TW202248193A - Compound - Google Patents

Abstract

The present invention provides a compound having an anion represented by the following formula (I). [In formula (I), ring W1 represents a ring which may have a substituent. Ring W2 represents a ring having at least one double bond as a constituent of the ring, and ring W2 may have a substituent. R1 and R2 each independently represent a hydrogen atom or a monovalent substituent, and at least one of R1 and 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 connected to each other to form a ring. R3 and R4 may be connected to each other to form a ring. R2 and R6 may be connected to each other to form a ring. R5 and R6 may be connected to each other to form a ring.].

Description

compound

The present invention relates to compounds.

Pigment compounds that absorb visible light are used for the purpose of coloring objects, penetrating or absorbing light of specific wavelengths, etc., and are used in a wide range of applications such as fibers, inks, paints, containers, packaging materials, printed materials, optical articles, glasses, and display devices. . As important characteristics of a pigment compound, selective absorption (sharpness of absorption spectrum) and durability (especially light fastness) can be cited. Among the pigment compounds, by controlling the number of methine carbons in the polymethine skeleton, it is possible to control the wavelength of the maximum absorption in a wide range 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 Anthocyanins are widely used for dots or dots in which many anthocyanins show high selective absorption (for example, US Pat. No. 6,004,536 specification (Patent Document 1)).

[Prior Art Literature]

[Patent Document 1] Specification of US Patent No. 6004536

However, although anthocyanins have high selective absorption, most of them are poor in durability (especially light fastness), so compounds with both high selective absorption and durability are sought.

The present invention includes the following inventions.

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

[式(I)中，環W¹表示可具有取代基之環；

[In formula (I), ring W represents ^a ring that may have a substituent;

^The ring W2 represents a ring having at least one double bond as a constituent element of the ring, and the 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 can be linked to each other and form a ring;

R ³ and R ⁴ can be connected to each other and form a ring;

R ² and R ⁶ can be connected to each other and form a ring;

R ⁵ and R ⁶ may be linked to each other and form a ring]

[2] The compound according to [1], wherein at least one selected from R ¹ and R ² is an electron attractive group.

[3] The compound according to [2], wherein at least one selected from R ¹ and R ² is cyano, nitro, halogenated alkyl, halogenated aryl, -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 a hydrocarbon group which may have a substituent 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 [1] to [3], wherein at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is an electron-attracting 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-attracting group.

[6] The compound as described in [5], wherein at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is cyano, nitro, halogenated alkyl, halogenated aryl, -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 a hydrocarbon group that may have a substituent 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 [1] to [6], which exhibits maximum absorption at a wavelength of 400 nm to 700 nm.

[8] The compound according to any one of [1] to [7], wherein the gram absorption coefficient at the maximum absorption wavelength is 50 [L/(g·cm)] or more.

[9] A resin composition comprising the compound described in any one of [1] to [8] and a resin.

[10] A composition comprising the compound described in any one of [1] to [8] and a polymerizable monomer.

[11] A molded body formed from the resin composition described in [9] or the composition described in claim 10.

[12] An optical layer composed of the resin composition described in [9] or the composition described in claim 10.

[13] An optical laminate comprising the optical layer described in [12].

[14] An image display device comprising the optical laminate described in [13].

[15] A method for producing a compound having an anion represented by formula (I), comprising the step of reacting a compound represented by formula (M-A) with a compound represented by formula (b-3).

[式(M-A)中，環W¹表示可具有取代基之環；

[In the formula (MA), the ring W represents ^a ring that may have a substituent;

^The ring W2 represents a ring having at least one double bond as a constituent element of the ring, and the 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 can be linked to each other and form a ring;

R ³ and R ⁴ can be linked to each other and form a ring;]

[式(b-3)中，R⁵及R⁶各自獨立地表示氫原子或1價之取代基，

[In formula (b-3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent,

X ₂ represents a divalent linking group]

[式中，環W¹、環W²、R¹、R²、R³、R⁴、R⁵及R⁶分別表示與上述者相同意義]

[wherein, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meanings as above]

[16] The production method described in [15] further comprises reacting the compound represented by the formula (M) with the compound represented by the formula (b-2) in the presence of a catalyst to obtain the compound represented by the formula (M-A). compound steps.

[式中，環W¹、環W²、R¹及R²分別表示與上述者相同意義]

[wherein, ring W ¹ , ring W ² , R ¹ and R ² have the same meanings as above]

[式中，R³及R⁴分別表示與上述者相同意義，

[wherein, R ³ and R ⁴ respectively represent the same meaning as above,

X ₁ represents a 2-valent linking group]

[17] A method for producing an anion compound represented by formula (I), comprising combining at least one compound selected from the compound represented by formula (M1-2) and the compound represented by formula (M1-3) with the compound represented by formula The step of reacting the anionic compound represented by (M1-1).

R ^2' ─── E ₁ (M1-2) [In the formula (M1-2), R ^2' represents a monovalent substituent, E ₁ represents a leaving group]

R ^1' ─── E ₂ (M1-3) [In the formula (M1-3), R ^1' represents a monovalent substituent, and E ₂ represents a leaving group]

[式(M1-1)中，環W¹表示可具有取代基之環；

[In the formula (M1-1), the ring W represents ^a ring that may have a substituent;

^The ring W2 represents a ring having at least one double bond as a constituent element of the ring, and the 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 can be connected to each other and form a ring;

R ⁵ and R ⁶ can be connected to each other and form a ring;]

[式中，環W¹、環W²、R³、R⁴、R⁵及R⁶分別表示與上述者相同意義；

[In the formula, ring W ¹ , ring W ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meanings 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]

[18] A compound represented by formula (M).

[式(M)中，環W¹表示可具有取代基之環；

[In the formula (M), the ring W represents ^a ring that may have a substituent;

^The ring W2 represents a ring having at least one double bond as a constituent element of the ring, and the 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 (M-A).

[式(M-A)中，環W¹表示可具有取代基之環；

[In the formula (MA), the ring W represents ^a ring that may have a substituent;

^The ring W2 represents a ring having at least one double bond as a constituent element of the ring, and the 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 can be linked to each other and form a ring;

R ³ and R ⁴ can be linked to each other and form a ring;]

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

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

[式(I)中，環W¹表示可具有取代基之環；

[In formula (I), ring W represents ^a ring that may have a substituent;

^The ring W2 represents a ring having at least one double bond as a constituent element of the ring, and the 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 can be linked to each other and form a ring;

R ³ and R ⁴ can be connected to each other and form a ring;

R ² and R ⁶ can be connected to each other and form a ring;

R ⁵ and R ⁶ can be connected to each other and form a ring;]

<anion>

The anions represented by the formula (I) also include all resonance structures as shown below.

Also, depending on the types of monovalent substituents represented by R ³ , R ⁴ , R ⁵ and R ⁶ , electron delocalization may extend to R ³ , R ⁴ , R ⁵ and R ⁶ . For example, when delocalization of electrons extends to monovalent substituents represented by R ³ , R ⁴ , R ⁵ and R ⁶ below, the resonance structure is also included in the anion represented by formula (I).

^The ring structure of ring W1 is not particularly limited. Ring W1 may be ^a single ring or a condensed ring.

The ring W1 may be ^a heterocyclic ring containing a heteroatom (such as an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as a constituent element of the ring, or may be a hydrocarbon ring composed of carbon atoms and hydrogen atoms. Ring W ¹ is preferably a ring composed of hydrocarbons. The ring W ¹ may be a non-aromatic ring (aliphatic ring) or an aromatic ring, but is preferably an aliphatic ring. If it is a non-aromatic ring, the selective absorption can be further improved.

Ring W ¹ is preferably a ring structure of 3-20-membered rings, more preferably 3-12-membered rings, more preferably 4-6-membered rings.

Ring W ¹ is preferably a monocyclic ring.

Ring W ² represents a ring structure having at least one double bond as a constituent element of the ring. Ring W2 has at least one ^double bond as a constituent element of the ring, but the double bond contained in ring W2 is usually ¹ to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 indivual.

Ring W ² may be monocyclic or polycyclic. The ring W ² may be an aromatic ring or a non-aromatic ring (aliphatic ring), preferably a non-aromatic ring. If it is a non-aromatic ring, the selective absorption can be further improved.

The ring W ² may be a heterocycle containing a heteroatom (such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.), or a ring composed of hydrocarbons. Ring W ² is preferably a ring composed of hydrocarbons.

Ring W ² is preferably a ring structure of 3-20-membered rings, more preferably 3-12-membered rings, more preferably 4-6-membered rings.

Ring W ¹ and ring W ² form a condensed ring. The condensed ring formed in ring W ¹ and ring W ² is preferably a condensed ring of an aliphatic hydrocarbon, more preferably a condensed ring of an aliphatic hydrocarbon having 6 to 40 carbon atoms.

Examples of the condensed ring formed by the ring W ¹ and the ring W ² include rings represented by the following formula (W ¹ -1) to formula (W ¹ -19). In addition, the condensed ring formed by the ring W ¹ and the ring W ² also includes all the above-mentioned anionic charge delocalized structures.

Ring W1 and ring ^W2 may each independently have ^a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl , octyl, nonyl, decyl, 2-ethylhexyl, 4-butyloctyl, vinyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, allyl, cyclohexyl Alkenyl, butadienyl and other aliphatic hydrocarbon groups with 1 to 25 carbons (preferably alkyl with 1 to 12 carbons); fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl , 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl, nine Alkyl halides with 1 to 25 carbons such as fluorobutyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, 4-butyloctyloxy and other alkoxy groups with 1 to 25 carbons; methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio Alkylthio groups with 1 to 12 carbon atoms; monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 1,1,2,2,2-pentafluoroethyl Fluorinated alkoxy groups with 1 to 12 carbons such as oxy and hexafluoroisopropoxy; fluorinated alkoxy groups with 1 to 12 carbons such as trifluoromethanethioalkoxy; amino group, methylamino group, Ethylamino, dimethylamino, diethylamino, diphenylamino, piperidinyl, pyrrolidinyl, methylethylamino, etc., which may be substituted by one or two hydrocarbon groups with 1 to 25 carbons ; Aminoformyl, N-methylaminoformyl, N,N-dimethylaminoformyl, and other aminoformyl groups whose N-position can be substituted by an alkyl group with 1 to 6 carbons; Alkylcarbonyloxy groups with 2 to 12 carbons such as methylcarbonyloxy and ethylcarbonyloxy; alkylsulfonyl groups with 1 to 12 carbons such as methylsulfonyl and ethylsulfonyl; phenyl and naphthyl , biphenyl, anthracenyl and other aromatic hydrocarbon groups with 6 to 25 carbons (preferably aryl with 6 to 18 carbons); arylsulfonyl with 6 to 12 carbons such as benzenesulfonyl; methoxy Alkoxysulfonyl groups with 1 to 12 carbon atoms such as sulfonyl and ethoxysulfonyl groups; trifluoromethylsulfonyl, pentafluoroethanesulfonyl, and trifluoroethanesulfonyl groups with 1 to 12 carbon atoms 12-fluoroalkylsulfonyl; acetyl, ethylcarbonyl and other acyl groups with 2 to 12 carbons; aldehyde groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butyloxycarbonyl, etc. Alkoxycarbonyl with 2 to 12 carbons; alkoxythiocarbonyl with 2 to 12 carbons such as methoxythiocarbonyl and ethoxythiocarbonyl; cyano; nitro; hydroxyl; thiol; Sulfonyl; Aminoformyl; Carboxyl; -SF ₃ ; -SF ₅ etc.

