JP2007210891A - New compound and optical recording material using the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound and its metal complex and an optical recording material, particularly suitable for formation of an optical recording layer in an optical recording medium for short-wavelength recording light. <P>SOLUTION: The oxime compound is represented by general formula (I) (wherein R<SP>1</SP>is a hydrogen atom, a 1-8C alkyl group, a 6-20C aryl group or a 7-20C arylalkyl group; R<SP>2</SP>is a 1-8C alkyl group, a 6-20C aryl group or a 7-20C arylalkyl group; R<SP>3</SP>is a hydrogen atom, a 1-18C alkyl group, a halogen atom, a nitro group, a cyano group or an amino group and adjacent R<SP>3</SP>may be connected to each other to form a ring; n is 1-4; the above 1-8C or 1-18C alkyl group, 6-20C aryl group, 7-20C arylalkyl group and amino group may have a substituent and the methyl group in the above 1-8C or 1-18C alkyl group may be substituted with -CH=CH<SB>2</SB>and methylene group may be substituted with -O-, -CO- or -CH=CH-). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  Optical recording media are generally widespread because they have excellent characteristics such as large recording capacity and non-contact recording or reproduction. In a write-once optical disc such as WORM, CD-R, DVD ± R, etc., the laser is focused on a very small area of the recording layer and recorded by changing the properties of the optical recording layer. Playback is performed by the difference.

  Currently, in the above optical disc, the wavelength of the semiconductor laser used for recording and reproduction is 750 to 830 nm for CD-R and 620 to 690 nm for DVD-R, but in order to realize further increase in capacity, An optical disk using a short wavelength laser has been studied. For example, an optical disk using light of 380 to 420 nm as recording light is being studied.

  In an optical recording medium for short wavelength recording light, various compounds are used for forming an optical recording layer. For example, Patent Documents 1 and 2 report optical recording materials containing a metal complex having a specific structure. However, these compounds are not always suitable for the absorption wavelength characteristics as optical recording materials used for forming an optical recording layer.

JP 2004-34645 A JP 2004-345212 A

  Accordingly, an object of the present invention is to provide an optical recording material suitable for forming an optical recording layer in a novel compound and a metal complex thereof, particularly an optical recording medium for short wavelength recording light.

  As a result of repeated studies, the present inventors have found a metal complex having a specific oxime compound as a ligand having an absorption wavelength characteristic suitable for forming an optical recording layer in an optical recording medium for short wavelength recording light, It has been found that the above problem can be solved by using this.

  This invention achieves the said objective by providing the oxime compound represented by the following general formula (I).

（式中、Ｒ¹は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｒ²は炭素原子数１〜８のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数７〜２０のアリールアルキル基を表し、Ｒ³は、水素原子、炭素原子数１〜１８のアルキル基、ハロゲン原子、ニトロ基、シアノ基又はアミノ基を表し、隣接するＲ³は互いに連結して環を形成していてもよく、ｎは１〜４の数である。上記炭素原子数１〜８又は１〜１８のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基及びアミノ基は、置換基を有していてもよく、上記炭素原子数１〜８又は１〜１８のアルキル基中のメチル基は−ＣＨ＝ＣＨ₂で置き換えられていてもよく、メチレン基は、−Ｏ−、−ＣＯ−又は−ＣＨ＝ＣＨ−で置き換えられていてもよい。）

(In the formula, 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 arylalkyl group having 7 to 20 carbon atoms, and R ² represents the number of carbon atoms. Represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and R ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a halogen atom, Represents a nitro group, a cyano group, or an amino group, and adjacent R ^{3 s} may be linked to each other to form a ring, and n is a number from 1 to 4. The number of carbon atoms is 1 to 8 or 1 to 18. The alkyl group, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms and the amino group may have a substituent, and the above-mentioned 1 to 8 or 1 to 18 carbon atoms. The methyl group in the alkyl group is replaced with —CH═CH ₂ And the methylene group may be replaced by —O—, —CO— or —CH═CH—.

  Moreover, this invention achieves the said objective by providing the metal complex which uses the oxime compound represented by the said general formula (I) as a ligand.

  Moreover, this invention achieves the said objective by providing the optical recording material characterized by containing at least 1 type of the said metal complex.

