JP5426158B2 - Methine dyes and their uses - Google Patents

Description

  The present invention relates to a novel methine dye and a use thereof, and in particular, bisindolenin in which two indolenine rings are bonded to each other via a divalent linking group via a 3-position carbon atom. The present invention relates to a methine dye having a skeleton.

  With the arrival of the information age, the demand for organic compounds that absorb light in the ultraviolet to infrared region is increasing rapidly. Its applications are now used in filter materials, such as the use of the property that organic compounds absorb and block light, information recording that actively uses light energy through organic compounds, solar power generation, etc. It was spread to the use of.

  The properties that organic compounds to be applied to such applications should have include absorption characteristics in the ultraviolet to infrared region, good light resistance, good solubility in solvents, and depending on the application. And exhibiting thermal characteristics. Examples of typical organic compounds that have been proposed so far include anthraquinone dyes, phthalocyanine dyes, cyanine dyes as methine dyes, styryl dyes, and the like (for example, JP-A-1-116611, JP-A-2002-202592, JP-A-2003-167343, JP-A-11-58961, JP-A-2003-231359), among these, anthraquinone dyes have difficulty in light absorption properties, It is said that phthalocyanine dyes have difficulty in light absorption characteristics and solubility in solvents. So far, methine dyes have been tried to improve the light absorption characteristics and solubility by introducing substituents, dimerizing the dye skeleton, etc., but in addition to the light absorption characteristics and solubility, light resistance and thermal characteristics are still available. At present, there are only a few that satisfy even the performance of the above.

By the way, in the field of information recording, with the advent of the multimedia era, CD-R, DVD-R, write-once Blu-ray disc (hereinafter abbreviated as BD-R) and HD
Optical recording media such as DVD-R are in the spotlight. Optical recording media can be broadly classified into magneto-optical recording media, phase change recording media, chalcogen oxide optical recording media, and organic optical recording media.

  Among these, an organic optical recording medium is usually prepared by dissolving a methine dye in an organic solvent such as 2,2,3,3-tetrafluoro-1-propanol (hereinafter abbreviated as “TFP”). Is coated on a polycarbonate substrate and dried to form a recording layer, and then a reflective layer made of a metal such as gold, silver, and copper and a protective layer made of an ultraviolet curable resin are sequentially adhered to each other. Although the organic optical recording medium has the disadvantage that the recording layer is easily changed by ambient light such as reading light or natural light, the recording layer is formed by applying a methine dye as a light-absorbing material directly to the substrate as a solution. Therefore, there is an advantage that an optical recording medium can be manufactured at low cost.

  Urgent issues in organic optical recording media are further increasing the recording density and increasing the information recording speed to cope with the multimedia era. In order to further increase the density, the wavelength of recording and reproducing light is being shortened. On the other hand, although it is desirable to use a methine dye with higher sensitivity for further speeding up, with the increase in sensitivity of the methine dye, an increase in fluctuation (jitter) in the time direction of the reproduction signal, There is a tendency to be accompanied by a decrease in light stability (light resistance). Applying a conventionally known methine dye to such an optical recording medium in order to cope with further higher speeds in the future can maintain sufficient sensitivity, jitter and light stability to record information at high speed. It is becoming difficult.

  In view of such circumstances, the present invention is a novel material that absorbs light in the ultraviolet to infrared region, has excellent light resistance and solubility in a solvent, and has thermal characteristics according to the application to which the organic compound is applied. It is an object of the present invention to provide a wide range of organic compounds that can be selected as a light-absorbing material in the above-described applications.

  Furthermore, the subject of this invention is providing the optical recording medium containing such an organic compound.

  Furthermore, the subject of this invention is providing the intermediate useful for manufacturing such an organic compound, and its manufacturing method.

  The present inventor has focused on methine dyes, which have been conventionally considered to have difficulty in light resistance and thermal properties, and conducted intensive research and search. As a result, two indolenine rings each have a carbon atom at the 3-position. Thus, a methine dye comprising a bisindolenin skeleton bonded by a divalent linking group is excellent in light resistance, efficiently absorbs light in the ultraviolet to infrared region, and in various organic solvents. It has been found that it exhibits a practically satisfactory solubility and excellent thermal properties. However, such a methine dye absorbs light in the ultraviolet to infrared region to block this, or as a novel light absorbing material that uses the energy of light in the ultraviolet to infrared region, has such properties. It has been found that it can be advantageously used in a wide variety of applications that require the methine dyes provided.

  Furthermore, it has been found that by applying such a methine dye to an optical recording medium, recording characteristics excellent in light resistance and jitter can be exhibited while having good sensitivity.

  That is, the present invention provides a methine dye comprising a bisindolenin skeleton in which two indolenine rings are bonded to each other through a carbon atom at the 3-position by a divalent linking group. The problem is solved.

  In particular, the present invention solves the above-mentioned problem by providing a methine dye comprising an atomic group represented by the general formula 1 as a preferred embodiment.

General formula 1:

(In General Formula 1, Z ¹ and Z ² each independently represent an aromatic ring, and these aromatic rings may have a substituent. R ¹ and R ² are each independently a hydrogen atom or a suitable group. R ³ and R ⁴ represent the same or different hydrocarbon groups, and these hydrocarbon groups may have a substituent, L represents a divalent linking group, and the linkage thereof. Q ¹ and Q ² each independently represent a monomethine chain or a polymethine chain having an aromatic ring group, a heterocyclic group, or an amino group on the other end side, and these monomethines The chain or polymethine chain may have a substituent and / or a cyclic group.)

  Furthermore, this invention solves the said subject by providing the methine pigment | dye which comprises the atomic group represented by General formula 2 as a preferable embodiment.

General formula 2:

(In General Formula 2, Z ^{1 to} Z ⁴ each independently represents an aromatic ring, and these aromatic rings may have a substituent. R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or an appropriate substituent, R ³ , R ⁴ , R ⁹ and R ¹⁰ represent the same or different hydrocarbon groups, and these hydrocarbon groups have a substituent. In addition, two of the substituents in R ^{5 to} R ⁸ or the hydrocarbon groups in R ⁹ and R ¹⁰ may be connected by a divalent linking group. Represents a linking group, and the linking group may have a substituent, J ¹ and J ² each independently represent a monomethine chain or a polymethine chain, and these monomethine chain and polymethine chain are each a substituent and / or may have a cyclic structure .Y ¹ and ^{Y 2} Each independently represent a carbon atom or a heteroatom, if Y ¹ and / or Y ² are hetero atoms, there is no part or all of R ⁵ to R ^8.)

  Furthermore, this invention solves the said subject by providing the optical recording medium containing such a methine dye.

  Furthermore, this invention solves the said subject by providing the indolenine compound represented by General formula 3 as a useful intermediate for manufacturing such a methine dye.

General formula 3:

(In General Formula 3, Z ¹ and Z ² each independently represent an aromatic ring, and these aromatic rings may have a substituent. R ¹ and R ² are each independently a hydrogen atom or a suitable group. L represents a divalent linking group, and the linking group may have a substituent.

  Furthermore, the present invention provides a method for producing an indolenine compound through a step of reacting a diketone compound represented by general formula 4 with one or two hydrazine compounds represented by general formula 5. The above-mentioned problem is solved.

General formula 4:
(In General Formula 4, L represents a divalent linking group corresponding to L in General Formula 3, and the linking group may have a substituent.)

General formula 5:
(In General Formula 5, Z ⁵ represents an aromatic ring Z ¹ or Z ² corresponding to General Formula 3, and these aromatic rings may have a substituent.)

  The present invention is based on the creation of a novel methine dye that substantially absorbs light in the ultraviolet to infrared region and the discovery of industrially useful properties.

It is an absorption spectrum in a solution state of a trimethine dye among the methine dyes according to the present invention having a bisindolenin skeleton. It is an absorption spectrum in a solution state of a conventionally known trimethine pigment having a bisindolenin skeleton. It is the schematic of the optical recording medium used in the Example.

Explanation of symbols

1 Substrate 2 Recording layer 3 Reflective layer 4 Protective layer

  As described above, the present invention relates to a methine dye comprising a bisindolenin skeleton in which two indolenine rings are bonded to each other through a carbon atom at the 3-position with a divalent linking group. It is.

  The bisindolenin skeleton as used in the present invention means a structure in which two indolenine rings are bonded to each other through a divalent linking group via a 3-position carbon atom. The methine dye according to the present invention is a novel compound that has not been described in any literature. Regardless of any methine dye, the two indolenine rings are divalent linking groups via the 3-position carbon atom. As long as it comprises a bisindolenin skeleton formed by bonding, it can be advantageously used in the present invention even if there is a difference in degree.

  Examples of the methine dyes according to the present invention include a mono- or dimethine chain, a trimethine chain, a tetramethine chain, a pentamethine chain, a hexamethine chain, a heptamethine chain, an azamethine chain, etc. Examples include those formed by bonding to one end side of a polymethine chain and bonding an aromatic ring, heterocyclic ring or amino group which may have one or more substituents to the other end side of such a methine chain.

  Examples of the aromatic ring in such a methine dye include monocyclic or polycyclic aromatic rings having a benzene ring as a basic unit, such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Further, the heterocyclic ring in such methine dyes includes imidazoline ring, imidazole ring, benzimidazole ring, α-naphthimidazole ring, β-naphthimidazole ring, indole ring, isoindole ring, indolenine ring, isoindoline. Renin ring, benzoindolenin ring, pyridinoindolenin ring, oxazoline ring, oxazole ring, isoxazole ring, benzoxazole ring, pyridinooxazole ring, α-naphthoxazole ring, β-naphthoxazole ring, selenazoline ring, selenazole ring , Benzoselenazole ring, α-naphthoselenazole ring, β-naphthoselenazole ring, thiazoline ring, thiazole ring, isothiazole ring, benzothiazole ring, α-naphthothiazole ring, β-naphthothiazole ring, tellrazoline ring, tellurazole Ring Nzotelrazole ring, α-naphthotelrazole ring, β-naphthotelrazole ring, acridine ring, anthracene ring, isoquinoline ring, isopyrrole ring, imidazoquinoxaline ring, indandione ring, indazole ring, indalin ring, oxadiazole ring , Carbazole ring, xanthene ring, quinazoline ring, quinoxaline ring, quinoline ring, chroman ring, cyclohexanedione ring, cyclopentanedione ring, cinnoline ring, thiodiazole ring, thiooxazolidone ring, thiophene ring, thionaphthene ring, thiobarbituric acid ring, Thiohydantoin ring, tetrazole ring, triazine ring, naphthalene ring, naphthyridine ring, piperazine ring, pyrazine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, pyrazolone ring, pyran ring, pyridine ring, pyridazi Ring, pyrimidine ring, pyrylium ring, pyrrolidine ring, pyrroline ring, pyrrole ring, phenazine ring, phenanthridine ring, phenanthrene ring, phenanthroline ring, phthalazine ring, pteridine ring, furazane ring, furan ring, purine ring, benzoxazine ring Benzopyran ring, morpholine ring, rhodanine ring and the like. Examples of the amino group in such methine dyes include phenylamino group, diphenylamino group, p-methoxyphenylamino group, methylamino group, dimethylamino group, ethylamino group, and diethylamino group.

  The methine dye according to the present invention is a combination of such a methine chain and an aromatic ring, a heterocycle, or an amino group. Specifically, for example, a cyanine dye, a styryl dye, a merocyanine dye, an oxonol dye, an azurenium dye And dyes such as squarylium dye, pyrylium dye, thiopyrylium dye, phenanthrene dye and aminovinyl dye.

  Although it depends on the application, examples of particularly preferred methine dyes include those comprising an atomic group represented by the general formula 1.