^The condensed ring formed by the ring W1 and the ring W2 may have ^a substituent, and examples ^of the substituent include substituents that the ring W1 or the 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 substituent represented by R1 and R2 is not particularly limited as long as it is not a ^hydrogen atom, and examples thereof include a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, an electron-attracting group, an electron-donating group, a heterocyclic group, a The base of polyoxyalkylene, etc.

^The monovalent aliphatic hydrocarbon groups represented by R1 and R2 include: methyl, ethyl, ⁿ -propyl, isopropyl, n-butyl, tert-butyl, second-butyl, n-pentyl, isopentyl , n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, lauryl , myristyl, cetyl, stearyl, 2-ethylhexyl, 4-butyloctyl and other straight-chain or branched-chain alkyl groups with 1 to 25 carbons: cyclopropyl, cyclobutyl, cyclo Cycloalkyl with 3 to 25 carbons such as pentyl and cyclohexyl; cycloalkyl with 4 to 25 carbons such as cyclohexylmethyl; alkylcycloalkyl with 4 to 25 carbons such as isobornyl; ethylene unsaturated aliphatic hydrocarbon groups such as propenyl, butenyl, pentenyl, ethynyl, propynyl, allyl, cyclohexenyl, butadienyl, etc. It is preferably a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms.

^The monovalent aromatic hydrocarbon groups represented by R1 and R2 can be exemplified: phenyl, naphthyl, anthracenyl, naphthacene, pentacene, phenanthrenyl, ^chrysenyl , tri-o-phenylene, tetraphenylene, Aryl groups with 6 to 18 carbons such as phenyl, pyrenyl, perylene, coronene phenyl, and biphenyl; aralkyl groups with 7 to 18 carbons such as benzyl, phenethyl, and naphthylmethyl; phenoxy Ethyl, phenoxydiethylene glycol, arylalkoxy of phenoxypolyalkylene glycol, etc., preferably aryl having 6 to 18 carbons, phenyl or benzyl.

^The electron donor groups represented by R1 and R2 can be ^listed as: hydroxyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, 4-butyloctyloxy and other alkoxy groups with 1 to 25 carbons; methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio Alkylthio groups with 1 to 12 carbons; amine, monomethylamino, monoethylamino, dimethylamino, diethylamino, methylethylamino, etc. can be modified by 1 or 2 carbons 1 Amino groups substituted with alkyl groups from 6 to 6, etc.

^The heterocyclic group represented by R1 and R2 can include ^: pyrrolidine ring group, piperidine ring group, pyrroline ring group, imidazolidine ring group, imidazoline ring group, oxazoline ring group, thiazoline ring group, piperidine ring group Pyridine ring group, morpholine ring group, hexahydropyrazine ring group, indole ring group, isoindole ring group, quinoline ring group, thiophene ring group, pyrrole ring group, thiazoline ring group and furan ring group, tetrahydrofuran An aliphatic heterocyclic group having 4 to 20 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms, such as a ring group.

The group having a polyoxyalkylene group represented by R ¹ and R ² is a group having an oxyvinyl group (-CH ₂ CH ₂ O-), an oxypropyl group (-CH ₂ CH ₂ CH ₂ O-) or the like. More specifically, a group represented by -(X ¹¹ O)mR ¹¹ (X ¹¹ represents an alkylene group having 1 to 6 carbons, R ¹¹ represents an alkyl group having 1 to 6 carbons which may have a hydroxyl group, m represents an integer from 1 to 6), etc.

The electron-attracting groups represented by R ¹ and R ² include, for example: halogen atoms, nitro groups, cyano groups, carboxyl groups, halogenated alkyl groups, halogenated aryl groups, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , - SO ₃ H, -SO ₂ H, and a group represented by the formula (z-1).

*-X ¹ -R ²²² (z-1)[In the formula (z-1), R ²²² represents a hydrogen atom, a halogen atom, a hydrocarbon group that may have a substituent, or a group with 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 with 1 to 6 carbons or a phenyl group;

＊Indicates a bond]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of halogenated alkyl groups include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosecond butyl, perfluorotertiary butyl, perfluoropentyl , perfluorohexyl, dichloromethyl, bromomethyl, iodomethyl and other halogenated alkyl groups with 1 to 25 carbons. Preferably it is a halogenated alkyl group having 1 to 12 carbons, more preferably a fluoroalkyl group having 1 to 12 carbons, still more preferably a perfluoroalkyl group having 1 to 12 carbons.

Halogenated aryl groups include: fluorophenyl, chlorophenyl, bromophenyl and other halogenated aryl groups with 6 to 18 carbon atoms, preferably fluoroaryl groups with 6 to 18 carbon atoms, more preferably fluoroaryl groups with 6 to 12 carbon atoms Perfluoroaryl, still more preferably pentafluorophenyl.

X ¹ is preferably -CO-, -COO- or -SO ₂ -.

The halogen atom represented by ^R222 includes fluorine atom, chlorine atom, bromine atom and iodine atom.

The hydrocarbon group represented by ^R222 includes an aliphatic hydrocarbon group with 1 to 25 carbon atoms or an aromatic hydrocarbon group with 6 to 18 carbon atoms.

Examples of aliphatic hydrocarbon groups with carbon numbers from 1 to 25 include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, second-butyl, n-pentyl, n-hexyl, 1-methyl butyl, 3-methylbutyl, n-octyl, n-decyl, 2-hexyl octyl, 4-butyl octyl, cyclohexyl, etc. straight chain, branched chain, cyclic carbon number 1 to 25 Alkyl; unsaturated aliphatic hydrocarbon groups such as vinyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, allyl, cyclohexenyl, butadienyl, etc., preferably carbon Alkyl groups of numbers 1 to 12.

Aromatic hydrocarbon groups with 6 to 18 carbons include: aryl groups with 6 to 18 carbons such as phenyl, naphthyl, anthracenyl, and biphenyl; phenylmethyl, phenethyl, and naphthylmethyl with 7 to 18 carbons. Aralkyl groups of 18, etc.

The substituents that the hydrocarbon group represented by ^R222 may have include halogen atoms, hydroxyl 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 .

R ²²³ and R ²²⁴ The alkyl groups with 1 to 6 carbons represented by: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, second butyl, n-pentyl, straight-chain or branched-chain alkyl having 1 to 6 carbons, such as n-hexyl and 1-methylbutyl.

The group represented by formula (z-1) is preferably -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 independently means a hydrocarbon group or a halogen atom which may have a substituent),

More preferably -CO-R ₁ , -CO-OR ₂ , -SO ₂ -R ₉ ,

Still more preferably -SO ₂ -R ₉ ,

Still more preferably -SO ₂ -R ₁₀ (R ₁₀ is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have substituents), -SO ₂ CF ₃ , -SO ₂ CHF ₂ , -SO ₂ CH ₂ F.

At least one selected from R ¹ and R ² is preferably an electron-attracting group, more preferably cyano, nitro, halogenated alkyl, halogenated aryl, -SCF ₃ , -SF ₃ , -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 that they may have Hydrocarbyl group or halogen atom of the substituent), -OCF ₃ or -SCF ₃ ,

Still more preferably cyano, nitro, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , -SO ₂ - _R9 ,

Still more preferably cyano, nitro, -OCF ₃ , -SCF ₃ , -SF ₅ , -SO ₂ CF ₃ , -SO ₂ -R ₁₀ ,

Most preferred are cyano or nitro.

Examples of the monovalent substituent represented by R ³ , R ⁴ , R ⁵ and R ⁶ are the same as the monovalent substituent represented by R ¹ .

At least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an electron-attracting group,

More preferably cyano, nitro, halogenated alkyl, halogenated aryl, -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 a hydrocarbon group which may have a substituent or a halogen atom), -OCF ₃ or -SCF ₃ ,

Still more preferably cyano, nitro, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , -SO ₂ - _R9 ,

Still more preferably cyano, nitro, -OCF ₃ , -SCF ₃ , -SF ₅ , -SO ₂ CF ₃ , -SO ₂ -R ₁₀ ,

Most preferred are cyano or nitro.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently preferably an electron-attracting group.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently more preferably cyano, nitro, halogenated alkyl, halogenated aryl, -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-R5, -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 a hydrocarbon group that may have a substituent or a halogen atom), -OCF ₃ or -SCF ₃ ,

Still more preferably cyano, nitro, -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₃ H, -SO ₂ H, -CO-R ₁ , -CO-OR ₂ , -SO ₂ - _R9 ,

Still more preferably cyano, nitro, -OCF ₃ , -SCF ₃ , -SF ₅ , -SO ₂ CF ₃ , -SO ₂ -R ₁₀ ,

Most preferred are cyano or nitro.

R ¹ and R ⁴ may be linked to each other to form a ring. The ring formed by connecting R ¹ and R ⁴ to each other is a ring formed by connecting R ¹ and R ⁴ to each other, and the ring W ¹ and ring W ² form at least three condensed rings. The anion represented by the formula (I) having a ring formed by linking R ¹ and R ⁴ to each other and a condensed ring formed by ring W ¹ and ring W ² includes, for example, the following anions.

The anion represented by formula (I) having a ring formed by R ¹ and R ⁴ connected to each other and a condensed ring formed by ring W ¹ and ring W ² is preferably formula (I-W2), formula (I-W3) , the anion represented by formula (I-W4), formula (I-W5), formula (I-W6), formula (I-W7) or formula (I-W14).

^The ring formed by connecting R1 and R4 to each other may have ^a substituent. Examples of the substituent include the same substituents that ring W ¹ and ring W ² may have.

R ² and R ⁶ may be linked to each other to form a ring. The ring formed by R ² and R ⁶ linked to each other is the ring formed by linked R ² and R ⁶ to each other, and ring W ¹ and ring W ² form a condensed ring of at least 3 rings. Examples of the anion represented by formula (1) having a ring formed by linking R ² and R ⁶ to each other, and a condensed ring formed by ring W ¹ and ring W ² include the following anions.

The anion represented by formula (I) having a ring formed by R ² and R ⁶ linked to each other and a condensed ring formed by ring W ¹ and ring W ² is preferably formula (I-w2), formula (I-w3) , the anion represented by formula (I-w4), formula (I-w5), formula (I-w6), formula (I-w7) or formula (I-w14).

The ring formed by connecting R ² and R ⁶ to each other may have a substituent. Examples of the substituent include the same substituents that ring W ¹ and ring W ² may have.

R ³ and R ⁴ may be linked to each other to form a ring. The ring formed by R ³ and R ⁴ linked to each other may be a single ring or a condensed ring, preferably a single ring. R ³ and R ⁴ are connected to each other to form a ring, which may contain heteroatoms (nitrogen atom, oxygen atom, sulfur atom) etc. as constituent elements of the ring.

The ring formed by R ³ and R ⁴ being connected to each other is usually a 3- to 10-membered ring, preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.

The ring formed by R ³ and R ⁴ being connected to each other includes the following rings and the like. In the rings described below, * represents ^a bond with the ring W1.

The ring formed by R ³ and R ⁴ being connected to each other is preferably formula (w-1), formula (w-4), formula (w-5), formula (w-6), formula (w-8), Formula (w-9), Formula (w-10), Formula (w-11), Formula (w-13), Formula (w-31), Formula (w-32), Formula (w-35), Formula A ring represented by (w-36), formula (w-37), formula (w-45), formula (w-47) or formula (w-48).

^The ring formed by mutual linkage of ^R5 and R6 includes the same rings as the ring formed by mutual linkage of ^R3 and R4 ^. R ⁵ and R ⁶ are connected to each other to form a ring, preferably formula (w-1), formula (w-4), formula (w-5), formula (w-6), formula (w-8), Formula (w-9), Formula (w-10), Formula (w-11), Formula (w-13), Formula (w-31), Formula (w-32), Formula (w-35), Formula A ring represented by (w-36), formula (w-37), formula (w-45), formula (w-47) or formula (w-48).