  In addition, the present invention achieves the above object by providing an optical recording medium in which an optical recording layer made of the above optical recording material is formed on a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the optical recording material suitable for formation of the optical recording layer in the optical recording medium for short wavelength recording light can be provided. Further, since the metal complex of the present invention has a low decomposition point, the heat storage property is low, the thermal interference is suppressed, the sensitivity and the light resistance are high, and it is suitable for forming an optical recording layer of an optical recording medium.

Hereinafter, preferred embodiments of the present invention will be described in detail.
First, the oxime compound represented by the general formula (I) will be described.

In the general formula (I), the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl , Isoamyl, tertiary amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, etc., and carbon represented by R ³ the alkyl group of atoms 1-18, other those exemplified above R ^1, nonyl, isononyl, decyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, stearyl and the like, R ¹ and R ² Examples of the aryl group having 6 to 20 carbon atoms are phenyl and naphthi. , Anthracene-1-yl, phenanthrene-1-yl and the like, and as the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ^2, benzyl, phenethyl, 2-phenylpropane, diphenylmethyl , Triphenylmethyl, styryl, cinnamyl, etc., and the halogen atom represented by R ³ includes fluorine, chlorine, bromine, iodine, etc., and the ring formed by connecting adjacent R ³ to each other Is a pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, urolidine ring, piperidine ring, piperazine ring, pyrrolidine ring, morpholine ring, thiomorpholine ring, Imidazolidine ring, pyrazolidine ring, isoxazolidine ring, isothiazolidine ring , Cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, tetrahydropyran ring and the like, and these rings may be condensed or substituted with other rings.

R ¹ and an alkyl group having 1 to 8 carbon atoms represented by R ^2, an alkyl group having 1 to 18 carbon atoms represented by R ^3, R ¹ and carbon atoms represented by R ² having 6 to 20 Any of the aryl group of R 7, the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ² , and the amino group represented by R ³ may have a substituent. Examples of the substituent include the following. In addition, R < ¹ > -R < ³ > is group containing carbon atoms, such as said C1-C8 alkyl group, and those groups contain a carbon atom among the following substituents. In the case of having a substituent, the total number of carbon atoms of R ^{1 to} R ³ including the substituent satisfies the specified range.
Examples of the substituent include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, and 3-hexyl. Alkyl groups such as cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl Methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, hex Alkoxy groups such as tiloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, Dibutylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, etc. Alkylthio group; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl , Alkenyl groups such as 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl; arylalkyls such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl Groups; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; Benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxy Heterocyclic groups such as oxazolidin-3-yl; halogen atoms such as fluorine, chlorine, bromine, iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoro Acyl groups such as methylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoylo Acyloxy groups such as bis; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino , Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbo Substituted amino groups such as ruamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl Group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, trialkylsilyl group, imide group, carbamoyl group, sulfonamide group and the like, and these groups may be further substituted. Further, the carboxyl group and the sulfo group may form a salt, complex or complex with an inorganic base or organic base.

  Specific examples of the oxime compound represented by the general formula (I) include the following compound No. 1-20 are mentioned.

The oxime compound represented by the general formula (I) is not particularly limited by its production method, and is obtained from, for example, a corresponding salicylaldehyde derivative and an amine compound as shown in the following [Chemical Formula 4]. Can do.

（式中、Ｒ¹、Ｒ²及びＲ³は上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² and R ³ are the same as those in the general formula (I).)

  The oxime compound represented by the general formula (I) can be used as a polymerization initiator, various polymer raw materials, pharmaceuticals, etc., in addition to a ligand of a metal complex.

Next, a metal complex having the oxime compound represented by the general formula (I) as a ligand will be described.
The metal complex having the oxime compound represented by the general formula (I) as a ligand is one in which at least one oxime compound represented by the general formula (I) is coordinated to a metal atom. In the oxime compound represented by the general formula (I), the hydrogen atom of the hydroxyl group and the metal atom are substituted, and X is coordinated to the metal atom to form at least one chelate structure. . The metal complex is preferably one that is chemically and thermally stable and has an appropriate absorption characteristic at the maximum absorption wavelength λmax in light absorption of a solution of the metal complex.

In the general formula (II), the metal atom represented by M is selected from the group consisting of Group 2, Group 8, Group 9, Group 10, Group 11, Group 11 and Group 12 elements of the Periodic Table Any metal atom is mentioned.
Among these metal atoms, a metal atom selected from copper, zinc, nickel, cobalt and iron is particularly preferable. When the metal atom is copper, a metal complex containing the metal atom can be produced at low cost. Since the light absorption property of the resulting metal complex is also good, it is more preferable.

