JP3967390B2 - Phthalonitrile compound and method for producing phthalocyanine compound - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a novel phthalocyanine near-infrared absorbing material that can be used for optical recording materials, photoelectric conversion materials, infrared cut filters, and the like, novel phthalonitrile compounds and diiminoisoindoline compounds that are intermediates thereof, and production methods thereof And an optical information recording medium containing the phthalocyanine near-infrared absorbing material.
[0002]
[Prior art]
Near-infrared absorbing materials are used in various applications. Examples of such applications include the following.
(1) Safe light filter for infrared photosensitive material
(2) Infrared cut filter for controlling plant growth
(3) Solar heat ray blocking material
(4) Infrared cut filter harmful to human eye tissue
(5) Infrared cut filter of semiconductor light receiving element.
As a larger application, an application as a recording material in an optical information recording medium can be mentioned.
[0003]
So far, as infrared absorbing substances, cyanine dyes, phenanthrene dyes, naphthoquinone dyes, pyrylium dyes, squarylium dyes, etc. are known, and information recording media using these dyes as recording materials are also known. (For example, JP-A-55-97033, JP-A-58-83344, JP-A-58-224793, JP-A-58-214162, JP-A-59-24692, etc.).
[0004]
However, the above dyes have various problems when used as recording materials. For example, phenanthrene dyes, naphthoquinone dyes, and squarylium dyes have the advantage of being easy to deposit, but have a problem of low reflectivity. When the reflectivity is low, the contrast related to the reflectivity between the portion recorded by the laser beam and the unrecorded portion becomes low, making it difficult to reproduce the recorded information. In addition, the pyrylium dyes and cyanine dyes have the advantage that they can be coated by coating, but have a problem that they are inferior in light resistance and easily deteriorate due to reproduction light (natural light).
[0005]
In contrast to the above dyes, phthalocyanine dyes have extremely high stability to heat and light, and recording media using an organic dye thin film as a recording layer are known in which a phthalocyanine compound is used for the organic dye thin film. (Japanese Patent Laid-Open Nos. 58-183296 and 58-37851). While phthalocyanine compounds have the feature of extremely high stability to heat and light, they are poorly soluble in organic solvents, etc., and can be thinned only by vapor deposition in the past. There is a problem that a high refractive index and a high reflectance cannot be obtained.
[0006]
On the other hand, recently, semiconductor lasers having an oscillation wavelength (up to 680 nm) in a wavelength shorter than the wavelength range used in conventional optical discs to increase the recording density have begun to be put into practical use. However, none of the conventional organic dye thin films have light absorption ability and light reflection ability in a wavelength region of 700 nm or less, and there is a limit to the high density recording property in terms of material.
[0007]
Furthermore, a write-once compact disc (CD-R) recording medium in which an organic dye thin film, a metal reflective layer, and a protective layer are sequentially laminated on a substrate requires a high reflectivity to satisfy the CD standard. Therefore, it is necessary to develop an organic dye material having a high refractive index in the reproduction wavelength region (700 to 830 nm) and high stability.
[0008]
Recently, in order to prevent the association of phthalocyanine compounds and achieve a high refractive index, an attempt has been made to introduce a bulky alkoxy group at the α-position of phthalocyanine, and further a wavelength-matched CD using a halogenated phthalocyanine. -R type recording media have been proposed (JP-A-3-62878, JP-A-3-215466, JP-A-4-348168, JP-A-4-226390, JP-A-4-15263-6, JP-A-5-17477, No. 5-86301, No. 5-25177, No. 5-25179, No. 5-17700, No. 5-1272, etc.).
[0009]
[Problems to be solved by the invention]
However, these phthalocyanine compounds certainly improve the refractive index and the like, but they are not yet fully satisfied, and further improvements are desired.
[0010]
Accordingly, a first object of the present invention is to provide a novel phthalocyanine near-infrared absorber having improved solubility, high productivity, and high absorption in the near-infrared without impairing the inherent stability of the phthalocyanine compound. And an intermediate thereof, and a production method thereof.
In addition, a second object of the present invention is to provide a recording medium using a phthalocyanine compound as a recording material that has high solubility in an organic solvent, high productivity, and can be applied with a solvent, while taking advantage of the characteristics of the phthalocyanine compound. There is to do.