The anion represented by formula (I) is more preferably an anion represented by formula (I-A).

[式(I-A)中，R¹至R⁶各自獨立地表示與前述相同意義]

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

Examples of the anion represented by the formula (I) include the following anions. In addition, Me in the formula represents a methyl group.

<cation>

The compound of the present invention consists of an anion represented by formula (I) and a pair of cations. The compound of the present invention is not limited to the combination of anion and cation represented by formula (I).

The cation may be an organic cation or an inorganic cation.

Examples of 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 Onium, N-octylpyridinium, N-octyl-4-methylpyridinium, 1,1'-dimethyl-4,4'-bipyridinium, 1,1'-benzhydryl-4 , 4'-bipyridinium and other pyridinium cations;

Piperidinium cations such as 1-butyl-1-methylpiperidinium and 1-methyl-1-propylpiperidinium;

1-allyl-1-methylpyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium Onium, 1-methyl-1-propylpyrrolidinium, 1-(2-methoxyethyl)-1-methylpyrrolidinium, 1-methyl-1-n-octylpyrrolidinium, 1 - pyrrolidinium cations such as methyl-1-pentylpyrrolidinium;

cations with 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-methylimidazolium Imidazolium cations such as base-3-(4-sulfobutyl)imidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium;

Amyltriethylammonium, Butyltrimethylammonium, Benzyl(ethyl)dimethylammonium, Cyclohexyltrimethylammonium, Diethyl(methyl)propylammonium, Diethyl(2-methoxyethyl)methylammonium Ammonium, ethyl(2-methoxyethyl)dimethylammonium, ethyl(dimethyl)(2-phenylethyl)ammonium, methyltri-n-octylammonium, tetrabutylammonium, tetrahexylammonium, Ammonium cations such as tetrapentammonium, tetra-n-octylammonium, tetraheptammonium, and tetrapropylammonium;

Trimethyl-Caudium, Tributyl-Caudium, Triethyl-Caudium and other trialkyl-Caudium cations;

Tributylhexadecylphosphonium, tributylmethylphosphonium, tributyl-n-octylphosphonium, tributyl-n-octylphosphonium, tetra-n-octylphosphonium, tributyl(2-methoxyethyl ) phosphonium, tributylmethylphosphonium, trihexyl (tetradecyl) phosphonium, trihexyl (tetradecyl) phosphonium and other phosphonium cations;

Morpholinium cations such as 4-ethyl-4-methylmorpholinium;

Triarylmethane cations such as triphenylmethylium, etc.

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, strontium ions, Alkaline earth metal ions such as barium ions; divalent metal ions such as copper (II) ions, nickel ions, cobalt ions, iron (II) ions, manganese ions, palladium ions, zinc ions, germanium (II) ions; cobalt (III) ions , iron (III) ions, chromium (III) ions, scandium ions, yttrium ions, ruthenium (III) ions, gallium ions and other trivalent metal ions; titanium ions, zirconium ions, hafnium ions, germanium (IV) ions, molybdenum ( IV) Tetravalent metal ions such as ions; NH4 ⁺ etc.

The cations are preferably 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 , more preferably potassium ions, calcium ions, barium ions, magnesium ions, copper (I) ions, copper (II) ions, nickel ions and organic cations, more preferably potassium ions and organic cations.

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

[式中，W¹、W²、R¹、R²、R³、R⁴、R⁵及R⁶分別表示與上述者相同意義；

[Wherein, W ¹ , W ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meanings as above;

g represents an integer from 1 to 4;

G represents 1-valent cation, 2-valent cation, 3-valent cation or 4-valent cation]

The molecular weight of the compound (I) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less. Also, it is preferably at least 100, more preferably at least 200, and still more preferably at least 300.

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

The gram light absorption coefficient ε in the maximum absorption wavelength (λ max) of compound (I) is preferably 50 [L/(g‧cm)] or more, more preferably 100 [L/(g‧cm)] or more, most preferably 150 [L/(g‧cm)] or more. Although the upper limit is not particularly limited, it is usually 100000 [L/(g·cm)] or less.

When the gram absorption coefficient ε in λ max of the compound (I) is 50 [L/(g·cm)] or more, it is preferable in terms 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, still more preferably 35 nm, most preferably 30 nm or less. The full width at half maximum can be measured by the method described in the Examples.

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

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

Compound (I) is preferably 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 ) to 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 ) to compound (138), compound (140) to compound (143), compound (145) to compound (147), compound (149) to compound (155), compound (158), compound (159), compound (161 ) to compound (164), compound (166) to compound (169), compound (171) to compound (173), compound (175), compound (176), compound (179) to compound (181), compound (184 ),change Compound (185), Compound (187) to Compound (189), Compound (191), Compound (193) to Compound (198).

<Production method (1) of compound (I)>

Compound (I) can, for example, be selected from a compound represented by formula (M1-2) (hereinafter also referred to as compound (M1-2)) and a compound represented by formula (M1-3) (hereinafter also referred to as compound (M1-3)) obtained by reacting at least one compound with a compound having an anion represented by formula (M1-1) (hereinafter also referred to as compound (M1-1)).

[式(M1-1)中，環W¹、環W²、R³、R⁴、R⁵及R⁶與前述相同意義；

[In formula (M1-1), ring W ¹ , ring W ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as above;

In the formula (M1-2), R ^2' represents a monovalent substituent, and E ₁ represents a leaving group;

In the 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 ones as the monovalent substituent represented by R ² .

Examples of the monovalent substituent represented by R ^1′ include the same ones as the monovalent substituent represented by R ¹ .

_The leaving groups represented by E1 and _E2 are independently independent, and examples include halogen atoms, succinimide groups, maleimide groups, o-sulfobenzyl imide groups, methylsulfonyl groups, and p-methoxyl groups. phenylsulfonyl, p-toluenesulfonyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl, etc.

The reaction of at least one compound selected from the group consisting of the compound (M1-2) and the compound (M1-3) with the compound (M1-1) can be performed by combining the compound selected from the compound (M1-2) and the compound ( At least one compound in the group consisting of M1-3) is mixed with the compound (M1-1).

Compound (M1-2) is usually used in an amount of 0.1 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of compound (M1-1).

Compound (M1-3) is usually used in an amount of 0.1 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of compound (M1-1).

The reaction of at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) with compound (M1-1) is preferably carried out in the presence of a base.

The base can be exemplified: 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 alkali metal alkoxide ), etc.; metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; metal hydrides such as sodium hydride, potassium hydride, lithium aluminum hydride, and sodium borohydride; sodium carbonate, sodium bicarbonate, potassium carbonate, and bicarbonate Metal carbonates such as potassium, lithium carbonate, lithium bicarbonate, and cesium carbonate; organic lithium compounds such as methyllithium, n-butyllithium, second-butyllithium, third-butyllithium, and phenyllithium; methylmagnesium bromide , isopropylmagnesium bromide, n-butylmagnesium bromide, isopropylmagnesium chloride and other alkyl metal halides; diisopropylamide lithium, 2,2,6,6-tetramethylpiperidine lithium, ( Metal amide compounds such as lithium bis(trimethylsilyl)amide, lithium tetramethylpiperidine; pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, triethylamine , diisopropylethylamine, triisopropylamine, 2,2,6,6-tetramethylpiperidine, piperidine, pyrrolidine, proline, aniline, N,N-dimethylaniline, ethylenediamine Other amine compounds; metal carboxylates such as sodium acetate, potassium acetate, sodium formate; ammonium carboxylate such as ammonium acetate, etc.

The amount of base used is usually 0.001 to 20 moles, preferably 0.03 to 10 moles, more preferably 0.05 to 5 moles, and even more preferably 0.1 to 3 moles, relative to 1 mole of compound (M1-1). ears, preferably 0.5 to 2 moles.

The reaction of at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) with compound (M1-1) can be performed 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; Chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, tetrachloroethylene, chloroform, etc. Halogen solvents; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, n-propyl acetate and other ester solvents; methanol, ethanol, isopropanol, hexafluoroisopropanol, n-butanol, isobutanol , tertiary butanol and other alcohol solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanol and other ketone solvents; tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl Ether, 4-methyltetrahydrofuran, dioxane, diethyl ether, tertiary butyl methyl ether, diisopropyl ether, dimethoxyethane, diethoxymethane and other ether solvents; N,N-dimethylacetamide Amide solvents such as amines, N,N-dimethylformamide, etc.; dimethylsulfoxide; 1,3-dimethyl-2-imidazolidinone; hexamethyltriamide phosphate; water, etc. 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, and more preferably It is acetonitrile, tetrahydrofuran, methanol, ethanol, isopropanol, 2-butanone, toluene, most preferably methanol, ethanol, isopropanol, acetonitrile, 2-butanone or toluene.

The reaction time of 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 at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1) is usually -100 to 200°C.

Compound (M1-1) includes the following compounds and the like.

Compound (M1-2) and compound (M1-3) can use a commercial item. Examples include: cyanogen chloride, cyanogen bromide, p-toluenesulfonyl cyanide, trifluoromethanesulfonyl cyanide, benzyl thiocyanate, tert-butylisocyanide, copper(I) cyanide, potassium cyanide, 1-cyano-4-(dimethylamino)pyridinium tetrafluoroborate, p-toluenesulfonylmethylisonitrile, 1-chloromethyl-4-fluoro-1,4-diazonium bicyclo[ 2.2.2] Octane bis(tetrafluoroborate) (also known as Selectfluor (registered trademark of Air Products and Chemicals), benzoyl (phenyl iodide) (trifluoromethanesulfonyl) Aniline, 2,8-difluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium triflate, 1-fluoro-3,3-dimethyl -1,2-benzoiodazole, 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-[(trifluoromethylthio) base) thio]-p-toluenesulfonamide, 1-trifluoromethyl-3,3-dimethyl-1,2-benzoiodazole, 1-trifluoromethyl-1,2-benzoiodide Azol-3(1H)-one, nitric acid, methyl iodide, dimethylsulfuric acid, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, acetyl chloride, etc.

In addition, when R ^1' and R ^2' are the same group and E ₁ and E ₂ are the same group, compound (M1-2) and compound (M1-3) are the same compound.

When at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is reacted with compound (M1-1), a compound having a cation derived from compound (M1-1) can be obtained. and compound (I) having an anion represented by formula (I).

When the cation of compound (I) is to be exchanged for a desired cation, ion exchange can be performed by mixing compound (I) with a salt having the desired cation. The aforementioned ion exchange can be performed in the presence of a solvent. Salts with desired cations include, for example, chloride salts composed of desired cations and chloride ions, bromide salts composed of desired cations and bromide ions, and salts composed of desired cations and iodide ions. Iodide salts composed of desired cations and fluoride ions, nitrate salts composed of desired cations and nitrate ions, sulfate salts composed of desired cations and sulfate ions, desired cations and Perchlorate composed of perchlorate ion, sulfonate composed of desired cation and sulfonate ion, carboxylate composed of desired cation and carboxylate ion, Hypochlorite, hexafluorophosphate salt consisting of a desired cation and hexafluorophosphoric acid, imide salt consisting of a desired cation and imide, and the like.

In addition, the compound (I) having a divalent or higher cation can be obtained by performing ion exchange after obtaining the compound (I) having a monovalent cation. In addition, when reacting at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) with compound (M1-1), it is also possible to use a compound having a divalent or higher cation Compound (M1-1) was obtained.

