TWI466865B - Novel compounds and optical recording materials using the compounds - Google Patents

Description

Novel compound and optical recording material using the same

The present invention relates to a novel compound and a metal complex thereof used in an optical recording material or the like, and more particularly to an optical recording which is recorded by imparting information by using an information pattern formed by laser or the like. The optical recording material used in the medium, more specifically, an optical recording used in an optical recording medium for high-density optical recording and reproduction in a laser having a low wavelength and a low energy laser capable of having ultraviolet and visible regions. material.

Optical recording media are widely used because they generally have excellent recording capacity and are excellent in recording or reproduction in a non-contact manner. In WORM, CD-R, DVD±R and other single-write multi-reading discs, the laser is condensed on a small area of the recording layer, and the properties of the optical recording layer are changed for recording, and the reflection is based on the recorded portion and the unrecorded portion. The difference in the amount of light is reproduced.

At present, the wavelength of the semiconductor laser used for recording and reproduction in the above-mentioned optical disc, CD-R is 750-830 nm, and DVD-R is 620 nm-690 nm. In order to further increase the capacity, the industry has studied using short wavelengths. Laser discs, for example, have been studied using light from 380 to 420 nm as the recording light.

In an optical recording medium for recording light of short wavelength, various compounds are used to form an optical recording layer. For example, Patent Documents 1 and 2 propose an optical recording material containing a metal complex having a specific structure. However, as the optical recording material for forming an optical recording layer, these compounds have an absorption wavelength characteristic which is not suitable.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-34645, Patent Document 2: Japanese Patent Laid-Open No. 2004-345212

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel compound and a complex thereof, and more particularly to provide an optical recording material suitable for forming an optical recording layer in an optical recording medium for recording short-wavelength light.

As a result of repeated studies, the inventors of the present invention have found a metal complex having a specific compound as a ligand having an absorption wavelength characteristic suitable for forming an optical recording layer for an optical recording medium for short-wavelength recording light. Use it to solve the above problems.

The present invention provides a compound represented by the following formula (I), whereby the above object is attained.

(wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms; and R ² represents a hydrogen atom; An alkyl group having 1 to 18 carbon atoms, a halogen atom, a nitro group, a cyano group or an amine group, and adjacent R ² groups may be bonded to each other to form a ring, n is a number from 1 to 4, and R ³ is a number of carbon atoms An alkyl group of ~8, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and the above-mentioned alkyl group having 1 to 8 or 1 to 18 carbon atoms and having 6 carbon atoms The aryl group of ~20, the aralkyl group having 7 to 20 carbon atoms and the amine group may have a substituent, the ring A represents a benzene ring or a naphthalene ring, and X represents an oxygen atom, a sulfur atom, a selenium atom, N-R or C. -R ⁴ (R ⁵ ), R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms or a heterocyclic group Or a halogen atom, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R ⁴ and R ⁵ can be linked to form a ring structure. The above benzene ring, naphthalene ring, alkyl group having 1-8 or 1-18 carbon atoms, and 6 to 2 carbon atoms The aryl group of 0, the aralkyl group having 7 to 20 carbon atoms, the amine group and the heterocyclic group may have a substituent, and the methyl group in the alkyl group having 1 to 8 or 1 to 18 carbon atoms may be - The CH=CH ₂ substitution, the methylene group in the above alkyl group having 1 to 8 or 1 to 18 carbon atoms may be replaced by -O-, -CO- or -CH=CH-.)

Further, the present invention provides a metal complex which is a ligand represented by the above formula (I), thereby achieving the above object.

Further, the present invention provides an optical recording material characterized by containing at least one of the above metal complexes, thereby achieving the above object.

Further, the present invention provides an optical recording medium characterized by forming an optical recording layer comprising the above optical recording material on a substrate, thereby achieving the above object.

Hereinafter, preferred embodiments of the present invention will be described in detail.

First, the compound represented by the above formula (I) will be described.