Furthermore, a third object of the present invention is to provide a recording medium applicable to an optical pickup using a 630-720 nm semiconductor laser capable of high density recording.
Furthermore, a fourth object of the present invention is a recording that has a high refractive index in a wavelength range of 770 to 830 nm and can achieve a high reflectivity CD-R media excellent in storage stability and reproduction stability. To provide a medium.
[0011]
[Means for Solving the Problems]
The phthalocyanine compound is a macrocyclic planar compound, and has extremely high associative properties. Therefore, when it is thinned, the absorption spectrum becomes broad and the reflectance (refractive index) becomes low.
Therefore, the present invention introduces a sterically bulky substituent as a substituent to the phthalocyanine ring, prevents association, realizes high absorption capacity and high reflectance (refractive index), and organic The solubility in a solvent is also improved.
[0015]
That is,According to the present invention, 3- or 4-nitrophthalonitrile and one residue selected from a bornane residue, a norbornane residue, and a norbornene residue.Mercaptan derivatives withIn the presence of sodium hydride in an organic solvent, a method for producing a phthalonitrile compound represented by the following general formula (I)Is provided.
[Chemical 1]
(Where X¹, R¹And y are as follows.
X¹:Sulfur atom, R¹: Optionally substituted or via a methylene group X¹One residue selected from a bornane residue, a norbornane residue and a norbornene residue, which may be bonded to Y, y: 1 or 2. )
[0016]
According to the present invention, at least one phthalonitrile compound represented by the general formula (I) orfollowingIt is characterized by reacting at least one diiminoisoindoline compound represented by the general formula (II) with a metal or a metal derivative in an organic solvent.followingA method for producing a metal phthalocyanine compound represented by the general formula (III) is provided.
[Chemical 2]
(Where X¹, R¹And y are as follows.
X¹:Sulfur atom, R¹: Optionally substituted or via a methylene group X¹One residue selected from a bornane residue, a norbornane residue and a norbornene residue, which may be bonded to Y, y: 1 or 2. )
[Chemical 3]
[Wherein M, X¹~ X^Four, R¹~ R^FourAnd k to n each represent the following.
M: a divalent, trivalent or tetravalent metal atom which may have two hydrogen atoms, a halogen atom or an oxygen atom, X¹~ X^Four:Sulfur atom, R¹~ R^Four: Each may be independently substituted or X through a methylene group¹One residue selected from a bornane residue, a norbornane residue and a norbornene residue, k, l, m, n: each independently an integer of 0 to 4, provided that all are 0 simultaneously In the case where k, l, m, and n are 3 or less, the other substituent of the benzene ring is a hydrogen atom or a halogen atom. ]
  In addition, lithium or sodium is allowed to act on at least one phthalonitrile compound represented by the general formula (I) or at least one diiminoisoindoline compound represented by the general formula (II) in an organic solvent. A method for producing a phthalocyanine compound in which M in the general formula (III) is two hydrogen atoms is provided.
[0017]
Furthermore, according to the present invention, in an optical information recording medium in which a recording layer is provided directly on a substrate or via an undercoat layer, and further, if necessary, a protective layer is provided on the recording layer, An optical information recording medium comprising the phthalocyanine compound represented by the general formula (III) is provided.
[0018]
According to the present invention, the optical information is a write-once compact disc type recording medium in which a metal reflective layer is provided between the recording layer and the protective layer and records a CD format signal. A recording medium is provided, and in the general formula (III), k = 1 = m = n = 1 or 2, the substitution position is 1 or / and 4 in the formula, and the other substituent is a hydrogen atom or The optical information recording medium that is a halogen atom is provided.
[0019]
The present invention will be described in detail below. The novel phthalonitrile compound of the present invention is useful as an intermediate of the phthalocyanine near-infrared absorbing material of the present invention, and is represented by the following general formula (I).
[Chemical 1]
(Where X¹, R¹And y are as follows.
X¹:Sulfur atom, R¹: Optionally substituted or via a methylene group X¹One residue selected from a bornane residue, a norbornane residue and a norbornene residue, which may be bonded to Y, y: 1 or 2. )
[0020]
In the above definition, R¹Specific examples of these include the residues shown in Table 1.
