MS measurement and ¹ H-NMR analysis were performed to confirm that the compound represented by formula (1) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis).
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.21-1.40 (m, 2H), 1.84-1.99 (m, 2H), 2.33-2.76 (m, 5H), 6.38 (s, 1H)
LC-MS; [M] ⁻ =284.2

(Example 5) Synthesis of compound represented by formula (2)

A 50 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 0.5 parts of the compound represented by the formula (a1), 5 parts of dehydrated acetonitrile, 0.3 parts of diisopropylethylamine, N-( Trifluoromethylthio)saccharin (0.7 part) was added and stirred for 3 hours in an ice bath. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 0.4 parts of the compound represented by the formula (2).

LC-MS measurement and ¹ H-NMR analysis were conducted to confirm that the compound represented by formula (2) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Furthermore, when the maximum absorption wavelength, gram extinction coefficient and full width at half maximum were measured in the same manner as described above, the maximum absorption wavelength of the compound represented by formula (2) was 526 nm, and the gram absorption coefficient ε (λmax ) was 189 L/(g·cm) and the full width at half maximum was 26 nm.
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.16-1.19 (m, 2H), 1.33-1.36 (m, 2H), 1.91-1.99 (m, 5H), 6.88-6.91 (m, 1H)
LC-MS; [M] ⁻ =359.4

(Example 6) Synthesis of compound represented by formula (3)

A 20 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 0.5 parts of the compound represented by the formula (a1), 5 parts of dehydrated acetonitrile, and 0.3 parts of N-chlorosuccinimide are added. The mixture was stirred in an ice bath for 3 hours. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 0.4 parts of the compound represented by the formula (3).

LC-MS measurement was performed to confirm that the compound represented by formula (3) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Furthermore, when the maximum absorption wavelength, gram extinction coefficient, and full width at half maximum were measured in the same manner as described above, the maximum absorption wavelength of the compound represented by formula (3) was 551 nm, and the gram absorption coefficient ε (λmax ) was 130 L/(g·cm) and the full width at half maximum was 28 nm.
LC-MS; [M] ⁻ =293.5

(Example 7) Synthesis of compound represented by formula (4)

A 20 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 0.5 parts of the compound represented by the formula (a1), 5 parts of dehydrated dimethylformamide, and 0.5 parts of N-chlorosuccinimide are added. In addition, the mixture was stirred in an ice bath for 3 hours. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 0.4 parts of the compound represented by the formula (4).

LC-MS measurement and ¹ H-NMR analysis were conducted to confirm that the compound represented by formula (4) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Furthermore, when the maximum absorption wavelength, gram extinction coefficient, and full width at half maximum were measured in the same manner as described above, the maximum absorption wavelength of the compound represented by formula (4) was 572 nm, and the gram absorption coefficient ε (λmax ) was 126 L/(g·cm) and the full width at half maximum was 44 nm.
LC-MS; [M] ⁻ =328.2
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.24-1.25 (m, 2H), 1.88-2.33 (m, 7H)

(Example 8) Synthesis of compound represented by formula (5)

A 20 mL four-necked flask equipped with a Dimroth condenser and a thermometer was set to a nitrogen atmosphere, and 1 part of the compound represented by the formula (a1), 10 parts of dehydrated dimethylformamide, and 0.7 parts of N-bromosuccinimide were added. Stirred in an ice bath for 3 hours. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 0.7 parts of the compound represented by the formula (5).

LC-MS measurement and ¹ H-NMR analysis were performed to confirm that the compound represented by formula (5) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Furthermore, when the maximum absorption wavelength, gram extinction coefficient, and full width at half maximum were measured in the same manner as described above, the maximum absorption wavelength of the compound represented by formula (5) was 548 nm, and the gram absorption coefficient ε (λmax ) was 180 L/(g·cm) and the full width at half maximum was 26 nm.
LC-MS; [M] ⁻ =338.2
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.31-1.37 (m, 2H), 1.82-1.99 (m, 2H), 2.43-2.79 (m, 5H), 6.46 (s, 1H)

(Example 9) Synthesis of compound represented by formula (M-4)

A 100 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 5 parts of the compound represented by the formula (M-2), 50 parts of dehydrated acetonitrile, and 0.7 parts of sodium hydride are added. Stirred in an ice bath for 30 minutes. 9.6 parts of p-toluenesulfonyl cyanide was added to the resulting mixture, and the mixture was stirred at 50°C for 4 hours. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 3.8 parts of the compound represented by the formula (M-4).