  As a metal complex which has said preferable property, what is represented by the following general formula (II) whose said metal atom is a bivalent metal atom is mentioned, for example.

（式中、Ｒ¹、Ｒ²、Ｒ³及びｎは上記一般式（Ｉ）と同じであり、Ｒ^1'は上記一般式（Ｉ）におけるＲ¹と同じであり、Ｒ^2'は上記一般式（Ｉ）におけるＲ²と同じであり、Ｒ^3'は上記一般式（Ｉ）におけるＲ³と同じであり、Ｍは、周期表の２族元素、８族元素、９族元素、１０族元素、１１族元素及び１２族元素からなる群から選ばれるいずれかの金属原子を表す。）

^{(Wherein, R 1, R 2, R} 3 and n are as defined for general formula (I), R ^{1 'is} the same as R ¹ in the general formula (I), R ^2' is the general R ² is the same as R ² in formula (I), R ^{3 ′} is the same as R ³ in formula (I), and M is a group 2 element, group 8 element, group 9 element or group 10 in the periodic table. It represents any metal atom selected from the group consisting of elements, group 11 elements and group 12 elements.)

  Specific examples of the metal complex represented by the general formula (II) include the metal complex No. 1 shown below. 1-12 are mentioned.

The metal complex having the oxime compound represented by the general formula (I) as a ligand is not particularly limited by the production method. For example, as a method for producing a metal complex represented by the above general formula (II) which is a preferred form, an oxime compound is synthesized from a corresponding salicylaldehyde derivative and an amine compound as shown in [Chemical Formula 8] below, Examples include a method of synthesizing by a chelation reaction between the oxime compound and a metal salt compound, or a method of reacting an amine compound with a metal complex obtained by a chelation reaction between a corresponding salicylaldehyde derivative and a metal salt compound.

（式中、Ｒ¹、Ｒ²及びＲ³は上記一般式（Ｉ）と同じであり、Ｒ^1'、Ｒ^2'、Ｒ^3'及びＭは、上記一般式(II)と同じである。）

(Wherein R ¹ , R ² and R ³ are the same as in the above general formula (I), and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and M are the same as in the above general formula (II)). )

  In the reaction represented by [Chemical Formula 8], the metal salt compound used for the chelation reaction includes inorganic metal salts such as metal halides, hydroxides, sulfates and nitrates; organic acid metals such as acetates Salts; lower metal alkoxides such as methoxide, ethoxide and isopropoxide; and chelate complexes such as acetylacetone salt and EDTA salt. In the chelation reaction, a basic compound such as sodium hydroxide, lithium hydroxide, sodium methoxide, sodium acetate, sodium hydride, sodium amide, lithium amide, or an organic amine compound is used as a reaction agent as necessary. It may be used.

  The metal complex of the present invention can be used for various catalysts, contrast agents, pharmaceuticals, oxygen adsorbents, developers, beauty agents, photosensitizers, anti-fading agents, bactericides, and the like.

  Next, an optical recording medium comprising at least one of the above metal complexes and an optical recording medium comprising an optical recording layer made of 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. The optical recording medium of the present invention is obtained by forming an optical recording layer made of the optical recording material on a substrate.
The optical recording material of the present invention can be applied to various optical recording media depending on the light absorption characteristics of the metal complex contained therein. Among the optical recording materials of the present invention, the optical complex for the short wavelength laser having a wavelength of 380 nm to 420 nm is particularly suitable for the metal complex contained in the light absorption characteristic in the solution state with a maximum absorption wavelength λmax of 300 to It has in the range of 450 nm. The absorption intensity is preferably 1.0 × 10 ⁴ or more because ε at λmax is less than 1.0 × 10 ⁴ because the recording sensitivity may be lowered. Measurement of λmax and ε in the solution state of the metal complex using the compound represented by the above general formula (I) as a ligand is performed by selecting the concentration of the sample solution, the solvent used for the measurement, and the like according to a conventional method. Can be done.