[0021]
[Table 1- (1)]
[0022]
[Table 1- (2)]
[0023]
The phthalonitrile compound represented by the general formula (II) of the present invention is:3- or 4-nitrophthalonitrileBy reacting with a mercaptan derivative having one residue selected from the above bornane residue, norbornane residue and norbornene residue in the presence of sodium hydride in an organic solvent,Reaction formula (II)Can be manufactured according to. In addition, the phthalonitrile compound represented by the following general formula (I) is:3- or 4-nitrophthalonitrileBy reacting with an alcohol derivative having one kind of residue selected from the above bornane residue, norbornane residue and norbornene residue in the presence of sodium hydride in an organic solvent,Reaction formula (I)Can be manufactured according to.
[Formula 4]
[0024]
Examples of the alcohol derivative and mercaptan derivative having the residue used herein include alcohols and mercaptan derivatives having the residues shown in Table 1. Examples of the organic solvent to be used include N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. In particular, N, N-dimethylformamide, N, N- Dimethylacetamide is preferred.
The usage-amount of the said alcohol derivative and mercaptan derivative is 0.5-2 times mole with respect to the said nitrophthalonitrile, Preferably it is 0.8-1.2 times mole. Moreover, the reaction temperature at this time is -20-120 degreeC, Preferably it is -10-60 degreeC.
[0027]
The novel diiminoisoindoline compound of the present invention is useful as an intermediate of the phthalocyanine near-infrared absorbing material of the present invention, and is represented by the following general formula (II).
[Chemical 2]
(Where X¹, R¹And y are as follows.
X¹:Sulfur atom, R¹: Optionally substituted or via a methylene group X¹One residue selected from a bornane residue, a norbornane residue and a norbornene residue, which may be bonded to Y, y: 1 or 2. )
In the above equation, R¹Specific examples of the residues are the same as those in the general formula (I).
[0028]
In the diiminoisoindoline compound represented by the general formula (II) of the present invention, at least one phthalonitrile compound represented by the general formula (I) is present in an alcohol solvent in the presence of sodium (metal sodium or sodium alkoxide). Below, it is obtained according to the following reaction formula (V) by reacting with ammonia gas.
[Chemical 6]
In this case, methanol is a typical alcohol.
[0029]
The novel phthalocyanine near-infrared absorbing material of the present invention is represented by the following general formula (III).
[Chemical 3]
[Wherein M, X¹~ X^Four, R¹~ R^FourAnd k to n each represent the following.
M: a divalent, trivalent or tetravalent metal atom which may have two hydrogen atoms, a halogen atom or an oxygen atom, X¹~ X^Four:Sulfur atom, R¹~ R^Four: Each may be independently substituted or X through a methylene group¹One residue selected from a bornane residue, a norbornane residue and a norbornene residue, k, l, m, n: each independently an integer of 0 to 4, provided that all are 0 simultaneously In the case where k, l, m, and n are 3 or less, the other substituent of the benzene ring is a hydrogen atom or a halogen atom. ]
[0030]
In the general formula (III), examples of the metal atom represented by M include Al, Si, Ca, Cd, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, and Pd. , In, Sn, Pt, Pb and the like.
[0031]
The phthalocyanine near-infrared absorbing material represented by the general formula (III) has high solubility in an organic solvent without impairing the inherent stability of the phthalocyanine compound, and of course has a high absorption power for near-infrared rays. Have That is, since the solubility is improved, a thin film can be formed by a solvent coating method, a film having excellent productivity, good stability, and high absorbability can be obtained, and can be applied to various electronic materials.
[0032]
The phthalocyanine near-infrared absorbing material represented by the general formula (III) of the present invention includes at least one phthalonitrile compound represented by the general formula (I) or at least one kind represented by the general formula (II). It can be produced by reacting a diiminoisoindoline compound with a metal or a metal derivative.
[0033]
In this case, the phthalocyanine ring synthesis is preferably carried out in an organic solvent. That is, at least one (1 to 4) phthalonitrile or diiminoisoindoline compound as a raw material is heated and reacted at 90 ° C. to 240 ° C. in a solvent with a metal or a metal derivative. Here, when the reaction temperature is lower than 90 ° C., problems such as slow or non-progression of the reaction occur. When the reaction temperature exceeds 240 ° C., a large amount of decomposition products are generated and the yield decreases. The amount of the solvent used is 1 to 100 times, preferably 3 to 25 times the weight of the phthalonitrile or diiminoisoindoline compound, and the solvent may have a boiling point of 90 ° C. or higher. As the solvent to be used, alcohol is preferable, and specific examples thereof include n-butyl alcohol, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, Examples include 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butkinethanol and the like. Moreover, as a metal or metal derivative used for reaction, Al, Si, Ca, Cd, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb and their halides, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes and the like can be mentioned.