In the above formula (I), R ¹ and R ³ , R in the N-R as a group in X, and R ⁴ and R ⁵ as a group in X are 1 to 1 carbon atoms. The alkyl group of 8 may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group or a third pentyl group. Hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, etc., as for R ² The alkyl group having 1 to 18 carbon atoms is exemplified, and examples of the above R ¹ include a mercapto group, an isodecyl group, a decyl group, a dodecyl group, a tridecyl group, and a tetradecane group. , pentadecyl, palmitoyl, heptadecyl, octadecyl, etc., as for R ¹ , R ³ , R in the N-R as a group in X, and R ⁴ as a group in X And an aryl group represented by R ⁵ having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an inden-1-yl group, a phenanthrene-1-yl group, and the like, and R ¹ and R ^{3 are} as X. in the group of N-R R, as well as the number indicated by R X in the ⁴ and R ⁵ groups of 7 to 20 carbon atoms of the Alkyl group include: benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, Guangxi basal etc. As R ² and X as in the group of Examples of the halogen atom represented by R in the N-R include fluorine, chlorine, bromine, and iodine. Examples of the ring formed by the adjacent R ² or R ⁴ and R ⁵ are bonded to each other, and examples thereof include a pyridine ring and a pyrazine. a ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, an oxazole ring, a juluolidine ring, a piperidine ring, a piperazine ring, a pyrrolidine ring, Morpholine ring, thiomorpholine ring, imidazolidinium ring, pyrazolidine ring, isoxazole ring, isothiazolidine ring, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, four Hydropyran rings, etc., which may also be condensed with other rings or may be substituted.

In the above formula (I), the heterocyclic group represented by R in the N-R which is a group in X may, for example, be a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a piperazinyl group or a piperidinyl group. Pyranyl, pyrazolyl, triazyl, pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furan Furanyl, benzofuranyl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, Isothiazolyl, isoxazolyl, indolyl, pyrrolidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-di Oxyimidazolidine-3-yl, 2,4-dioxyoxazolidin-3-yl and the like.

R ¹ , R ³ , R in the N-R as a group in X, and an alkyl group having 1 to 8 carbon atoms represented by R ⁴ and R ⁵ as a group in X, represented by R ² An alkyl group having 1 to 18 carbon atoms, R ¹ , R ³ , R in the N-R as a group in X, and R ⁴ and R ⁵ as a group in X are 6 carbon atoms. An aryl group of ~20, R ¹ , R ³ , R in the N-R as a group in X, and an aralkyl group having 7 to 20 carbon atoms represented by R ⁴ and R ⁵ as a group in X The amine group represented by R ² and the heterocyclic group represented by R in the N-R which is a group in X may each contain a substituent. The following may be mentioned as this substituent. In addition, when R ¹ to R ⁵ and R are a group having a carbon atom such as an alkyl group having 1 to 8 carbon atoms, and the group contains a substituent having a carbon atom in the following substituent; The number of carbon atoms of R ¹ to R ⁵ and R including the substituent satisfies a predetermined range.

Examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a second butyl group, a tert-butyl group, an isobutyl group, a pentyl group, and an isopentyl group. Third amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, dicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, An alkyl group such as a third heptyl group, an n-octyl group, an isooctyl group, a third octyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group or a fluorenyl group; a methoxy group, an ethoxy group, a propoxy group, and a different group Propyloxy, butoxy, second butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, third pentyloxy, hexyloxy, cyclohexyloxy, g Alkoxy groups such as oxy, isoheptyloxy, third heptyloxy, n-octyloxy, isooctyloxy, trioctyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; Methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, third pentylene Sulfur, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, third heptylthio An alkylthio group such as n-octylthio, isooctylthio, trioctylthio, 2-ethylhexylthio; vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl , 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclo Alkenyl groups such as hexenyl, heptenyl, octenyl, nonenyl, pentadecenyl, eicosyl, and docosacenyl; benzyl, phenethyl, diphenylmethyl , an aralkyl group such as a triphenylmethyl group, a styryl group or a cinnamyl group; an aryl group such as a phenyl group or a naphthyl group; an aryloxy group such as a phenoxy group or a naphthyloxy group; an arylthio group such as a phenylthio group or a naphthylthio group; ; pyridyl, pyrimidinyl, pyridazinyl, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl , furyl, furyl, benzofuranyl, thienyl, thienyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, Isoxazolyl, fluorenyl, 2-pyrrolidone-1-yl a heterocyclic group such as 2-piperidone-1-yl, 2,4-dioxyimidazol-3-yl or 2,4-dioxyoxazolidin-3-yl; fluorine, chlorine, bromine, Halogen atom such as iodine; ethyl hydrazino, 2-chloroethyl fluorenyl, propyl fluorenyl, octyl decyl, acryl fluorenyl, methacryl fluorenyl, phenylcarbonyl (benzylidene), fluorenyl, 4-trifluoro Methyl benzhydryl, trimethylethyl fluorenyl, o-hydroxybenzhydryl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-eight An alkoxycarbonyl group, an amine group such as an indenyl group; a methoxy group such as an ethoxy group or a benzyl group; an amine group; an ethylamine group, a dimethylamino group, a diethylamino group, a butylamine group, and a ring; Pentylamino, 2-ethylhexylamino, dodecylamino, anilino, chloroanilino, toluidine, methoxyaniline, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, etidinyl, benzhydrylamine, formylamino, trimethylethenylamine, dodecane Amino group, amine mercaptoamine group, N,N-dimethylaminocarbonylamino group, N,N-diethylamine Amine, morpholinylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamine, N-methyl-methyl Oxycarbonylamino group, phenoxycarbonylamino group, aminesulfonylamino group, N,N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group, Substituted amine group such as phenylsulfonylamino; sulfonylamino, sulfonyl, carboxy, cyano, sulfo, hydroxy, nitro, decyl, trialkyldecyl, quinone, amidoxime A group, a sulfonamide group or the like, which may be further substituted. Further, the carboxyl group and the sulfo group may form a salt, a complex or a complex with an inorganic base or an organic base.