The anion part in the compound (M1-1) can be obtained by making the compound represented by the formula (M1-4) (hereinafter, also referred to as the compound (M1-4)), the compound represented by the formula (b-2) (hereinafter, Also referred to as compound (b-2)) and a compound represented by formula (b-3) (hereinafter, also referred to as compound (b-3)) are produced by reacting.

[式(M1-4)中，環W¹及環W²表示與上述者相同意義；

[In formula (M1-4), ring W ¹ and ring W ² represent the same meaning as above;

In formula (b-2), R ³ and R ⁴ represent the same meaning as above, and X ₁ represents a divalent linking group;

In formula (b-3), R ⁵ and R ⁶ represent the same meaning as above, and X ₂ represents a divalent linking group]

The reaction of compound (M1-4), compound (b-2) and compound (b-3) can be implemented by mixing compound (M1-4), compound (b-2) and compound (b-3) .

The reaction of compound (M1-4), compound (b-2) and compound (b-3) is preferably implemented in the presence of a base, so that Compound (M1-4), compound (b-2) and compound (b-3) are preferably mixed with a base.

The mixing of compound (M1-4), compound (b-2) and compound (b-3) with a base is preferably by adding compound (b-2) to a mixture (1) of compound (M1-4) and a part of the base ) to obtain a mixture (2), and to the obtained mixture (2), add a mixture (3) of the compound (b-3) and the remainder of the base.

The reaction of compound (M1-4), compound (b-2) and compound (b-3) with a base can be carried out in the presence of a solvent. Examples of the solvent include the same solvents as those used for the reaction of at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1). Preferred are acetonitrile, ethanol, methanol, 2-butanone, toluene, 2-butanone, tetrahydrofuran, and dioxane.

Also, the solvent is preferably a dehydration solvent.

The reaction time of compound (M1-4), compound (b-2) and compound (b-3) with the base is usually 0.05 to 100 hours.

The reaction temperature of compound (M1-4), compound (b-2) and compound (b-3) with a base is usually -100 to 200°C.

Compound (b-2) is usually used in an amount of 0.01 to 10 moles relative to 1 mole of compound (M1-4).

Compound (b-3) is usually used in an amount of 0.01 to 10 moles relative to 1 mole of compound (M1-4).

The base is usually used in an amount of 0.01 to 10 moles relative to 1 mole of compound (M1-4).

Compound (M1-4) can use a commercial item, and 7-hydroxy-2,3,4,4a,5,6-hexahydronaphthalene-2-one etc. are mentioned.

Compound (b-2) and compound (b-3) each independently can use a commercial item, for example: malononitrile, 2-cyanoacetamide, cyanoacetic acid, methyl cyanoacetate, cyano Ethyl acetate, propyl cyanoacetate, isopropyl cyanoacetate, butyl cyanoacetate, tert-butyl cyanoacetate, 2-ethylhexyl cyanoacetate, 2-ethoxyethyl cyanoacetate ester, 2-cyano-N,N-dimethylacetamide, pivalylacetonitrile, cyanoacetylurea, Benzoylacetonitrile, 2-cyanoacetylaniline, 3-oxo-3-(2-thienyl)propionitrile, methyl acetylacetate, dimedone, 1,3-cyclopropanedione , Tetronic acid, acetylacetone, malonamide, malonic acid, 1,3-cyclohexanedione, 2,4-piperidinedione, 1,3-cycloheptane Diketone, barbituric acid, 3,5-heptanedione, dimethyl malonate, Michaelis acid, 1,3-indandione, trifluoroacetylacetone, 1,3-dimethyl Base barbituric acid, 1,3-dicyclohexyl barbituric acid, 2-thiobarbituric acid, 1,3-diethyl-2-thiobarbituric acid, etc.

_In addition, when X1 and X2 are the same group, ^R3 and R4 are the same group, and ^R5 and R6 are the same group, compound (b ^- ₂ ) and compound (b- ³ ) are the same compound .

Examples of the base include the same bases as those used in the reaction between at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1).

Compound (M1-1) usually has a cation derived from a base. For example, as long as the cation derived from the base is monovalent, a compound composed of a monovalent cation and one anion represented by the formula (M1-1) can be obtained. As long as the cation derived from the base is divalent, a compound composed of a divalent cation and two anions represented by the formula (M1-1) can be obtained.

<Production method (2) of compound (I)>

The anion portion of compound (I) can be produced by reacting a compound represented by formula (M-A) (hereinafter also referred to as compound (M-A)) and compound (b-3).

[式中，R¹、R²、R³、R⁴、R⁵、R⁶、X₂、W¹及W²分別表示與上述者相同意義]

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

The reaction of compound (M-A) and compound (b-3) is preferably carried out in the presence of a catalyst.

Catalysts include: carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; ammonium chloride; titanium tetrachloride, aluminum chloride, aluminum isopropoxide, boron tribromide, boron trifluoride, ferric chloride, potassium chloride , tin tetrachloride, lanthanide trifluoromethane Sulfonates and other Lewis acids; methanesulfonic anhydride, p-toluenesulfonic anhydride, trifluoromethanesulfonic anhydride, nonafluorobutanesulfonic anhydride and other sulfonic anhydrides; p-toluenesulfonic acid, trifluoromethanesulfonic acid, fluorosulfuric acid and other sulfonic acids; Electrophilic alkylating agents such as methyl sulfuric acid, methyl trifluoromethanesulfonate (methyl trifluoromethanesulfonate), methyl iodide, trimethyloxonium tetrafluoroborate, dimethyl fluorosulfate, etc.; p-toluene Sulphonic acid halides such as sulfonyl chloride and trifluoromethanesulfonyl chloride, etc. Preferred are electrophilic alkylating agents, sulfonic anhydrides or sulfonic acid halides, more preferred are dimethylsulfuric acid, methyl trifluoromethanesulfonate, p-toluenesulfonic anhydride or trifluoromethanesulfonic anhydride, p-toluenesulfonyl Chlorine, trifluoromethanesulfonyl chloride, more preferably methyl trifluoromethanesulfonate or trifluoromethanesulfonic anhydride.

The reaction of compound (M-A) and compound (b-3) is preferably carried out in the presence of a base.

Examples of the base include the same bases as those used in the reaction between at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1).

The reaction of compound (M-A) and compound (b-3) can be carried out in the presence of a solvent. Examples of the solvent include the same solvents as those used for the reaction of at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1).

Also, the solvent is preferably a dehydration solvent.

The reaction of compound (M-A) and compound (b-3) is preferably carried out by mixing catalyst with compound (M-A) and compound (b-3), more preferably by catalyst, base, compound (M-A) and Compound (b-3) is mixed and implemented.

The reaction between compound (M-A) and compound (b-3) is preferably carried out in a deoxygenated environment (such as nitrogen environment).

Compound (b-3) is usually used in an amount of 0.01 to 20 mol, preferably 0.1 to 10 mol, relative to 1 mol of compound (M-A).

The catalyst is usually used in an amount of 0.001 to 20 moles, preferably 0.1 to 10 moles, relative to 1 mole of compound (M-A).

The base is usually used in an amount of 0.001 to 20 moles, preferably 0.1 to 10 moles, relative to 1 mole of compound (M-A).

The reaction time of compound (M-A) and compound (b-3) is usually 0.01 to 200 hours.

The reaction temperature of compound (M-A) and compound (b-3) is usually -100 to 200°C.

Compound (M-A) includes, for example, the following compounds.

When compound (M-A) and compound (b-3) are reacted 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 performed by mixing compound (I) with a salt having the desired cation. The aforementioned ion exchange can be performed in the presence of a solvent. Salts with desired cations include, for example, chloride salts composed of desired cations and chloride ions, bromide salts composed of desired cations and bromide ions, and iodides composed of desired cations and iodide ions. Salts, fluoride salts consisting of desired cations and fluoride ions, nitrates consisting of desired cations and nitrate ions, sulfate salts consisting of desired cations and sulfate ions, desired cations and perchlorate ions Perchlorate, sulfonate composed of desired cation and sulfonate ion, carboxylate composed of desired cation and carboxylate ion, hypochlorite composed of desired cation and hypochlorite ion, A hexafluorophosphate salt consisting of a desired cation and hexafluorophosphoric acid, an imide salt consisting of a desired cation and an imide, and the like.

Compound (M-A) can be produced by reacting a compound represented by formula (M) (hereinafter also referred to as compound (M)) and compound (b-2) in the presence of a catalyst.

[式中，環W¹、環W²、R¹、R²、R³、R⁴及X₁分別表示與上述者相同意義]

[wherein, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , R ⁴ and X ₁ represent the same meanings as above]

Examples of the catalyst include the same catalysts as those usable for the reaction between the compound (M-A) and the compound (b-3). Preferred are electrophilic alkylating agents, sulfonic anhydrides or sulfonic acid halides, more preferred are dimethylsulfuric acid, methyl trifluoromethanesulfonate, p-toluenesulfonic anhydride or trifluoromethanesulfonic anhydride, p-toluenesulfonyl Chlorine, trifluoromethanesulfonyl chloride, more preferably methyl trifluoromethanesulfonate or trifluoromethanesulfonic anhydride.

The reaction between compound (M) and compound (b-2) is preferably further carried out in the presence of a base.

Examples of the base include the same base as the base that can be used in the reaction between at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1), preferably It is metal alkoxide, metal hydroxide, metal hydride, metal carbonate, organic lithium, metal amide compound, amine compound or metal carboxylate, more preferably potassium ethylate, sodium tertiary butoxide, tertiary butanol Potassium, sodium hydroxide, potassium hydroxide, sodium hydride, lithium aluminum hydride, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, methyl lithium, n-butyl lithium, tertiary butyl lithium, diisopropyl Lithium amide, lithium 2,2,6,6-tetramethylpiperidine, lithium (bistrimethylsilyl)amide, lithium tetramethylpiperidine, pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, triethylamine, diisopropylethylamine, triisopropylamine, 2,2,6,6-tetramethylpiperidine, piperidine, pyrrolidine, proline, Aniline, N,N-dimethylaniline, sodium acetate, sodium formate, ammonium acetate.

The reaction of compound (M) and compound (b-2) can be carried out in the presence of a solvent. Examples of the solvent include the same solvents as those used for the reaction of at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1). The solvent is preferably acetonitrile, methanol, ethanol, toluene, 2-butanone, dioxane, tetrahydrofuran, dimethylsulfoxide, dimethylformamide or dimethylacetamide.

Also, the solvent is preferably a dehydration 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), preferably by mixing the catalyst, the base, the compound (M) and the compound ( b-2) mixed and implemented.

The reaction between compound (M) and compound (b-2) is preferably carried out in a deoxygenated environment (for example, nitrogen environment).

The compound (b-2) is usually used in an amount of 0.01 to 20 mol, preferably 0.1 to 10 mol, relative to 1 mol of compound (M).

The catalyst is usually used in an amount of 0.001 to 20 mol, preferably 0.1 to 10 mol, relative to 1 mol of compound (M).

The base is usually used in an amount of 0.001 to 20 moles, preferably 0.1 to 10 moles, relative to 1 mole of compound (M).

The reaction time of compound (M) and compound (b-2) is usually 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 is a synthetic intermediate of compound (I).

[式中，環W¹、環W²、R¹及R²表示與上述者相同意義]

[wherein, ring W ¹ , ring W ² , R ¹ and R ² have the same meanings as above]

As compound (M), the following compounds etc. are mentioned.

<Method for producing compound (M)>

Compound (M) can be obtained by making a compound represented by formula (M1-4) (hereinafter also referred to as compound (M1-4)) and a group selected from compound (M1-2) and formula (M1-3) At least one compound in the group is reacted to produce.