General formula 1:

In General Formula 1, Z ¹ and Z ² each independently represent an aromatic ring, and these aromatic rings may have a substituent. The aromatic ring in Z ¹ and Z ² is selected from monocyclic or polycyclic, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc. having a benzene ring as a basic unit. Such aromatic rings may have one or more substituents without departing from the object of the present invention. Examples of the individual substituents include methyl, ethyl, propyl, isopropyl, Propenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl Group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group and other aliphatic hydrocarbon groups, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , Cycloaliphatic hydrocarbon group such as cyclohexenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xyl Group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group and other aromatic hydrocarbon groups, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, Ether groups such as sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group, dimethylamino group, diethylamino group , Amino groups such as dipropylamino group, diisopropylamino group, dibutylamino group, dipentylamino group, halogen groups such as fluoro group, chloro group, bromo group, iodo group, hydroxy group, carboxy group, cyano group, nitro group, Furthermore, the combination of these Substituents.

R ¹ and R ² in General Formula 1 each independently represent a hydrogen atom or an appropriate substituent. Examples of the substituent in R ¹ and R ² include a methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2- Aliphatic hydrocarbon group such as pentene-4-ynyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group and the like, phenyl group, o-tolyl group, m-tolyl group Group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, Aromatic hydrocarbon groups such as phenylyl group, ether groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, Ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group, amino groups such as dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group and dipentylamino group , Fluoro groups, chloro groups, bromo groups, iodo groups and other halogen groups, hydroxy groups, carboxy groups, cyano groups, nitro groups, and combinations thereof.

R ³ and R ⁴ in the general formula 1 represent the same or different hydrocarbon groups, and these hydrocarbon groups may have a substituent. Examples of the hydrocarbon group for R ³ and R ⁴ include those having 1 to 20 carbon atoms, usually 1 to 8 carbon atoms, such as methyl group, ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, and isopropenyl. Group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group , Neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, etc. One or more of the hydrogen atoms in the aliphatic hydrocarbon group are, for example, phenyl group, o-tolyl group, m-tol. Group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and other aromatic hydrocarbon groups, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy Group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, benzyloxy group and other ether groups, fluoro group, chloro group, bromo group, iodo group and other halogen groups, and It may be substituted with a group, nitro group, cyano group or the like.

  L in the general formula 1 represents a divalent linking group, and the linking group may have a substituent. The divalent linking group in the present invention means a substituent having two binding sites for connecting the indolenine rings as described above. Examples of individual divalent linking groups include aliphatic carbonization such as methylene group, ethylene group, vinylene group, trimethylene group, propylene group, propenylene group, tetramethylene group, pentamethylene group, hexamethylene group, and octamethylene group. An alicyclic hydrocarbon group such as a hydrogen group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclohexenylene group, cyclohexadienylene group, o-phenylene group, m- Phenylene group, p-phenylene group, diphenylene group, naphthylene group, 1,2-phenylenedimethylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1,4-phenylenedimethylene group, methylene Aromatic hydrocarbon groups such as diphenylene group and ethylenediphenylene group, Group, oxygen-containing characteristic group such as carbonyl group, ether group such as methylenedioxy group and ethylenedioxy group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, spheroyl group, o-phthaloyl group, m -Acyl groups such as phthaloyl group and p-phthaloyl group, characteristic groups containing sulfur such as thio group and thiocarbonyl group, characteristic groups containing nitrogen such as imino group and azo group, cyclopentylene dimethylene group, cyclohexylene dimethylene And cycloalkylenedialkylene groups such as a group, alkylenedicycloalkylene groups such as a methylenedicyclohexylene group and an ethylenedicyclohexylene group, and combinations thereof. Among these, in terms of ease of synthesis of methine dyes and solubility of methine dyes in organic solvents, the chain length of the divalent linking group is less than 20 in terms of the number of constituent atoms such as carbon atoms, Specifically, 1 to 10 and more specifically 3 to 8 are preferable. In addition, in such a divalent linking group, one or more of its hydrogen atoms are, for example, an amino group, a carboxy group, a cyano group, a nitro group, a halogen group, a hydroxy group, etc., without departing from the object of the present invention. May be substituted.

Q ¹ and Q ² in the general formula 1 each independently represent a monomethine chain or a polymethine chain having an aromatic ring, a heterocyclic ring, or an amino group on the other end side, and the monomethine chain or polymethine chain is a substituent and / or You may have a cyclic group.

The aromatic ring in Q ¹ and Q ² is selected from monocyclic or polycyclic, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc. having a benzene ring as a basic unit. Such aromatic rings may have one or more substituents without departing from the object of the present invention. Examples of the individual substituents include methyl, ethyl, propyl, isopropyl, Propenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl Group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene-4-ynyl group and other aliphatic hydrocarbon groups, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , Cycloaliphatic hydrocarbon group such as cyclohexenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xyl Group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group and other aromatic hydrocarbon groups, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, Ether groups such as sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group, dimethylamino group, diethylamino group , Amino groups such as dipropylamino group, diisopropylamino group, dibutylamino group, dipentylamino group, halogen groups such as fluoro group, chloro group, bromo group, iodo group, hydroxy group, carboxy group, cyano group, nitro group, Furthermore, the combination of these Substituents.

The heterocyclic ring in Q ¹ and Q ² contains one or more heteroatoms selected from Group 15 or Group 16 elements in the periodic table such as nitrogen atom, oxygen atom, sulfur atom, selenium atom and tellurium atom. Monocyclic or polycyclic, for example, imidazoline ring, imidazole ring, benzimidazolol ring, α-naphthimidazole ring, β-naphthimidazole ring, indole ring, isoindole ring, indolenine ring, isoindo Renin ring, benzoindolenin ring, pyridinoindolenin ring, oxazoline ring, oxazole ring, isoxazole ring, benzoxazole ring, pyridinooxazole ring, α-naphthoxazole ring, β-naphthoxazole ring, selenazoline ring, selenazole ring , Benzoselenazole ring, α-naphthoselenazole ring, β- Ftselenazole ring, thiazoline ring, thiazole ring, isothiazole ring, benzothiazole ring, α-naphthothiazole ring, β-naphthothiazole ring, tellurazoline ring, tellurazole ring, benzotelrazole ring, α-naphthotelrazole ring, β -Naphtelrazole ring, further acridine ring, anthracene ring, isoquinoline ring, isopyrrole ring, imidazoquinoxaline ring, indandione ring, indazole ring, indalin ring, oxadiazole ring, carbazole ring, xanthene ring, quinazoline ring, quinoxaline Ring, quinoline ring, chroman ring, cyclohexanedione ring, cyclopentanedione ring, cinnoline ring, thiodiazole ring, thiooxazolidone ring, thiophene ring, thionaphthene ring, thiobarbituric acid ring, thiohydantoin ring, tetra Ring, triazine ring, naphthalene ring, naphthalene ring, naphthyridine ring, piperazine ring, pyrazine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, pyrazolone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrylium ring, pyrrolidine ring, pyrroline Ring, pyrrole ring, phenazine ring, phenanthridine ring, phenanthrene ring, phenanthroline ring, phthalazine ring, pteridine ring, furazane ring, furan ring, purine ring, benzoxazine ring, benzopyran ring, morpholine ring, rhodanine ring, etc. . Such a heterocyclic ring may have one or more substituents without departing from the scope of the present invention, and examples of the individual substituents include the same substituents as described above for the aromatic ring. It is done.

Examples of the amino group in Q ¹ and Q ² include a phenylamino group, a diphenylamino group, a p-methoxyphenylamino group, a methylamino group, a dimethylamino group, an ethylamino group, and a diethylamino group.

Examples of the polymethine chain in Q ¹ and Q ² include an even number of polymethine chains in which an odd number of methine groups are linked, such as a trimethine chain, a pentamethine chain, and a heptamethine chain, a dimethine chain, a tetramethine chain, and a hexamethine chain. It is selected from polymethine chains in which methine groups are linked, or polymethine chains such as azamethine chains. Such a monomethine chain or polymethine chain may have a substituent and / or a cyclic group. Examples of the substituent include a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, aliphatic hydrocarbon group such as tert-pentyl group, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, Ether groups such as butoxy group and tert-butoxy group, halogen groups such as fluoro group, chloro group, bromo group and iodo group, amino groups such as diphenylamino group and p-methoxydiphenylamino group, nitro group, cyano group In addition, examples of the cyclic group include a cyclopentene ring and a cyclopenta ring. Ene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, cyclooctene ring, cyclooctadiene ring and a benzene ring.

  More preferable methine dyes include those having an atomic group represented by the general formula 2.

General formula 2:

In General Formula 2, Z ^{1 to} Z ⁴ each independently represent an aromatic ring, and these aromatic rings may have a substituent. The aromatic ring in Z ^{1 to} Z ⁴ is selected from monocyclic or polycyclic benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and the like having a benzene ring as a basic unit. Such aromatic rings may have one or more substituents without departing from the object of the present invention. Examples of the individual substituents include the same substituents as in the general formula 1.

Y ¹ and Y ² in the general formula 2 represents a carbon atom or a heteroatom, examples of heteroatoms such as nitrogen atom, oxygen atom, sulfur atom, selenium atom, Group 15 in the periodic table, such as tellurium atoms And Group 16 atoms. The carbon atom in Y ¹ and Y ² may be an atomic group mainly composed of two carbon atoms such as an ethylene group and a vinylene group. Y ¹ and Y ² in general formula 1 may be the same or different from each other.

R ¹ , R ² , R ^{5 to} R ⁸ in General Formula 2 each independently represent a hydrogen atom or an appropriate substituent. Examples of the substituent in R ¹ , R ² , and R ^{5 to} R ⁸ include the same substituents as R ¹ and R ² in General Formula 1. In the general formula 2, when Y ¹ and / or Y ² is a heteroatom, a part or all of R ^{5 to} R ⁸ are not present.

R ³ , R ⁴ , R ⁹ and R ¹⁰ in the general formula 2 represent the same or different hydrocarbon groups, and these hydrocarbon groups may have a substituent. Examples of the hydrocarbon group in R ³ , R ⁴ , R ⁹ and R ¹⁰ include the same hydrocarbon groups as those in R ³ and R ⁴ in the general formula 1.

In General Formula 2, two of the substituents in R ^{5 to} R ⁸ or the hydrocarbon groups in R ⁹ and R ¹⁰ are, for example, a methylene group, an ethylene group, a vinylene group, a trimethylene group, a propylene group, or a propenylene. Group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and other aliphatic hydrocarbon groups, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclohexenylene group Alicyclic hydrocarbon groups such as cyclohexadienylene group, o-phenylene group, m-phenylene group, p-phenylene group, diphenylene group, naphthylene group, 1,2-phenylenedimethylene group, 1,3-phenylene Range methylene group, 1,4-phenylenedimethylene group, 1,4-phenylenediethylene Group, aromatic hydrocarbon group such as methylenediphenylene group and ethylenediphenylene group, characteristic group containing oxygen such as oxy group and carbonyl group, ether group such as methylenedioxy group and ethylenedioxy group, oxalyl group, malonyl Group, succinyl group, glutaryl group, adipoyl group, speroyl group, o-phthaloyl group, m-phthaloyl group, p-phthaloyl group and other characteristic groups containing sulfur such as thio group and thiocarbonyl group, imino group, Specific groups containing nitrogen such as azo groups, cycloalkylene dialkylene groups such as cyclopentylene dimethylene groups, cyclohexylene dimethylene groups, alkylene dicycloalkylene groups such as methylene dicyclohexylene groups, ethylene dicyclohexylene groups, and more By a divalent linking group such as a combination thereof Bonds may be in.

  L in General Formula 2 represents a divalent linking group corresponding to L in General Formula 1, and the linking group may have a substituent. Examples of the individual divalent linking group include the same divalent linking groups as in general formula 1.