[0034]
As for the usage-amount of a metal or a metal derivative, and a phthalonitrile or a diiminoisoindoline compound, 1: 3-6 mol is preferable by molar ratio.
As a catalyst for the ring formation reaction, an organic base, for example, a strong base auxiliary such as diazabicycloundecene or diazabicyclononene may be added, and the addition amount thereof may be phthalonitrile or diiminoisoindoline. It is 0.1-10 mol with respect to 1 mol of compounds, Preferably it is 0.5-2 mol.
[0035]
Further, in the case of the so-called metal-free phthalocyanine in which M is two hydrogen atoms in the general formula (III), at least one phthalonitrile compound represented by the general formula (I) or the general formula (II) It can be produced by allowing lithium or sodium to act on at least one diiminoisoindoline compound represented by
[0036]
This reaction is also preferably carried out in an organic solvent (particularly an alcohol). That is, phthalonitrile or diiminoisoindoline compound and Na, Li, CH_ThreeThe reaction is carried out at 70 to 150 ° C. in alcohol in the presence of ONa, NaH or butyllithium. Here, the addition amount of the metal Li or Na is preferably 0.5 to 4 times the mole of the phthalonitrile or diiminoisoindoline compound. Specific examples of the alcohol to be used and the amount of alcohol are the same as those in the above-described production of metal phthalocyanine, but the reaction temperature is 150 ° C. or lower. When it exceeds 150 ° C., the generation of decomposition products increases.
[0037]
The optical information recording medium of the present invention is an optical information recording medium in which a recording layer is provided on a substrate directly or via an undercoat layer, and further, if necessary, a protective layer is provided on the recording layer. And a phthalocyanine compound represented by the general formula (III), and in a preferred embodiment, a metal reflective layer is provided between the recording layer and the protective layer, and a CD format signal is recorded. This is a write-once compact disc type recording medium.
[0038]
The phthalocyanine compound used in the present invention is a sterically bulky substituent on the benzene ring of the phthalocyanine skeleton.¹R¹) By introducing a substituent represented by y, association is prevented, high absorption and high reflectance (refractive index) are realized, and solubility in organic solvents is improved. Therefore, since the CD-R recording medium using the present phthalocyanine has a high reflectance and excellent storage stability and reproduction stability because it exhibits a high refractive index at wavelengths of 770 to 830 nm and has high stability. Further, since it has high absorption ability and light reflectivity at a wavelength of 630 to 720 nm and can be applied to a pickup using a semiconductor laser with a wavelength of 630 to 720 nm, it is 1.5 to 1 compared with the current recording medium compatible with 770 to 830 nm. .8 times higher density is possible.
[0039]
Among the phthalocyanine compounds represented by the above general formula (III) used in the present invention, in particular, substitution in which k = l = m = n = 1 or 2 and the substitution position is 1 or / and 4 in the formula In which other substituents are hydrogen atoms or halogen atoms (bromine atoms), the absorption wavelength can be easily controlled, the association is prevented, the refractive index of the film is increased, and the reflection is improved. It is particularly preferable because the rate can be improved.
[0040]
First, the configuration of the recording medium will be described.
FIG. 1 is a diagram showing an example of a layer structure applicable to the recording medium of the present invention. A recording layer 2 is provided on a substrate 1 via an undercoat layer 3 as necessary, and further protected as necessary. Layer 4 is provided.
FIG. 2 is a diagram showing another example of the layer structure that can be applied to the recording medium of the present invention. A metal reflection layer 5 is provided on the recording layer 2 having the structure shown in FIG.
[0041]
The recording medium of the present invention may have an air sandwich structure in which the recording layer (organic thin film layer) having the configuration shown in FIGS. 1 and 2 is disposed inside and sealed with another substrate through a space, and a protective layer. It is also possible to have a laminated structure bonded via
[0042]
Next, the required characteristics of the constituent layers and the constituent materials will be described.