[式中，環W¹、環W²、R¹、R²、R^1’、R^2’、E₁及E₂表示與上述者相同意義]

[wherein, 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 groups as the leaving group represented by E1.

The reaction between compound (M1-4) and at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) is preferably performed in the presence of a base.

Examples of the base include the same base as the base that can be used in the reaction between at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1), preferably It is metal alkoxide, metal hydroxide, metal hydride, metal carbonate, organic lithium, metal amide compound, amine compound or metal carboxylate, more preferably potassium ethylate, sodium tertiary butoxide, tertiary butanol Potassium, sodium hydroxide, potassium hydroxide, sodium hydride, lithium aluminum hydride, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, methyl lithium, n-butyl lithium, tertiary butyl lithium, diisopropyl Lithium amide, lithium 2,2,6,6-tetramethylpiperidine, lithium (bistrimethylsilyl)amide, lithium tetramethylpiperidine, pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, triethylamine, diisopropylethylamine, triisopropylamine, 2,2,6,6-tetramethylpiperidine, piperidine, pyrrolidine, proline, Aniline, N,N-dimethylaniline, sodium acetate, sodium formate, ammonium acetate.

The base is usually used in an amount of 0.001 to 20 moles, preferably 0.1 to 10 moles, relative to 1 mole of compound (M1-4).

The reaction between compound (M1-4) and at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) can be performed in the presence of a solvent. Examples of the solvent include the same solvents as those used in the reaction of at least one compound selected from the group consisting of compound (M1-2) and compound (M1-3) and compound (M1-1). Preferred are acetonitrile, methanol, ethanol, toluene, 2-butanone, dioxane, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, and dimethylacetamide.

Also, the solvent is preferably a dehydration solvent.

The reaction of the compound (M1-4) with at least one compound selected from the group consisting of the compound (M1-2) and the compound (M1-3) is carried out by combining the compound (M1-4) with the compound selected from the compound ( ( M1-3) at least one compound in the group consisting of mixed and implemented.

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 a deoxygenated environment (for example, nitrogen environment).

Compound (M1-2) is usually used in an amount of 0.1 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of compound (M1-4).

Compound (M1-3) is usually used in an amount of 0.1 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of compound (M1-4).

The base is usually used in an amount of 0.001 to 20 moles, preferably 0.1 to 10 moles, relative to 1 mole of compound (M1-4).

The reaction time between 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.

Compound (M1-4) and at least one selected from the group consisting of compound (M1-2) and compound (M1-3) The reaction temperature of one compound is usually -100 to 200°C.

<Composition Containing Compound (I)>

The present invention also includes compositions containing compound (I). The shaped article formed from a composition containing compound (I) preferably has a transmittance at the maximum absorption wavelength [nm] of the compound (I) contained at 50% or less, more preferably 30% or less, even more preferably Below 15%, the best is below 10%.

The composition containing compound (I) is preferably a resin composition containing compound (I) and a resin (hereinafter also referred to as "resin composition") or a composition containing compound (I) and a polymerizable monomer (hereinafter , also referred to as "composition (1)").

The composition containing compound (I) can be used in all applications, and among them, it is particularly suitable for applications that may be exposed to sunlight or light containing ultraviolet rays. Specific examples include: glass substitutes and their surface coating materials; window glass, lighting glass, and light source protection glass for housing, equipment, and conveying equipment; coating materials for housing, equipment, and conveying equipment, etc.; window films for housing, equipment, and conveying equipment; , equipment, conveying machines, etc., internal and external materials, internal and external coatings and coating films formed by such coatings; alkyd resin coatings and coating films formed by such coatings; acrylic paint coatings and coating films formed by such coatings; Materials for light sources emitting ultraviolet rays such as fluorescent lamps and mercury lamps; materials for precision machinery, electronic and electrical equipment, and materials for blocking electromagnetic waves generated from various displays; containers or packaging materials for food, chemicals, medicines, etc.; bottles, Boxes, blisters, cups, special packaging, disc jackets, sheet or film materials for agricultural industry; anti-fading agents for printed matter, dyed matter, dyed pigments, etc.; for polymer carriers (such as plastic parts for machinery and automobile parts) ) protective film; outer coating of printed matter; inkjet media coating; laminated matte; optical light film; safety glass/windshield interlayer; electrochromic/photochromic applications; Cosmetics such as sunscreen, shampoo, conditioner, and hair styling materials; fiber products and fibers for clothing such as sportswear, stockings, and hats; household interior products such as curtains, carpets, and wallpapers; plastic lenses, contact lenses , prosthetic eye and other doctors Medical appliances; optical products such as optical filters, backlight display films, screens, mirrors, and photographic materials; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, inks, etc.; sign boards, markers, etc. and their surface coatings materials etc.

The shape of the molded body formed by the composition of the present invention can be flat film, powder, spherical particle, broken particle, block continuous body, fiber, tube, hollow fiber, granular, plate, porous Any kind of shape.

The resin used in the above-mentioned resin composition includes various known moldings, thermoplastic resins and thermosetting resins conventionally used in the production of sheets, films, and the like.

Examples of thermoplastic resins include olefin resins such as polyethylene resins, polypropylene resins, and polycycloolefin resins, poly(meth)acrylate resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile- Butadiene-styrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-ethylene Polyester resins such as alcohol resins, polyethylene terephthalate resins, polybutylene terephthalate resins, liquid crystal polyester resins, polyacetal resins, polyamide resins, polycarbonate resins , polyurethane resin and polyphenylene sulfide resin, etc. These resins can also be used as one or two or more polymer blends or polymer alloys.

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

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

The above-mentioned resin composition can be obtained by mixing compound (I) with 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 with respect to 100 parts by mass of the resin.

The resin composition may contain other additives such as solvents, crosslinking catalysts, tackifying resins, plasticizers, softeners, dyes, pigments, inorganic fillers, etc. as needed.

The polymerizable monomer used in the above composition (1) is not particularly limited, but is preferably a radical polymerizable monomer, more preferably a photoradical polymerizable monomer, and even more preferably a (meth)acrylate.

(Meth)acrylates include monofunctional (meth)acrylate monomers with one (meth)acryloxy group in the molecule, and bifunctional (meth)acrylate monomers with two (meth)acryloxy groups in the molecule. (Meth)acrylate monomers, polyfunctional (meth)acrylate monomers having 3 or more (meth)acryloxy groups in the molecule.

The composition (1) preferably further contains a polymerization initiator. When the polymerizable monomer is a radical 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 to impart desired performance, for example, 0.01 to 20 parts by mass based on 100 parts by mass of the polymerizable monomer.

The composition (1) may contain solvents, crosslinking catalysts, tackifier resins, plasticizers, softeners, dyes, pigments, inorganic fillers, and other additives as needed.

When the composition of the present invention is used in optical articles such as optical films, it can be applied to image display devices, for example. When the composition of the present invention is applied to an image display device, the optical layer formed from the composition of the present invention can be applied to any of film layer, adhesive layer, coating layer, etc., preferably adhesive layer or coating layer.

When the composition of the present invention is used in an optical article, it may be an optical layer formed only of the composition of the present invention, or an optical layered product in which an optical layer formed of the composition of the present invention is laminated with other layers. As for other layers, a polarizing film, a retardation film, a thermoplastic resin film, etc. are mentioned, for example. The optical layer of the present invention is preferably an optical layer (optical film) formed of the composition of the present invention as long as the optical layered product is a laminate in which the optical layer of the present invention, the adhesive layer, and the polarizing film are laminated in this order. As long as the optical laminate is based on The optical layer of the present invention, a thermoplastic resin film, an adhesive layer, and a polarizing film are laminated in this order, and the optical layer of the present invention is preferably an optical layer (coating layer) formed of the composition of the present invention. The optical layer of the present invention is preferably an optical layer (adhesive layer) formed of the composition of the present invention as long as 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. .

<Adhesive composition>

When the layer formed by the composition of the present invention is an adhesive layer, the layer is composed of an adhesive composition (hereinafter, also referred to as It is called the formation of adhesive composition (i)). The adhesive composition (i) may further contain a radical curable component (D), an initiator (E), and a light-absorbing compound (F) other than the compound (I) (hereinafter also referred to as a light-selective absorption compound ( F)), antistatic agent, etc., preferably contain at least one selected from the group consisting of radical curable component (D), initiator (E) and photoselective absorption compound (F).

Resin (A) will not be specifically limited if it is resin used for an adhesive composition. The resin (A) is preferably one that does not show the maximum absorption in the wavelength range from 300 nm to 780 nm.

The 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, most preferably 0°C or lower. Also, 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, still more preferably -55°C or higher, most preferably -50°C or higher. If the glass transition temperature of the resin (A) is 40° C. or lower, it is advantageous in improving the adhesion to the adherend of the adhesive layer formed from the adhesive composition (i). In addition, when the glass transition temperature of the resin (A) is -80° C. or higher, it is advantageous in improving the durability of the adhesive layer formed from the adhesive composition (i). In addition, the glass transition temperature can be measured by differential scanning calorimetry (DSC).

Examples of the resin (A) include (meth)acrylic resins, silicone-based resins, rubber-based resins, and urethane-based resins, and are preferably (meth)acrylic resins.

The (meth)acrylic resin is preferably a copolymer having a (meth)acrylate-derived structural unit as a main component (preferably containing 50% by mass or more). Structural units derived from (meth)acrylate may contain more than one structural unit derived from monomers other than (meth)acrylate (such as structures derived from monomers with polar functional groups such as hydroxyl, carboxyl, and amino groups) unit).

The content of the resin (A) in the solid content of the adhesive composition (i) is usually 50 to 99.9% by mass, preferably 60 to 95% by mass, more preferably 70 to 95% by mass. 90% by mass.

Relative to 100 parts by mass of resin (A), 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 10 parts by mass, most preferably 0.5 to 5 parts by mass .

Cross-linking agent (B) can include: isocyanate-based cross-linking agent, epoxy-based cross-linking agent, aziridine-based cross-linking agent, metal chelate-based cross-linking agent, etc., especially from the pot life of the adhesive composition From the viewpoints of the durability of the adhesive layer and the crosslinking speed, etc., an isocyanate-based crosslinking agent is preferred.

With respect to 100 parts by mass of the resin (A), the content of the crosslinking agent (B) is usually 0.01 to 25 parts by mass, preferably 0.1 to 15 parts by mass, more preferably 0.15 to 7 parts by mass, and more preferably 0.2 to 7 parts by mass. 5 parts by mass, preferably 0.25 to 2 parts by mass.

Silane compounds (C) include, for example: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

The silane compound (C) may also be a polysiloxane oligomer.

The content of the silane compound (C) is usually 0.01 to 20 parts by mass relative to 100 parts by mass of the resin (A). Preferably it is 0.1 to 10 parts by mass, more preferably 0.15 to 7 parts by mass, still more preferably 0.2 to 5 parts by mass, most 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 are cured by a radical polymerization reaction.

As a radical polymerizable component (D), a (meth)acrylate type compound, a styrene type compound, a vinyl type compound, etc. are mentioned.

The adhesive composition (i) may contain two or more radical curable components (D).

Examples of (meth)acrylate compounds include (meth)acrylate monomers having at least one (meth)acryloxy group in the molecule, (meth)acrylamide monomers and at least two (meth)acryloxy groups in the molecule. Compounds containing (meth)acryl groups such as (meth)acryl oligomers of (meth)acryl groups. The (meth)acrylic oligomer is preferably a (meth)acrylate oligomer having at least two (meth)acryloxy groups in the molecule. A (meth)acrylate type compound may be used individually by 1 type, and may use 2 or more types together.