^{J 1} and ^{J 2} in the general formula 2 represents a monomethine chain or the polymethine chain. Examples of individual polymethine chains include, for example, trimethine chain, pentamethine chain, heptamethine chain, etc., polymethine chain in which an odd number of methine groups are linked, or even number of methine groups, such as dimethine chain, tetramethine chain, and hexamethine chain. Are selected from the polymethine chain. Such a monomethine chain or polymethine chain may have a substituent and / or a cyclic group.

  Examples of the substituent of the monomethine chain or polymethine chain include, for example, methyl group, trifluoromethyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group , Aliphatic hydrocarbon groups such as isopentyl group, neopentyl group, tert-pentyl group, ether groups such as methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, cyclopropyl group, cyclobutyl Groups, cyclopentyl groups, cyclopentenyl groups, cyclohexyl groups, cyclohexenyl groups and other alicyclic hydrocarbon groups, phenyl groups, naphthyl groups and other aromatic hydrocarbon groups, fluoro groups, chloro groups, bromo groups, iodo groups, etc. Halogen group, diphenylamino group, p-methoxydiphenyl Amino group such as amino group, piperidino group, a heterocyclic group such as morpholino group, a nitro group, a cyano group, further include a substituent by combination thereof. As the cyclic structure in the polymethine chain, for example, the cyclic structure has at least one unsaturated bond such as an ethylenic double bond, and the unsaturated bond electronically resonates as part of the polymethine chain. , Cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, cyclooctene ring, cyclooctadiene ring, benzene ring, etc., all of which are the same as in the polymethine chain as described above. It may have a substituent.

  When the methine dye of the present invention requires a counter ion, such counter ion may be appropriately determined in consideration of the solubility of the methine dye in an organic solvent and the stability in the glass state. Ion, chlorine ion, bromine ion, iodine ion, perchlorate ion, periodate ion, hexafluorophosphate ion, hexafluoroantimonate ion, hexafluorostannate ion, nitrate ion, phosphate ion, borofluorination Inorganic acid anions such as hydrogenate ion and tetrafluoroborate ion, salicylic acid, p-hydroxysalicylic acid, thiocyanate ion, benzenesulfonate ion, naphthalenesulfonate ion, naphthalene disulfonate ion, p-toluenesulfonate ion, alkylsulfone Acid ion, benzene sulfonate ion, alkyl carboxylate ion, trihaloalkyl cation Organic acid anions such as borate ion, alkyl sulfate ion, trihaloalkyl sulfate ion, nicotinate ion, azo, bisphenyldithiol, thiocatechol chelate, thiobisphenolate chelate, bisdiol-α-diketone It is selected from organometallic complex anions, and bisalkylsulfonylimide systems such as bistrifluoromethylsulfonylimide and pentafluoroethylsulfonylimide.

  In the methine dyes represented by the general formula 1 and the general formula 2, any isomer such as a cis / trans isomer or an enantiomer is structurally present in the present invention. Shall be included.

Each of the methine dyes according to the present invention has a major absorption maximum in the ultraviolet region to the infrared region, specifically, a wavelength longer than 300 nm, and more specifically, in the vicinity of a wavelength of 350 to 850 nm. The extinction coefficient (hereinafter, the molecular extinction coefficient at the absorption maximum wavelength may be abbreviated as “ε”) is 1.0 × 10 ⁵ or more, usually 1.5 × 10 ⁵ or more, and the decomposition point. Is characterized by high heat resistance. Therefore, these methine dye compounds use laser light having a wavelength of around 405 nm as writing light, for example, BD-R and HD
A high-density optical recording medium having a recording capacity of 15 to 23.3 GB per side, such as a DVD-R, a DVD-R that uses laser light with a wavelength of 635 to 660 nm, and a CD-R that uses laser light with a wavelength of around 780 nm It can be used extremely advantageously in optical recording media such as

  Here, among the methine dyes of the present invention having a bisindolenin skeleton, the trimethine dye represented by Chemical Formula 2 shows a visible absorption spectrum as shown in FIG. 1 in a solution state. As shown in the visible absorption spectrum of FIG. 1, such a trimethine dye has absorption maxima near wavelengths of 550 nm and 600 nm, respectively, and writing light in the vicinity of wavelengths 635 to 660 nm on the long wavelength side of these absorption maxima. Is substantially absorbed. On the other hand, a conventionally known trimethine dye having a bisindolenin skeleton and represented by Chemical Formula 67 shows a visible absorption spectrum in a solution state as shown in FIG. When both are compared, a difference in absorption waveform is seen. Compared with a conventionally known trimethine dye having a bisindolenin skeleton bonded by a divalent linking group via a nitrogen atom in the indolenine ring, the trimethine dye according to the present invention is a bisindole dye. The renin skeleton is bonded by a divalent linking group via the carbon atom at the 3-position of the indolenine ring, thereby easily forming an H aggregate that is a dimer structure of a methine dye; Presumed. Therefore, the absorption maximum of the methine dye according to the present invention is slightly shifted to the short wavelength side as compared with conventionally known methine dyes.

  Specific examples of the methine dye according to the present invention include those represented by Chemical Formulas 1 to 45.

Chemical formula 1:

Chemical formula 2:

Chemical formula 3:

Chemical formula 4:

Chemical formula 5

Chemical formula 6:

Chemical formula 7:

Chemical formula 8:

Chemical formula 9:

Chemical formula 10:

Chemical formula 11:

Chemical formula 12:

Chemical formula 13:

Chemical formula 14:

Chemical formula 15:

Chemical formula 16:

Chemical formula 17:

Chemical formula 18:

Chemical formula 19:

Chemical formula 20:

Chemical formula 21:

Chemical formula 22:

Chemical formula 23:

Chemical formula 24:

Chemical formula 25:

Chemical formula 26:

Chemical formula 27:

Chemical formula 28:

Chemical formula 29:

Chemical formula 30:

Chemical formula 31:

Chemical formula 32:

Chemical formula 33:

Chemical formula 34:

Chemical formula 35:

Chemical formula 36:

Chemical formula 37:

Chemical formula 38:

Chemical formula 39:

Chemical formula 40:

Chemical formula 41:

Chemical formula 42:

Chemical formula 43:

Chemical formula 44:

Chemical formula 45:

Although the methine dyes according to the present invention can be synthesized by various methods, a method using a nucleophilic substitution reaction between an active methine group and an appropriate leaving group is preferable if the economy is important. When synthesizing a methine dye having an atomic group represented by general formula 1 by this method, for example, Z ¹ and Z ² corresponding to general formula 1, R ^{1 to} R ⁴ , and general formula having L 6 is reacted with an aromatic compound or a hetero compound having an appropriate leaving group derived from Q ¹ and / or Q ² , or Z ¹ and Z corresponding to general formula 1 ² , R ^{1 to} R ⁴ , and the compound represented by the general formula 7 having L, and the methine according to the present invention by reacting the aromatic compound or the hetero compound derived from Q ¹ and / or Q ² A desired amount of the system dye can be obtained.

General formula 6:

General formula 7:

When a methine dye having an atomic group represented by general formula 2 is synthesized by such a method, for example, a compound having an atomic group represented by general formula 6 and a Z corresponding to general formula 2 are synthesized. ³ , R ⁵ , R ⁶ , R ⁹ , and a compound having an atomic group represented by General Formula 8 having Y ¹ and / or Z ⁴ , R ⁷ , R ⁸ , R ¹⁰ corresponding to General Formula 2, and A compound having an atomic group represented by General Formula 9 having Y ² is reacted, or a compound having an atomic group represented by General Formula 7 and Z ³ , R ⁵ , corresponding to General Formula 2, The compound represented by the general formula 10 having R ⁶ , R ⁹ and Y ¹ and / or the general formula 11 having Z ⁴ , R ⁷ , R ⁸ , R ¹⁰ and Y ² corresponding to the general formula 2 The methine color according to the present invention by reacting It is possible to obtain the desired amount. X ₁ ⁻ and X ₂ ⁻ in the general formulas 6 to 11 are, for example, fluorine ion, chlorine ion, bromine ion, iodine ion, fluoric acid ion, chlorate ion, bromate ion, iodate ion, perchloric acid. Ions, periodate ions, phosphate ions, hexafluorophosphate ions, hexafluoroantimonate ions, hexafluorostannate ions, boron hydrofluoride ions, tetrafluoroborate ions and other inorganic acid ions, thiocyanic acid Ion, benzene sulfonate ion, naphthalene sulfonate ion, naphthalene disulfonate ion, benzene carboxylate ion, alkyl carboxylate ion, trihaloalkyl carboxylate ion, alkyl sulfate ion, trihaloalkyl sulfate ion, nicotinate ion, tetracyanoquinodi Organic acid ions such as methane ion, bistrifluoromethylsulfonyl ion Suitable anions including bisalkylsulfonylimide ions such as amide and pentafluoroethylsulfonylimide. M in the general formulas 7 to 9 is an appropriate leaving group, and is usually an anilino group, p-toluidino group, p-methoxyanilino group, p-ethoxycarbonylanilino group, N-acetylanilino group. Monovalent groups of aniline or aniline derivatives such as, or sulfur-containing characteristic groups such as mercapto group, methylthio group, ethylthio group, 3-sulfonylpropyl group, 4-sulfonylbutyl group are employed. n represents an integer of 0 to 3.

General formula 8:

Formula 9:

General formula 10:

General formula 11:

  In the synthesis, the compound represented by the general formula 6 and the compound represented by the general formula 8 and / or the general formula 9 in the reaction vessel, or the compound represented by the general formula 7 and the general formula 10 and / or An appropriate amount of each compound represented by the general formula 11 is taken and dissolved in a solvent as needed, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, Basic compounds such as triethylamine, piperidine, pyridine, pyrrolidine, aniline, N, N-dimethylaniline, N, N-diethylaniline, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid , Acidic compounds such as trifluoromethanesulfonic acid, aluminum chloride, zinc chloride, tin chloride, titanium tetrachloride After addition of the Lewis acidic compounds such as, the reaction is carried out at a temperature above ambient temperature or ambient temperature while heating and stirring by heating reflux.

  Examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichlorobenzene, 1,2-dibromobenzene, trichloroethylene, tetrachloroethylene, chlorobenzene. , Halides such as bromobenzene, α-dichlorobenzene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2 Alcohols such as methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene glycol, glycerin And ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, acetic acid, anhydrous Acetic acid, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide Acids and acid derivatives such as hexamethylphosphoric triamide, nitriles such as acetonitrile, propionitrile, succinonitrile and benzonitrile, and nitric acids such as nitromethane and nitrobenzene. Toro compounds, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, water and the like can be mentioned, and these are used in combination as necessary.

  In the case of using a solvent, generally, when the amount of the solvent is increased, the efficiency of the reaction is lowered. On the other hand, when the amount is decreased, it becomes difficult to uniformly heat and stir or a side reaction is likely to occur. Accordingly, it is desirable that the amount of the solvent is up to 100 times the mass of the raw material compound, usually 5 to 50 times as much as the mass ratio. Although depending on the type of raw material compound and reaction conditions, the reaction is completed within 10 hours, usually 0.5 to 5 hours. The progress of the reaction can be monitored by a general method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like. A desired amount of the methine dye according to the present invention can be produced by this method or according to this method. The progress of the reaction can be monitored by a general method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like.

  Here, the compounds represented by the general formula 6 and the general formula 7 are converted to, for example, an indolenine compound represented by the general formula 3 according to the present invention, for example, supervised by Masaaki Hayami, “Photosensitive dye”, October 1997. 17th, published by Sangyo Tosho Co., Ltd., pages 24 to 30, etc. Similarly, the compounds represented by the general formula 8, the general formula 9, the general formula 10 and the general formula 11 are, for example, supervised by Masaaki Hayami, “Photosensitive Dye”, published on October 17, 1997, published by Sangyo Tosho Co., Ltd., 24 Thru | or thirty pages etc., and can obtain according to the method described.