LC-MS measurement and ¹ H-NMR analysis were conducted to confirm that the compound represented by formula (M-4) was produced.
LC-MS; [M] ⁻ =213.1
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.46-1.57 (m, 2H), 1.82-1.91 (m, 2H), 2.16-2.39 (m, 5H)

(Example 10) Synthesis of compound represented by formula (6)

A 200 mL four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 4.5 parts of the compound represented by the formula (M-4), 68 parts of dehydrated acetonitrile, and 0.6 parts of sodium hydride. In addition, the mixture was stirred in an ice bath for 30 minutes. To the resulting mixture, 7.1 parts of trifluoromethanesulfonic anhydride was added and stirred in an ice bath for 30 minutes, 1.7 parts of malononitrile and 3.5 parts of potassium carbonate were added and the mixture was stirred at 50°C for 2 hours. . After distilling off the solvent from the obtained mixture, the mixture was purified to obtain 2.1 parts of the compound represented by the formula (M-5).

A 300 mL-four-necked flask equipped with a Dimroth condenser and a thermometer is set to a nitrogen atmosphere, and 1.2 parts of the compound represented by the formula (M-5), 36 parts of acetonitrile, 8.8 parts of ditertiarybutylpyridine, 7.5 parts of p-toluenesulfonic anhydride and 1.5 parts of malononitrile were mixed and stirred in an ice bath for 24 hours. After distilling off the solvent from the resulting mixture, the mixture was purified to obtain 0.4 parts of the compound represented by the formula (6). The potassium ion in the compound represented by formula (6) is derived from potassium hydrogen carbonate used during purification.

LC-MS measurement and ¹ H-NMR analysis were performed to confirm that an anion was generated in the compound represented by formula (6). Also, the presence of potassium atoms (potassium cations) was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis).
Furthermore, when the maximum absorption wavelength, gram extinction coefficient, and full width at half maximum were measured in the same manner as described above, the maximum absorption wavelength of the compound represented by formula (6) was 511 nm, and the gram absorption coefficient ε (λmax ) was 211 L/(g·cm) and the full width at half maximum was 29 nm.
LC-MS; [M] ⁻ =309.3
¹ H-NMR (heavy dimethyl sulfoxide) δ: 1.16-1.21 (m, 2H), 1.30-1.37 (m, 2H), 1.62-1.65 (m, 2H), 1.88-1.91 (m, 3H)

<Preparation of acrylic resin>
Polymerization Example 1: Preparation of acrylic resin (A1) Into a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, 81.8 parts of ethyl acetate, 96 parts of butyl acrylate and 2-hydroxy acrylate were added as solvents. A mixed solution of 3 parts of ethyl methyl and 1 part of acrylic acid was charged, and the internal temperature was raised to 55° C. while replacing the air in the apparatus with nitrogen gas to make it oxygen-free. Thereafter, a solution obtained by dissolving 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added to the whole amount. After adding the polymerization initiator, this temperature was maintained for 1 hour, and then ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/hr while maintaining the internal temperature at 54 to 56° C. to remove the acrylic resin. When the concentration reached 35%, the addition of ethyl acetate was stopped, and the mixture was kept at this temperature until 12 hours after the start of addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20% to prepare an ethyl acetate solution of the acrylic resin. The obtained acrylic resin had a polystyrene-equivalent weight average molecular weight Mw of 1,400,000 and an Mw/Mn of 5.5 by GPC. This is designated as acrylic resin (A1).