(Meth)acrylate monomers include monofunctional (meth)acrylate monomers with one (meth)acryloxy group in the molecule, and monofunctional (meth)acrylate monomers with two (meth)acryloxy groups in the molecule. Bifunctional (meth)acrylate monomers, polyfunctional (meth)acrylate monomers with 3 or more (meth)acryloxy groups in the molecule.

Preferably it is a (meth)acrylate compound, More preferably, it is a polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate compound is preferably trifunctional or more.

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

The initiator (E) can be a compound that causes a polymerization reaction by absorbing heat energy (thermal polymerization Initiator), any of compounds (photopolymerization initiators) that cause polymerization by absorbing light energy. In addition, the light here is preferably visible rays, ultraviolet rays, X-rays, or active energy rays such as electron rays.

Examples of thermal polymerization initiators include compounds that generate radicals by heating, etc. (thermal radical generators), compounds that generate acids by heating, etc. (thermal acid generators), compounds that generate bases by heating, etc. (thermal bases) generating agent), etc.

Examples of photopolymerization initiators include compounds that generate free radicals by absorbing light energy (photoradical generators), compounds that generate acid by absorbing light energy (photoacid generators), and Compounds that generate bases (photobase generators), etc.

The initiator (E) is preferably selected to be suitable for the polymerization reaction of the above radical curable component (D), preferably a radical polymerization initiator, more preferably a photoradical polymerization initiator.

As a radical polymerization initiator, an alkylphenone compound, a benzophenone compound, a benzophenone compound, an oxime ester compound, a phosphine compound, etc. are mentioned, for example. The radical polymerization initiator is preferably a photoradical polymerization initiator, and more preferably an oxime ester-based photoradical polymerization initiator from the viewpoint of polymerization reactivity. Using an oxime ester-based photoradical polymerization initiator can increase the reaction rate of the radical curing component (D) even under curing conditions with low illuminance or light intensity.

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

The selective absorption compound (F) is a light-absorbing compound other than compound (I), such as a compound (ultraviolet absorber) that absorbs light with a wavelength of 250nm to 380nm (preferably a wavelength of 250nm or more but less than 360nm) or a compound (ultraviolet absorber) that absorbs light from 380nm to 380nm Compounds (pigments) at 780nm or compounds that absorb 780 to 1500nm (infrared absorbers).

The structure of the ultraviolet absorber is not particularly limited as long as it is a compound that absorbs light with a wavelength of 250nm to 380nm, and is preferably a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, or a salicylic acid-based compound , cyanoacrylate-based compounds, benzoxazine-based compounds, and the like.

With respect to 100 parts by mass of the resin (A), the content of the light selective absorption compound (F) is usually 0.1 to 50 parts by mass, preferably 0.2 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, and more preferably 1 to 25 parts by mass, preferably 2 to 20 parts by mass.

The optical layer of the present invention and the optical laminate containing the optical layer can be laminated with display elements such as organic EL elements and liquid crystal cells, and can be used in image display devices such as organic EL display devices or liquid crystal display devices (FPD: flat panel display) .

[Example]

Examples and comparative examples are shown below to describe the present invention more specifically, but the present invention is not limited to these examples. In the examples, % and parts indicating the content or usage amount are based on mass unless otherwise specified.

(Embodiment 1) Synthesis of the compound represented by formula (1)

Set a 300mL-four-neck flask equipped with a Dimroth condense and a thermometer to a nitrogen environment, add 7-hydroxy-2,3,4,4a,5,6-hexahydronaphthalene-2-one 7 parts, 70 parts of ethanol, 2.4 parts of potassium hydroxide, and 6.2 parts of malononitrile, heated at reflux and stirred 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, followed by heating under reflux at 80° C. and stirring for 3 hours. The obtained mixture was purified by distilling off the solvent to obtain 6.9 parts of the compound represented by the formula (a1).

Set the 20mL-four-neck flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, feed 1.5 parts of the compound represented by formula (a1), 1.0 parts of p-toluenesulfonyl cyanide, 0.3 parts of potassium hydroxide, and 10 parts of ethanol , heated to reflux and stirred for 3 hours. The obtained mixture was purified by distilling off the solvent to obtain 0.7 parts of the compound represented by the formula (1).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the 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 dimethyloxide) 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

<Determination of maximum absorption wavelength and gram absorption coefficient ε>

The 2-butanone solution (0.003g/L) of the compound represented by the obtained formula (1) was fed into a 1cm quartz cell (quartz cell), and the quartz cell was installed in a spectrophotometer UV-2450 (Shimadzu Corporation (stock) manufactured by the company), the absorbance in the wavelength range of 300 to 800 nm was measured at every 1 nm distance by the double-beam method. 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, the gram absorption coefficient of each wavelength was calculated.

ε(λ)=A(λ)/CL [In the formula, ε(λ) represents the gram absorption coefficient (L/(g‧cm)) of the compound represented by the formula (1) at a wavelength of λ nm, and A(λ) represents Absorbance at wavelength λ nm, C represents the concentration (g/L), L represents the optical path length of the quartz cell (m)]

The maximum absorption wavelength of the compound represented by the obtained formula (1) was 518 nm. The ε(λ max) of the obtained compound represented by the formula (1) was 444 L/(g·cm).

<Measurement of Full Width at Half Maximum of Compound>

The 2-butanone solution (concentration: 0.003 g/L) of the compound represented by the obtained formula (1) was fed into a 1 cm quartz cell, and the quartz cell was installed in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation Co., Ltd. ), the absorbance in the wavelength range from 300 to 800 nm was measured at every 1 nm distance by the double-beam method. Confirm the two wavelengths that become the half-absorbance of the maximum absorption wavelength absorbance. The wavelength of the short-wave side is subtracted from the wavelength of the long-wave side from the wavelength of the two points, and it is used as the full width at half maximum. The full width at half maximum of the compound represented by formula (1) is 26 nm.

(Embodiment 2) Synthesis of the compound represented by formula (M-2)

Set the 500mL-four-necked flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, and add the compound represented by formula (M-1) (7-hydroxy-2,3,4,4a,5,6-hexahydro Naphthalene-2-one) 25 parts, ethanol 150 parts, potassium hydroxide 10.3 parts, p-toluenesulfonyl cyanide 33.11 parts, stirred in an ice bath for 4 hours. The obtained mixture was purified by distilling off the solvent to obtain 17.4 parts of the compound represented by the formula (M-2).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (M-2) was produced.

¹ H-NMR (heavy dimethyloxide) 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

(Embodiment 3) Synthesis of the compound represented by formula (M-3)

Set the 300mL-four-necked flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, add 5 parts of the compound represented by formula (M-2), 100 parts of dehydrated acetonitrile, 4.4 parts of diisopropylethylamine, trifluoro 9 parts of methanesulfonic anhydride were 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, followed by stirring for 30 minutes. The obtained mixture was purified by distilling off the solvent to obtain 5.4 parts of the compound represented by the formula (M-3).

LC-MS measurement and ¹ H-NMR were performed, and it was confirmed that the compound represented by the formula (M-3) was produced.

¹ H-NMR (heavy dimethyloxide) 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

(Embodiment 4) Synthesis of the compound represented by formula (1)

Set the 100mL-four-neck flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, and add 2 parts of the compound represented by formula (M-3), 20 parts of dehydrated methyl ethyl ketone, 1.2 parts of potassium carbonate, trifluoro 2.8 parts of methyl methanesulfonate 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, followed by stirring for 30 minutes. The obtained mixture was purified by distilling off the solvent to obtain 1.4 parts of the compound represented by the formula (1).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the 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 dimethyloxide) 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

(Embodiment 5) Synthesis of the compound represented by formula (2)

Set the 50mL-four-neck flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, add 0.5 parts of the compound represented by formula (a1), 5 parts of dehydrated acetonitrile, 0.3 parts of diisopropylethylamine, N-(three Fluoromethylthio) saccharin 0.7 parts, stirred in ice bath for 3 hours. The obtained mixture was purified by distilling off the solvent to obtain 0.4 parts of the compound represented by the formula (2).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (2) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Further, when measuring the maximum absorption wavelength, gram absorption coefficient and full width at half maximum with the same operation as above, the maximum absorption wavelength of the compound represented by formula (2) is 526nm, and the gram absorption coefficient ε(λ max) at the maximum absorption wavelength It is 189L/(g‧cm), and the full width at half maximum is 26nm.

¹ H-NMR (heavy dimethyloxide) 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

(Embodiment 6) Synthesis of the compound represented by formula (3)

Set the 20mL-four-neck flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, add 0.5 parts of the compound represented by formula (a1), 5 parts of dehydrated acetonitrile, and 0.3 parts of N-chlorosuccinimide, and place in an ice bath Stir for 3 hours. The obtained mixture was purified by distilling off the solvent to obtain 0.4 parts of the compound represented by the formula (3).

LC-MS measurement was performed, and it was confirmed that the compound represented by the formula (3) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Further, when measuring the maximum absorption wavelength, gram absorption coefficient and full width at half maximum with the same operation as above, the maximum absorption wavelength of the compound represented by formula (3) is 551nm, and the gram absorption coefficient ε(λ max) at the maximum absorption wavelength It is 130L/(g‧cm), and the full width at half maximum is 28nm.

LC-MS; [M] ^- =293.5

(Embodiment 7) Synthesis of the compound represented by formula (4)

Set the 20mL-four-necked flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, add 0.5 parts of the compound represented by formula (a1), 5 parts of dehydrated dimethylformamide, and 0.5 parts of N-chlorosuccinimide portion, stirred in an ice bath for 3 hours. The obtained mixture was purified by distilling off the solvent to obtain 0.4 parts of the compound represented by the formula (4).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (4) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Further, when measuring the maximum absorption wavelength, gram absorption coefficient and full width at half maximum with the same operation as above, the maximum absorption wavelength of the compound represented by formula (4) is 572nm, and the gram absorption coefficient ε(λ max) at the maximum absorption wavelength It is 126L/(g‧cm), and the full width at half maximum is 44nm.

LC-MS; [M] ^- =328.2

¹ H-NMR (heavy dimethyloxide) δ: 1.24-1.25 (m, 2H), 1.88-2.33 (m, 7H)

(Embodiment 8) Synthesis of the compound represented by formula (5)

Set the 20mL-four-necked flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, add 1 part of the compound represented by formula (a1), 10 parts of dehydrated dimethylformamide, and 0.7 parts of N-bromosuccinimide portion, stirred in an ice bath for 3 hours. The obtained mixture was purified by distilling off the solvent to obtain 0.7 parts of the compound represented by the formula (5).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (5) was produced. Also, the presence of potassium cations was confirmed by energy dispersive X-ray spectroscopy (SEM-EDX analysis). Furthermore, when measuring the maximum absorption wavelength, gram absorption coefficient and full width at half maximum with the same operation as above, the maximum absorption wavelength of the compound represented by formula (5) is 548nm, and the gram absorption coefficient ε(λ max at the maximum absorption wavelength ) is 180L/(g‧cm), and the full width at half maximum is 26nm.

LC-MS; [M] ^- =338.2

¹ H-NMR (heavy dimethyloxide) 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 the compound represented by formula (M-4)

Set the 100mL-four-necked flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, and add the formula (M- 2) 5 parts of the indicated compound, 50 parts of dehydrated acetonitrile, and 0.7 part of sodium hydride were stirred in an ice bath for 30 minutes. 9.6 parts of p-toluenesulfonyl cyanide was added to the obtained mixture, and it stirred at 50 degreeC for 4 hours. The obtained mixture was purified by distilling off the solvent to obtain 3.8 parts of the compound represented by the formula (M-4).