General formula 3:

  The indolenine compound represented by the general formula 3 according to the present invention passes through a step of reacting the diketone compound represented by the general formula 4 with one or more hydrazine compounds represented by the general formula 5. Can be obtained.

General formula 4:

General formula 5:

  In the indolenine compound represented by the general formula 3, when an isomer such as an enantiomer is structurally present, any isomer is included in the present invention.

  Specific examples of the indolenine compound according to the present invention include those represented by chemical formula 46 to chemical formula 53, for example. Any of these functions as an intermediate for producing the methine dye according to the present invention.

Chemical formula 46:

Chemical formula 47:

Chemical formula 48:

Chemical formula 49:

Chemical formula 50:

Chemical formula 51:

Chemical formula 52:

Chemical formula 53:

  In synthesizing such an indolenine compound, an appropriate amount of each of the compounds represented by the general formula 4 and the general formula 5 is taken in a reaction vessel, and if necessary, dissolved in a solvent, and further sodium acetate, potassium acetate, potassium carbonate. , Calcium carbonate, triethylamine, N, N-dimethylaniline, piperidine, morpholine, pyridine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like, and then heated by heating under reflux • React at ambient temperature or above ambient temperature with stirring. As the solvent, the same solvent as described above in the synthesis of the methine dye compound according to the present invention can be used. The reaction is completed within 10 hours, usually within 5 hours, depending on the type of raw material compound and reaction conditions. The progress of the reaction can be monitored by a general method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like.

  Although the methine dyes and indolenine compounds thus obtained may be used in the form of a reaction mixture depending on the application, they are usually dissolved, separated, decanted, filtered, extracted, concentrated, thin-layer chromatographed before use. Purified by general-purpose methods for purifying similar compounds such as chromatography, column chromatography, gas chromatography, high performance liquid chromatography, distillation, sublimation, crystallization, etc., and these methods are applied in combination as needed The Depending on the type and use of methine dyes and indolenine compounds, high-purity organic dye compounds are required. For example, when applied to information recording or solar power generation, for example, distillation It is desirable to purify by a method such as sublimation or crystallization.

As described above, the methine dye according to the present invention has a major absorption maximum in a longer wavelength region than 300 nm in a solution state, usually in the vicinity of a wavelength of 350 to 850 nm, and a molecular extinction coefficient (hereinafter referred to as absorption) at the absorption maximum wavelength. The molecular extinction coefficient at the maximum wavelength is sometimes abbreviated as “ε”.) Is also 1.0 × 10 ⁵ or more, usually 1.5 × 10 ⁵ or more. Absorb well. Moreover, the methine dyes according to the present invention are frequently used in various fields such as information recording and solar power generation, for example, for amide, alcohol, ketone, nitrile, and halogen organic solvents. In addition to exhibiting practically undissolvable solubility, many exhibit a decomposition point of about 200 ° C. or higher. As is well known, the decomposition point in an organic compound is considered as one of the important indicators of thermal characteristics, and the higher the decomposition point, the greater the thermal stability. However, the methine dye of the present invention absorbs light in the ultraviolet to infrared region to block it, or as a light absorbing material that uses the energy of light in the ultraviolet to infrared region, for example, information recording, It is extremely useful in a wide variety of applications including solar power generation, electrical machinery and equipment, telecommunication equipment, optical equipment, clothing, bedding products, health supplies, and agricultural materials. Incidentally, the decomposition point of an organic compound such as a methine dye can be determined, for example, by general-purpose differential scanning calorimetry (hereinafter abbreviated as “DSC analysis”).

  That is, the methine dye according to the present invention absorbs light in the ultraviolet to infrared region in information recording applications, and is used as a polymerizable compound or polymerized for optical card, plate making, thermal transfer recording, thermal recording, hologram recording, and the like. It is useful as a photosensitizer or photothermal exchange agent for accelerating polymerization by sensitizing an initiator or the like. As another application as a photosensitizer, for example, in the field of photovoltaic power generation, when a methine dye according to the present invention is supported on a semiconductor electrode of a dye-sensitized wet solar cell, a semiconductor for visible light having a short wavelength is used. The sensitivity of an electrode improves and the photoelectric conversion efficiency of a solar cell can be improved significantly. Since the methine dye according to the present invention exhibits light resistance that is practically unaffected by ambient light such as natural light and artificial light, a solar cell using the methine dye according to the present invention as a photosensitizer is long. Even if it is used for a long time, there is an actual advantage that it is difficult to cause a decrease in electromotive force due to the photosensitizer.

  In applications of telecommunications equipment, electrical machinery equipment, and optical equipment, when applying the methine dye according to the present invention as a filter material, for example, to an imaging tube, a semiconductor light receiving element, an optical fiber, a front member for a video display device, etc. In addition, there is an advantage that it is possible to suppress an increase in the ambient temperature due to noise derived from light in the infrared region, radiated heat rays, or the like, and to adjust the visibility to a desired level. Another application for filter materials is in agricultural materials, for example, by applying fruit trees, grains, vegetables, and florets to glass plates for greenhouses or plastic substrates for vinyl houses formed into sheets or films. The wavelength distribution of light reaching useful plants such as ornamental plants, garden plants, edible plants, and medicinal plants can be adjusted to control plant growth.

  In addition to the above uses, the methine dye according to the present invention and, if necessary, one or more of other materials that absorb light in the ultraviolet region, visible region, and / or infrared region, together with a light shielding agent and heat ray shielding Apparel, heat insulating agents, heat insulation agents, etc. in general clothing, in particular, clothing using heat insulation fibers, fibers having disguise performance for reconnaissance by ultraviolet rays, visible light, infrared rays, etc., other than clothing, for example, casement , Shirring, drape, pleat, print, venetian blind, lace, roman shade, roll screen, shutter, goodwill, blanket, duvet, duvet, duvet cover, sheets, cushion, pillowcase, pillowcase, cushion, mat, Interior / exterior materials for carpets, sleeping bags, window glass, buildings, vehicles, trains, ships, aircraft, etc., bedding products such as window glass Health supplies such as paper diapers, diaper covers, eyeglasses, monocles, lownets, insoles of shoes, linings of shoes, linings, furoshiki, umbrellas, umbrellas, stuffed animals, lighting equipment, sunglasses, sun visors, sunroofs, microwave ovens, Viewing windows such as ovens, as well as packaging materials, packing materials, containers, etc. for packaging, filling or containing these items, undesirable temperature changes and eye strain caused by visible light, Not only can it prevent or reduce damage and inconvenience of organisms and articles such as cell aging and cataracts, but also adjust the chromaticity, color tone, color, texture, etc. of the article, and reflect from the article There is an advantage that the transmitted light can be maintained or trimmed to a desired level. In addition, the methine dye of the present invention is used for falsification preventing ink, falsification / counterfeiting bar code ink, light absorbing ink, light absorbing paint, photo and film positioning as well as conventionally known organic compounds that absorb visible light. Marking agents, sorting dyes for recycling plastics, preheating aids for molding PET bottles, and pharmaceuticals for treating tumors that are generally sensitive to visible light It is useful as an active ingredient and an ingredient that helps the active ingredient function.

  The methine dye according to the present invention has a remarkable light resistance against ambient light such as natural light and artificial light. However, when the methine dye according to the present invention is used for the above-mentioned applications, for example, irradiation with a laser beam or the like. One or more of so-called light fastness improvers (quenchers) as necessary for the purpose of suppressing fading, deterioration, modification, alteration, degradation, etc. of methine dyes due to singlet oxygen, etc. It is by no means to exclude embodiments in which. Examples of the light fastness improver used in combination with the methine dye according to the present invention include, for example, the republished patent WO 00/075111 by the same applicant, edited by the Color Material Association, “Color Material Engineering Handbook”, first edition, 1,274. To 1,282 pages, Asakura Shoten Co., Ltd., published on November 25, 1989, Masahiro Fukami et al., “Dyes and Drugs”, Vol. 37, No. 7, pages 185 to 197 (1992). Amine compounds, carotene compounds, sulfide compounds, phenol compounds, acetylacetonate chelate systems, salicylaldehyde oxime systems, diimmonium systems, dithiol systems, thiocatechol chelate systems, thiobisphenolate chelate systems, bisdithio-α-diketone chelate systems Including formazan-based inorganic complexes, chelate complexes, and organometallic complexes Metal complex and the like, if necessary, they are used in combination. Among these, formazan-based and dithiol-based metals are provided in that the light resistance of the methine dye according to the present invention is remarkably improved and a good amorphous solid is realized in a mixed state with the methine dye according to the present invention. Complexes are particularly preferred. Although it depends on the use, the amount of the light fastness improver used in combination is usually adjusted to 1% by mass or more, preferably 3 to 30% by mass with respect to the methine dye. When the light resistance improver is used in combination, is the methine dye of the present invention uniformly mixed with the light resistance improver in advance and applied to the target article in the form of a liquid, semi-solid or solid composition? Alternatively, while adjusting the mixing ratio of the methine dye and the light resistance improver in the article so as to be within a predetermined range, each is individually applied to the target article in liquid, semi-solid or solid form. .

  As described above, the indolenine compound according to the present invention is useful as an intermediate for producing the methine dye of the present invention. Further, such an indolenine compound absorbs light in the ultraviolet region, usually light having a wavelength of 200 to 350 nm. Therefore, as an ultraviolet absorber, for example, an ultraviolet cut filter in an optical display such as a computer monitor or a television screen, thermal paper. Electron-donating dyes for pressure-sensitive paper, paints for automobile painting, paints for outdoor clothing, paints for coated wires, paints for magnetic paints, ballpoint pens, fountain pens, dot printers, copier toners, inkjets, permanent markers, dry erasure It is extremely useful in ophthalmic devices such as inks, windows, spectacle lenses and binoculars, goggles, hand shields, contact lenses, intraocular lenses in markers, newspaper printing, magazine printing, laser jet printers and the like.

  By the way, the methine dye of the present invention has an ultraviolet region to an infrared region, usually a wavelength region longer than a wavelength of 300 nm, specifically, a wavelength of 350 to 850 nm, more specifically, a wavelength of around 350 to 450 nm, 630 to 680 nm, In addition, it substantially absorbs light of 750 to 800 nm and has high light resistance to ambient light such as natural light and artificial light. For example, a high-density optical recording medium having a recording capacity of 15 to 23.3 GB per side, a DVD-R using a laser beam having a wavelength of about 630 to 680 nm, and a wavelength of 750, such as BD-R and HD DVD-R. For forming a recording layer of an optical recording medium such as a CD-R using a laser beam of up to 800 nm It is particularly useful as a light absorbing material.

  Therefore, the use of the methine dye of the present invention in an optical recording medium will be described. Since the methine dye of the present invention does not require any special treatment or operation when used in an optical recording medium, the optical recording medium according to the present invention is used. Can be produced according to conventionally known optical recording media. That is, one or more of the methine dyes of the present invention as the light absorbing material may contain one or more of other light absorbing materials to adjust the reflectance and light absorption rate in the recording layer, if necessary, Add one or more general light resistance improvers, binders, dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers, etc. to the organic solvent to improve the production work and performance of the recording medium. Dissolve and apply the solution uniformly on one side of the substrate by spraying, dipping, roller coating, spin coating, etc., and after drying to form a thin film of light-absorbing material that will be the recording layer, if necessary, Gold, silver, copper, platinum, aluminum, cobalt, tin, nickel by vacuum deposition, chemical vapor deposition, sputtering, ion plating, etc., so that the reflectance is 45% or more, preferably 55% or more. Flame retardants and stabilizers for the purpose of forming a reflective layer that adheres to the recording layer using a metal such as iron or chrome, or a general-purpose organic reflective layer material, or protecting the recording layer from scratches, dust, dirt, etc. Then, a protective layer that adheres to the reflective layer is formed by spin-coating an ultraviolet curable resin or a thermosetting resin containing an antistatic agent, etc., and curing by irradiation with light or heating.