1) Substrate
As a necessary characteristic of the substrate, when recording / reproducing is performed from the substrate side, it must be transparent to the laser beam used. However, when recording / reproducing is performed from the recording layer side, it is not necessary to be transparent. As the substrate material, for example, polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, polyimide or other plastic, glass, ceramic, metal, or the like can be used. A tracking guide groove or guide pit and a preformat such as an address signal may be formed on the surface of the substrate.
[0043]
2) Recording layer
The recording layer is capable of causing some optical change upon irradiation with laser light and recording information by the change, and the recording layer needs to contain the phthalocyanine compound of the general formula (I). . In forming the recording layer, the compounds of the present invention may be used alone or in combination of two or more. Furthermore, the compounds of the present invention may be other dyes such as polymethine dyes, naphthalocyanine series, squarylium series, croconium series, pyrylium series, naphthoquinone series, anthraquinone (indanthrene) series, xanthene series, triphenylmethane series, azulene series, Tetrahydrocholine, phenanthrene, triphenothiazine dyes or metal complex compounds may be used in combination. In this case, the above dyes may be used alone or in combination of two or more.
[0044]
In addition, the compound of the present invention is a metal, a metal compound such as In, Al, Te, Bi, Al, Be, TeO.₂SnO, As, Cd, etc. can also be used in the form of dispersion mixing or lamination. Further, various compounds such as ionomer resin, polyamide resin, vinyl resin, natural polymer, silicone, liquid rubber, or silane coupling agent are dispersed and mixed in the compound of the present invention. Alternatively, it may be used together with a stabilizer (for example, a transition metal complex), a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer and the like for the purpose of improving characteristics.
[0045]
The recording layer can be formed by ordinary means such as vapor deposition, sputtering, CVD or solvent coating. In the case of using a coating method, the above compound or the like is dissolved in an organic solvent, and a conventional coating method such as spraying, roller coating, dipping or spinner coating is performed. As the organic solvent, generally alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylacetamide and N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, Ethers such as tetrahydrofuran, dioxane, diethyl ether and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogenated carbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride and trichloroethane, benzene and xylene , Aromatics such as monochlorobenzene and dichlorobenzene, or cellsolves such as methylcellosolve and ethylcellosolve, hexane, pentane, cyclohexane Hexane, or the like can be used hydrocarbons such as methylcyclohexane.
The film thickness of the recording layer is 100 to 10 μm, preferably 200 to 1000 μm in the case of the medium configuration as shown in FIG. 1, and 300 to 5 μm, preferably 500 μm in the case of the medium configuration as shown in FIG. ˜2000 cm is appropriate.
[0046]
3) Undercoat layer
The undercoat layer comprises (a) improved adhesion, (b) a barrier against water or gas, (c) improved storage stability of the recording layer, (d) improved reflectivity, (e) substrate from solvent And (f) formation of guide grooves, guide pits, and preformats. For the purpose of (a), polymers such as ionomer resins, polyamides, vinyl resins, natural resins, natural polymers, silicones, liquid rubbers, various polymer substances, and silane coupling agents may be used. For the purposes of (b) and (c), in addition to the above polymer materials, inorganic compounds such as SiO₂, MgF₂, SiO, TiO₂ZnO, TiN, SiN, and metals such as Zn, Cu, Ni, Cr, Ge, Se, Au, Ag, and Al, or semimetals can be used. For the purpose of (b), metals such as Al and Ag, and organic thin films having metallic luster such as methine dyes and xanthene dyes can be used, and (e) and (f) For the purpose, an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. The thickness of the undercoat layer is 0.01 to 30 μm, preferably 0.05 to 10 μm.
[0047]
4) Metal reflective layer
The metal reflective layer can be made of a metal or semi-metal that is highly resistant to corrosion and is not easily corroded. Specific examples of the material include Au, Ag, Cu, Al, Cr, and Ni, and Au and Al are preferable. These metals and metalloids may be used alone or in combination of two or more. Examples of the film forming method include vapor deposition and sputtering. The film thickness is 50 to 3000 mm, preferably 100 to 1000 mm.