Specific examples of the compound represented by the above formula (I) include the following compounds No. 1 to 34.

The method of producing the compound represented by the above formula (I) is not particularly limited. For example, the compound represented by the above formula (I), wherein G is represented by i), can be represented by the following [Chemical Formula 5], from the carbonyl group. Derivatives are obtained with amine compounds.

(wherein R ¹ , R ² , R ³ and n are the same as the above formula (I).)

Further, the compound represented by ii) in the above formula (I) can be obtained from the carbonyl derivative and the amine compound as shown in the following [Chemical Formula 6].

(wherein A, R ¹ , R ² , X and n are the same as those of the above formula (I).)

The compound represented by the above formula (I) can be used in a polymerization initiator, various polymer materials, medicines and the like in addition to a ligand for a metal complex.

Next, a metal complex which is a ligand represented by the above formula (I) will be described.

The metal complex according to the compound represented by the above formula (I) as a ligand, wherein at least one compound represented by the above formula (I) is coordinated to a metal atom, is a formula (I) The hydrogen atom and the metal atom of the hydroxyl group in the compound represented by the compound are substituted, and the nitrogen atom is coordinately bonded to the metal atom, thereby forming at least one chelate structure. The metal complex is stable in chemical and thermal properties, and the absorption characteristics at the maximum absorption wavelength λmax of the light absorption of the metal complex solution are preferably as appropriate.

Examples of the metal complex having the above-mentioned preferred properties include those in which the above metal atom is a divalent metal atom and are represented by the following general formulae (II) and (III).

^{(Wherein, R 1, R 2, R} 3 and n in the general formula (I) the same, ^'the same as the above general formula (I), the R ^1, R ^2' R ¹ in the general formula (I), the same as R ^{2, 'the} same as R ³ in the general formula (I), the R ^3, M represents a group 2 element of the Periodic table of freedom, group 8 elements, group 9 elements, group 10 elements, group 11 Any metal atom selected from the group consisting of elements and group 12 elements.)

(wherein A, R ¹ , R ² , X and n are the same as the above formula (I), and R ^{1 '} , R ^{2 '} and M are the same as those of the above formula (II).)

In the above formula (II), examples of the metal atom represented by M include a Group 2 element, a Group 8 element, a Group 9 element, a Group 10 element, a Group 11 element, and the Any one of the metal atoms selected from the group consisting of 12 elements.

Among these metal atoms, particularly preferred are metal atoms selected from copper, zinc, nickel, cobalt and iron. If the metal atom is a copper or cobalt atom, a metal complex containing the metal atom can be produced at low cost. The light-absorbing property of the obtained metal complex is also good, so it is more preferable.

Specific examples of the metal complex represented by the above formula (II) include metal complexes Nos. 1 to 12 shown below.

Specific examples of the compound represented by the above formula (III) include metal complexes Nos. 13 to 20 shown below.

The metal complex of the compound represented by the above formula (I) as a ligand is not particularly limited. For example, the method for producing a metal complex represented by the above formula (II), which is a preferred embodiment, is synthesized from the carbonyl derivative and the amine compound as shown in the following [Chemical Formula 12]. a compound represented by (I), a method of synthesizing a compound by chelation reaction with a metal salt compound, or a metal complex obtained by chelation reaction of the carbonyl derivative with a metal salt compound A method of reacting with an amine compound.

(wherein R ¹ , R ² , R ³ and n are the same as the above formula (I), and R ^{1 '} , R ^{2 '} , R ³ and M are the same as those of the above formula (II).)

In addition, as a method of producing the metal complex represented by the above formula (III), as shown in the following [Chemical Formula 13], the carbonyl derivative and the amine compound are synthesized by the above formula (I). a compound represented by the chelate reaction of the compound with a metal salt compound, or a metal complex obtained by chelation reaction of the carbonyl derivative with a metal salt compound and an amine compound Methods.