  The method for producing the optical recording material of the present invention and the method for producing an optical recording medium characterized by forming an optical recording layer comprising the optical recording material on the substrate of the present invention are not particularly limited. Generally, lower alcohols such as methanol and ethanol; ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, ethyl acetate, Esters such as butyl acetate and methoxyethyl acetate; acrylic acid esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; benzene, toluene, xylene and the like Hydrocarbons: In a solvent such as chlorinated hydrocarbons such as methylene dichloride, dichloroethane, and chloroform, the metal complex of the present invention and, if necessary, various compounds described below are dissolved to prepare a solution optical recording material. . Subsequently, the optical recording medium is manufactured by forming the optical recording layer by a wet coating method in which the optical recording material is applied onto a substrate by spin coating, spraying, dipping, or the like. In addition to this method, a vapor deposition method, a sputtering method, or the like is also used. When using the said organic solvent, it is preferable that the usage-amount is made into the quantity from which the content of the said metal complex in the optical recording material of this invention will be 0.1-10 mass%.

  The optical recording layer is formed as a thin film, and the thickness is usually suitably 0.001 to 10 [mu] m, preferably 0.01 to 5 [mu] m.

  In the optical recording material of the present invention, the content of the metal complex of the present invention is preferably 1 to 100% by mass in the solid content contained in the optical recording material of the present invention. The optical recording layer is preferably formed so as to contain 5 to 100% by mass of the metal complex in the optical recording layer. In order to form an optical recording layer having such a metal complex content, the present invention The optical recording material further preferably contains 5 to 100% by mass of the above metal complex based on the solid content contained in the optical recording material of the present invention.

  In addition to the metal complex of the present invention, the optical recording material of the present invention includes, as necessary, an azo compound, a phthalocyanine compound, an oxonol compound, a squarylium compound, an indole compound, a styryl compound, a porphine compound, and azulium. Compounds, croconic methine compounds, pyrylium compounds, thiopyrylium compounds, triarylmethane compounds, diphenylmethane compounds, tetrahydrocholine compounds, indophenol compounds, anthraquinone compounds, naphthoquinone compounds, xanthene compounds, thiazines Compounds, such as polyethylene compounds, acridine compounds, oxazine compounds, spiropyran compounds, fluorene compounds, rhodamine compounds, etc., which are usually used in optical recording layers; polyethylene, polyester, polystyrene Resins such as polycarbonate, surfactants, antistatic agents, lubricants, flame retardants, radical scavengers such as hindered amines, pit formation accelerators such as ferrocene derivatives, dispersants, antioxidants, cross-linking agents, and light resistance-imparting agents Etc. may be contained. Furthermore, the optical recording material of the present invention may contain an aromatic nitroso compound, an aminium compound, an iminium compound, a bisiminium compound, a transition metal chelate compound, or the like as a quencher such as singlet oxygen. In the optical recording material of the present invention, these various compounds are used in an amount ranging from 0 to 50% by mass in the solid content contained in the optical recording material of the present invention.

  The optical recording material of the present invention may contain a diimonium compound. By containing the dimonium compound, it is possible to more effectively prevent a decrease in the residual absorbance with time of the optical recording medium of the present invention. The content of the diimonium compound is preferably in the range of 0 to 99% by mass, and more preferably 50 to 95% by mass in the solid content contained in the optical recording material of the present invention. .

  The material of the substrate on which such an optical recording layer is provided is not particularly limited as long as it is substantially transparent to writing (recording) light and reading (reproducing) light. For example, polymethyl methacrylate, A resin such as polyethylene terephthalate or polycarbonate, glass, or the like is used. Moreover, the shape can use arbitrary shapes, such as a tape, a drum, a belt, a disk, according to a use.

  On the optical recording layer, a reflective film can be formed by vapor deposition or sputtering using gold, silver, aluminum, copper or the like, and a protective layer is formed by acrylic resin, ultraviolet curable resin, or the like. You can also

Hereinafter, the present invention will be described in more detail with examples, comparative examples, and evaluation examples. However, the present invention is not limited by the following examples.
Examples 1 and 2 below are oxime compound Nos. Represented by the above general formula (I). 1 and no. 2 and the compound No. 2 1 or No. No. 2 metal complex No. 2 1 and no. 2 shows a production example.
In addition, Examples 3 and 4 below are the metal complex Nos. Obtained in Examples 1 and 2. 1 or No. Of an optical recording material containing No. 2 and an optical recording medium No. 2 using the optical recording material. 1 and no. 2 shows a production example. Further, Example 5 below shows an optical recording medium No. 1 obtained by further adding a diimonium compound to the optical recording material of Example 4. A production example of 2A is shown.