  Examples of the light resistance improver include nitroso compounds such as nitrosodiphenylamine, nitrosoaniline, nitrosophenol, nitrosonaphthol, tetracyanoquinodimethane compounds, diimmonium salts, bis [2′-chloro-3-methoxy-4- ( 2-methoxyethoxy) dithiobenzyl] nickel (trade name “NKX-1199”, manufactured by Hayashibara Biochemical Laboratories Co., Ltd.), metal complexes such as azo dye metal complexes and formazan metal complexes are used. Are used in appropriate combination. Desirable light fastness improving agents are those comprising a nitroso compound or a formazan metal complex, and particularly desirable is disclosed in Japanese Patent Application Laid-Open No. 2000-344750 (name of the invention "phenylpyridylamine derivative") by the same patent applicant. Or a nitroso compound having a phenylpyridylamine skeleton, or a pyridine ring at the 5-position of the formazan skeleton disclosed in re-published patent WO00 / 075111 (name of invention "formazan metal complex") And a formazan compound in which a pyridine ring or a furan ring is bonded to the 3-position or one or more of its tautomers, for example, nickel, zinc, cobalt, iron, copper, palladium And a metal complex. When used in combination with such a light fastness improver, methine by exposure to reading light, ambient light, etc. without reducing the solubility of the methine dye of the present invention in an organic solvent or substantially impairing desirable optical properties. Undesirable changes such as degradation, fading, discoloration, and modification of the system dye can be effectively suppressed. As a compounding ratio, usually, a light resistance improving agent is contained in an amount of 0.01 to 5 mol, preferably 0.1 to 1 mol with respect to 1 mol of a methine dye while being adjusted.

  Since the methine dye of the present invention exhibits practically no solubility in various organic solvents, there is no restriction on the organic solvent for applying the methine dye to the substrate. Therefore, in the production of the optical recording medium according to the present invention, for example, TFP frequently used in the production of the optical recording medium, or hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, isopropylcyclohexane, tert-butyl. Hydrocarbons such as cyclohexane, octane, cyclooctane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, α-dichlorobenzene Halides such as methanol, ethanol, 2,2,2-trifluoroethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-ethoxy- -Propanol, 1-butanol, 1-methoxy-2-butanol, 3-methoxy-1-butanol, 4-methoxy-1-butanol, isobutyl alcohol, pentyl alcohol, isopentyl alcohol, cyclohexanol, 2-methoxyethanol (methyl Cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-isopropoxy-1-ethanol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, phenol, benzyl alcohol, cresol, diacetone alcohol, and phenols, Diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol Cole dimethyl ether, cyclohexyl-18-crown-6, ethers such as methyl carbitol, ethyl carbitol, ketones such as furfural, acetone, ethyl methyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, phosphoric acid Esters such as trimethyl, amides such as formamide, N-methylformamide, N, N-dimethylformamide, hexamethylphosphoric triamide, nitriles such as acetonitrile, propionitrile, succinonitrile, nitro compounds such as nitromethane, nitrobenzene, Other than TFP including amines such as ethylenediamine, pyridine, piperidine, morpholine, N-methylpyrrolidone, and sulfur-containing compounds such as dimethyl sulfoxide and sulfolane Select from organic solvent use, if necessary, or a mixture of them.

  In particular, the methine dye of the present invention has a high solubility in an easily evaporated organic solvent such as TFP, diacetone alcohol, methyl cellosolve, ethyl cellosolve, etc., so the methine dye of the present invention is dissolved in such a solvent, Even when applied to the substrate, dye crystals do not appear after drying, and the film thickness and surface of the recording layer do not become nonuniform. The methine dye of the present invention also exhibits good solubility in non-halogen solvents such as alcohols such as methyl cellosolve, ethyl cellosolve and diacetone alcohol, and ketones such as cyclohexanone. When the methine dye of the present invention is dissolved in such an alcohol and applied to a substrate, the alcohol is a non-halogen solvent, so that it is difficult to damage the substrate by the solvent or to pollute the environment.

  The substrate may be a general-purpose one, and usually an appropriate material is obtained by an extrusion molding method, an injection molding method, an extrusion injection molding method, a photopolymer method (2P method), a thermosetting integral molding method, a photocuring integral molding method, or the like. Depending on the final application, for example, it is formed into a disk shape having a diameter of 12 cm and a thickness of 0.6 mm or 1.2 mm, and this is used as a single plate, or it is used by suitably bonding with an adhesive sheet, an adhesive or the like. The material of the substrate is not particularly limited as long as it is substantially transparent and has a light transmittance of 80% or more, preferably 90% or more in the wavelength range of 300 to 800 nm. Examples of the individual materials include glass, ceramics, polyacrylate, polymethyl methacrylate, polycarbonate, polystyrene (styrene copolymer), polymethylpentene, polyester, polyolefin, polyimide, polyetherimide, polysulfone, and polyether. Plastics such as sulfone, polyarylate, polycarbonate / polystyrene-alloy, polyester carbonate, polyphthalate carbonate, polycarbonate acrylate, amorphous polyolefin, methacrylate copolymer, diallyl carbonate diethylene glycol, epoxy resin, phenol resin are used, usually polycarbonate Is frequently used. In the case of a plastic substrate, the sync signal and the recess for displaying the track and sector addresses are usually transferred to the track inner circumference during molding. Although there is no particular limitation on the shape of the recess, it is desirable that the average width is in the range of 0.2 to 1.8 μm and the depth is in the range of 70 to 200 nm.

  The light-absorbing material comprising the methine dye according to the present invention is made into a solution having a concentration of 0.5 to 5% by mass in the organic solvent as described above in consideration of the viscosity, and the thickness of the recording layer after drying is 10 to 1%. It is uniformly applied to the substrate so as to have a thickness of 1,000 nm, preferably 50 to 300 nm. Prior to the application of the solution, an undercoat layer may be provided on the substrate as necessary for the purpose of protecting the substrate and improving adhesion. Examples of the material of the undercoat layer include ionomer resins. , Polymer materials such as polyamide resin, vinyl resin, natural resin, silicon, and liquid rubber. When using a binder, cellulose esters such as nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose palmitate, cellulose acetate / propionate, methyl cellulose, ethyl cellulose, propyl cellulose, Cellulose ethers such as butyl cellulose, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl acetal, polyvinyl butyral, polyvinyl formal, polyvinyl alcohol, polyvinyl pyrrolidone and other vinyl resins, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene -Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, maleic anhydride copolymer Copolymer resins such as polymethyl methacrylate, polymethyl acrylate, polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile and other acrylic resins, polyethylene terephthalate and other polyesters, polyethylene, chlorinated polyethylene, polypropylene and other polyolefins These polymers are used alone or in combination, and are used in a mass ratio of 0.01 to 10 times that of the methine dye.

The method of using the optical recording medium according to the present invention will be described. For example, BD-R and HD according to the present invention thus obtained are described.
High-density optical recording media such as DVD-R having a recording capacity of 15 to 23.3 GB per side, and optical recording media such as DVD-R and CD-R are, for example, GaN, AlGaInP, GaAsP, and GaAlAs. Laser light with a wavelength of 850 nm or less using an InGaP-based, InGaAsP-based, or InGaAlP-based semiconductor laser, or a Nd-YAG laser combined with a distributed feedback type, Bragg reflection type second harmonic generation element (SHG element), or the like In particular, various kinds of information can be written with high density using laser light having a wavelength of 350 to 450 nm, 630 to 680 nm, or 750 to 800 nm. For reading, a laser beam having the same wavelength as that for writing or slightly higher wavelength is used. Regarding the laser output at the time of writing and reading, although it depends on the kind and blending amount of the light fastness improving agent used in combination with the methine dye in the present invention, the optical recording medium according to the present invention is used for writing information. It is desirable to set the output of the laser beam to be relatively strong beyond the threshold value of the energy at which the mark is formed, while the output when reading the written information is set to be relatively weak below the threshold value. Generally, writing is performed in a range exceeding 1 mW and not exceeding 50 mW, and reading is adjusted in a range of 0.1 to 4 mW. The recorded information is read by detecting a change in the reflected light amount or transmitted light amount of the mark on the recording surface of the optical recording medium and the portion where the mark is not formed by the optical pickup.

  Thus, in the optical recording medium according to the present invention, an optical pickup using a laser beam having a wavelength of 850 nm or less, particularly a laser beam having a wavelength of 350 to 450 nm, 630 to 680 nm, or 750 to 800 nm is used. With the following track pitch, it is possible to stably form minute marks with a mark length of 0.9 μm or less and with high density. Therefore, for example, in a disk-shaped substrate having a diameter of 12 cm, when laser light having a wavelength of 750 to 800 nm is used, the recording capacity is 0.7 GB per side, and when laser light having a wavelength of 630 to 680 nm is used, the recording capacity is per side. When a laser beam having a wavelength of 4.7 GB and a wavelength of 350 to 450 nm is used, a recording capacity of 15 GB to 23.3 GB per side can be achieved, and an extremely high density optical recording medium can be realized.

  Since the optical recording medium according to the present invention can record character information, image information, audio information and other digital information with high density, it is a consumer and business recording medium for recording and storing documents, data, computer programs, etc. As extremely useful. Examples of individual industries and forms of information to which the optical recording medium according to the present invention can be applied include, for example, construction and civil engineering drawings in construction and civil engineering, maps, road and river accounts, aperture cards, architectural sketches, disaster prevention materials, wiring Drawings, layouts, newspaper / magazine information, regional information, construction reports, etc., manufacturing blueprints, composition tables, prescriptions, product specifications, product price lists, parts lists, maintenance information, accident / failure cases, complaint handling Customer information, business partner information, company information, contracts, newspaper / magazine information, sales reports such as casebooks, manufacturing process charts, technical materials, drawings, details, in-house works, technical reports, inspection reports, etc. , Corporate credit surveys, inventory lists, etc., financial company information, stock price records, statistical materials, newspaper / magazine information, contracts, customer lists, various applications / reports / licenses / licensing documents, business Real estate / transport property information, building plans, maps, regional information, newspaper / magazine information, lease contracts, company information, inventory list, traffic information, supplier information, etc. Figures, disaster prevention materials, work standards tables, survey materials, technical reports, medical records, medical history / case files, medical charts, academic and academic papers, academic records, monthly research reports, research data, literature, etc. , Index of literature, survey data in information, paper, patent bulletin, weather map, data analysis record, customer file, legal case, member list, past book, work record, competition record, tournament record, etc. , Tourism information in tourism, traffic information, etc., index of company publications in the media and publishing, newspaper / magazine information, person files Sports record, ticker file, such as a broadcast script, map in government relations, roads and rivers ledger, fingerprint files, resident card, various types of application and notification and licensing, licensing documents, statistical data, such as public documents, and the like. In particular, the optical recording medium of the present invention that can be written only once must not have the recorded information altered or erased. For example, in addition to record storage of medical records, official documents, etc., such as art museums, libraries, museums, broadcasting stations, etc. It is extremely useful as an electronic library.

  The optical recording medium according to the present invention has some special applications such as a compact disk, digital video disk, laser disk, MD (information recording system using a magneto-optical disk), CDV (laser disk using a compact disk), DAT (magnetic). Information recording system using tape), CD-ROM (read-only memory using compact disc), DVD-ROM (read-only memory using digital versatile disc), DVD-RAM (using digital versatile disc) Writable reading memory), digital photography, movies, video software, audio software, computer graphics, publications, broadcast programs, commercial messages, game software editing, proofreading, and for large computers and car navigation Applications include as a part program storage unit.