[0048]
5) Protective layer, substrate surface hard coat layer
The protective layer or the substrate surface hard coat layer is used for the purpose of (a) protecting the recording layer from scratches, dust, dirt, etc., (b) improving the storage stability of the recording layer, and (c) improving the reflectance. Is done. For these purposes, the materials shown for the undercoat layer can be used. In addition, SiO, SiO₂Organic resins such as acrylic resin, polycarbonate, epoxy resin, polystyrene, polyester resin, vinyl resin, cellulose, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, natural rubber, styrene-butadiene resin, chloroprene rubber Also, heat softening and heat melting resins such as waxes, alkyd resins, drying oils and rosins can be used. Among the above materials, the most preferable material for the protective layer or the substrate surface hard coat layer is an ultraviolet curable resin excellent in productivity. The film thickness of the protective layer or the substrate surface hard coat layer is 0.01 to 30 μm, preferably 0.05 to 10 μm.
In the present invention, the undercoat layer and the protective layer can contain a stabilizer, a dispersant, a flame retardant, a lubricant, an antistatic agent, a surfactant, a plasticizer, and the like, as in the case of the recording layer. .
[0049]
In the present invention, the phthalocyanine compound represented by the general formula (III) is contained in the recording layer. As specific examples of the compound represented by the general formula (III),For example, Compound No. 2, 11, 13, 18, and 20. The other compounds in Table 2 are reference examples.
[0050]
[Table 2- (1)]
[0051]
[Table 2- (2)]
[0052]
[Table 2- (3)]
[0053]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0054]
Reference example 1(Synthesis of phthalonitrile)
(I) 15 g (97.2 mmol) of borneol is dissolved in 80 ml of Dry DMF under an argon atmosphere and kept at about 5 ° C. in an ice bath. Then 3.89 g (97.2 mmol) of sodium hydride (60%) is added. Here, a solution of 16.82 g (97.2 mmol) of 3-nitrophthalonitrile dissolved in DMF is gradually added dropwise. After completion of the addition, the ice bath is removed and the mixture is stirred at room temperature for 36 hours. The reaction product is poured into 400 ml of dilute hydrochloric acid, extracted with about 1 liter of toluene, the toluene layer is washed thoroughly with water, an appropriate amount of magnesium sulfate is added, stirred, allowed to stand and filtered, and the toluene in the filtrate is distilled off. Purified with toluene silica gel, and the obtained crystals were washed with methanol and then with hexane and dried to obtain 23.48 g (yield: 86.) of a compound represented by the following formula (a) (white crystals). 2%).
[Chemical 7]
The elemental analysis values of the obtained compound are as follows, and its IR spectrum is shown in FIG.
C (%) H (%) N (%) O (%) Theoretical value 77.14 7.14 10.0% 5.71 Actual value 77.38 7.01 10.21 5.40
[0059]
Reference example 2(Synthesis of phthalocyanine)
  8 g (28.6 mmol) of the compound represented by the formula (a) was dissolved by heating in 22 g of n-pentanol and 3.04 g (28.6 × 0.7 mmol) of diazabicycloundecene under an argon atmosphere. Add 1.27 g (286/4 mmol) of palladium (II) chloride and stir at a temperature of 120 to 130 ° C. for 30 hours. After cooling to room temperature, the toluene insoluble matter of the reaction product was collected by filtration, 300 ml of methanol was distilled off from the filtrate, the precipitated crystals were collected by filtration, washed with methanol and dried. Purified with 8/2 silica gel and expressed by the following formulas (f1), (f2), (f3) and (f4) (f1) / (f2) / (f3) / (f4) = 15/75 4.86 g (yield 55.54%) of a mixture of 5/5/5 (dark green crystals). Note that λmax of this mixture in chloroform was 696 nm. The IR spectrum is shown in FIG.
[0060]
Embedded image
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However, in said formula (f1)-(f4), R represents the following group.
Embedded image
[0061]
Example 1(Synthesis of phthalocyanine)
  The same procedure as in Reference Example 2 was conducted except that the borneol of Reference Example 1 was obtained by replacing the oxygen atom in the borneol with a sulfur atom and obtaining a compound in which the oxygen atom in the compound represented by the formula (a) was replaced with a sulfur atom. TheThe phthalocyanine compounds shown in Table 3 were obtained. Also in this embodiment,Reference example 2Similar isomers exist but are not listed separately.
[0062]
[Table 3]
[0064]
(Evaluation)Example 1The phthalocyanine compound obtained in the above is soluble in various solvents, a coating film obtained by a solvent coating method can be easily obtained, and has an excellent absorption ability in the near infrared region.