  In Comparative Examples 1 and 2 below, preparation of a comparative optical recording material using a cyanine compound having a structure different from that of the compound of the present invention, and comparative optical recording medium No. 1 using the comparative optical recording material. 1 and no. 2 shows a production example. Further, Comparative Examples 3 and 4 below are comparative optical recording media Nos. 1 and 4 obtained by further adding a diimonium compound to the comparative optical recording material of Comparative Example 3 or 4. 1A and No. 2A production example is shown

In the following Evaluation Examples 1-1 and 1-2 and Comparative Evaluation Examples 1-1 and 1-2, the metal complex Nos. Obtained in Examples 1 and 2 were used. 1 and no. 2 and Comparative Compound No. 1 obtained in Comparative Examples 1 and 2. The decomposition temperature of 1 and 2 was evaluated. The results are shown in [Table 1].
Further, in the following Evaluation Examples 2-1 and 2-2 and Comparative Evaluation Example 2-1, the optical recording media No. 1 obtained in Examples 3 and 4 were used. 1 and no. 2 and Comparative Optical Recording Medium No. 1 obtained in Comparative Example 2. For 2, the suitability of recording and reproduction with a short wavelength laser was evaluated by measuring the UV absorption spectrum. The results are shown in [Table 2].
Further, in the following Evaluation Examples 3-1 and 3-2 and Comparative Evaluation Examples 3-1 to 3-4, the optical recording media Nos. Obtained in Examples 4 and 5 were used. 2 and no. 2A and comparative optical recording media No. 1 obtained in Comparative Examples 1 to 4. 1, no. 1A, no. 2 and no. The light resistance of 2A was evaluated by measuring the residual absorbance at the maximum absorption wavelength (λmax) of the UV absorption spectrum. The results are shown in [Table 3].

[Example 1]
<Step 1> Compound No. Production Example 1 (oxime compound) 3.86 g (20.0 mmol) of 4-diethylamino-2-hydroxybenzaldehyde and 100 ml of ethanol were charged, and 3.19 g (20.0 mmol) of benzyloxyamine hydrochloride and sodium acetate 1. 64 g (20.0 mmol) was added and stirred for 1 hour. The solvent was distilled off, 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 5.37 g of a pale yellow transparent oil (yield 90%). As a result of various identifications, the obtained pale yellow transparent oil was compound No. 1 as the target product. 1 was confirmed. The identification result about the obtained pale yellow transparent oil is shown below.

(Identification result)
¹ H-NMR (CDCl ₃ solvent)
(Chemical shift ppm at peak top; multiplicity; number of protons)
(9.86; s; 1H), (8.07; s; 1H), (7.45-7.25; m; 5H), (6.91; d; 1H, J = 9.3 Hz), (6.22-6.14; m; 2H), (5.10; s; 2H), (3.32; q; 4H, J = 7.1 Hz), (1.14; t; 6H, J = 7.1Hz)

<Step 2> Metal Complex No. Production Example 1 Compound No. 1 obtained in Step 1 was prepared. 5.37 g (18.0 mmol) of No. 1 and 76 ml of methanol were added, and 3.47 g of a 28% methanol solution of sodium methoxide was added at room temperature, followed by stirring for 1 hour. Subsequently, 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 filtered and dissolved in 100 g of chloroform, and 200 g of water was added in two portions and washed with water. The organic layer was separated, dried over magnesium sulfate and evaporated, and then recrystallized from a chloroform / methanol mixed solvent to obtain 4.66 g of brown flake crystals (yield 79%). As a result of various identifications, the obtained brown flake crystals were metal complex No. 1 was confirmed. The identification result about the obtained brown flake crystal is shown below.

(Identification result)
(1) IR absorption (cm ^-1 )
2972, 1609, 1578, 1507, 1500, 1247, 1141
(2) UV absorption measurement (chloroform solvent)
λmax; 344.0 nm, ε; 5.71 × 10 ⁴ (concentration 3.19 × 10 ⁻⁶ mol / l)
(3) Elemental analysis: Cu / C / H / N (mass%)
9.59 / 65.8 / 6.5 / 8.3
(Theoretical value 9.65 / 65.7 / 6.4 / 8.5)

[Example 2]
<Step 1> Compound No. Preparation of 2- (oxime compound) 4-Diethylamino-2-hydroxybenzaldehyde (8.81 g, 45.6 mmol) and ethanol (227 ml) were charged, and allyloxyamine hydrochloride (5.00 g, 45.6 mmol) and sodium acetate were charged at room temperature. 74 g (45.6 mmol) was added and stirred for 16 hours. The solvent was distilled off, 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 with magnesium sulfate, and evaporated to obtain 10.6 g of a yellow transparent oil (yield 94%). As a result of various identifications, the obtained yellow transparent oil was compound No. 2 was confirmed. The identification result about the obtained yellow transparent oil is shown below.