  The optical recording medium referred to in the present invention has the property that the methine dye of the present invention substantially absorbs light having a wavelength of 850 nm or less, particularly light having a wavelength of 350 to 450 nm, 630 to 680 nm, or near 750 to 800 nm. It means the general recording media to be used, and in addition to the heat deformation type, for example, a thermal coloring method using a chemical reaction between a color former and a developer due to heat generation due to light absorption of a methine dye, The so-called “brown-eye method” may be used in which a periodic uneven pattern provided on the surface of the substrate is flattened by such heat generation.

  Hereinafter, embodiments of the present invention will be described based on examples.

<Indolenine compounds>
In a reaction vessel, 40 g of the compound represented by Chemical Formula 54 and 76.6 g of the compound represented by Chemical Formula 55 were added, and the mixture was heated and reacted for 1 hour with stirring. After cooling the reaction mixture, 80 ml of concentrated hydrochloric acid was added, and the mixture was further reacted by heating for 30 minutes. The reaction mixture was cooled and 25% aqueous sodium hydroxide solution was added dropwise, followed by extraction with chloroform. The chloroform layer was collected by decanting, washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and then chloroform was distilled off. The obtained oil was purified by silica gel column chromatography using a mixed solution of chloroform and methanol as a developing solvent. As a result, 29.8 g of an oil of the indolenine compound according to the present invention represented by the white chemical formula 46 was obtained. .

Chemical formula 54:

Chemical formula 55:

When an absorption spectrum in a methanol solution was measured by a conventional method as a light absorption characteristic of a part of the oily substance, the indolenine compound of this example showed a plurality of absorption peaks in the ultraviolet region near the wavelength of 215 nm to 305 nm (ε = 7.94 × 10 ^{3 to} 5.45 × 10 ⁴ ). ^{In 1} H-NMR analysis, the indolenine compound of this example in a chloroform-d solution has a chemical shift δ (ppm, TMS) of 0.15 to 0.21 (2H, m, —CH ₂ —), 0.30. To 0.36 (2H, m, —CH ₂ —), 1.37 (6H, s, CH ₃ —), 1.60 to 1.70 (2H, m, —CH ₂ —), 2.00 to 2.10 (2H, m, —CH ₂ —), 2.14 (6H, s, CH ₃ —), 7.41 to 7.51 (4H, m, ArH), 7.68 to 7.72 ( 2H, m, ArH), 7.78 to 7.85 (4H, m, ArH), and 7.92 to 7.95 (2H, m, ArH).

  The indolenine compound of this example is useful as an intermediate for producing the methine dye of the present invention having a bisindolenin skeleton. Furthermore, since the indolenine compound of this example absorbs light in the ultraviolet region, it is useful as an ultraviolet absorber in ultraviolet cut filters, dyes, inks and ophthalmic devices.

<Indolenine compounds>
An indolenine compound according to the present invention represented by the white chemical formula 51 was reacted in the same manner as in Example 1 except that the compound represented by the chemical formula 56 was used instead of the compound represented by the chemical formula 54. 8.3 g of an oily product was obtained.

Chemical formula 56:

When an absorption spectrum in a methanol solution was measured by an ordinary method as a light absorption characteristic for a part of the oily substance, the indolenine compound of this example showed a plurality of absorption peaks in the ultraviolet region near the wavelength of 215 nm to 305 nm (ε = 8.35 × 10 ^{3 to} 5.81 × 10 ⁴ ). ^{In 1} H-NMR analysis, the indolenine compound of this example in a chloroform-d solution has a chemical shift δ (ppm, TMS) of 0.10 to 0.25 (2H, m, —CH ₂ —), 0.30. To 0.45 (2H, m, —CH ₂ —), 0.70 to 0.85 (4H, m, —CH ₂ —), 1.43 (6H, s, CH ₃ —), 1.74 to _{1.84 (2H, m, -CH 2} -), 2.12 to _{2.22 (2H, m, -CH 2} -), 2.20 (6H, s, CH 3 -), 7.38 to 7 Peaks were shown at positions of .51 (4H, m, ArH) and 7.70 to 7.92 (8H, m, ArH).

  The indolenine compound of this example is useful as an intermediate for producing the methine dye of the present invention having a bisindolenin skeleton. Furthermore, since the indolenine compound of this example absorbs light in the ultraviolet region, it is useful as an ultraviolet absorber in ultraviolet cut filters, dyes, inks and ophthalmic devices.

<Indolenine compounds>
The indolenine compound according to the present invention represented by the white chemical formula 47 was reacted in the same manner as in Example 1 except that the compound represented by the chemical formula 57 was used instead of the compound represented by the chemical formula 54. 12.8 g of an oily product was obtained.

Chemical formula 57:

A portion of the oil was taken and the absorption spectrum in a methanol solution was measured as a light absorption characteristic by a conventional method. As a result, the indolenine compound of this example showed a plurality of absorption peaks in the ultraviolet region near a wavelength of 216 nm to 350 nm. ^{In 1} H-NMR analysis, the indolenine compound of this example in a chloroform-d solution has a chemical shift δ (ppm, TMS) of 1.52 (6H, s, CH ₃ ), 2.20 (6H, s, CH ₃ ), 3.00 (2H, d, CH ₂ ), 3.38 (2H, d, CH ₂ ), 6.01 (4H, s, ArH), 7.25 to 7.56 (6H, m, ArH), 7.74 (2H, d, ArH), 7.91 (2H, d, ArH), and 7.98 (2H, d, ArH) at the peak.

  The indolenine compound of this example is useful as an intermediate for producing the methine dye of the present invention having a bisindolenin skeleton. Furthermore, since the indolenine compound of this example absorbs light in the ultraviolet region, it is useful as an ultraviolet absorber in ultraviolet cut filters, dyes, inks and ophthalmic devices.

  The indolenine compound according to the present invention has some differences in preparation conditions and yield depending on the structure. For example, all of the indolenine compounds including those represented by chemical formulas 46 to 53 other than those described above are examples 1 to 3. The desired amount can be obtained by these methods or according to those methods.

<Methine dye>
To the reaction vessel, 12.5 g of the compound represented by Chemical Formula 46 and 16.9 g of ethyl p-toluenesulfonate were respectively added and stirred for 3.5 hours. After that, 125 ml of acetone was added dropwise to the reaction mixture and cooled. As a result, 16.65 g of a white crystal of the compound represented by Chemical Formula 58 was obtained.

Chemical formula 58:

  Next, an appropriate amount of acetonitrile is taken into a reaction vessel, and 1.5 g of the compound represented by the chemical formula 58 obtained previously, 1.82 g of the compound represented by the chemical formula 59, and 0.75 ml of acetic anhydride are added, and the mixture is stirred for 30 minutes. Thereafter, 0.99 ml of triethylamine was further added dropwise, and the mixture was heated and stirred for 1.5 hours. An appropriate amount of isopropyl ether was added to the reaction mixture, the supernatant was removed by decantation, 15 ml of methanol was added, and the mixture was heated to reflux for 30 minutes. Thereafter, 8 ml of a methanol solution of 0.87 g of ammonium hexafluorophosphate was added dropwise to the reaction solution and cooled. As a result, 1.37 g of brown crystals of the methine dye of the present invention represented by Chemical Formula 1 were obtained.

Chemical formula 59:

When a part of the crystal was taken and the melting point and decomposition point were measured by DSC analysis as thermal characteristics, the methine dye of this example showed a melting point near 252 ° C. and a decomposition point near 300 ° C. As a light absorption characteristic, when a visible absorption spectrum in a methanol solution was measured by a conventional method, the cyanine dye of this example showed a main absorption maximum near a wavelength of 544 nm (ε = 1.94 × 10 ⁵ ). When the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in a dimethyl sulfoxide-d ₆ solution was measured, the chemical shift (ppm, TMS) was 0.15 to 0.32 (2H, m, —CH ₂ -), 0.65 to _{0.82 (2H, m, -CH 2} -), 1.10 (6H, t, CH 3 -), 1.23 (6H, t, CH 3 -), 1. _{62 (6H, s, CH 3} -), 1.80 (6H, s, CH 3 -), 1.87 (6H, s, CH 3 -), 1.85 to 2.07 (2H, m, - CH ₂ -), 2.70 to _{2.90 (2H, m, -CH 2} -), 3.95 to _{4.20 (8H, m, -CH 2} -), 6.39 (2H, d, - CH =), 6.48 (2H, d, -CH =), 7.51 (2H, t, ArH), 7.59 (2H, t, ArH), 7.61 (2H, d, ArH), 7.66 (2H, t, ArH), 7.75 (2H, d, ArH), 7.78 (2H, t, ArH), 8.01 (4H, t, ArH), 8.13 (4H, t, ArH), 8.16 (2H, d, ArH), 8.24 (2H, d, ArH), and 8.32 (2H, t, -CH = ) Was observed at a position.

  The methine dye of this example efficiently absorbs light in the visible region near 500 nm to 600 nm and is excellent in solubility in solvents and thermal characteristics. For example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

<Methine dye>
When the reaction was carried out in the same manner as in Example 4 except that the compound represented by Chemical Formula 60 was used instead of the compound represented by Chemical Formula 59, brown crystals of the methine dye of the present invention represented by Chemical Formula 2 were obtained. Of 1.71 g was obtained.

Chemical formula 60:

A part of the crystal was taken and its melting point and decomposition point were measured by DSC analysis as thermal characteristics. As a result, the methine dye of this example showed a decomposition point that was difficult to distinguish from the melting point near 211 ° C. As a light absorption characteristic, when a visible absorption spectrum in a methanol solution was measured by a conventional method, the methine dye of this example showed a main absorption maximum near a wavelength of 551 nm (ε = 1.87 × 10 ⁵ ). In addition, when the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in a dimethyl sulfoxide-d ₆ solution was measured, the chemical shift (ppm, TMS) was 0.10 to 0.30 (2H, m, —CH ₂ -), 0.70 to _{0.90 (2H, m, -CH 2} -), 0.50 to _{1.30 (12H, m, CH 3} -), 1.50 to 2.00 (16H, m _{, CH 3 -, - CH 2} -), 1.90 to _{2.10 (2H, m, -CH 2} -), 2.80 to _{3.00 (2H, m, -CH 2} -), 3.80 Peaks were observed at positions from 4.20 (8H, m, —CH ₂ —), 5.90 to 8.50 (40H, m, ArH, —CH═).

  The methine dye of this example efficiently absorbs light in the visible region near 500 nm to 600 nm and is excellent in solubility in solvents and thermal characteristics. For example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

<Methine dye>
When the reaction was carried out in the same manner as in Example 4 except that the compound represented by Chemical Formula 61 was used instead of the compound represented by Chemical Formula 59, a green crystal of the methine dye of the present invention represented by Chemical Formula 3 was obtained. 1.37 g was obtained.

Chemical formula 61:

When a part of the crystal was taken and the melting point and decomposition point were measured by DSC analysis as thermal characteristics, the methine dye of this example showed a decomposition point that was difficult to distinguish from the melting point in the vicinity of 235 ° C. As a light absorption characteristic, when a visible absorption spectrum in a methanol solution was measured by a conventional method, the methine dye of this example showed a main absorption maximum near a wavelength of 551 nm (ε = 1.92 × 10 ⁵ ). When the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in a dimethyl sulfoxide-d ₆ solution was measured, the chemical shift (ppm, TMS) was 0.00 to 0.20 (2H, m, —CH ₂ -), 0.60 to _{0.75 (2H, m, -CH 2} -), 1.21 (6H, t, CH 3 -), 1.33 (6H, t, CH 3 -), 1. 45 to 2.10 (18H, m, —CH ₂ —), 1.78 (6H, s, CH ₃ —), 2.25 to 2.50 (4H, m, —CH ₂ —), 2.60. To 2.80 (2H, m, —CH ₂ —), 4.00 to 4.12 (4H, m, —CH ₂ —), 4.12 to 4.22 (4H, m, —CH ₂ —) 6.56 (2H, d, -CH =), 6.72 (2H, d, -CH =), 7.48 to 7.72 (12H, m, ArH), 7.98 to 8.21 (14H, m, ArH, -CH =), peaks were observed.