Polymerization Example 2: Preparation of acrylic resin (A2) Into a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer, 81.8 parts of ethyl acetate, 60 parts of methyl acrylate, 10 parts of acrylic acid, and A mixed solution of 10 parts of 2-hydroxyethylmethyl acrylate and 20 parts of 2-phenoxyethyl acrylate was charged, and the internal temperature was raised to 55° C. while replacing the air in the apparatus with nitrogen gas to make it oxygen-free. Thereafter, a solution obtained by dissolving 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added to the whole amount. After adding the polymerization initiator, this temperature was maintained for 1 hour, and then ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/hr while maintaining the internal temperature at 54 to 56° C. to remove the acrylic resin. When the concentration reached 35%, the addition of ethyl acetate was stopped, and the mixture was maintained at this temperature until 12 hours had passed since the addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20% to prepare an ethyl acetate solution of the acrylic resin. The obtained acrylic resin had a polystyrene equivalent weight average molecular weight Mw of 920,000 and an Mw/Mn of 4.7 by GPC. This is designated as acrylic resin (A2).

(Example 11) Production of Resin Composition (1) (Adhesive Composition (1)) <Preparation of Resin Composition (1)>
Per 100 parts of solid content of ethyl acetate solution (resin concentration: 20%) of acrylic resin (A1), cross-linking agent (manufactured by Tosoh Corporation: trade name “Coronate L”, isocyanate compound, solid content 75%) 0 .5 parts, 0.28 parts of a silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.: product name "KBM3066"), and 1.5 parts of the compound represented by formula (1) are mixed, and the solid content concentration is 14%. 2-butanone was added to obtain a resin composition (1) (adhesive composition (1)). In addition, the compounding amount of the said crosslinking agent is the number of mass parts as an active ingredient.

(Examples 12 to 18, Comparative Example 1) Production of resin compositions (2) to (9) In the same manner as in Example 11, except that each component and the content of each component were changed as shown in Table 7. Adhesive compositions (2) to (9) were produced. The amount of the cross-linking agent is the number of parts by mass as the active ingredient, and the amount of the resin (A) is the number of parts by mass of the solid content.

Each abbreviation in Table 7 means the following.
Acrylic resin (A1): Acrylic resin (A1) synthesized in Polymerization Example 1
Acrylic resin (A2): Acrylic resin (A2) synthesized in Polymerization Example 2
Formula (1): Compound represented by Formula (1) synthesized in Example 1 or Example 4 Formula (6): Compound represented by Formula (6) synthesized in Example 10 Coronate L: Tosoh Corporation Product name: Coronate L, isocyanate cross-linking agent KBM3066: Shin-Etsu Chemical Co., Ltd., product name: KBM3066, silane coupling agent A-DPH-12E: Shin-Nakamura Chemical Co., Ltd., product name: A-DPH -12E, hexafunctional (meth) acrylate compound NCI-730: manufactured by ADEKA Co., Ltd., trade name: NCI-730, photoradical generator that is an oxime ester compound RUV-93: manufactured by Otsuka Chemical Co., Ltd., benzotriazole-based ultraviolet rays Absorbent, trade name: RUVA-93, maximum absorption wavelength λmax = 337 nm
Formula (B): A compound represented by the following formula (B) synthesized with reference to US Pat. No. 6,004,536 (3-butyl-2-[3-(-3-butyl-5-phenyl-2( 3H)-benzolylidene)-1-propen-1-yl]-5-phenyl-benzoxazolium p-toluenesulfonate), the full width at half maximum determined in the same manner as above was 44 nm.

<Evaluation of Molded Body of Resin Composition (1)>
[Preparation of resin molding (1)]
The resulting resin composition (1) (adhesive composition (1)) was applied to a separate film (trade name “PLR-382190” obtained from Lintec Corporation) made of polyethylene terephthalate film subjected to mold release treatment. It was applied to the release-treated surface using an applicator and dried at 100° C. for 1 minute to form a resin molded body (adhesive layer) (1), thereby producing a resin molded body (1) with a separate film. The thickness of the obtained resin molding (1) was 15 μm.

The resulting resin molded product (1) with a separate film was laminated with a laminator to a 23 μm UV absorber-containing cycloolefin film [trade name “ZEONOR” obtained from Nippon Zeon Co., Ltd.]. A laminate (1-1) having a laminate structure of cycloolefin film/resin molding (1)/separate film was obtained by curing for 7 days under conditions of 65% humidity.