(wherein R ¹ , R ² and n are the same as the above formula (I), and R ^{1 '} , R ^{2 '} and M are the same as the above formula (II).)

In the reaction represented by the above-mentioned [Chemical Formula 12] and [Chemical Formulation 13], the metal salt compound used in the chelation reaction may, for example, be an inorganic metal such as a halogenated metal salt, a hydroxide, a sulfate or a nitrate. a salt; an organic acid metal salt such as an acetate; a lower metal alkoxide such as a methoxide, an ethanol salt or an isopropoxide; a chelate complex such as an ethyl acetonate or an EDTA salt; and the like. Further, in the chelation reaction, a basic compound such as sodium hydroxide, lithium hydroxide, sodium methoxide, sodium acetate, sodium hydride, sodium amine, lithium amine or organic amine compound may be used as a reaction. Agent.

The metal complex of the invention can be used for various catalysts, contrast agents, medicines, oxygen absorbers, developers, cosmetic agents, photosensitizers, anti-fading agents, bactericides, light absorbers, optical recording agents, ultraviolet absorbers , an acid generator, and the like.

Next, an optical recording material characterized by containing at least one of the above metal complexes and an optical recording medium characterized by forming an optical recording layer containing the optical recording material on a substrate will be described.

The optical recording material of the present invention contains at least one of the above metal complexes. Further, the optical recording medium of the present invention is obtained by forming an optical recording layer containing the optical recording material on a substrate.

The optical recording material of the present invention can be applied to various optical recording media in accordance with the light absorption characteristics of the metal complex contained therein. In the optical recording material of the present invention, particularly suitable for short-wavelength laser discs having a wavelength of 380 nm to 420 nm, the optical absorption characteristics of the metal complex contained in the solution state are 300 to 450. The maximum absorption wavelength λmax is in the range of nm. Further, as for the absorption intensity, when ε at λmax is less than 1.0 × 10 ⁴ , the recording sensitivity is lowered, so that it is preferably 1.0 × 10 ⁴ or more. The measurement of λmax and ε in the solution state of the metal complex as a ligand using the compound represented by the above formula (I) can be selected according to a usual method, the concentration of the sample solution, the solvent used in the measurement, and the like. And proceed.

The preparation of the optical recording material of the present invention and the method of producing an optical recording medium characterized by the optical recording layer comprising the optical recording material formed on the substrate of the present invention are not particularly limited. Usually, it is a lower alcohol such as methanol or ethanol; an ethereal alcohol such as methyl cellosolve, ethyl cellosolve, butyl cellosolve or diethylene glycol butyl ether; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketone, cyclohexanone and diacetone; esters such as ethyl acetate, butyl acetate and methoxyacetate; acrylates such as ethyl acrylate and butyl acrylate; 2, 2, 3, 3 - fluorinated alcohols such as tetrafluoropropanol; hydrocarbons such as benzene, toluene, and xylene; and organic solvents such as chlorinated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, which dissolve the metal complex of the present invention and Accordingly, it is necessary to dissolve the various compounds described below to prepare a solution-like optical recording material. When the optical recording material is applied to a substrate, a wet coating method such as spin coating, spray coating, or dip coating may be used, or may be used. Evaporation method, sputtering method, and the like. In the case of using the above organic solvent, the amount of the metal complex in the optical recording material of the present invention is preferably from 0.1 to 10% by mass.

The optical recording layer is formed into a film, and the thickness thereof is usually suitably 0.001 to 10 μm, preferably 0.01 to 5 μm.

Further, in the optical recording material of the present invention, the content of the metal complex of the present invention is preferably from 10 to 100% by mass based on the solid content contained in the optical recording material of the present invention. The optical recording layer is preferably formed by containing 50 to 100% by mass of the above metal complex in the optical recording layer, and is an optical recording layer for forming the content of the metal complex, and more preferably the present invention. The optical recording material contains 50 to 100% by mass of the above metal complex according to the solid content standard contained in the optical recording material of the present invention.