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed that the compound represented by the formula (M-4) was produced.

LC-MS; [M] ^- =213.1

¹ H-NMR (heavy dimethyloxide) δ: 1.46-1.57 (m, 2H), 1.82-1.91 (m, 2H), 2.16-2.39 (m, 5H)

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

Set the 200mL-four-necked flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, add 4.5 parts of the compound represented by formula (M-4), 68 parts of dehydrated acetonitrile, and 0.6 parts of sodium hydride, and stir in an ice bath for 30 minute. To the obtained mixture was added 7.1 parts of trifluoromethanesulfonic anhydride, stirred in an ice bath for 30 minutes, further added 1.7 parts of malononitrile and 3.5 parts of potassium carbonate, and stirred at 50° C. for 2 hours. The obtained mixture was purified by distilling off the solvent to obtain 2.1 parts of the compound represented by the formula (M-5).

Set the 300mL-four-neck flask equipped with a Dairy cooling tube and a thermometer into a nitrogen environment, and add 1.2 parts of the compound represented by formula (M-5), 36 parts of acetonitrile, 8.8 parts of di-tert-butylpyridine, p-toluenesulfonate 7.5 parts of acid anhydride, propane 1.5 parts of dinitrile were mixed and stirred in an ice bath for 24 hours. The obtained mixture was purified by distilling off the solvent to obtain 0.4 parts of the compound represented by the formula (6). In addition, potassium ions in the compound represented by formula (6) are derived from potassium bicarbonate used for purification.

LC-MS measurement and ¹ H-NMR analysis were performed, and it was confirmed 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).

Further, when measuring the maximum absorption wavelength, gram absorption coefficient and full width at half maximum with the same operation as above, the maximum absorption wavelength of the compound represented by formula (6) is 511nm, and the gram absorption coefficient ε(λ max) at the maximum absorption wavelength It is 211L/(g‧cm), and the full width at half maximum is 29nm.

LC-MS; [M] ^- =309.3

¹ H-NMR (heavy dimethyloxide) 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)

Feed a mixed solution of 81.8 parts of ethyl acetate, 96 parts of butyl acrylate, 3 parts of 2-hydroxyethyl methyl acrylate and 1 part of acrylic acid as a solvent into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer , while substituting the air in the apparatus with nitrogen so as not to contain oxygen, the internal temperature was raised to 55°C. Thereafter, the entire amount of a solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added. After adding the polymerization initiator, keep this temperature for 1 hour, then, while maintaining the internal temperature at 54 to 56°C, continuously add ethyl acetate into the reaction vessel at an addition rate of 17.3 parts/hour, between the acrylic resin Addition of ethyl acetate was stopped when the concentration became 35%, and the temperature was kept at this temperature until 12 hours from the start of addition of ethyl acetate. Finally, the concentration of the acrylic resin becomes 20%, adding ethyl acetate Adjust to prepare an ethyl acetate solution of acrylic resin. The weight average molecular weight Mw of polystyrene conversion of the obtained acrylic resin by GPC was 1.4 million, and Mw/Mn was 5.5. Let this be an acrylic resin (A1).

Polymerization Example 2: Preparation of Acrylic Resin (A2)

Feed 81.8 parts of ethyl acetate, 60 parts of methyl acrylate, 10 parts of acrylic acid, 10 parts of 2-hydroxyethyl methyl acrylate and 2 - The mixed solution of 20 parts of phenoxyethyl ester was heated up to 55° C. while replacing the air in the apparatus with nitrogen to make it free of oxygen. Thereafter, the entire amount of a solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added. After adding the polymerization initiator, keep this temperature for 1 hour, and then, while maintaining the internal temperature at 54 to 56°C, continuously add ethyl acetate into the reaction vessel at an addition rate of 17.3 parts/hour, at the concentration of the acrylic resin Addition of ethyl acetate was stopped at the point when it reached 35%, and the temperature was kept at this temperature until 12 hours from the start of addition of ethyl acetate. Finally, ethyl acetate was added and adjusted so that the concentration of the acrylic resin would be 20%, and an ethyl acetate solution of the acrylic resin was prepared. The obtained acrylic resin had a weight average molecular weight Mw of 920,000 in terms of polystyrene by GPC, and Mw/Mn was 4.7. Let this be an acrylic resin (A2).

(Example 11) Preparation of resin composition (1) (adhesive composition (1))

<Preparation of resin composition (1)>

With respect to the solid content of 100 parts of the ethyl acetate solution (resin concentration: 20%) of the acrylic resin (A1), a crosslinking agent (manufactured by Toso Co., Ltd.: trade name "Coronate L", isocyanate compound, solid 75%) 0.5 parts, 0.28 parts of a silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name "KBM3066"), and 1.5 parts of a compound represented by formula (1), and further make the solid content concentration 14% 2-Butanone was added to obtain a resin composition (1) (adhesive composition (1)). In addition, the compounding amount of the above-mentioned cross-linking agent is as It is the mass parts of active ingredients.

(Examples 12 to 18, Comparative Example 1) Production of Resin Compositions (2) to (9)

Except for changing each component and the content of each component as shown in Table 7, the same operation as in Example 11 was carried out to produce adhesive composition (2) to adhesive composition (9). Also, the compounding amount of the above-mentioned crosslinking agent is the mass fraction of the active ingredient, and the resin (A) is the mass fraction of the solid content.

[Table 7]

In addition, each abbreviation in Table 7 has the following meanings.

Acrylic resin (A1): Acrylic resin (A1) synthesized in Polymerization Example 1

Acrylic resin (A2): Acrylic resin (A2) synthesized in Polymerization Example 2

Formula (1): the compound represented by the formula (1) synthesized in Example 1 or Example 4

Formula (6): the compound represented by the formula (6) synthesized in Example 10

Coronate L: manufactured by Toso Co., Ltd., trade name: Coronate L, isocyanate-based crosslinking agent

KBM3066: Manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM3066, silane coupling agent

A-DPH-12E: manufactured by Shin-Nakamura Chemical Co., Ltd., trade name; A-DPH-12E, hexafunctional (meth)acrylate compound

NCI-730: Manufactured by ADEKA Co., Ltd., trade name: NCI-730, belongs to the light of the oxime ester compound radical generator

RUV-93: Otsuka Chemical Co., Ltd., benzotriazole-based ultraviolet absorber, trade name: RUVA-93, maximum absorption wavelength λ max = 337nm

Formula (B): The compound represented by the following formula (B) (3-butyl-2-[3-(-3-butyl-5-phenyl-2(3H) -benzylidene)-1-propen-1-yl]-5-phenyl-benzoxazolium p-toluenesulfonate), the full width at half maximum obtained in the same manner as above was 44 nm.

<Evaluation of resin composition (1) molded body>

[Production of resin molded body (1)]

The obtained resin composition (1) (adhesive composition (1)) was coated on a release film made of polyethylene terephthalate film [purchased from Linte (stock) company (LINTEC Corporation, trade name "PLR-382190"]'s release treatment surface, dried at 100 ° C for 1 minute to form a resin molded body (adhesive layer) (1), produced with a release A resin molded body (1) of a film. The obtained resin molded body (1) had a thickness of 15 μm.

The obtained resin molded body (1) with a separation film was bonded to a cycloolefin film containing a 23 μm ultraviolet absorber [purchased from Zeon Corporation, trade name "ZEONOR" by a laminator. ”], and aged for 7 days at a temperature of 23°C and a relative humidity of 65% to obtain a laminate (1-1) having a laminated structure of cycloolefin film/resin molded article (1)/separation membrane.

[Measurement of Absorbance of Resin Molded Article (1)]

The obtained laminate (1-1) was cut into a size of 30mm×30mm, the separation membrane was peeled off, and the resin molded body (1) and an alkali-free glass [manufactured by Corning Incorporated, trade name "EAGLE XG"] were bonded together, and this was made into the sample (1). Using a spectrophotometer (UV-2450: manufactured by Shimadzu Corporation), the absorbance of the prepared sample (1) in the wavelength range of 300 to 800 nm was measured at every 1 nm distance. The measured absorbance at a wavelength of 330 nm was defined as the absorbance at a wavelength of 330 nm of the resin molded article (1). In addition, the absorbance of the alkali-free glass monomer and the cycloolefin film monomer at a wavelength of 330 nm is zero.

Also, based on the following formula, the transmittance at a wavelength of 330 nm was obtained. The results are shown in the column of the transmittance in Table 8.

T=10 ^-A ×100 (T means transmittance, A means absorbance)

The maximum absorption wavelength of the sample (1) was determined from the absorbance measured above, and the absorbance at the determined maximum absorption wavelength was used as the absorbance at the above maximum absorption wavelength of the resin molded article (1). In addition, the absorbance of the above-mentioned maximum absorption wavelengths of the alkali-free glass monomer and the cycloolefin film monomer is zero.

Based on the following formula, the transmittance (%) of the above-mentioned maximum absorption wavelength was obtained. The results are shown in Table 9.

T1=10 ^-A1 ×100

(T1 represents the transmittance at the above-mentioned maximum absorption wavelength, A1 represents the absorbance at the above-mentioned maximum absorption wavelength)

[Evaluation of Bleeding Resistance of Resin Molded Articles (1)]

A separation film is further laminated on one side of the obtained resin molded body (1) with a separation film to obtain an adhesive layer (1) with a separation film on both sides. The obtained adhesive layer (1) with separation films on both sides was stored in the air at 23 to 25° C. for 1 month. After storage, use a microscope to confirm whether there is crystallization of the compound on the surface of the adhesive layer (1) with the separation film on both sides. Those without crystallization were designated as a, and those with crystallization were designated as b. The evaluation results are shown in the anti-bleeding column of Table 8.

[Measurement of Absorbance Retention of Resin Molded Article (1)]

Prepare to use an adhesive layer on one side of the polarizer with a thickness of 8 μm and attach a 13 μm cycloolefin film Polarizer.

After laminating the resin molded body (1) side of the resin molded body (1) with a separation film on the polarizer side of the polarizer by a laminator, it was aged for 7 days at a temperature of 23°C and a relative humidity of 65%. A laminate having a laminated structure of cycloolefin film/polarizer/resin molded body (1)/separation film was obtained.

The obtained laminate was cut into a size of 30 mm × 30 mm, the separation film was peeled off, and the resin molded body (1) and alkali-free glass [manufactured by Corning, trade name "EAGLEXG"] were bonded to obtain a cycloolefin film/polarizer /Resin molded body (1)/Laminate (1-2) of laminated structure of glass.

The obtained laminate (1-2) was put into a sunshine weather instrument (manufactured by Suga Test Instruments Co., Ltd.) at a temperature of 63° C. and a relative humidity of 50% RH for 75 hours to perform a weather resistance test. The absorbance of the taken-out laminate (1-2) was measured in the same manner as above. From the measured absorbance, the absorbance retention [%] of the laminate (1-2) at a wavelength of 540 nm was obtained based on the following formula. The results are shown in Table 8. The closer the absorbance retention rate is to 100%, the more it means that the light selective absorption function has not deteriorated and has good weather resistance.

In addition, the absorption wavelength used to evaluate the absorbance retention rate is selected from the measured absorbance at which the absorbance on the long-wave side of the maximum absorption wavelength becomes 1 to 1.5. These are the absorbance regions at which the aforementioned wavelengths have the best sensitivity in terms of the measurement accuracy of the spectrometer.