[Measurement of Absorbance of Resin Mold (1)]
The obtained laminate (1-1) was cut into a size of 30 mm × 30 mm, the separate film was peeled off, and the resin molded body (1) and alkali-free glass [trade name “EAGLE XG” manufactured by Corning Incorporated] were obtained. were pasted together, and this was used as sample (1). The absorbance of the prepared sample (1) in the wavelength range of 300 to 800 nm was measured in steps of 1 nm using a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation). The measured absorbance at a wavelength of 330 nm was defined as the absorbance at a wavelength of 330 nm of the resin molding (1). The absorbance at a wavelength of 330 nm for each of the alkali-free glass alone and the cycloolefin film alone is zero.
Also, the transmittance at a wavelength of 330 nm was obtained based on the following formula. The results are shown in the transmittance column of Table 8.
T = 10 ^{- A} × 100 (T represents transmittance and A represents absorbance.)

From the absorbance measured above, the maximum absorption wavelength of the sample (1) was determined, and the absorbance at the determined maximum absorption wavelength was taken as the absorbance at the maximum absorption wavelength of the resin molding (1). The absorbance at the maximum absorption wavelength for each of the alkali-free glass alone and the cycloolefin film alone is zero.
Based on the following formula, the transmittance (%) of the maximum absorption wavelength was obtained. Table 9 shows the results.
T1=10- ^A1 ×100
(T1 represents the transmittance at the maximum absorption wavelength, and A1 represents the absorbance at the maximum absorption wavelength.)

[Evaluation of bleeding resistance of resin molded product (1)]
A separate film was further laminated on one side of the obtained resin molding (1) with a separate film to obtain an adhesive layer (1) with a double-sided separate film. The obtained pressure-sensitive adhesive layer (1) with a double-sided separate film was stored in air at 23 to 25°C for 1 month. After storage, the pressure-sensitive adhesive layer (1) with a double-sided separate film was examined under a microscope for in-plane crystal precipitation of the compound. If there was no crystal precipitation, it was rated as a, and if there was crystal precipitation, it was rated as b. The evaluation results are shown in the column of bleed resistance in Table 8.

[Measurement of absorbance retention rate of resin molding (1)]
A polarizing plate was prepared by laminating a 13 μm cycloolefin film on one side of a 8 μm thick polarizer using an adhesive layer.
After laminating the resin molded body (1) side of the resin molded body (1) with a separate film to the polarizer side of the polarizing plate with a laminator, it was cured for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65%. A laminate having a laminate structure of cycloolefin film/polarizer/resin molding (1)/separate film was obtained.
The resulting laminate was cut into a size of 30 cm x 30 cm, the separate film was peeled off, and the resin molding (1) and non-alkali glass [trade name "EAGLE XG" manufactured by Corning] were laminated. , a laminate (1-2) having a laminate structure of cycloolefin film/polarizer/resin molding (1)/glass was obtained.
The resulting laminate (1-2) was placed in a Sunshine Weather Meter (manufactured by Suga Test Instruments Co., Ltd.) for 75 hours under conditions of a temperature of 63° C. and a relative humidity of 50% RH to conduct a weather resistance test. The absorbance of the laminate (1-2) taken out was measured in the same manner as above. Based on the measured absorbance, the absorbance retention rate [%] of the laminate (1-2) at a wavelength of 540 nm was determined according to the following formula. Table 8 shows the results. The closer the absorbance retention rate is to 100%, the better the weather resistance without deterioration of the selective light absorption function.
As the absorption wavelength for evaluating the absorbance retention rate, the wavelength at which the absorbance is 1 to 1.5 on the long-wave side of the maximum absorption wavelength was selected among the measured absorbances. This is because the wavelength is the most sensitive absorbance region in terms of measurement accuracy of the spectrometer.
Absorbance retention rate (%)
= (A (540) after durability test/A (540) before durability test) x 100
[A (540) represents the absorbance of the laminate (1-2) at a wavelength of 540 nm. ]

Using the resin composition (2) instead of the resin composition (1), a resin molding (2), a laminate (2-1) and a laminate (2-2) were produced and evaluated in the same manner. rice field. Table 8 shows the results.