The optical recording material of the present invention may contain, in addition to the metal complex of the present invention, an azo compound, a phthalocyanine compound, an oxonium compound, a squary salt compound, an anthraquinone compound, or styrene. a compound, a porphin compound, an anthraquinone compound, a croconic methine compound, a pyran compound, a thiopyran compound, a triarylmethane compound, a diphenylmethane compound, a tetrahydrocholine compound, An indophenol compound, an anthraquinone compound, a naphthoquinone compound, a dibenzopyran compound, a thiazine compound, an acridine compound, an oxazine compound, a spiropyran compound, an anthraquinone compound, and a rhodamine a compound used in a general optical recording layer such as a brightening compound; a resin such as polyethylene, polyester, polystyrene or polycarbonate; a surfactant; an antistatic agent; a lubricant; a flame retardant; Base trapping agent; porphyrin derivative and other pore-forming accelerator; dispersing agent; antioxidant; cross-linking agent; Further, the optical recording material of the present invention may contain an aromatic nitroso compound, an ammonium compound, an imine cation compound, a bisimine cation compound, a transition metal chelate compound, or the like as a quenching of singlet oxygen or the like. Agent. In the optical recording material of the present invention, the various components are used in an amount of from 0 to 50% by mass based on the solid content contained in the optical recording material of the present invention.

The optical material of the present invention may contain a diimonium compound. By containing the diimonium compound, the decrease in the residual rate of the absorbance over time of the optical recording medium of the present invention can be more effectively prevented. Further, the content of the imidium compound is preferably in the range of from 0 to 99% by mass, more preferably from 50 to 95% by mass, based on the solid content contained in the optical recording material of the present invention. .

The material of the substrate on which the optical recording layer is provided is not particularly limited as long as it is substantially transparent to writing (recording) light and reading (reproducing) light, and for example, polymethyl methacrylate or poly pair can be used. A resin such as ethylene phthalate or polycarbonate, glass or the like. Further, as for the shape thereof, any shape such as a tape measure, a drum shape, a belt shape, or a dish shape may be used for the corresponding use.

Further, on the optical recording layer, a reflective film may be formed by a vapor deposition method or a sputtering method using gold, silver, aluminum, copper, or the like, or a protective layer may be formed by an acrylic resin, an ultraviolet curable resin, or the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples, comparative examples and evaluation examples. However, the present invention is not limited by the following examples and the like.

In the following Examples 1 to 9, the production examples of the compound No. 1, No. 2, and No. 21 to No. 27 represented by the above formula (I) and the compounds No. 1, No. 2 and No. 21 to No. 27 are production examples of metal complexes No. 1, No. 2, and No. 13 to No. 19 as ligands. The identification of the obtained Compound No. 1, No. 2, No. 21 to No. 27, and the metal complexes No. 1, No. 2, and No. 13 to No. 19 was performed by ¹ H- NMR, UV absorption spectroscopy, IR, elemental analysis, and the like were carried out. The results of the identification are shown in the following [Table 1] to [Table 4].

Further, in the following Examples 10 to 18, optical recording materials containing the metal complexes No. 1, No. 2 or No. 13 to No. 19 obtained in Examples 1 to 9 are disclosed, and the optical recording material is used. A manufacturing example of the optical recording medium No. 1 to No. 9. Further, in the following Example 19, a production example of the optical recording medium No. 10 obtained by further adding a diimonium compound to the optical recording material of Example 11 is disclosed.

Comparative Examples 1 and 2 below disclose the preparation of a comparative optical recording material using a cyanine compound having a structure different from the compound of the present invention, and comparative optical recording media No. 1 and No. 2 using the comparative optical recording material. Further, in Comparative Examples 3 and 4 below, a comparative example of the comparative optical recording media No. 3 and No. 4 obtained by further adding a diimonium compound to the comparative optical recording material of Comparative Example 1 or 2 was disclosed.

In the following evaluation examples 1-1 and 1-2 and comparative evaluation examples 1-1 and 1-2, the metal complexes No. 1 and No. 2 and Comparative Example 1 obtained in Examples 1 and 2 and The comparative compounds No. 1 and No. 2 obtained in 2 were evaluated for decomposition temperature. These results are shown in [Table 5].

Further, in Comparative Examples 2-1 to 2-9 and Comparative Evaluation Example 2-1, comparisons were made between the optical recording media No. 1 to No. 9 and Comparative Example 2 obtained in Examples 10 to 18. In Optical Recording Medium No. 2, it was evaluated by UV absorption spectroscopy whether it is suitable for recording and reproduction using a short-wavelength laser. These results are shown in [Table 6].

Further, in the following evaluation examples 3-1 and 3-2 and comparative evaluation examples 3-1 to 3-4, the optical recording media No. 2 and No. 10 and Comparative Example 1 obtained in Examples 11 and 19 were used. The light resistance of the comparative optical recording media No. 1 to No. 4 obtained in ~4 was evaluated by measuring the absorbance residual ratio of the maximum absorption wavelength (λmax) of the UV absorption spectrum. These results are shown in [Table 7].