[0065]
Reference example 3
  On a substrate having a guide groove having a depth of 1000 mm, a half width of 0.4 μm, and a track pitch of 1.4 μm formed of a photopolymer on a polymethyl methacrylate plate having a thickness of 1.2 μm, compound No. 2 in Table 2 was used. A 1,2-dichloroethane solution of No. 1 was applied by a spinner, and a recording layer having a thickness of 800 mm was provided to obtain a recording medium.
[0066]
(Examples 2 and 3) Reference Example 3No. 1 of the compounds in Table 2. Instead,Each of the compound Nos. 18, no. Twenty 1,2-dichloroethane solutions were applied by a spinner, and a recording layer having a thickness of 800 mm was provided as a recording medium.
[0067]
(Comparative Example 1)Reference example 3In Table 2, compound No. Except for using a compound represented by the following formula (XI) instead of 18,Reference example 3In the same manner, a recording medium of Comparative Example 1 was obtained.
Embedded image
(Where t-Bu is a mixture of those at positions 2 to 2 "" and positions 3 to 3 "".
[0068]
AboveExample 2, Example 3 andUsing the recording medium of Comparative Example 1, recording was performed through the substrate under the following recording conditions, after which the recording position was reproduced with continuous laser light, and C / N was measured under the following conditions. The reflectance was also measured. The results are shown in Table 4.
Recording conditions: Linear velocity 2.1m / sec
Recording frequency 1.25MHz
Laser oscillation wavelength 680nm
Pickup lens A. 0.5
Playback conditions:
Scanning filter 30KHz
Reproduction power 0.25-0.3mW
[0069]
[Table 4]
[0070]
Reference example 4
Compound No. 1 of Table 2 was formed on an injection-molded polycarbonate substrate having a depth of 1000 mm, a half width of 0.45 μm, and a guide groove having a track pitch of 1.6 μm and a thickness of 1.2 mm. 4 of 2-ethoxyethanol / 1,2-dichloroethane / THF [= 8 / 1.5 / 0.5 (weight ratio)] mixed solution was applied by a spinner, and a recording layer having a thickness of 1800 mm was provided thereon. The film was vacuum-deposited with a thickness of 1200 mm to form a reflective layer, and an acrylic photopolymer was applied thereon as a spinner and UV-cured to form a protective layer to obtain a CD-R type recording medium.
[0071]
Example 4
  Reference example 4In Table 2, compound No. In place of Compound No. 4, Compound No. Except for using 2Reference example 4In the same manner as described above, a recording medium of Example 4 was obtained.
[0072]
(Comparative Example 2)Reference example 4In Table 2, compound No. Except that the phthalocyanine used in Comparative Example 1 was used instead of 4,Reference example 4In the same manner, a recording medium of Comparative Example 2 was obtained.
[0073]
(Comparative Example 3)Reference example 4In Table 2, compound No. Except for using the compound of the following formula (XII) instead of 4,Reference example 4In the same manner, a recording medium of Comparative Example 3 was obtained.
Embedded image
[0074]
Comparative Example 4
In Comparative Example 3, Comparative Example 4 was used in the same manner as Comparative Example 3 except that a mixture obtained by adding 10% by weight of the nickel complex compound of the following formula (XIII) to the compound of the above formula (XII) was used. A recording medium was obtained.
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[0075]
Example 4The EFM signal was recorded under the recording conditions of the laser oscillation wavelength of 790 nm and the linear velocity of 1.4 m / sec using the recording media of Comparative Examples 2 to 4, and the reflectance and optimum power of the unrecorded part before recording and after light irradiation. C at₁The number of errors was measured. The results are shown in Table 5.
[0076]
[Table 5]
[0077]
(Evaluation)
The optical information recording medium of the present invention has a high light absorption ability and light reflectivity at a wavelength of 630 to 720 nm, can be applied to a pickup using a semiconductor laser of 630 to 720 nm, and has a high refractive index at a wavelength of 770 to 830 nm. And having high stability, it is possible to provide a CD-R medium having high reflectivity and excellent storage stability and reproduction stability.