  The methine dye of this example efficiently absorbs light in the visible region near 500 nm to 600 nm and is excellent in solubility in solvents and thermal characteristics. For example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

<Methine dye>
The reaction was carried out in the same manner as in Example 4 except that the compounds represented by the chemical formulas 47 and 60 were used in place of the compounds represented by the chemical formulas 46 and 59, respectively. 10.47 g of dark blue crystals of the system dye was obtained.

A part of the crystal was taken and its melting point and decomposition point were measured by DSC analysis as thermal characteristics. As a result, the methine dye of this example showed a decomposition point that was difficult to distinguish from the melting point in the vicinity of 220 ° C. As an absorption characteristic, when an absorption spectrum in a methanol solution was measured by a conventional method, the methine dye of this example showed a main absorption maximum at a wavelength of 599 nm (ε = 1.54 × 10 ⁵ ). In addition, when the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in the dimethyl sulfoxide-d ₆ solution was measured, the chemical shift δ (ppm, TMS) was 0.7 to 0.9 (6H, m), 2.0 to 2.2 (12H, m), 3.2 to 3.6 (10H, m), 3.9 to 4.2 (8H, m), 6.0 to 8.8 (44H, m) ) Showed a peak.

  The methine dye of this example efficiently absorbs light in the visible region near 500 nm to 600 nm and is excellent in solubility in solvents and thermal characteristics. For example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

<Methine dye>
To the reaction vessel, 2.0 g of the compound represented by Chemical Formula 51 and 2.54 g of ethyl p-toluenesulfonate were added and stirred for 2 hours. After that, 20 ml of acetone was added dropwise to the reaction mixture and cooled. 2.64 g of a white crystal of the compound represented by Chemical Formula 62 was obtained.

Chemical formula 62:

  Next, an appropriate amount of acetonitrile is taken into the reaction vessel, and 2.0 g of the compound represented by the chemical formula 62 obtained previously, 2.35 g of the compound represented by the chemical formula 59, and 0.97 ml of acetic anhydride are added and stirred for 30 minutes. Then, 1.28 ml of triethylamine was further added dropwise and stirred with heating for 1.0 hour. An appropriate amount of isopropyl ether was added to the reaction mixture, the supernatant was removed by decantation, 20 ml of methanol was added, and the mixture was heated to reflux for 30 minutes. Thereafter, 5 ml of a methanol solution of 1.12 g of ammonium hexafluorophosphate was added dropwise to the reaction solution and cooled. As a result, 2.31 g of dark blue crystals of the methine dye of the present invention represented by Chemical Formula 8 were obtained.

When a part of the crystal was taken and the melting point and decomposition point were measured by DSC analysis as thermal characteristics, the methine dye of this example showed a melting point near 251 ° C. and a decomposition point near 300 ° C. As a light absorption characteristic, when a visible absorption spectrum in a methylene chloride solution was measured by a conventional method, the cyanine dye of this example showed a main absorption maximum at a wavelength of about 545 nm (ε = 1.79 × 10 ⁵ ). When the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in a dimethyl sulfoxide-d ₆ solution was measured, the chemical shift (ppm, TMS) was 0.00 to 0.20 (2H, m, —CH _2- ), 0.50 to 0.65 (2H, m, —CH ₂ —), 0.65 to 0.80 (4H, m, —CH ₂ —), 1.25 (6H, t, CH _{3 -), 1.35 (6H, t} , CH 3 -), 1.72 (6H, s, CH 3 -), 1.87 (6H, s, CH 3 -), 1.91 (6H, s, CH ₃ -), 2.00 to _{2.20 (2H, m, -CH 2} -), 2.60 to _{2.75 (2H, m, -CH 2} -), 4.15 to 4.30 (8H _{, m, -CH 2 -),} 6.49 (2H, d, -CH =), 6.51 (2H, d, -CH =), 7.38 (2 , T, ArH), 7.54 (4H, m, ArH), 7.67 (4H, m, ArH), 7.78 (2H, t, ArH), 7.89 (2H, d, ArH), 7.96 (2H, d, ArH), 8.06 to 8.16 (6H, m, ArH), 8.20 (2H, d, ArH), and 8.42 (2H, t, -CH =) A peak was observed at the position of.

  The methine dye of this example efficiently absorbs light in the visible region near 500 nm to 600 nm and is excellent in solubility in solvents and thermal characteristics. For example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

<Methine dye>
A suitable amount of acetonitrile was taken in a reaction vessel, 5.0 g of the compound represented by Chemical Formula 63, 7.44 g of the compound represented by Chemical Formula 64, and 7.37 ml of triethylamine were added and stirred with heating for 30 minutes. After adding an appropriate amount of isopropyl alcohol to the reaction mixture, the reaction mixture was cooled and the precipitated crystals were collected by filtration. Next, after adding the crystals obtained above and an appropriate amount of methanol to the reaction vessel and heating to reflux for 30 minutes, an aqueous solution of 4.5 g of sodium perchlorate was added dropwise to the reaction solution and cooled. As a result, 3.17 g of brown crystals of the methine dye of the present invention were obtained.

Chemical formula 63:

Chemical formula 64:

When a part of the crystal was taken and its melting point and decomposition point were measured by DSC analysis as thermal characteristics, the methine dye of this example showed a decomposition point that was difficult to distinguish from the melting point near 285 ° C. As a light absorption characteristic, when a visible absorption spectrum in a methanol solution was measured by a conventional method, the cyanine dye of this example showed a main absorption maximum near a wavelength of 415 nm (ε = 5.52 × 10 ⁵ ). When the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in a dimethyl sulfoxide-d ₆ solution was measured, the chemical shift (ppm, TMS) was 0.20 to 0.30 (2H, m, —CH ₂ -), 0.40 to _{0.50 (2H, m, -CH 2} -), 1.64 (6H, s, CH 3 -), 1.80 to 2.00 (2H, m, -CH ₂ -), 2.70 to _{2.90 (2H, m, -CH 2} -), 3.50 (6H, s, CH 3 -), 3.65 (6H, s, CH 3 -), 5.55 Peaks were observed at (2H, s, -CH =), and 7.20 to 7.80 (20H, m, ArH).

  Since the methine dye of this example efficiently absorbs light in the visible region of 400 nm to 500 nm and is excellent in solubility in solvents and thermal characteristics, for example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

<Methine dye>
To the reaction vessel were added 5.0 g of the compound represented by Chemical Formula 63 and 2.08 g of N, N′-diphenylformamidine, and the mixture was heated and stirred for 3 hours. After adding an appropriate amount of acetone to the reaction mixture, it was cooled and the precipitated crystals were collected by filtration. Next, after adding the crystals obtained above and an appropriate amount of methanol to the reaction vessel and heating to reflux for 30 minutes, an aqueous solution of 4.5 g of sodium perchlorate was added dropwise to the reaction solution and cooled. As a result, 4.19 g of brown crystals of the methine dye of the present invention were obtained.

When a part of the crystal was taken and the melting point and decomposition point were measured by DSC analysis as thermal characteristics, the methine dye of this example showed a decomposition point that was difficult to distinguish from the melting point in the vicinity of 300 ° C. As a light absorption characteristic, when a visible absorption spectrum in a methanol solution was measured by a conventional method, the cyanine dye of this example showed a main absorption maximum near a wavelength of 428 nm (ε = 1.62 × 10 ⁵ ). When the ¹ H-nuclear magnetic resonance spectrum of the methine dye of this example in a dimethyl sulfoxide-d ₆ solution was measured, the chemical shift (ppm, TMS) was 0.15 to 0.30 (2H, m, —CH _2- ), 0.65 to 0.82 (2H, m, —CH ₂ —), 1.62 (6H, s, CH ₃ —), 1.82 to 2.02 (2H, m, —CH ₂ -), 2.75 to _{2.95 (2H, m, -CH 2} -), 3.40 (6H, s, CH 3 -), 6.43 (2H, d, -CH =), 7.20 Peaks were observed at ˜8.20 (22H, m, ArH), and 8.51 (2H, d, —CH═).

  Since the methine dye of this example efficiently absorbs light in the visible region of 400 nm to 500 nm and is excellent in solubility in solvents and thermal characteristics, for example, information recording, solar power generation, electric machinery In various fields including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials, this can be blocked by absorbing visible light, It is useful as a light-absorbing material that uses energy.

  Although the methine dyes according to the present invention have slight differences in preparation conditions and yield depending on the structure, for example, all of those including those represented by chemical formulas 1 to 45 other than those described above are used in Examples 4 to 10. The desired amount can be obtained by these methods or according to those methods.

<Solubility of methine dyes>
About the methine dye of this invention shown in Table 1, according to a conventional method, the mass of the methine dye dissolved in 100 ml of TFP at 20 ° C. was measured as solubility. At the same time, the solubility of the related compounds represented by Chemical Formula 65 to Chemical Formula 67 was measured in the same manner. The results are shown in Table 1.

Chemical formula 65:

Chemical formula 66:

Chemical formula 67:

  As is apparent from the results in Table 1, the methine dyes according to the present invention exhibited a solubility in TFP that surpassed that of known similar compounds represented by Chemical Formulas 65 to 67. That is, while the solubility of a known related compound was 1.10% or less, all of the methine dyes according to the present invention used for the test showed significantly higher solubility than the known related compound.

<Light resistance of cyanine dyes>
15 mg of any one of the methine dyes represented by Chemical Formulas 1 to 3, 8 and Chemical Formula 36 obtained by the methods of Examples 4 to 8 was taken and added to 3 ml of TFP, and ultrasonic waves were applied for 5 minutes at room temperature. Dissolved. The solution is uniformly dropped onto one side of a polished glass substrate (5 cm × 5 cm) by spin coating, and the substrate is uniformly applied onto the substrate by rotating at 1,000 rpm for 1 minute. By blowing and drying in this order, a methine dye thin film according to the present invention was formed on a glass substrate.

Next, after measuring the transmittance (T ₀ ) of the methine dye at the absorption maximum wavelength (near 550 nm) in a thin film state, a 7.5 kW xenon lamp is fixed at a predetermined interval from the glass substrate, and cold air is blown to the substrate. Then, it was exposed to a xenon lamp for 2 hours (light irradiation energy on the substrate surface 180 W / m ² ). Then, immediately, the absorption transmittance at the maximum wavelength (T) is measured again, was calculated dye residual rate (%) by substituting the transmittance T and T ₀ is obtained by thus the number 1. In parallel, thin films formed of similar compounds represented by chemical formulas 65 to 68 were treated in the same manner as described above, and the transmittance at the absorption maximum wavelength was measured and used as a control. The results are shown in Table 2.

Chemical formula 68:

  As can be seen from the results in Table 2, in the control thin film composed only of the compounds represented by Chemical Formulas 66 to 68, a significant amount of the compound was changed by exposure for only 2 hours, and the initial absorbance was 50% to 60%. %. On the other hand, the thin films composed of the methine dyes of the present invention represented by the chemical formulas 1 to 3, 8 and 36 are all found to have a dye residual ratio of 64 to 75% even when exposed in the same manner. As described above, the decrease in absorbance was alleviated. Incidentally, the control thin film represented by the chemical formula 65 and constituted by a conventionally known methine dye showed a dye residual ratio (73%) almost the same as that of the methine dye of the present invention when exposed in the same manner.

  These experimental results indicate that the methine dye of the present invention has substantially the same or significantly superior light resistance in the visible region as compared with conventionally known methine dyes.