Further, in the following evaluation examples 4-1 to 4-5 and comparative evaluation example 4-1, the optical recording media No. 3, No. 4, and No obtained in Examples 12, 13, 16, 17, and 18 were obtained. The light resistance of the comparative optical recording medium No. 2 obtained in .7, No. 8 and No. 9 and Comparative Example 2 was evaluated by measuring the absorbance residual ratio of the maximum absorption wavelength (λmax) of the UV absorption spectrum. These results are shown in [Table 8].

[Example 1] Production of Metal Complex No. 1

<Step 1> Production of Compound No. 1 (Compound represented by G in the above formula (I) by i)) 4-Diethylamino-2-hydroxybenzaldehyde 3.86 g (20.0 mmol) and ethanol 100 ml Benzyloxyamine hydrochloride 3.19 g (20.0 mmol) and sodium acetate 1.64 g (20.0 mmol) were added at room temperature and stirred for 1 hour. The solvent was evaporated, and 100 g of chloroform and 100 g of water were added to the residue and washed with water. The organic layer was separated, dried over magnesium sulfate, and evaporated to give a pale yellow transparent oil (yield: 90%). The pale yellow transparent oil obtained was identified by the identification, and it was confirmed that it was the target compound No. 1. The results of the identification of the obtained pale yellow transparent oil are shown in the following [Table 1].

<Step 2> Preparation of Metal Complex No. 1 5.37 g (18.0 mmol) of Compound No. 1 obtained in Step 1, and 76 ml of methanol were charged, and a 28% methanol solution of sodium methoxide was added at room temperature. 3.47 g, stir for 1 hour. Then, 1.63 g (9.00 mmol) of copper (II) acetate was added, and the mixture was stirred at room temperature for 5 hours. The precipitate was removed by filtration and dissolved in 100 g of chloroform, and 200 g of water was added thereto twice to wash with water. The organic layer was separated, dried over magnesium sulfate, and then evaporated, and then recrystallized from chloroform/methanol mixed solvent to obtain 4.63 g (yield: 79%) of brown crystals. The obtained brown sheet crystals were confirmed to be the target metal complex No. 1 by various analyses. The results of the identification of the obtained brown flaky crystals are shown in the following [Table 2] to [Table 4].

[Example 2] Production of Metal Complex No. 2

<Step 1> Production of Compound No. 2 (Compound represented by G in the above formula (I), i)) 4-Ethylamino-2-hydroxybenzaldehyde 8.81 g (45.6 mmol) and ethanol 227 ml The allyloxyamine hydrochloride 5.00 g (45.6 mmol) and sodium acetate 3.74 g (45.6 mmol) were added at room temperature and stirred for 16 hours. The solvent was evaporated, and 100 g of chloroform and 100 g of water were added to the residue and washed with water. The organic layer was separated, dried over magnesium sulfate, and evaporated to give a pale yellow oil (10.6 g) (yield: 94%). The yellow transparent oil obtained was identified by the identification, and it was confirmed that it was the target compound No. 2. The results of the identification of the obtained yellow transparent oil are shown in the following [Table 1].

<Step 2> Preparation of Metal Complex No. 2 10.6 g (42.7 mmol) of Compound No. 2 obtained in Step 1, and 130 ml of methanol were added, and a 28% methanol solution of sodium methoxide was added at room temperature. 8.24 g, stir for 1 hour. Then, 3.78 g (21.3 mmol) of copper (II) acetate was added, and the mixture was stirred at room temperature for 14 hours. The precipitate was removed by filtration and dissolved in 100 g of chloroform, and 200 g of water was added thereto twice to wash with water. The organic layer was separated, dried over magnesium sulfate, and evaporated to ethyl ether. The crystals were recrystallized from ethyl acetate to afford 10.4 g (yield: 88%). The obtained brown solid was confirmed to be the target metal complex No. 2 by various analysis. The results of the identification of the obtained brown solids are shown in the following [Table 2] to [Table 4].

[Examples 3 to 9] Production of Metal Complex No. 13 to No. 19

<Step 1> Production Example of Compound No. 21 to No. 27 (Compound represented by G in the above formula (I), ii)) 13.6 mmol of a carbonyl derivative and 38 ml of ethanol were charged, and an amine salt was added at room temperature. 13.6 mmol, heated to reflux for 30 minutes. Then, 0.14 mmol of (+)-10-camphorsulfonic acid was added, and the mixture was heated under reflux for 6 hours. The solvent was distilled off, and the residue was washed with 100 ml of ethanol, and then removed by filtration and dried to give the object. As a result of the identification, it was confirmed that the obtained reaction products were respectively corresponding to the compound No. 21 to No. 27. The results of the identification of the obtained Compound No. 21 to No. 27 are shown in the following [Table 1].