Using the resin composition (3) instead of the resin composition (1), a resin molding (3), a laminate (3-1) and a laminate (3-2) were produced and evaluated in the same manner. rice field. Table 8 shows the results.

Using the resin composition (5) instead of the resin composition (1), a resin molding (5) having a thickness of 20 μm was produced. A laminate (5-1) and a laminate (5-2) were prepared in the same manner except that the resin molded body (5) was used instead of the resin molded body (1), and evaluated for bleeding resistance and absorbance retention. was evaluated. The absorbance retention rate was evaluated at a wavelength of 520 nm. Table 8 shows the results.

Using the resin composition (6) instead of the resin composition (1), a resin molding (6) with a thickness of 20 μm was produced. A laminate (6-1) and a laminate (6-2) were prepared in the same manner except that the resin molded body (6) was used instead of the resin molded body (1), and evaluated for bleeding resistance and absorbance retention. was evaluated. The absorbance retention rate was evaluated at a wavelength of 530 nm. Table 8 shows the results.

Using the resin composition (7) instead of the resin composition (1), a resin molding (7) having a thickness of 20 μm was produced. Laminated body (7-1) and laminated body (7-2) were prepared in the same manner except that resin molded body (7) was used instead of resin molded body (1), and evaluated for bleeding resistance and absorbance retention. was evaluated. The absorbance retention rate was evaluated at a wavelength of 520 nm. Table 8 shows the results.

Using the resin composition (8) instead of the resin composition (1), a resin molding (8) with a thickness of 20 μm was produced. A laminate (8-1) and a laminate (8-2) were prepared in the same manner except that the resin molded body (8) was used instead of the resin molded body (1), and evaluated for bleeding resistance and absorbance retention. was evaluated. The absorbance retention rate was evaluated at a wavelength of 520 nm. Table 8 shows the results.

Using the resin composition (9) instead of the resin composition (1), a resin molding (9) having a thickness of 20 μm was produced. Laminated body (9-1) and laminated body (9-2) were prepared in the same manner except that resin molded body (9) was used instead of resin molded body (1), and evaluated for bleeding resistance and absorbance retention. was evaluated. The absorbance retention rate was evaluated at a wavelength of 510 nm. Table 8 shows the results.

<Evaluation of Molded Body of Resin Composition (4)>
[Preparation of Resin Molded Body (4)]
The resin composition (4) is applied to the release-treated surface of a release-treated polyethylene terephthalate film [PLR-382190, available from Lintec Corporation] and dried using an applicator. It was applied so that the thickness afterward would be 5 μm, and dried at 100° C. for 1 minute. After that, from the separate film side, UV-A (wavelength 320-390 nm) was adjusted to an illuminance of 500 mW and an integrated light amount of 500 mJ using an ultraviolet irradiation device ("Electrodeless UV lamp system H bulb" manufactured by Fusion UV Systems). A resin molded body (adhesive layer) (4) was formed by irradiating with ultraviolet rays, and a resin molded body (4) with a separate film was produced.
The obtained resin molded article (4) with a separate film was attached to non-alkali glass, and after peeling off the separate film, a 23 μm ultraviolet absorber-containing cycloolefin film [from Nippon Zeon Co., Ltd. was applied to the resin molded article (4). Obtained product name "ZEONOR"] was laminated to prepare a laminate (4-1) having a laminate structure of cycloolefin film/resin molding (4)/glass.
The produced laminate (4-1) was set in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and absorbance was measured in a wavelength range of 300 to 800 nm in 1 nm steps by the double beam method. The measured absorbance at a wavelength of 330 nm was defined as the absorbance at a wavelength of 330 nm of the resin molding (4). Both the alkali-free glass alone and the cycloolefin film have an absorbance of 0 at a wavelength of 330 nm.
Also, the transmittance (%) at a wavelength of 330 nm was obtained based on the following formula. Table 8 shows the results.
T = 10 ^{- A} × 100 (T represents transmittance and A represents absorbance.)