Absorbance retention (%)=(A(540) after durability test/A(540) before durability test)×100

[A(540) represents the absorbance of the laminate (1-2) at a wavelength of 540nm]

Using the resin composition (2) instead of the resin composition (1), the resin molding (2), the laminate (2-1), and the laminate (2-2) were produced, and the same evaluation was performed. The results are shown in Table 8.

Using the resin composition (3) instead of the resin composition (1), the resin molding (3), the laminate (3-1), and the laminate (3-2) were produced, and the same evaluation was performed. The results are shown in Table 8.

The resin composition (5) was used instead of the resin composition (1), and the 20-micrometer-thick resin molding (5) was produced. Except that the resin molded body (5) was used instead of the resin molded body (1), the same operation was carried out to make laminates (5-1) and laminates (5-2), and evaluations of bleeding resistance and absorbance retention were performed. . In addition, the evaluation of the absorbance retention rate was performed at a wavelength of 520 nm. The results are shown in Table 8.

The resin composition (6) was used instead of the resin composition (1), and the resin molding (6) of thickness 20 micrometers was produced. Except for using the resin molded body (6) instead of the resin molded body (1), perform the same operation to make a laminate (6-1) and a laminate (6-2), and evaluate the bleeding resistance and the absorbance retention rate . In addition, the evaluation of the absorbance retention rate was performed at a wavelength of 530 nm. The results are shown in Table 8.

The resin composition (7) was used instead of the resin composition (1), and the 20-micrometer-thick resin molding (7) was produced. Except that the resin molded body (7) was used instead of the resin molded body (1), the same operation was carried out to produce laminates (7-1) and laminates (7-2), and evaluations of bleeding resistance and absorbance retention were performed. . In addition, the evaluation of the absorbance retention rate was performed at a wavelength of 520 nm. The results are shown in Table 8.

The resin composition (8) was used instead of the resin composition (1), and the resin molding (8) of thickness 20 micrometers was produced. Except for using the resin molded body (8) instead of the resin molded body (1), perform the same operation to make laminates (8-1) and laminates (8-2), and evaluate the bleeding resistance and absorbance retention rate. . In addition, the evaluation of the absorbance retention rate was performed at a wavelength of 520 nm. The results are shown in Table 8.

Using the resin composition (9) instead of the resin composition (1), a resin molded body (9) having a thickness of 20 μm was produced. Except for using the resin molded body (9) instead of the resin molded body (1), perform the same operation to make laminates (9-1) and laminates (9-2), and evaluate the bleeding resistance and absorbance retention rate. . In addition, the evaluation of the absorbance retention rate was performed at a wavelength of 510 nm. The results are shown in Table 8.

<Evaluation of resin composition (4) molded body>

[Production of resin molded body (4)]

The resin composition (4) was coated on a separation film made of a release-treated polyethylene terephthalate film using an applicator so that the thickness after drying would be 5 μm [purchased from Lin Special Co., Ltd., product name "PLR-382190"], the release treatment surface was dried at 100°C for 1 minute. After that, from the separation membrane side, use an ultraviolet irradiation device (manufactured by Fusion UV Systems Inc. "electrodeless ultraviolet lamp system H bulb") to adjust the UV-A (wavelength 320 to 390nm) so that the illuminance becomes 500mW and the integrated light intensity becomes 500mJ, and then irradiates with ultraviolet rays A resin molded body (adhesive layer) (4) is formed to produce a resin molded body (4) with a separation film.

The obtained resin molded body (4) with a separation film was attached to an alkali-free glass, and after the separation film was peeled off, a cycloolefin film containing a 23 μm ultraviolet absorber [purchased from Nippon Zeon Co., Ltd., commercial product name "ZEONOR"] was bonded to the resin molded body (4) to produce a laminate (4-1) having a laminated structure of cycloolefin film/resin molded body (4)/glass.

The produced laminate (4-1) was installed in a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance in the wavelength range of 300 to 800 nm at a distance of 1 nm was measured by the double-beam method. The measured absorbance at a wavelength of 330 nm was used as the absorbance at a wavelength of 330 nm of the resin molded article (4). In addition, both the alkali-free glass monomer and the cycloolefin film have an absorbance of 0 at a wavelength of 330 nm.

Also, based on the following formula, the transmittance (%) at a wavelength of 330 nm was obtained. The results are shown in Table 8.

T=10 ^-A ×100 (T means transmittance, A means absorbance)

The maximum absorption wavelength of the laminate (4-1) was determined from the absorbance measured above, and the determined absorbance at the maximum absorption wavelength was used as the absorbance of the resin molded article (4) at the above maximum absorption wavelength. In addition, the absorbance of the above-mentioned maximum absorption wavelengths of the alkali-free glass monomer and the cycloolefin film monomer is zero.

Based on the following formula, the transmittance (%) of the above-mentioned maximum absorption wavelength was found. The results are shown in Table 9.

T1=10 ^-A1 ×100

(T1 represents the transmittance at the above-mentioned maximum absorption wavelength, A1 represents the light absorption at the above-mentioned maximum absorption wavelength Spend)

[Evaluation of Bleeding Resistance of Resin Molded Article (4)]

A separation film is further laminated on one side of the obtained resin molded body (4) with a separation film to obtain an adhesive layer (4) with a separation film on both sides. The obtained adhesive layer (4) with separation films on both sides was stored in the air at 23 to 25° C. for 1 month. Use a microscope to check whether there is crystallization of the compound on the surface of the adhesive layer (4) with the separation film on both sides after storage. Those without crystallization were designated as a, and those with crystallization were designated as b. The evaluation results are shown in the anti-bleeding column of Table 8.

[Measurement of Absorbance Retention of Resin Molded Article (4)]

Prepared a polarizing plate with an adhesive layer on one side of the polarizer with a thickness of 8 μm and a cycloolefin film of 13 μm attached.

After laminating the resin molded body (4) side of the resin molded body (4) with a separation film on the polarizer side of the polarizer by a laminator, it was aged for 7 days at a temperature of 23°C and a relative humidity of 65%. A laminate having a laminated structure of cycloolefin film/polarizer/resin molded body (1)/separation film was obtained.

The separation film was peeled off from the obtained laminate, and the resin molded body (4) was attached to an alkali-free glass [manufactured by Corning, trade name "EAGLE XG"] to obtain a cycloolefin film/polarizer/resin molded body (4 )/glass laminate structure (4-2).

The obtained laminate (4-2) was put into a sunshine weather instrument (manufactured by Suga Test Instruments Co., Ltd.) at a temperature of 63° C. and a relative humidity of 50% RH for 75 hours to perform a weather resistance test. The absorbance of the taken-out laminate (4-2) was measured in the same manner as above. From the measured absorbance, based on the following formula, obtain the absorbance retention [%] of the sample at a wavelength of 540nm. The results are shown in Table 8. The closer the absorbance retention rate is to 100%, the more it means that the light selective absorption function has not deteriorated and has good weather resistance.

Absorbance retention rate (%) =(A(540) after durability test/A(540) before durability test)×100

[A(540) represents the absorbance of the laminate (4-2) at a wavelength of 540nm]

[Table 8]

[Table 9]

The transmittance value of the maximum absorption wavelength in Examples 11 to 13 shows that it exceeds the spectroscopic light The measurement limit of the absorbance of the meter (absorbance: 5).

The compounds of the present invention have high absorption selectivity for light near the maximum absorption wavelength. In addition, the resin composition containing the compound of the present invention also has a high absorbance retention rate after a weather resistance test, and has good weather resistance.

Claims (19)

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

In formula (I), ring W ¹ represents a ring which may have a substituent, The ring W ² represents a ring having at least one double bond as a constituent element of the ring, and the ring W ² may have a substituent, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, 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 to each other and form a ring, R ³ and R ⁴ may be linked to each other and form a ring, R ² and R ⁶ may be connected to each other and form a ring, R ⁵ and R ⁶ may be linked to each other to form a ring. The compound according to claim 1, wherein at least one selected from R ¹ and R ² is an electron-attracting group. The compound according to claim 2, wherein at least one selected from R ¹ and R ² is cyano, nitro, halogenated alkyl, halogenated aryl, -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 a hydrocarbon group which may have a substituent or a halogen atom), -OCF ₃ , -SCF ₃ , -SF ₅ , -SF ₃ , -SO ₂ H or -SO ₃ H. 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-attracting group. The 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-attracting group. The compound as described in Claim 5, wherein at least one selected from R ³ , R ⁴ , R ⁵ and R ⁶ is cyano, nitro, halogenated alkyl, halogenated aryl, -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 a hydrocarbon group or a halogen atom which may have a substituent), -OCF ₃ , - SCF ₃ , -SF ₅ , -SF ₃ , -SO ₂ H or -SO ₃ H. The compound according to any one of Claims 1 to 6 exhibits maximum absorption at a wavelength between 400nm and 700nm. The compound according to any one of Claims 1 to 7, wherein the gram absorption coefficient at the maximum absorption wavelength is 50 [L/(g·cm)] or more. A resin composition containing the compound and resin described in any one of claims 1 to 8. A composition comprising the compound described in any one of claims 1 to 8 and a polymerizable monomer. A molded body formed from the resin composition described in Claim 9 or the composition described in Claim 10. An optical layer composed of the resin composition described in Claim 9 or the composition described in Claim 10. An optical laminate comprising the optical layer described in claim 12. An image display device comprising the optical laminate described in claim 13. A method for producing a compound having an anion represented by the following formula (I), the production method comprising the step of reacting a compound represented by formula (M-A) with a compound represented by formula (b-3),

In formula (MA), ring W ¹ represents a ring that may have a substituent, The ring W ² represents a ring having at least one double bond as a constituent element of the ring, and the ring W ² may have a substituent, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, 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 to each other and form a ring, R ³ and R ⁴ can be connected to each other and form a ring;

In formula (b-3), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, X ₂ represents a 2-valent linking group;

In the formula, ring W ¹ , ring W ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meanings as above, respectively. The manufacturing method as described in claim item 15 is further included in the presence of a catalyst, so that the formula The compound represented by (M) is reacted with the compound represented by formula (b-2), and the step of obtaining the compound represented by formula (M-A),

In the formula, ring W ¹ , ring W ² , R ¹ and R ² represent the same meanings as above;

In the formula, R ³ and R ⁴ respectively represent the same meaning as above, X ₁ represents a divalent linking group. A method for producing a compound having an anion represented by the following formula (I), the production method comprising making at least one compound selected from the compound represented by the formula (M1-2) and the compound represented by the formula (M1-3) A step of reacting with a compound having an anion represented by formula (M1-1), R ^2' ─── E ₁ (M1-2) In the formula (M1-2), R ^2' represents a monovalent substituent, and E ₁ represents a leaving group; R ^1' ─── E ₂ (M1-3) In the formula (M1-3), R ^1' represents a monovalent substituent, and E ₂ represents a leaving group;

In formula (M1-1), ring W ¹ represents a ring that may have a substituent, The ring W ² represents a ring having at least one double bond as a constituent element of the ring, and the ring W ² 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 to each other and form a ring, R ⁵ and R ⁶ can be connected to each other and form a ring;

In the formula, ring W ¹ , ring W ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent the same meanings 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 compound represented by formula (M),

In formula (M), ring W ¹ represents a ring which may have a substituent, The ring W ² represents a ring having at least one double bond as a constituent element of the ring, and the ring W ² 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. A compound represented by formula (M-A),

In formula (MA), ring W ¹ represents a ring that may have a substituent, The ring W ² represents a ring having at least one double bond as a constituent element of the ring, and the ring W ² may have a substituent, R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, 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 to each other and form a ring, R ³ and R ⁴ may be linked to each other to form a ring.