[0078]
【The invention's effect】
Since the phthalonitrile compound of claim 1 and the diiminoisoindoline compound of claim 2 have the structures represented by the general formula (I) and the general formula (II), respectively, the phthalocyanine near-infrared absorption of claim 3 It is useful as an intermediate for materials.
[0079]
Since the phthalocyanine near-infrared absorbing material of claim 3 has the structure represented by the general formula (III), various organic materials can be used while maintaining the stability of the phthalocyanine compound inherently to heat, light, and the like. It is soluble in a solvent and has high infrared absorption ability. As a result, it is possible to form a coating film by a solvent coating method, and the utilization form is greatly expanded, and it is particularly useful for an optical recording medium described later.
[0080]
Claim 1A process for producing a phthalonitrile compound represented by the general formula (I):Claim 2A process for producing a metal phthalocyanine compound represented by the general formula (III):Claim 3Any of the production methods of the metal-free phthalocyanine compound represented by the general formula (III) can easily obtain the target product under mild conditions. .
[0081]
An optical information recording medium using a compound produced by the method of the present invention isSince the recording layer contains the phthalocyanine compound represented by the general formula (III), the following excellent effects are obtained.
B) Since it has a high light absorption ability and light reflectivity at a wavelength of 630 to 720 nm, it can be applied to a pickup using a semiconductor laser of 630 to 720 nm capable of high density recording, and the current optical recording of 770 to 830 nm. The recording density can be increased by 1.6 to 1.7 times that of the medium.
B) Since it has a high refractive index at wavelengths of 770 to 830 nm and has high stability, it can provide a CD-R recording medium having high reflectivity and excellent storage stability and reproduction stability.
[0082]
Optical information recording mediaIn the general formula (III), a phthalocyanine compound in which k = 1 = m = n = 1 or 2, the substitution position is 1 or / and 4 in the formula, and the other substituent is a hydrogen atom or a halogen atom In the recording layer, the absorption wavelength can be easily controlled, the ability to prevent association is further improved, the refractive index of the film can be further increased, and the reflectance can be further improved. Join.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a layer structure that can be applied to a recording medium of the present invention.
FIG. 2 is a diagram showing another type of layer configuration example applicable to the recording medium of the present invention.
3 is an IR spectrum diagram of the phthalonitrile compound obtained in Example 1. FIG.
5 is an IR spectrum diagram of the phthalocyanine compound obtained in Example 2. FIG.

Claims (3)

A 3- or 4-nitrophthalonitrile is reacted with a mercaptan derivative having one residue selected from a bornane residue, a norbornane residue and a norbornene residue in an organic solvent in the presence of sodium hydride. A method for producing a phthalonitrile compound represented by the following general formula (I):
(Where X ¹ , R ¹ as well as y Represents the following:
X ¹ : Sulfur atom, R ¹ : Optionally substituted or via a methylene group X ¹ A residue selected from a bornane residue, a norbornane residue and a norbornene residue, y 1 or 2. ) Reacting at least one phthalonitrile compound represented by the general formula (I) or at least one diiminoisoindoline compound represented by the following general formula (II) with a metal or a metal derivative in an organic solvent. A method for producing a metal phthalocyanine compound represented by the following general formula (III):
(Where X ¹ , R ¹ as well as y Represents the following:
X ¹ : Sulfur atom, R ¹ : Optionally substituted or via a methylene group X ¹ A residue selected from a bornane residue, a norbornane residue and a norbornene residue, y 1 or 2. )
[Wherein M, X ¹ ~ X ^Four , R ¹ ~ R ^Four And k to n each represent the following.
M: a divalent, trivalent or tetravalent metal atom which may have two hydrogen atoms, a halogen atom or an oxygen atom, X ¹ ~ X ^Four : Sulfur atom, R ¹ ~ R ^Four : Each may be independently substituted or X through a methylene group ¹ One residue selected from a bornane residue, a norbornane residue and a norbornene residue, k, l, m, n: each independently an integer of 0 to 4, provided that all are 0 simultaneously In the case where k, l, m, and n are 3 or less, the other substituent of the benzene ring is a hydrogen atom or a halogen atom. ] Lithium or sodium is allowed to act on at least one phthalonitrile compound represented by the general formula (I) or at least one diiminoisoindoline compound represented by the general formula (II) in an organic solvent. In the general formula (III) A method for producing a phthalocyanine compound, wherein M is two hydrogen atoms.