<Electrical properties of methine dyes>
According to a conventional method, as shown in FIG. 3, an optical recording medium in which the substrate 1, the recording layer 2, the reflective layer 3, and the protective layer 4 were laminated in this order was produced. That is, one of the methine dyes of the present invention represented by Chemical Formulas 1 to 3, 8 or Chemical Formula 36 is added to an appropriate amount of TFP so as to have a concentration of 1.6% by mass, heated for a while, and then applied with ultrasonic waves. And dissolved. According to a conventional method, this solution is uniformly spin-coated on one side of a polycarbonate disk-shaped substrate 1 (diameter 12 cm, thickness 0.6 mm) and dried to form a recording layer 2 made of a light-absorbing material having a thickness of 100 nm. did. Thereafter, silver is deposited on the substrate 1 to a thickness of 30 to 100 nm to form a reflective layer 3 that is in close contact with the recording layer 2, and is then brought into close contact with the reflective layer 3 using a general-purpose adhesive to form a disk made of polycarbonate. A protective optical layer 4 (diameter 12 cm, thickness 0.6 mm) was attached to prepare an optical recording medium for testing. In parallel, an optical recording medium was prepared and used as a control in the same manner as described above except that a conventionally known methine dye represented by Chemical Formula 65 or 68 was used instead of the methine dye of the present invention. The conventionally known methine dyes represented by the chemical formulas 66 and 67 have low solubility in TFP, and a thin film could not be formed, so that an optical recording medium could not be produced.

  With respect to the seven types of optical recording media thus produced, a commercially available optical disk evaluation apparatus (trade name “DDU-1000 type” manufactured by Pulstec Industrial Co., Ltd.) was used and the writing wavelength was 658 nm (aperture ratio 0.60). 8-16 modulated test signals are written at transfer rates of 11.08 Mbps (1 × speed), 44.32 Mbps (4 × speed), and 88.64 Mbps (8 × speed), and recording sensitivity and electrical characteristics (reproducing light) at that time are written. Output 0.7 mW). The results are also shown in Table 3.

  The results in Table 3 show that by using the methine dye of the present invention, the reflectance, modulation degree, and jitter are higher than those of conventionally known methine dyes at any recording speed of 1 × speed, 4 × speed, and 8 × speed. It shows that the recording power of the optical recording medium can be significantly improved while maintaining the electrical characteristics such as the value. In particular, the knowledge that the recording sensitivity is improved by having the bisindolenin skeleton according to the present invention is the first point that has been revealed by the present invention. That is, by using the methine dye of the present invention, it is possible to realize an optical recording medium that has high sensitivity and excellent electrical characteristics such as jitter.

<Optical recording medium>
As a light-absorbing material, a methine dye represented by any one of Chemical Formulas 1 to 3, 8 or 36 is added to TFP so as to have a concentration of 1.2% by mass per unit volume. The formazan metal complex was added to the light-absorbing material so as to have a concentration of 5.0% by mass, heated for a while, and then dissolved by applying ultrasonic waves. According to a conventional method, this solution is subjected to membrane filtration, and then a recess (track pitch: 0.74 μm, width: 0.03 μm, depth: 76 nm) is displayed by injection molding on the inner periphery of the track to display the synchronization signal and the address of the track and sector. The recording layer having a thickness of 200 nm was formed by spin-coating evenly on one side of a transferred polycarbonate disk substrate (diameter 12 cm, thickness 1.2 mm) and drying. Thereafter, pure silver is deposited on the substrate by a sputtering method so as to have a thickness of 100 nm to form a reflective layer that adheres to the recording layer, and a known ultraviolet curable resin (trade name “Dicure Clear SD1700” is formed on the reflective layer. ”, Manufactured by Dainippon Ink and Chemicals, Inc.) was uniformly spin-coated, and five types of optical recording media were prepared by forming a protective layer that adhered to the reflective layer by ultraviolet irradiation. When tested in the same manner as in Example 13, the optical recording medium of this example exhibits recording characteristics, electrical characteristics such as modulation characteristics, reflectance, and jitter characteristics equivalent to those of the optical recording medium in Example 13. did.

  All of the optical recording media of this example having excellent electrical characteristics such as recording sensitivity, modulation characteristics, reflectance, and jitter characteristics have a recording capacity exceeding 4 GB, and visible light having a wavelength shorter than 700 nm, in particular, wavelength 630. A large amount of document information, image information, audio information, and other digital information can be written with high density by using an optical pickup with a laser beam of about 680 nm to 680 nm. When the recording surface of the optical recording medium of the present example in which information was written using a semiconductor laser element having an oscillation wavelength of 658 nm was observed with an electron microscope, a random signal including a minute mark having a minimum mark length of less than 1.0 μm was found. It was formed on the track with high density.

<Optical recording medium>
A methine dye represented by any one of Chemical Formula 26 to Chemical Formula 28 is added to TFP so as to have a concentration of 1.2% (w / vol) as a light absorbing material, and a general-purpose formazan metal as a light resistance improver. The complex was added to the light-absorbing material so as to have a concentration of 5.0% (w / w), heated for a while, and then dissolved by applying ultrasonic waves. The solution was subjected to membrane filtration according to a conventional method, and then uniformly spin-coated on one side of a CD-R disk substrate (diameter 12 cm, thickness 1.2 mm, track pitch 1.6 μm), and dried to a thickness of 200 nm. The recording layer was formed. Thereafter, pure silver is added to the coated substrate to a thickness of 100 nm by a sputtering method to form a reflective layer that adheres closely to the recording layer. Further, a known ultraviolet curable resin (trade name “ Dicure Clear SD1700 ”(manufactured by Dainippon Ink & Chemicals, Inc.) was uniformly spin-coated, and three types of optical recording media were produced by forming a protective layer that adhered to the reflective layer by ultraviolet irradiation. When tested in the same manner as in Example 13, the optical recording medium of this example exhibits recording characteristics, electrical characteristics such as modulation characteristics, reflectance, and jitter characteristics equivalent to those of the optical recording medium in Example 13. did.

  All of the optical recording media of this example having excellent electrical characteristics such as sensitivity, modulation characteristics, reflectance, and jitter characteristics have a recording capacity exceeding 600 MB, and visible light having a wavelength shorter than 850 nm, in particular, wavelengths from 750 to A large amount of document information, image information, audio information, and other digital information can be written with high density by using an optical pickup with a laser beam of about 800 nm. When the recording surface of the optical recording medium of this example in which information was written using a semiconductor laser element having an oscillation wavelength of 780 nm was observed with an electron microscope, a random signal including a minute mark with a minimum mark length of less than 1.0 μm was found. It was formed on the track with high density.

<Optical recording medium>
Add either methine dye represented by Chemical Formula 21 or Chemical Formula 24 to TFP as a light-absorbing material so as to have a concentration of 1.0% by mass, and add a general-purpose formazan metal complex as a light-fastening agent to the light-absorbing material. After adding to a concentration of 20.0% by mass, ultrasonic waves were applied and dissolved. This solution is added to HD
A DVD-R disk substrate (diameter 12 cm, thickness 0.6 mm, track pitch 0.4 μm) is applied by spin coating, and a pure silver reflective film 120 nm is formed by sputtering, and an ultraviolet curable resin is used. Two types of optical recording media were produced by bonding to a 6 mm thick back plate.

The optical recording medium of this example uses a tester (manufactured by Pulstec Industrial Co., Ltd.) with a wavelength of 405 nm and NA (numerical aperture) of 0.65 to record at a linear velocity of 6.61 m / s and a shortest mark length of 0.2 μm. went. The recording and playback test is an HD defined by the DVD Forum.
The method was based on the DVD-R standard Ver1.0, and PRSNR (Partial Response SNR) in the standard was evaluated.

  As a result of such an evaluation test, the optical recording medium recording of this example showed a LOW TO HIGH type mechanism, and the PRSNR at the optimum recording power greatly exceeded the standard value of 15.

  As a result, the optical recording medium of this example has a recording capacity of 15 GB or more, and writes a large amount of document information, image information, and audio information at high density by using a laser element having an oscillation wavelength of about 405 nm. It tells you that you can. As a matter of course, the optical recording medium of this example has a useful life generally required for optical recording media. According to the result of the acceleration test, once written information is read repeatedly or exposed to ambient light. Can be read over a long period of time.

  As described above, the present invention is based on the creation of a novel methine pigment and the discovery of various industrially useful properties. The methine dye of the present invention is excellent in light resistance, efficiently absorbs light in the ultraviolet to infrared region, exhibits a practically undissolvable solubility in various organic solvents, and has excellent thermal characteristics. As a light-absorbing material that absorbs light in the ultraviolet to infrared region and blocks this or absorbs light in the ultraviolet to infrared region, for example, information recording, solar power generation, electric machinery It is extremely useful in a wide variety of applications including appliances, telecommunications appliances, optical appliances, clothing, bedding products, health supplies, and agricultural materials.

In particular, in the field of information recording, the methine dye of the present invention having sensitivity to light having a wavelength of 350 nm to 850 nm is suitable for DVD-R, BD- R, HD
It is extremely useful as a light-absorbing material constituting a recording layer in a high-density optical recording medium having a recording capacity of 15 to 23.3 GB per side such as a DVD-R. In addition, the methine dye of the present invention can be advantageously used as a light-absorbing material constituting a recording layer in an optical recording medium such as the current CD-R, DVD-R compatible with 1 × speed and 4 × speed.

Claims (3)

A methine dye represented by General Formula 1 or General Formula 2.
General formula 1:
(In General Formula 1, Z ¹ and Z ² each independently represent a monocyclic or polycyclic aromatic ring having a benzene ring as a basic unit, and these aromatic rings may have a substituent. R ¹ and R ² each independently represents a hydrogen atom or a substituent, and R ³ and R ⁴ represent the same or different hydrocarbon groups, and these hydrocarbon groups may have a substituent. L represents a divalent linking group, and the linking group may have a substituent, Q ¹ and Q ² each independently have an aromatic ring, a heterocyclic ring, or an amino group on the other end side. A monomethine chain or a polymethine chain is represented, and the monomethine chain and the polymethine chain may have a substituent and / or a cyclic group.
General formula 2:
(In General Formula 2, Z ^{1 to} Z ⁴ each independently represent a monocyclic or polycyclic aromatic ring having a benzene ring as a basic unit, and these aromatic rings may have a substituent. R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or an appropriate substituent, and R ³ , R ⁴ , R ⁹ and R ¹⁰ are the same or different hydrocarbons. These hydrocarbon groups may have a substituent, and two of the substituents in R ^{5 to} R ⁸ or the hydrocarbon groups in R ⁹ and R ¹⁰ are divalent. L may represent a divalent linking group, and the linking group may have a substituent, and J ¹ and J ² each independently represents a monomethine chain or a polymethine chain. The monomethine and polymethine chains are substituted and / or Good .Y ¹ and Y ² have a Jo structure each independently represent a carbon atom or a heteroatom, if Y ¹ and / or Y ² are hetero atoms, part of R ⁵ through R ⁸ Or not all.)   An optical recording medium comprising the methine dye according to claim 1. The methine of Claim 1 represented by General formula 3 through the process with which the diketone compound represented by General formula 4 and the 1 type, or 2 or more types of hydrazine compound represented by General formula 5 are made to react. A method for producing an indolenine compound as an intermediate for producing a pigment .
General formula 3:
(In General Formula 3, Z ¹ and Z ² each independently represent a monocyclic or polycyclic aromatic ring having a benzene ring as a basic unit, and these aromatic rings may have a substituent. R ¹ and R ² each independently represents a hydrogen atom or a substituent, L represents a divalent linking group, and the linking group may have a substituent.
General formula 4:
(In General Formula 4, R ¹ and R ² represent a hydrogen atom or a substituent corresponding to General Formula 3. L represents a divalent linking group corresponding to General Formula 3, and the linking group represents a substituent. (You may have it.)
General formula 5:
(In General Formula 5, Z ⁵ represents a monocyclic or polycyclic aromatic ring Z ¹ or Z ² having a benzene ring corresponding to General Formula 3 as a basic unit, and the aromatic ring has a substituent. May be.)