<Step 2> Production Example of Metal Complex No. 13 to No. 19 Each of Compound No. 21 to No. 27 obtained in Step 1 was charged with 9.03 mmol and 60 ml of methanol, and sodium hydroxide was added at room temperature. 0.38 g (9.48 mmol) was dissolved in 20 ml of methanol and heated to reflux for 30 minutes. Then, 4.50 mmol of cobalt (II) acetate tetrahydrate was dissolved in 20 ml of methanol, and the mixture was heated under reflux for 3 hours. The precipitate was removed by filtration, washed with 100 ml of methanol, and filtered and dried to obtain a reaction product. From the results of various analyses, it was confirmed that the obtained reaction products were respectively corresponding to the metal compounds No. 13 to No. 19. The results of the identification of the obtained reaction product are shown in the following [Table 2] to [Table 4].

[Examples 10 to 18]

The metal complexes No. 1, No. 2, or No. 13 to No. 19 obtained in the above Examples 1 to 9 were each dissolved in 2, 2 so that the metal complex concentration became 1.0% by mass. An optical recording material as a 2,2,3,3-tetrafluoropropanol solution was obtained in a 3,3-tetrafluoropropanol solution. On a polycarbonate disk substrate having a base layer (0.01 μm) and a diameter of 12 cm, which was coated and hydrolyzed with a titanium chelate compound (T-50: manufactured by Nippon Soda Co., Ltd.), the above coating was applied by spin coating. The optical recording material was formed into an optical recording layer having a thickness of 100 nm, and optical recording media No. 1 to No. 9 were obtained, respectively.

[Embodiment 19]

In the above-mentioned Example 11, in addition to the above-mentioned metal complex No. 2, the diimmonium compound represented by the following [Chemical Formula 14] was further added to 2, 2, 3, 3 so that the concentration became 10% by mass. An optical recording material was prepared in the same manner as in the above Example 11 except for the tetrafluoropropanol solution, and an optical recording medium No. 10 was obtained using the optical recording material.

[Comparative Examples 1 and 2]

A comparative optical recording material was prepared in the same manner as in the above Examples 10 to 19 except that the following comparative compounds No. 1 and No. 2 were used instead of the metal complex, and the optical recording material was used to obtain a comparative optical recording medium No. 1 and No. 2.

[Comparative Examples 3 and 4]

In the above Comparative Examples 1 and 2, in addition to the above-mentioned comparative compound No. 1 or No. 2, the diimmonium compound represented by the above [Chem. 14] was further added to 2, 2 so that the concentration became 10% by mass. Comparative optical recording materials were prepared in the same manner as in Comparative Examples 1 and 2 except for the 3,3-tetrafluoropropanol solution, and comparative optical recording media No. 3 and No. 4 were obtained using the comparative optical recording materials.

[Evaluation Examples 1-1 and 1-2 and Comparative Evaluation Examples 1-1 and 1-2]

The metal complexes No. 1 and No. 2 and Comparative Compound No. 1 and No. 2 were measured for TG-DTA under a nitrogen gas flow of 100 ml/min at a temperature of 10 ° C/min. Further, in [Table 5], the decomposition temperature is the mass reduction start temperature. The evaluation results are shown in the following [Table 5].

It is clear from [Table 5] that among the metal complexes of the present invention, in particular, the metal complex represented by the above formula (II) has a lower decomposition point, so that the heat of the animal is lower and the heat interference can be suppressed. It is therefore suitable for forming an optical recording layer of an optical recording medium.

[Evaluation Examples 2-1 to 2-9 and Comparative Evaluation Example 2-1]

UV-spectrum absorption was measured for the optical recording media No. 1 to No. 9 obtained in Examples 10 to 18 and Comparative Optical Recording Media No. 2 obtained in Comparative Example 2. The evaluation results are shown in the following [Table 6].

As apparent from [Table 6], an optical recording material medium including an optical recording layer formed by the optical recording material of the present invention exhibits λ max in the vicinity of 300 to 450 nm in UV spectral absorption, and can confirm any optical recording. The media can be recorded by laser light from 380 to 420 nm. On the other hand, an optical recording medium comprising an optical recording layer formed by an optical recording material containing a comparative compound does not exhibit λ max in the vicinity of 300 to 450 nm in the UV spectral absorption, and cannot be used by 380 to 420 nm. The laser light is recorded.

[Evaluation Examples 3-1 and 3-2 and Comparative Evaluation Examples 3-1 to 3-4]

The optical recording media No. 2 and No. 10 of Examples 11 and 19 and the optical recording media No. 1 to No. 4 of Comparative Examples 1 to 4 were evaluated for light resistance. The optical recording medium was irradiated with light of 55,000 lux, and after irradiation for 24 hours and 48 hours, respectively, the absorbance residual ratio at λ max of the UV absorption spectrum before irradiation was measured. Further, in [Table 7], the diimonium compound shown in the above [Chemical Formula 14] was used as a concomitant. The evaluation results are shown below [Table 7].