From the absorbance measured above, the maximum absorption wavelength of the laminate (4-1) was determined, and the absorbance at the determined maximum absorption wavelength was taken as the absorbance at the maximum absorption wavelength of the resin molded body (4). The absorbance at the maximum absorption wavelength for each of the alkali-free glass alone and the cycloolefin film alone is zero.
Based on the following formula, the transmittance (%) of the maximum absorption wavelength was obtained. Table 9 shows the results.
T1=10- ^A1 ×100
(T1 represents the transmittance at the maximum absorption wavelength, and A1 represents the absorbance at the maximum absorption wavelength.)

[Evaluation of bleed resistance of resin molding (4)]
A separate film was further laminated on one side of the obtained resin molding (4) with a separate film to obtain an adhesive layer (4) with a double-sided separate film. The obtained pressure-sensitive adhesive layer (4) with a double-sided separate film was stored in air at 23-25°C for 1 month. After storage, the pressure-sensitive adhesive layer (4) with the double-sided separate film was checked for the presence or absence of in-plane crystal precipitation of the compound using a microscope. If there was no crystal precipitation, it was rated as a, and if there was crystal precipitation, it was rated as b. The evaluation results are shown in the column of bleed resistance in Table 8.

[Measurement of absorbance retention rate of resin molding (4)]
A polarizing plate was prepared by laminating a 13 μm cycloolefin film on one side of a 8 μm thick polarizer using an adhesive layer.
After laminating the resin molded body (4) side of the resin molded body (4) with a separate film to the polarizer side of the polarizing plate with a laminator, it was cured for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65%. A laminate having a laminate structure of olefin film/polarizer/resin molding (4)/separate film was obtained.
The separate film was peeled off from the resulting laminate, and the resin molded article (4) was laminated to non-alkali glass [trade name "EAGLE XG" manufactured by Corning Incorporated] to form a cycloolefin film/polarizer/resin molded article ( 4)/A laminate (4-2) having a laminated structure of glass was obtained.
The resulting laminate (4-2) was placed in a Sunshine Weather Meter (manufactured by Suga Test Instruments Co., Ltd.) for 75 hours under conditions of a temperature of 63° C. and a relative humidity of 50% RH to carry out a weather resistance test. The absorbance of the laminate (4-2) taken out was measured in the same manner as above. Based on the measured absorbance, the absorbance retention rate of the sample at a wavelength of 540 nm was determined according to the following formula. Table 8 shows the results. The closer the absorbance retention rate is to 100%, the better the weather resistance without deterioration of the selective light absorption function.
Absorbance retention rate (%)
= (A (540) after durability test/A (540) before durability test) x 100
[A (540) represents the absorbance of the laminate (4-2) at a wavelength of 540 nm. ]

The values of transmittance at the maximum absorption wavelength of Examples 11 to 13 show that they exceeded the absorbance measurement limit (absorbance: 5) of a spectrophotometer.

The compound of the present invention has high absorption selectivity for light near the maximum absorption wavelength. Moreover, the resin composition containing the compound of the present invention has high absorbance retention even after the weather resistance test, and has good weather resistance.

Claims (19)

1. A compound having an anion represented by the following formula (I).
   

   