(Identification result)
¹ H-NMR (CDCl ₃ solvent)
(Chemical shift ppm at peak top; multiplicity; number of protons)
(9.91; s; 1H), (8.06; s; 1H), (7.00-6.85; m; 1H), (6.29-6.13; m; 2H), (6 .02; ddt; 1H, J = 17.1, 10.2, 6.1 Hz), (5.35; dd; 1H, J = 17.3, 1.7 Hz), (5.26; dd; 1H , J = 10.5, 1.2 Hz), (4.59; d; 2H, J = 6.1 Hz), (3.35; q; 4H, J = 7.1 Hz), (1.17; t ; 6H, J = 7.1 Hz)

<Step 2> Metal Complex No. Production Example 2 Compound No. 2 obtained in Step 1 10.6 g (42.7 mmol) of No. 2 and 130 ml of methanol were added, and 8.24 g of a 28% methanol solution of sodium methoxide was added at room temperature, followed by stirring for 1 hour. Subsequently, 3.78 g (21.3 mmol) of copper (II) acetate was added and stirred at room temperature for 14 hours. The precipitate was filtered and dissolved in 100 g of chloroform, and 200 g of water was added in two portions and washed with water. The organic layer was separated, dried over magnesium sulfate and evaporated, and then recrystallized from ethyl acetate to obtain 10.4 g (yield 88%) of a brown solid. As a result of various identifications, the obtained brown solid was found to be the target metal complex No. 2 was confirmed. The identification result about the obtained brown solid is shown below.

(Identification result)
(1) IR absorption (cm ^-1 )
2993, 1610, 1578, 1506, 1245, 1140, 1005
(2) UV absorption measurement (chloroform solvent)
λmax; 352.5 nm, ε; 5.73 × 10 ⁴ (concentration 6.10 × 10 ⁻⁶ mol / l)
(3) Elemental analysis: Cu / C / H / N (mass%)
10.1 / 60.9 / 6.0 / 9.9
(Theoretical value 10.7 / 60.3 / 6.9 / 10.0)

[Examples 3 and 4]
The metal complex No. obtained in Examples 1 and 2 above. 1 or No. 2 is dissolved in a 2,2,3,3-tetrafluoropropanol solution so that the concentration of the metal complex is 1.0% by mass, respectively, and is optically recorded as a 2,2,3,3-tetrafluoropropanol solution. Obtained material. A titanium chelate compound (T-50: manufactured by Nippon Soda Co., Ltd.) is applied, hydrolyzed, and the above optical recording material is spin-coated on a 12 cm diameter polycarbonate disk substrate provided with a base layer (0.01 μm). The optical recording layer was coated to form an optical recording layer having a thickness of 100 nm. 1 and no. 2 were obtained respectively.

[Example 5]
In the above Example 4, the metal complex No. In addition to 2, the diimonium compound concentration represented by the following [Chemical Formula 9] was added to the 2,2,3,3-tetrafluoropropanol solution so that the concentration was 10% by mass. An optical recording material was prepared in the same manner, and an optical recording medium No. 1 was prepared using the optical recording material. 2A was obtained.

[Comparative Examples 1 and 2]
In place of the metal complex, the following comparative compound No. 1 and no. An optical recording material was prepared in the same manner as in Examples 3 to 4 except that the optical recording medium No. 2 was used. 1 and no. 2 was obtained.

[Comparative Examples 3 and 4]
In Comparative Examples 1 and 2, the above Comparative Compound No. 1 or No. 2 except that the concentration of the diimonium compound represented by the above [Chemical Formula 9] was further added to the 2,2,3,3-tetrafluoropropanol solution so as to be 10% by mass. A comparative optical recording material was prepared in the same manner as in Nos. 2 and 2, and the comparative optical recording medium No. 1A and No. 2A was obtained.