It is clear from [Table 7] that the optical recording medium containing the optical recording layer formed by the optical recording material of the present invention has a high residual ratio of absorbance after 48 hours of irradiation, and in the case of using a diimmonium compound in combination, irradiation 48 After the hour, no decrease in the residual rate of absorbance was observed. On the other hand, in an optical recording medium including an optical recording layer formed of an optical recording material containing a comparative compound, the residual ratio of the absorbance decreased after 24 hours of irradiation, and after 48 hours of irradiation, the residual ratio of the absorbance was found to be remarkable. decline. Further, when the comparative compound and the diimonium compound were used in combination, the residual ratio of the absorbance after the irradiation for 24 hours was high and the initial light resistance was improved. However, after 48 hours of irradiation, the residual ratio of the absorbance was remarkably lowered, and the light resistance was not good.

[Evaluation Examples 4-1 to 4-5 and Comparative Evaluation Example 4-1]

Comparative optical recording medium Nos obtained in Optical Recording Media No. 3, No. 4, No. 7, No. 8 and No. 9 and Comparative Example 2 obtained in Examples 12, 13, 16, 17, and 18, respectively. .2, perform light resistance evaluation. The optical recording medium and the comparative optical recording medium were irradiated with light of 55,000 lux, and after irradiation for 50 hours and 100 hours, respectively, the absorbance residual ratio at λmax of the UV absorption spectrum before irradiation was measured. The results are shown in [Table 8].

An optical recording medium comprising an optical recording layer formed of the optical recording material of the present invention containing the metal complex of the present invention has a high residual absorbance after 50 hours of irradiation, and almost no absorbance remains after 100 hours of irradiation. The rate has dropped. On the other hand, the comparative optical recording medium including the optical recording layer formed of the comparative optical recording material containing the comparative compound showed a significant decrease in the absorbance residual ratio after the irradiation for 50 hours and after 100 hours of irradiation, and the light resistance was not good.

Industrial availability

According to the present invention, an optical recording material suitable for forming an optical recording layer of an optical recording medium for short-wavelength recording light can be provided. The specific metal complex has a low decomposition point, so that the heat storage property is low, the heat drying can be suppressed, and the sensitivity and light resistance are high, so that it is suitable for forming an optical recording layer of an optical recording medium.

Claims (8)

a compound represented by the following formula (I), (wherein R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ^{2 is} at G=i When represented by an alkyl group substituted with an alkyl group, adjacent R ² may be bonded to each other to form a ring, n is a number from 1 to 4, and R ³ represents an alkyl group having 1 to 8 carbon atoms and having 6 carbon atoms. An aryl group of ~20 or an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a aryl group having 7 to 20 carbon atoms The alkyl group may also have a substituent, and the methyl group in the above alkyl group having 1 to 8 carbon atoms may be substituted by -CH=CH ₂ , and the methylene group in the alkyl group having 1 to 8 carbon atoms is also Can be replaced by -O-, -CO- or -CH=CH-). A metal complex compound having a compound represented by the above formula (I) as a ligand, and the above metal complex is represented by the following formula (II): ^{(Wherein, R 1, R 2, R} 3 and n in the general formula (I) the same, ^'the same as the above general formula (I), the R ^1, R ^2' R ¹ in the general formula (I), the same as R ^{2, 'the} same as R ³ in the general formula (I), the R ^3, M represents a group 2 of the periodic table from the elements, group 8 elements, group 9 elements, group 10 elements, group 11 elements And any one of the metal atoms selected from the group consisting of elements of Group 12.). A metal complex which has a compound represented by the above formula (I) as a ligand, and the above metal complex is represented by the following formula (III): (wherein A, R ¹ , R ² , X and n are the same as the above formula (I), and R ^{1 '} , R ^{2 '} and M are the same as the above formula (II)). The metal complex of claim 2, wherein in the above formula (II), M is copper. The metal complex of claim 3, wherein in the above formula (III), M is cobalt. An optical recording material comprising at least one metal complex according to any one of claims 2 to 5. An optical recording material according to claim 6, wherein the optical recording material is In the solid content contained in the solid content, the content of the metal complex according to any one of claims 2 to 5 is from 10 to 100% by mass. An optical recording medium characterized in that an optical recording layer comprising the optical recording material of claim 6 or 7 is formed on a substrate.