   
   [In formula (I), ring W ¹ represents a ring optionally having a substituent.
   Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
   R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
   R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
   R ¹ and R ⁴ may be linked together to form a ring.
   R ³ and R ⁴ may be linked together to form a ring.
   R ² and R ⁶ may be linked together to form a ring.
   ^R5 and ^R6 may be linked together to form a ring. ]
2. 2. The compound according to claim 1, wherein at least one selected from ^R1 and ^R2 is an electron-withdrawing group.
3. at least one selected from R ¹ and R ² is a cyano group, a nitro group, a halogenated alkyl group, a halogenated aryl group, -CO-R ₁ , -CO-OR ₂ , -CO-NR ₃ R _3z , —CO—S—R ₄ , —CS—R ₅ , —CS—OR ₆ , —CS—S—R ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent an optionally substituted hydrocarbon group or a halogen atom.), —OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₂ H or -SO ₃ H.
4. The compound according to any one of claims 1 to 3, wherein at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is an electron-withdrawing group.
5. A compound according to any one of claims 1 to 4, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an electron withdrawing group.
6. at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is a cyano group, a nitro group, a halogenated alkyl group, a halogenated aryl group, —CO—R ₁ , —CO—OR ₂ , —CO —NR ₃ R _3z , —CO—S—R ₄ , —CS—R ₅ , —CS—OR ₆ , —CS—S—R ₇ , —SO—R ₈ , —SO ₂ —R ₉ (R ₁ , R ₂ , R ₃ , R _3z , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently represent an optionally substituted hydrocarbon group or a halogen atom; ), -OCF _{3 , -SCF 3 ,} -SF ₅ , -SF ₃ , -SO ₂ H or -SO ₃ H.
7. The compound according to any one of claims 1 to 6, which exhibits a maximum absorption between wavelengths of 400 nm and 700 nm.
8. The compound according to any one of claims 1 to 7, which has a gram extinction coefficient of 50 [L/(g·cm)] or more at the maximum absorption wavelength.
9. A resin composition containing the compound according to any one of claims 1 to 8 and a resin.
10. A composition comprising the compound according to any one of claims 1 to 8 and a polymerizable monomer.
11. A molded article molded from the resin composition according to claim 9 or the composition according to claim 10.
12. An optical layer made of the resin composition according to claim 9 or the composition according to claim 10.
13. An optical laminate comprising the optical layer according to claim 12.
14. An image display device comprising the optical laminate according to claim 13.
15. Formula (MA)
    

    

    
    [In formula (MA), ring W ¹ represents a ring optionally having a substituent.
    Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
    R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
    R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent.
    R ¹ and R ⁴ may be linked together to form a ring.
    R ³ and R ⁴ may be linked together to form a ring. ]
    A compound represented by the formula (b-3)
    

    

    
    [In formula (b-3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
    X2 represents a _divalent linking group. ]
    Formula (I) comprising the step of reacting with a compound represented by
    

    

    
    [In the formula, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each have the same meaning as above. ]
    A method for producing a compound having an anion represented by
16. Furthermore, in the presence of a catalyst, formula (M)
    

    

    
    [In the formula, ring W ¹ , ring W ² , R ¹ and R ² each have the same meaning as above. ]
    A compound represented by the formula (b-2)
    

    

    
    [In the formula, R ³ and R ⁴ each have the same meaning as above.
    X ₁ represents a divalent linking group. ]
    16. The production method according to claim 15, comprising a step of obtaining a compound represented by formula (MA) by reacting with a compound represented by.
17. Formula (M1-2)
    

    

    
    [In formula (M1-2), R ^2′ represents a monovalent substituent, and E ₁ represents a leaving group. ]
    A compound represented by and the formula (M1-3)
    

    

    
    [In formula (M1-3), R ^1′ represents a monovalent substituent, and E ₂ represents a leaving group. ]
    At least one compound selected from compounds represented by the formula (M1-1)
    

    

    
    [In formula (M1-1), ring W ¹ represents a ring optionally having a substituent.
    Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
    R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.
    R ³ and R ⁴ may be linked together to form a ring.
    ^R5 and ^R6 may be linked together to form a ring. ]
    Formula (I) by reacting with a compound having an anion represented by
    

    

    
    [In the formula, ring W ¹ , ring W ² , R ³ , R ⁴ , R ⁵ and R ⁶ each have the same meaning as above.
    R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a substituent. ]
    A method for producing a compound having an anion represented by
18. A compound represented by formula (M).
    

    

    
    [In formula (M), ring W ¹ represents a ring optionally having a substituent.
    Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
    R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent. ]
19. A compound represented by the formula (MA).
    

    

    
    [In formula (MA), ring W ¹ represents a ring optionally having a substituent.
    Ring W2 represents a ring having at ^least one ^double bond as a ring constituent, and ring W2 may have a substituent.
    R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and at least one of R ¹ and R ² has a monovalent substituent.
    R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent substituent.
    R ¹ and R ⁴ may be linked together to form a ring.
    R ³ and R ⁴ may be linked together to form a ring. ]