[Evaluation Examples 1-1 and 1-2 and Comparative Evaluation Examples 1-1 and 1-2]
Metal Complex No. 1 and 2 and comparative compound no. About 1 and 2, TG-DTA was measured on condition of temperature rising 10 degree-C / min in 100 ml / min nitrogen stream. In Table 1, the decomposition temperature is the mass decrease start temperature. The evaluation results are shown in the following [Table 1].

  As is apparent from [Table 1], the metal complex of the present invention has a low decomposition point, and therefore has low heat storage properties and suppresses thermal interference, and is suitable for forming an optical recording layer of an optical recording medium.

[Evaluation Examples 2-1 and 2-2 and Comparative Evaluation Example 2-1]
The optical recording media No. 1 obtained in Examples 3 and 4 were used. 1 and no. 2 and Comparative Example 2 obtained in Comparative Example 2 For 2, UV spectral absorption was measured. The evaluation results are shown in [Table 2] below.

  As apparent from [Table 2], the optical recording medium having the optical recording layer formed of the optical recording material of the present invention exhibits λmax in the vicinity of 300 to 450 nm in UV spectrum absorption. It was confirmed that recording was possible with a laser beam of 380 to 420 nm. On the other hand, a comparative optical recording material medium having an optical recording layer formed of an optical recording material containing a comparative compound does not exhibit λmax near 300 to 450 nm in UV spectrum absorption, and is recorded with a laser beam of 380 to 420 nm. I could not.

[Evaluation Examples 3-1 and 3-2 and Comparative Evaluation Examples 3-1 to 3-4]
The optical recording media of Examples 4 and 5 2 and no. 2A and comparative optical recording media No. 1 to Comparative Examples 1-4. 1, NO. 2, no. 1A and No. The light resistance of 2A was evaluated. Evaluation was performed by irradiating the optical recording medium with light of 55000 lux, irradiating for 24 hours and 48 hours, respectively, and then measuring the residual absorbance at λmax of the UV absorption spectrum before irradiation. The evaluation results are shown in [Table 3] below.

  As apparent from [Table 3], the optical recording medium having the optical recording layer formed of the optical recording material of the present invention has a high residual absorbance even after 48 hours of irradiation, and in the case of using a diimonium compound in combination. Even after 48 hours of irradiation, no decrease in the residual absorbance was observed. On the other hand, a comparative optical recording medium having an optical recording layer formed of a comparative optical recording material containing a comparative compound may show a decrease in the residual absorbance after 24 hours of irradiation, and is marked after 48 hours of irradiation. A decrease in the residual absorbance was observed. Furthermore, when the comparative compound and the diimonium compound were used in combination, the absorbance remaining rate after 24 hours of irradiation was high and the initial light resistance was improved. However, after 48 hours of irradiation, a significant decrease in absorbance remaining rate was observed, and light resistance was improved. Was not good.

Claims (7)

An oxime compound represented by the following general formula (I).

(In the formula, 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 arylalkyl group having 7 to 20 carbon atoms, and R ² represents the number of carbon atoms. Represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, and R ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a halogen atom, Represents a nitro group, a cyano group, or an amino group, and adjacent R ^{3 s} may be linked to each other to form a ring, and n is a number from 1 to 4. The number of carbon atoms is 1 to 8 or 1 to 18. The alkyl group, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms and the amino group may have a substituent, and the above-mentioned 1 to 8 or 1 to 18 carbon atoms. The methyl group in the alkyl group is replaced with —CH═CH ₂ And the methylene group may be replaced by —O—, —CO— or —CH═CH—.   A metal complex having the oxime compound represented by the general formula (I) as a ligand. The metal complex according to claim 2 represented by the following general formula (II).

^{(Wherein, R 1, R 2, R} 3 and n are as defined for general formula (I), R ^{1 'is} the same as R ¹ in the general formula (I), R ^2' is the general R ² is the same as R ² in formula (I), R ^{3 ′} is the same as R ³ in formula (I), and M is a group 2 element, group 8 element, group 9 element or group 10 in the periodic table. It represents any metal atom selected from the group consisting of elements, group 11 elements and group 12 elements.)   The metal complex according to claim 3, wherein in the general formula (II), M is copper.   An optical recording material comprising at least one metal complex according to claim 2.   The optical recording material according to claim 5, wherein the content of the metal complex according to any one of claims 2 to 4 is 1 to 100% by mass in a solid content contained in the optical recording material. An optical recording medium comprising an optical recording layer made of the optical recording material according to claim 5 or 6 formed on a substrate.